JP7040089B2 - Photosensitive resin composition for partition wall formation, partition wall, organic electroluminescent element, image display device and lighting - Google Patents

Description

The present invention relates to a partition wall forming photosensitive resin composition used for forming a partition wall, in particular, a partition wall made of the partition wall forming photosensitive resin composition, an organic electric field light emitting element provided with the partition wall, and the organic electric field. The present invention relates to an image display device including a light emitting element and lighting.

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

Further, as a method of laminating various functional layers in the region surrounded by the partition wall, first, an ink containing the material constituting the functional layer is prepared, and then the prepared ink is injected into the region surrounded by the partition wall. How to do it is known. Among these methods, the inkjet method is often adopted because it is easy to accurately inject a predetermined amount of ink into a predetermined location.

Further, when the functional layer is formed by using ink, the partition wall is provided with ink repellency for the purpose of preventing the ink from adhering to the partition wall and preventing the inks injected between adjacent regions from being mixed with each other. It may be required to grant. Further, in recent years, various properties other than ink repellency are required for 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 agent, and a specific surfactant, there is no disconnection of electrodes and high-resolution images can be supported.
On the other hand, in Patent Document 2, a resin obtained by adding (meth) acrylic acid to a bisphenol A type epoxy resin, further adding anhydrous succinic acid, and then further adding a bisphenol A type epoxy resin is used. , It is described that a coating film having excellent heat-resistant coloring property can be obtained.

JP-A-2010-061093 Japanese Unexamined Patent Publication No. 2010-15397

In recent years, in order to improve the drive life of an element, there is a demand to reduce the outgas generated from the partition wall when the partition wall and the element emit light after the element is formed. The demand for higher brightness is also increasing, and higher performance is required.
As a result of studies by the present inventors, it has been difficult to sufficiently reduce the amount of outgas during operation of the light emitting element with the photosensitive resin composition for forming a partition wall described in Patent Document 1.
Patent Document 2 does not describe a partition wall, and when the present inventors examined the application of the photosensitive resin composition described in Patent Document 2 to a partition wall, the taper angle of the obtained partition wall was low, and the partition wall was obtained. The area of the opening surrounded by is small, and it is difficult to secure a sufficient area of the light emitting part.
Therefore, an object of the present invention is to provide a photosensitive resin composition for forming a partition wall, which has a small amount of outgas during operation of a light emitting element, is highly reliable, has a high taper angle, and can secure a sufficient area of a light emitting portion.
Another object of the present invention is to provide a partition wall formed by using the photosensitive resin composition for forming a partition wall, an organic electroluminescent element provided with the partition wall, an image display device including the organic electroluminescent element, and lighting. do.

As a result of diligent studies by the present inventors, it has been found that the above-mentioned problems can be solved by setting the acid value of the photosensitive resin composition within a specific range and further 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 photosensitive resin composition for forming a partition wall containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin.
The acid value of the photosensitive resin composition for forming a partition wall is 20 mgKOH / g or more with respect to the total solid content, and the acid value is 20 mgKOH / g or more.
A photosensitive resin composition for forming a partition wall, wherein the alkali-soluble resin (C) contains an alkali-soluble resin (c) having a partial structure represented by the following general formula (1).

(In the above 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 forming a partition wall 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) contains (c1) an epoxy (meth) acrylate resin.
[4] The (c1) epoxy (meth) acrylate resin has 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 wall formation according to [3], which contains at least one selected from the group consisting of an epoxy (meth) acrylate resin containing an epoxy (meth) acrylate resin and an epoxy (meth) acrylate resin containing a partial structure represented by the following general formula (iii). For photosensitive resin compositions.

(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) further represents. It may be substituted with any substituent. * Represents a bond.)

(In formula (ii), 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, and γ may have a single bond, —CO—, an alkylene group which may have a substituent, or a substituent. 2 Represents a cyclic hydrocarbon group of valence. The benzene ring in formula (iii) may be further substituted with any substituent. * Represents a bond.)

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

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

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a photosensitive resin composition for forming a partition wall, which has a small amount of outgas during operation of a light emitting element, is highly reliable, has a high taper angle, and can secure a sufficient area of a light emitting portion.

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

Hereinafter, the present invention will be described in detail. The following description is an example of an embodiment of the present invention, and the present invention is not specified thereto unless the gist thereof is exceeded.
In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic", and "(meth) acrylate" means "acrylate and / or methacrylate". , "Total solid content" shall mean all components other than the solvent in the photosensitive resin composition. Further, the numerical range represented by using "-" in the present invention means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present invention, the "(co) polymer" means that both a monopolymer (homopolymer) and a copolymer (copolymer) are contained, and also "(acid) anhydride" and "" (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 the polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).

In the present invention, the partition wall material refers to a bank material, a wall material, and a wall material, and similarly, the partition wall material refers to a bank, a wall, and a wall.
Further, 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 wall The photosensitive resin composition for forming a partition wall of the present invention contains (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator, and (C) an alkali-soluble resin. A photosensitive resin composition for forming a partition wall, wherein the acid value of the photosensitive resin composition for forming a partition wall is 20 mgKOH / g or more with respect to the total solid content, and the alkali-soluble resin (C) is described later. It is characterized by containing an alkali-soluble resin (c) having a partial structure represented by the general formula (1). If necessary, other components may be further contained, and for example, (D) a liquid repellent agent, a chain transfer agent, or an ultraviolet absorber may be contained.

In the present invention, the partition wall is for partitioning the functional layer (organic layer, light emitting portion) in the active drive type organic electroluminescent element, and for forming the functional layer in the partitioned region (pixel region). It is used to form pixels and the like composed of a functional layer and a partition wall by ejecting and drying the ink which is the material of the above.

[1-1] Components and Composition of Photosensitive Resin Composition for Forming a Partition walls The components constituting the photosensitive resin composition for forming a partition wall of the present invention and their compositions will be described.
The photosensitive resin composition for forming a partition wall of the present invention (hereinafter, may be simply referred to as “photosensitive resin composition”) is (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator and (C) an alkali. It contains a soluble resin and, more usually, a solvent. Further, the photosensitive resin composition for forming a partition wall of the present invention is preferably used for forming a liquid-repellent partition wall, and from such a viewpoint, it is preferable to contain (D) a liquid-repellent agent. As the components A) to (C), those exhibiting an action as a liquid repellent may be used.

[1-1-1] Component (A); Ethylene Unsaturated Compound The photosensitive resin composition for forming a partition wall of the present invention contains (A) an ethylenically unsaturated compound. (A) It is considered that the sensitivity becomes high by containing the ethylenically unsaturated compound.
The ethylenically unsaturated compound used here means a compound having one or more ethylenically unsaturated bonds in the molecule, and is polymerizable, crosslinkable, and a developing solution for exposed and non-exposed parts associated therewith. A compound having two or more ethylenically unsaturated bonds in the molecule is preferable from the viewpoint of expanding the difference in solubility, and the unsaturated bond is derived from a (meth) acryloyloxy group. That is, it is more preferably a (meth) acrylate compound.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups contained in the polyfunctional ethylenically 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. Further, the number is preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 7 or less. When it is at least the above lower limit value, the polymerizable property tends to be improved and the sensitivity tends to be high, and when it is at least the above upper limit value, the developability tends to be better.
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. Examples thereof include an ester obtained by an esterification reaction between an unsaturated carboxylic acid and a polybasic carboxylic acid with a polyvalent hydroxy compound such as the above.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylol propanetriacrylate, trimethylol ethanetriacrylate, pentaerythritol diacrylate, and pentaerythritol triacrylate. Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters in which the acrylates of these exemplary compounds are replaced with methacrylates. Similarly, an itaconic acid ester replaced with itaconate, a crotonic acid ester replaced with clonate, a maleic acid ester replaced with maleate, and the like can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include the acrylic acid ester and the methacrylic acid ester of the aromatic polyhydroxy compound such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcindiacrylate, resorcindimethacrylate, and pyrogalloltriacrylate. And so on.
The ester obtained by the esterification reaction of a polyvalent hydroxy compound such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound with an unsaturated carboxylic acid or a polybasic carboxylic acid is not necessarily a single substance, but is representative. Specific examples thereof include condensates of acrylic acid, phthalic acid, and ethylene glycol, condensates of acrylic acid, maleic acid, and diethylene glycol, condensates of methacrylic acid, terephthalic acid, and pentaerythritol, acrylic acid, adipic acid, and the like. Examples thereof include a condensate of butanediol and glycerin.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound is reacted with a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound is reacted with a polyol and a hydroxyl group-containing (meth) acrylic acid ester. Urethane (meth) acrylates as obtained; epoxy acrylates such as an addition reaction product of a 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-5003D, 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 Industry 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 Kayaku Kagaku Kogyo Co., Ltd.) and the like can be mentioned.

Among these, ester (meth) acrylates or urethane (meth) acrylates are preferably used as the (A) ethylenically unsaturated compound from the viewpoint of appropriate taper angle and sensitivity, and dipentaerythritol hexa (meth) acrylate is preferable. , Dipentaerythritol penta (meth) acrylate, 2-tris (meth) acryloyloxymethylethyl phthalic acid, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate It is more preferable to use a basic acid anhydride adduct, a dibasic acid anhydride adduct of pentaerythritol tri (meth) acrylate, and the like.
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, still more preferably 200 or more, from the viewpoint of sensitivity, liquid repellency, and taper angle. It is even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, and even more preferably 700 or less. The carbon number of the (A) ethylenically unsaturated compound is not particularly limited, but is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, and even more, from the viewpoint of sensitivity, liquid repellency, and taper angle. It is preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, and particularly preferably 30 or less.
Ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable from the viewpoints of sensitivity, liquid repellency, and taper angle, and among them, pentaerythritol tetra (meth) acrylate and pentaerythritol. Tri (meth) acrylates Dipentaerythritol hexa (meth) acrylates, dipentaerythritol penta (meth) acrylates and other trifunctional or higher-functional ester (meth) acrylates, 2,2,2-tris (meth) acryloyloxymethylethylphthal Addition of acid anhydride to trifunctional or higher functional ester (meth) acrylates such as acid, dibasic acid anhydride adduct of dipentaerythritol penta (meth) acrylate is a surface of sensitivity, liquid repellency and taper angle. Is even 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 set to the lower limit value or more, the sensitivity and the taper angle at the time of exposure tend to be good, and when it is set to the upper limit value or less, the developability tends to be good.

The content ratio of (A) ethylenically unsaturated compound 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, still more preferably 80 parts by mass. By mass or more, particularly preferably 90 parts by mass or more, usually 150 parts by mass or less, preferably 130 parts by mass or less, more preferably 120 parts by mass or less, still more preferably 110 parts by mass or less. When it is set to the lower limit value or more, the sensitivity tends to be good at the time of exposure and the taper angle tends to be good, and when it is set to the upper limit value or less, 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 active light, and a known photopolymerization initiator may be used. Can be done.

In the photosensitive resin composition of the present invention, a photopolymerization initiator usually used in this field can be used as the (B) photopolymerization initiator. Examples of such photopolymerization initiators include hexaarylbiimidazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime-based photopolymerization initiators, acetophenone-based photopolymerization initiators, and benzophenone-based photopolymerization initiators. Agent, hydroxybenzene photopolymerization initiator, thioxanthone photopolymerization initiator, anthraquinone photopolymerization initiator, ketal photopolymerization initiator, titanosen photopolymerization initiator, halogenated hydrocarbon derivative photopolymerization initiator, organic Boranolate-based photopolymerization initiator, onium salt-based photopolymerization initiator, sulfone compound-based photopolymerization initiator, carbamate derivative-based photopolymerization initiator, sulfonamide-based photopolymerization initiator, triarylmethanol-based photopolymerization initiator Can be 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 with the absorption wavelength of the ultraviolet absorber. The hexaarylbiimidazole-based compound represented is preferable.

In the above formula, R ¹¹ to R ¹³ are independently an alkyl group having 1 to 4 carbon atoms which may have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, or an alkoxy group having 1 to 4 carbon atoms. Representing a halogen atom, m, n and l each independently represent an integer of 0 to 5.

The carbon number of the alkyl group of R ¹¹ to R ¹³ is not particularly limited as long as it is in the range of 1 to 4, but from the viewpoint of sensitivity, it is preferably 3 or less, more preferably 2 or less. The alkyl group may be chain-like or cyclic. Specific examples of the alkyl group include, for example, a methyl group, an ethyl group, a propyl group and an isopropyl group, and among them, a methyl group and an ethyl group are preferable. As the substituent which the alkyl group having 1 to 4 carbon atoms of R ¹¹ to R ¹³ may have, a group of a monovalent non-metal atomic group excluding hydrogen is used, and a preferred example is a halogen atom (-). Examples thereof include F, -Br, -Cl, -I), a hydroxyl group, and an alkoxy group.

Further, the carbon number of the alkoxy group of R ¹¹ to R ¹³ is not particularly limited as long as it is in the range of 1 to 4, but from the viewpoint of sensitivity, it is preferably 3 or less, more preferably 2 or less. The alkyl group portion of the alkoxy group may be chain-like or cyclic. Specific examples of the alkoxy group include, for example, 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 which the alkoxy group having 1 to 4 carbon atoms of R ¹¹ to R ¹³ may have are an alkyl group and an alkoxy group, but an alkyl group is preferable.

Examples of the halogen atoms of R ¹¹ to R ¹³ include chlorine atom, iodine atom, bromine atom, and fluorine atom. Among them, chlorine atom or fluorine atom is preferable, and chlorine atom is more preferable from the viewpoint of easiness of synthesis. preferable.
Among these, from the viewpoint of sensitivity and ease of synthesis, it is preferable that R ¹¹ to R ¹³ are independently halogen atoms, and more preferably chlorine atoms.

Although m, n and l each independently represent an integer of 0 to 5, from the viewpoint of ease of synthesis, it is preferable that at least one of m, n and l is an integer of 1 or more, and m, n and l. It is more preferable that any one of them is 1 and the remaining 2 are 0.

Examples of the hexaarylbiimidazole-based 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'-tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (o, p-) Examples thereof include dichlorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like. Of these, 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. It is preferable that the benzene ring bonded to the 4,4', 5,5'-position on the imidazole ring is unsubstituted or substituted with a halogen atom or a methoxy group.

(B) As the photopolymerization initiator, either a hexaarylbiimidazole-based compound represented by the general formula (1-1) or a hexaarylbiimidazole-based compound represented by the general formula (1-2) is used. It is also good, and both may be used in combination. When used in combination, the ratio is not particularly limited. The b-1 used in the examples has a structure satisfying the general formula (1-1).

Further, as the acylphosphine oxide-based photopolymerization initiator, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and the like can be mentioned as preferable ones. ..

Examples of the oxime-based photopolymerization initiator include JP-A-2004-534797, JP-A-2000-80068, JP-A-2006-36750, JP-A-2008-179611, JP-A-2012-526185, and Japanese Patent Publication No. 2012-526185. Examples thereof include oxime ester compounds described in Table 2012-591991. Above all, from the viewpoint of sensitivity, N-acetoxy-N- {4-acetoxyimimino-4- [9-ethyl-6- (o-toluoil) -9H-carbazole-3-yl] butane-2-yl} acetamide, N- Acetoxy-N- {3- (acetoxyimino) -3- [9-ethyl-6- (1-naphthoyl) -9H-carbazole-3-yl] -1-methylpropyl} acetamide, 4-acetoxyimimino-5 [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -methyl 5-oxopentanoate is also available as product names, OXE-01, OXE-02, OXE-03 (BASF). , TR-PBG-304, TR-PBG-305 (manufactured by Changshu Power Co., Ltd.), NCI-831, NCI-930 (manufactured by ADEKA) and the like can be mentioned as preferable ones.

Examples of the acetophenone-based photopolymerization initiator include 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenyl ketone, and 1-hydroxy-1- (p-dodecylphenyl) ketone. , 1-Hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-trichloromethyl- (p-butylphenyl) ketone, α-hydroxy-2-methylphenylpropanol, 2-methyl-1 [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1-one, 2-benzyl-2-dimethylamino-1 -(4-Morphorinophenyl) butane-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethyl Examples thereof include aminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 4- (diethylamino) chalcone and the like.
Examples of the benzophenone-based photopolymerization initiator include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and Michler ketone.

Examples of the hydroxybenzene-based photopolymerization initiator include 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-benzylbenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, and 4-. Examples thereof include di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate.
Examples of the thioxanthone-based 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-based photopolymerization initiator include 2-methylanthraquinone and the like, and examples of the ketal-based photopolymerization initiator include benzyldimethyl ketal and the like.

Examples of the titanosen-based photopolymerization initiator include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis (2,4-difluorophenyl), and dicyclopentadienyltitanium. 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) Examples thereof include titanium bis (2,3,4,5,6-pentafluorophenyl) and dicyclopentadienyl titanium bis [2,6-difluoro-3- (1-pyrrolill) phenyl]. Among them, a titanium compound having a dicyclopentadienyl structure and a bisphenyl structure is preferable from the viewpoint of sensitivity, and a compound in which the o-position of the bisphenyl ring is substituted with a halogen atom is particularly preferable.

Examples of the halogenated hydrocarbon derivative-based photopolymerization initiator include halomethylated s-triazine derivatives, for example, 2,4,6-tris (monochromomethyl) -s-triazine, 2,4,6-tris (1,4,6-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) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6- Bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine , 2- (p-methoxy-m-hydroxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (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-triazi Examples thereof include halomethylated s-triazine derivatives such as bis (trihalomethyl) -s-triazines from the viewpoint of sensitivity.

Examples of the organic boronic acid salt-based photopolymerization initiator include an organic boron ammonium complex, an organic boron phosphonium complex, an organic boron sulfonium complex, an organic boron oxosulfonium complex, an organic boron iodonium complex, and an organic boron transition metal coordination complex. Examples of the organic boron anion include n-butyl-triphenylborone anion, n-butyl-tris (2,4,6-trimethylphenyl) boron anion, and n-butyl-tris (p-methoxyphenyl). ) Borone 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) Alkyl-triphenyl boron anion such as -pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion, n-butyl-tris (2,6-difluoro-3-pyrrolillphenyl) boron anion As the counter cation, an onium compound such as an ammonium cation, a phosphonium cation, a sulfonium cation, and an iodonium cation is preferable from the viewpoint of sensitivity, and an organic ammonium cation such as tetraalkylammonium is particularly preferable from the viewpoint of sensitivity. ..

Examples of the onium salt-based 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, triphenylsulfonium p -Sulfonium salts such as toluene sulfonate, triphenyl sulfonium camphor sulfonate, tricyclohexyl sulfonium hexafluoroarsenate, tricyclohexyl sulfonium tetrafluoroborate, tricyclohexyl sulfonium p-toluene sulfonate, tricyclohexyl sulfonium camphor sulfonate and the like can be mentioned.

Examples of the sulfonyl compound-based photopolymerization initiator include bis (phenylsulfonyl) methane, bis (p-hydroxyphenylsulfonyl) methane, bis (p-methoxyphenylsulfonyl) methane, and 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) methane, phenylcarbonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (tert-butylcarbonyl) methane Carbonyl (sulfonyl) methane compounds such as bis (phenylsulfonyl) diazomethane, bis (p-hydroxyphenylsulfonyl) diazomethane, bis (p-methoxyphenylsulfonyl) diazomethane, bis (α-naphthylsulfonyl) diazomethane, bis (β-naphthyl) Sulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazomethane, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane, Carbonyl (sulfonyl) diazomethanes such as phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, tert-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (tert-butylcarbonyl) diazomethane Examples include compounds.

Examples of the carbamic acid derivative-based photopolymerization initiator include benzoylcyclohexylcarbamate, 2-nitrobenzylcyclohexylcarbamate, 3,5-dimethoxybenzylcyclohexylcarbamate, 3-nitrophenylcyclohexylcarbamate and the like.
Examples of the sulfonamide-based photopolymerization initiator include N-cyclohexyl-4-methylphenylsulfonamide and N-cyclohexyl-2-naphthylsulfonamide, and examples of the triarylmethanol-based photopolymerization initiator include. Examples thereof include triphenylmethanol and tri (4-chlorophenyl) methanol.

One of these photopolymerization initiators may be contained alone in the photosensitive resin composition, or two or more of these photopolymerization initiators may be contained. Among these photopolymerization initiators, the hexaarylbiimidazole-based compound is particularly preferable because it has high surface curability because of its high absorbance and high liquid repellency and high taper angle.

The content ratio of the (B) photopolymerization initiator in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.1% by mass, based on the total solid content of the photosensitive resin composition. % Or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, particularly preferably 1.5% by mass or more, usually 25% by mass or less, preferably 10% by mass or less, more preferably 8 It is mass% or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. When it is at least the above lower limit value, a coating film is formed without causing film loss during development, and there is a tendency for sufficient liquid repellency to occur, and when it is at least the above upper limit value, a desired pattern shape is formed. It tends to be easier to do.

The compounding ratio of the (B) photopolymerization initiator to the (A) ethylenically unsaturated compound in the photosensitive resin composition is 1 part by mass or more with respect to 100 parts by mass of the (A) ethylenically unsaturated compound. Is preferable, 2 parts by mass or more is more preferable, 3 parts by mass or more is further preferable, 200 parts by mass or less is preferable, 100 parts by mass or less is more preferable, 50 parts by mass or less is further preferable, and 20 parts by mass or less is more preferable. More preferably, 10 parts by mass or less is particularly preferable, and 5 parts by mass or less is most preferable. When it is at least the lower limit value, the sensitivity tends to be appropriate, and when it is at least the upper limit value, it tends to be easy to form a desired pattern shape.

Further, it is preferable to use a chain transfer agent in combination with (B) a photopolymerization initiator. The inclusion of the chain transfer agent tends to increase the taper angle and also tends to increase the contact angle.
Examples of the chain transfer agent include a mercapto group-containing compound, carbon tetrachloride, and the like, and since the chain transfer effect tends to be high, it is more preferable to use a compound having a mercapto group. Since the binding energy is small, bond cleavage is likely to occur and a chain transfer reaction is likely to occur. Therefore, radical deactivation in the vicinity of the surface due to oxygen inhibition or the like can be improved to improve surface curability, and the taper angle is increased. It is considered to be effective for doing so. Further, it is considered that by enhancing the surface curability, the outflow of the liquid repellent can be suppressed, the liquid repellent can be easily fixed in the vicinity of the surface, and the contact angle can be increased.

Among the chain transfer agents, a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are preferable 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 represent a hydrogen atom or a monovalent substituent.
Of these, from the viewpoint of the taper angle, Z is preferably —S— or —NH—, and more preferably —NH—.
Further, 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 a hydrogen atom is more preferable.

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

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

In equation (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 represent 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. Further, from the viewpoint of surface curability, n is preferably 3 or 4, more preferably 4.
The alkyl groups of R ⁷¹ and R ⁷² are preferably those having 1 to 3 carbon atoms from the 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, in which case R ⁷¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. 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 easiness of synthesis, an alkylene group having 1 to 6 carbon atoms is more preferable, and an alkylene group having 4 carbon atoms is further preferable.

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

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 the taper angle.

In 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 the taper angle.

On the other hand, when n is 4, it is preferable that X has 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, trimethyl propanthris (3-). Mercaptopropionate), Trimethylol Propanetristhioglycolate, Trishydroxyethyl Tristhiopropionate, Pentaerythritol Tetrakiss (3-Mercaptopropionate), Pentaerythritol Tris (3-Mercaptopropionate), Butanediolbis (3-Mercaptobutyrate), Ethylene Glycolbis (3-Mercaptobutyrate), Trimethylol Propanthris (3-Mercaptobutyrate), Pentaerythritol Tetrakiss (3-Mercaptobutyrate), Pentaerythritol Tris (3-Mercaptobutyrate) Rate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione and the like.

Of these, trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritoltris (3-mercaptopropionate), trimethylolpropanthris (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) -trion is preferable, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferable.

Various of these can be used alone or in admixture of two or more.

Among these, from the viewpoint of increasing the taper angle, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole are combined with a photopolymerization initiator to obtain light. It is suitable to be used as a polymerization initiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
Further, 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).

Further, 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, and pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto). It is preferable to use one or more selected from the group consisting of (butylate) in combination with a photopolymerization initiator.

The content ratio 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. It is 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. Is. When it is set to the lower limit value or more, the sensitivity tends to be high, and the taper angle and the contact angle tend to be high, and when it is set to the upper limit value or less, a desired pattern tends to be easily formed.

When a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used in combination as a chain transfer agent, the content ratio thereof is 100 parts by mass of the mercapto group-containing compound having an aromatic ring. On the other hand, 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. It is preferably 200 parts by mass or less, more preferably 150 parts by mass or less. When it is at least the lower limit value, the taper angle tends to be high, and when it is at least the upper limit value, the surface curability tends to be high and the contact angle tends to be high.

The blending ratio of the chain transfer agent to the (B) photopolymerization initiator in the photosensitive resin composition is preferably 10 parts by mass or more, preferably 25 parts by mass, based on 100 parts by mass of the (B) photopolymerization initiator. More than parts are more preferable, 50 parts by mass or more is further preferable, 80 parts by mass or more is particularly preferable, 500 parts by mass or less is more preferable, 400 parts by mass or less is more preferable, 300 parts by mass or less is further preferable, and 200 parts by mass is more preferable. The following is even more preferable, and 150 parts by mass or less is particularly preferable. When it is set to the lower limit value or more, the sensitivity tends to be high, and the taper angle and the contact angle tend to be high, and when it is set to the upper limit value or less, a desired pattern tends to be easily formed.

Further, a sensitizer may be used in combination with the above-mentioned photopolymerization initiator. The sensitizer improves the sensitivity and at the same time reduces the light transmittance inside the photosensitive resin composition, so that the taper angle tends to increase.

As the sensitizer, a sensitizer usually used in this field can be used. The sensitizer has a characteristic that the energy obtained by absorption is transferred to the photopolymerization initiator or causes electron transfer with the photopolymerization initiator to efficiently promote the reaction radical polymerization reaction. Examples of such a sensitizer include unsaturated ketones represented by chalcone derivatives and dibenzalacetone, 1,2-diketone compounds represented by benzyl and camphorquinone, benzoin compounds, and fluorene. Phosphorus compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonoal derivatives, etc. Polymethine dyes, acridin-based compounds, azine-based compounds, thiazine-based compounds, oxazine-based compounds, indolin-based compounds, azulene-based compounds, azulene-based compounds, squarylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds. , Tetrabenzoporphyrin-based compounds, tetrapyrazinoporphyrazine-based compounds, phthalocyanine-based compounds, tetraazaporphyrazine-based compounds, tetraquinoxalyloporphyrazine-based compounds, naphthalocyanine-based compounds, subphthalocyanine-based compounds, pyririum-based compounds, thiopyrilium Examples thereof include system compounds, tetraphyllin system compounds, anurene compounds, spiropyran compounds, spiroxazine compounds, thiospiropirane compounds, metal arene complexes, organic ruthenium complexes, benzophenone compounds and the like.
These may be used alone or in combination of two or more.

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

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

Examples of the benzophenone compound include benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and 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 ratio 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.% 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. It is more preferably 5% by mass or less, still more preferably 3% by mass or less. When it is set to the lower limit value or more, the sensitivity tends to be improved and the taper angle tends to be increased, and when it is set to the upper limit value or less, it tends to be easy to form a desired pattern.

[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 developing solution, but since an alkaline developing solution is preferable as the developing solution, 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 outflow of the liquid repellent agent due to thermal melting of the partition wall surface during post-baking can be suppressed and the liquid repellent property can be maintained. A resin having a sex unsaturated group is more preferable.

(Alkali-soluble resin (c) having a partial structure represented by the general formula (1))
In the present invention, among the alkali-soluble resins, the alkali-soluble resin (c) having a partial structure represented by the following general formula (1) (hereinafter, may be abbreviated as “resin (c)”) is preferable. As described above, 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 easily being thermally decomposed, heat when forming a partition wall is used. Since most of the acid component is removed as gas during curing, it is considered that the amount of outgas generated when driving the organic electric field light emitting element is small and the reliability is high.

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.

(R ¹ )
In the general formula (1), R ¹ represents a divalent hydrocarbon group having 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 a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of development solubility. The number of carbon atoms is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 4 or less and 3 or less. When the value is equal to or higher than the lower limit, the residual film ratio tends to increase, and when the value is equal to or higher than the upper limit, the amount of outgas generated during light emission of the device tends to decrease.

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 a straight chain or a branched chain, but is preferably a straight chain 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 is preferable. When the value is equal to or higher than the lower limit, the residual film ratio tends to increase, and when the value is equal to or higher than the upper limit, the amount of outgas generated during light emission of the device tends to decrease.

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 outgas.

The substituent that the divalent hydrocarbon group having 1 to 4 carbon atoms may have is not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a benzoyl group, and a hydroxyl group, from the viewpoint of ease of synthesis. It is preferable that it is not substituted.

Among these, from the viewpoint of reducing outgas, R ¹ is preferably a divalent alkylene group having 1 to 4 carbon atoms, 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), but from the viewpoint of development solubility, the (c1) epoxy (c1) epoxy ( Meta) acrylate resin and / or (c2) acrylic copolymer resin are preferable. Further, from the viewpoint of reducing outgas, (c1) epoxy (meth) acrylate resin is preferable, while (c2) acrylic copolymer resin is preferable from the viewpoint of taper angle.
The (c1) epoxy (meth) acrylate resin will be described in detail below.

[(C1) Epoxy (meth) acrylate resin]
(C1) In the epoxy (meth) acrylate resin, an ethylenically unsaturated monocarboxylic acid or an ester compound is added to the epoxy resin, and an isocyanate group-containing compound is optionally reacted, and then a polybasic acid or an anhydride thereof is further added. It is a resin that has been made to. For example, by opening and adding a carboxyl group of an unsaturated monocarboxylic acid to the epoxy group of an epoxy resin, an ethylenically unsaturated bond is added to the epoxy resin via an ester bond (-COO-), and at the same time, an ethylenically unsaturated bond is added. Examples thereof include a hydroxyl group generated at that time to which a carboxy group of one of a polybasic acid or an anhydride thereof is added. Further, when a polybasic acid or an anhydride thereof is added, a polyhydric alcohol may be added at the same time to add the polyhydric acid. Further, 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 reacting is also included in the (c1) epoxy (meth) acrylate resin.
As described above, the epoxy (meth) acrylate resin has substantially no epoxy group due to its chemical structure and is not limited to "(meth) acrylate", but the epoxy compound (epoxy resin) is the raw material. Yes, and since "(meth) acrylate" is a typical example, it is named in this way according to convention.

Here, the epoxy resin includes a raw material compound before forming the resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. Further, as the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. 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 novolak epoxy resin, biphenyl novolak epoxy resin, trisphenol epoxy resin, phenol and dicyclopentane. Polymerized epoxy resin with, dihydrooxylfluorene type epoxy resin, dihydrooxylalkyleneoxylfluorene type epoxy resin, 9,9-bis (4'-hydroxyphenyl) fluorene diglycidyl etherified product, 1,1-bis (4) '-Hydroxyphenyl) adamantan diglycidyl etherified product, etc., and those having an aromatic ring in the main chain as described above can be preferably 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 of the above is preferable, and the bisphenol A type epoxy resin is more preferable.

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 anhydride succinic acid adduct, pentaerythritoltri ( Meta) Acrylate Tetrahydrochloride Hydrochloride Additive, Dipentaerythritol Penta (Meta) Acrylate Anhydrous Crotonic Acid Additive, Dipentaerythritol Penta (Meta) Acrylate Anhydrous Crotonic Acid Additive, Dipentaerythritol Penta (meth) Acrylate Tetrahydrochloride Anhydrous phthalic acid Additives, reaction products of (meth) acrylic acid and ε-caprolactone, and the like can be mentioned. Of 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, and 4 -Ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , Benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides and the like. These may be used alone or in combination of two or more. Among these, succinic acid anhydride, maleic anhydride, and itaconic acid anhydride are preferable, and succinic acid 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, the molecular weight of the (c1) epoxy (meth) acrylate resin can be increased, branches 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 for the sensitivity, adhesion, and the like to be easily balanced.
The polyhydric alcohol may be, for example, one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable to have.

The acid value of the (c1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, further preferably 40 mgKOH / g or more, still more preferably 60 mgKOH / g or more. 80 mgKOH / g or more is particularly preferable, 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 150 mgKOH / g or less is further preferable, 120 mgKOH / g or less is further preferable, and 100 mgKOH / g or less is particularly preferable. When it is set to the lower limit value or more, the residue tends to be reduced and the taper angle tends to be high, and when it is set to the upper limit value or less, the outgas at the time of light emission of the element tends to be reduced.

(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 6000 or more, most preferably 7,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less. When it is set to the lower limit value or more, the outgas at the time of light emission of the element tends to be reduced, and when it is set to the upper limit value or less, the residue tends to be reduced.

The content ratio of the (c1) epoxy (meth) acrylate resin contained in the (C) alkali-soluble resin is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more. 80% by mass or more is more preferable, 90% by mass or more is particularly preferable, and usually 100% by mass or less. Outgas tends to decrease when the value is equal to or higher than the lower limit.

(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 coexistence of a catalyst and a thermal polymerization inhibitor. A method of reacting and further adding a polybasic acid or an anhydride thereof to continue the reaction can be used.

Here, examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, trimethylbenzylammonium chloride and the like. Examples thereof include one or more of quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, and stibins such as triphenylstibin. Further, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone 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. It can be an amount that becomes. The temperature at the time of the addition reaction is usually 60 to 150 ° C, preferably 80 to 120 ° C. Further, the amount of the polybasic acid or its anhydride used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, with respect to one chemical equivalent of the hydroxyl group generated in the addition reaction. It can be an amount that is a chemical equivalent.

(C1) The epoxy (meth) acrylate resin may contain a partial structure other than the general formula (1), and is repeatedly represented by the following general formula (i) from the viewpoint of outgas at the time of light emission of the element. 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 (meth) 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.

The epoxy (meth) acrylate resin (c1) 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 when the device emits light. .. It is inferred that one of the reasons is that it is difficult to decompose with heat because it has a rigid main skeleton.

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 any substituent. * Represents a bond.

(R ^b )
In the formula (i), R ^b represents a divalent hydrocarbon group which may have a substituent.
As the divalent hydrocarbon group, a divalent aliphatic group, a divalent aromatic ring group, a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked is used. 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, while a cyclic one is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

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, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of reducing the residue.
Specific examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group and the side chains of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group and an n-. Examples thereof include a structure having a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings contained in 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. When it is set to the lower limit value or more, the residual film ratio tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced. Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a cyclododecane ring. The group that was used is mentioned. Among these, from the viewpoint of development adhesion, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

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; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of easiness 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, more preferably 20 or less, still more preferably 15 or less, still more preferably 10 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring, which have two free atomic valences. Examples thereof include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic 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 pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free atomic valences. Ring, Carbazole Ring, Pyrroloimidazole Ring, Pyrrolopyrazole Ring, Pyrrolopyrrole Ring, Thienopyrazole Ring, Thienothiophene Ring, Flopyrole Ring, Flofuran Ring, Thienofuran Ring, Benzoisoxazole Ring, Benzimidazole Ring, Benzoimidazole Ring, pyridine Ring, Examples include groups such as pyrazine ring, pyridazine ring, pyrimidin ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazolin ring, quinazolinone ring, and azulene ring. .. Among these, from the viewpoint of photocurability, a benzene ring or a 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, a propoxy group and the like. Of these, no substitution is preferable from the viewpoint of curability.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic group is used. Examples thereof include a group in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually preferably 1 or more, 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more, 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

Specific examples of a 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 (ia) to (iE). Can be mentioned. Among these, the group represented by the following formula (iA) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicity of the membrane.

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

Further, 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 the 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 those in formula (i). R ¹ has the same meaning as that of the above formula (1). * Represents a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.

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

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

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

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) containing a partial structure represented by the following general formula (ii) from the viewpoint of development adhesion. Is preferable.

In formula (ii), R ^c each 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 contained in the aliphatic ring group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 10 or less, 5 or less is preferable, and 3 or less is more preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, the adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but usually 1 or more, 2 or more is preferable, 3 or more is more preferable, and usually 10 or less, 5 or less is preferable, and 4 or less is more preferable. When it is at least the lower limit value, the residue tends to be reduced, and when it is at least the upper limit value, 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 carbon number of 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, 20 or less is further preferable, and 15 or less is particularly preferable. When it is at least the lower limit value, the residue tends to be reduced, and when it is at least the upper limit value, the development adhesion tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, and a fluoranthene ring. Examples include fluorene rings. Among these, the 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, but for example, a divalent aliphatic group, a divalent aromatic ring group, 1 or more. Examples thereof include a group in which a divalent aliphatic group of 1 or more and a divalent aromatic ring group of 1 or more are linked.

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, while a cyclic one is preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, preferably 25 or less, more preferably 20 or less, still more preferably 15 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

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, an n-heptylene group and the like. Among these, a methylene group is preferable from the viewpoint of residue.
Specific examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group and the side chains of a methyl group, an ethyl group, an n-propyl group, an iso-propyl group and an n-. Examples thereof include a structure having a butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group and the like.
The number of rings contained in the divalent cyclic aliphatic group is not particularly limited, but is usually preferably 1 or more, 2 or more, and usually 10 or less, 5 or less, more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced. Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms removed from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, or a cyclododecane ring. The group that was used is mentioned. Among these, from the viewpoint of development adhesion, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable.

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; a carboxyl group and the like. Among these, unsubstituted is preferable from the viewpoint of easiness 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, preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysene ring, which have two free atomic valences. Examples thereof include groups such as a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
Further, the aromatic heterocycle in the aromatic heterocyclic group may be a monocyclic 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 pyrazole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole having two free atomic valences. Ring, Carbazole Ring, Pyrroloimidazole Ring, Pyrrolopyrazole Ring, Pyrrolopyrrole Ring, Thienopyrazole Ring, Thienothiophene Ring, Flopyrole Ring, Flofuran Ring, Thienofuran Ring, Benzoisoxazole Ring, Benzimidazole Ring, Benzoimidazole Ring, pyridine Ring, Examples include groups such as pyrazine ring, pyridazine ring, pyrimidin ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazolin ring, quinazolinone ring, and azulene ring. .. Among these, from the viewpoint of photocurability, a benzene ring or a 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, a propoxy group and the like. Of these, no substitution is preferable from the viewpoint of curability.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, the above-mentioned divalent aliphatic group is 1 or more, and the above-mentioned divalent aromatic group is used. Examples thereof include a group in which one or more ring groups are linked.
The number of divalent aliphatic groups is not particularly limited, but is usually preferably 1 or more, 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The number of divalent aromatic ring groups is not particularly limited, but is usually preferably 1 or more, 2 or more, usually 10 or less, 5 or less, and more preferably 3 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

Specific examples of a 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). Can be mentioned. Among these, the group represented by the above formula (iC) is preferable from the viewpoint of reducing the residue.

The bonding mode of the cyclic hydrocarbon group, which is a side chain, is not particularly limited with respect to these divalent hydrocarbon groups, but for example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with the side chain. Examples thereof include the above-mentioned embodiment and the embodiment in which a cyclic hydrocarbon group as a side chain is formed including one of the carbon atoms of the aliphatic group.

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

In the formula (ii-1), R ^c is synonymous with the above formula (ii). ^Rα represents a monovalent cyclic hydrocarbon group which may have a substituent. n is an integer of 1 or more. The benzene ring in the formula (ii-1) may be further substituted with any 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 contained in the aliphatic ring group is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 6 or less, 4 or less is preferable, and 3 or less is more preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less. preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, the adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually preferably 1 or more, 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 5 or more, more preferably 6 or more, and more preferably. , 30 or less is preferable, 20 or less is more preferable, and 15 or less is further preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring and the like. Among these, the 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 and a tert-butyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; 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; a carboxyl group and the like. Of these, no substitution is preferable from the viewpoint of ease of synthesis.

Although n represents an integer of 1 or more, 2 or more is preferable, and 3 or less is preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

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

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

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

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

In the formula (ii-2), R ^c is synonymous with the above formula (ii). ^Rβ represents a divalent cyclic hydrocarbon group which may have a substituent. The benzene ring in the formula (ii-2) may be further substituted with any 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 contained in the aliphatic ring 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. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, the adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually preferably 1 or more, 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The aromatic ring group usually has 4 or more carbon atoms, preferably 6 or more, more preferably 8 or more, and 10 or more. 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. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring and the like. Among these, the 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 and a tert-butyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; 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; a carboxyl group and the like. Of these, no substitution is preferable from the viewpoint of simplicity of synthesis.

Among these, from the viewpoint of curability, R ^β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.
On the other hand, from the viewpoint of development adhesion, R ^β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

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

Specific examples of the partial structure represented by the above formula (ii-2) will be 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 the formula (ii-3), R ^c and R ^d are synonymous with the above formula (ii). R ¹ has the same meaning as the above equation (1).

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

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

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 during light emission of the device. Is preferable.

In formula (iii), R ^e represents a hydrogen atom or a methyl group, and γ is a single bond, —CO—, an alkylene group which may have a substituent, or a divalent group which may have a substituent. Represents a cyclic hydrocarbon group of. The benzene ring in the formula (iii) may be further substituted with any 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 a straight chain or a branched chain, but is preferably a straight chain from the viewpoint of development solubility and is preferably a branched chain from the viewpoint of development adhesion. The number of carbon atoms is not particularly limited, but is usually preferably 1 or more and 2 or more, and usually 6 or less and 4 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

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 achieving both development adhesion and development solubility. , Propylene groups are more preferred.

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 easiness 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 contained in the aliphatic ring 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. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, the adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually preferably 1 or more, 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
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, further preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferable, and 15 or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a fluorene ring and the like. Among these, the 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 and a tert-butyl group. Examples thereof include an alkyl group having 1 to 5 carbon atoms such as an amyl group and an iso-amyl group; 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; a carboxyl group and the like. Of these, no substitution is preferable from the viewpoint of simplicity of synthesis.

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

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

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

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

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

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. It is preferable to have.

(Partial structure represented by the general formula (I))
(C2) The partial structure containing the side chain having an ethylenically unsaturated group contained in the acrylic copolymer resin is not particularly limited, but from the viewpoint of development solubility, for example, the portion represented by the following general formula (I). It preferably contains a structure.

In formula (I), ^RA represents a hydrogen atom or a methyl group. ^RB 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), ^RC 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 with a carbonyl carbon.

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

Examples of the alkenyl group in ^RB 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, still more preferably 8 or less. It is particularly preferably 6 or less, and most preferably 4 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the curability tends to be improved.

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

The substituents 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 and a thiol group. Examples include sulfide groups. Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability. When it has two or more substituents, the substituents may be linked to form a ring.

Among these, ^RB is preferably an ethenyl group or a propenyl group, and more preferably an ethenyl group, from the viewpoint of developability and curability.

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

Examples of the alkenyl group in ^RC include a linear, branched chain or cyclic alkenyl group. The carbon number is preferably 2 or more, preferably 20 or less, more preferably 16 or less, further preferably 12 or less, still more preferably 8 or less. It is particularly preferably 6 or less, and most preferably 4 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the curability tends to be improved.

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

The substituents 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 and a thiol group. Examples include a sulfone group. Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability. When it has two or more substituents, the substituents may be linked to form a ring.

As described above, ^RC represents an alkenyl group which may have a substituent, and among these, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable, from the viewpoint of developability. ..

(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 in α include a linear, branched or cyclic alkylene group. The carbon number is preferably 1 or more, more preferably 2 or more, preferably 22 or less, more preferably 20 or less, still more preferably 18 or less. It is more preferably 16 or less, particularly preferably 14 or less, and most preferably 12 or less. When it is at least the lower limit value, the adhesion tends to be improved, and when it is at least the upper limit value, the curability tends to be improved.

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

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, a sulfide group and the like. Can be mentioned. Among these, alkenyl is preferable from the viewpoint of development adhesion. Further, when it has two or more substituents, the substituents may be linked to each other to form a ring.

Further, examples of the arylene group in 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, still more preferably 18 or less. It is particularly preferably 16 or less, and most preferably 14 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, or pyrene. Examples thereof include a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, or a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, furofran ring, thienofran ring, benzoisoxazole ring, benzoiso Thiazol ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone Examples include a ring and an aromatic ring. Among these, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable, from the viewpoint of developability.

The substituents 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 and a thiol group. Examples include a sulfone group. Among these, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable, from the viewpoint of developability. Further, when it has two or more substituents, the substituents may be linked to each other to form a ring.

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

Examples of the alkenylene group in α include a linear, branched or cyclic alkenylene group. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less. It is particularly preferably 14 or less, and most preferably 12 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

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

The substituents 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 and a thiol group. Examples include sulfide groups. Among these, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable, from the viewpoint of developability. Further, when it has two or more substituents, the substituents may be linked to each other to form a 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, it is preferably an alkylene group or an alkenylene group, and more preferably an alkylene group.

Further, 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 developability. The repeating unit structure represented by the formula (I-1) includes the partial structure represented by the general formula (1) in the formula.

In formula (I ^- 1), ^RA and RB have the same meaning as those in formula (I). R ¹ has the same meaning as that of the above formula (1).

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

In formula (I ^- 2), ^RA and RB have the same meaning 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 even more preferable, 50 mol% or more is further preferable, 70 mol% or more is particularly preferable, 80 mol% or more is most preferable, 99 mol% or less is preferable, 97 mol% or less is more preferable, and 95 mol% or less. Is even more preferable. When it is at least the lower limit value, the residue tends to be reduced, and when it is at least the upper limit value, the development adhesion tends to be improved.

(C2) The content ratio 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 further preferable, 15 mol% or more is further 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 it is at least the above lower limit value, the sensitivity tends to be high and the residue tends to be reduced, and when it is at least the above upper limit value, the development adhesion tends to be improved.

(C2) The content ratio 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 further preferable, 30 mol% or more is further 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% is more preferable. The following is more preferable, and 70 mol% or less is particularly preferable. When it is at least the lower limit value, the sensitivity tends to be high, and when it is at least the upper limit value, the developability tends to be improved.

(Partial structure represented by the general formula (I'))
(C2) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), the other partial structures are not particularly limited, but 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 ^RE represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an alkenyl group that may have.

( ^RE )
In the formula (I'), ^RE 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 RE include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, and even more preferably 18 or less. It is more preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When it is at least the above lower limit value, the film strength tends to be high and the development adhesion tends to be improved, and when it is at least the above upper limit value, the residue tends to be reduced.

Specific examples of the alkyl group include a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentanyl group, a dodecanyl group and the like. 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 a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the aryl group in ^RE include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The carbon number is preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a monocyclic ring or a fused ring, and may be, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, or pyrene. Examples thereof include a ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluorene ring, and a fluorene ring.
The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a fused ring, and may be, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, or a pyrazole ring. , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolobymidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrazole ring, thienothiophene ring, flopyrol ring, furofran ring, thienofran ring, benzoisoxazole ring, benzoiso Thiazol ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxalin ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone Examples include a ring and an aromatic ring. Among these, a benzene ring group or a naphthalene ring group is preferable, and a benzene ring group is more preferable, from the viewpoint of curability.
The substituents that the aryl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group and an oligo. 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 in RE include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less. , 14 or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

Specific examples of the alkenyl group include an ethenyl group, a propenyl group, a butylenel group, a cyclohexenyl group and the like. Among these, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable, from the viewpoint of curability.
The substituents that the alkenyl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group and an oligo. 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.

As described above, ^RE 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 an 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 .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 further preferable, and 30 mol% or less is further preferable. 10 mol% or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

(Partial structure represented by the general formula (I''))
(C2) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), it is represented by the following general formula (I'') from the viewpoint of heat resistance and film strength as the other partial structure contained. It is preferable that the partial structure to be used is included.

In the above formula (I''), ^{RF represents a hydrogen atom or a methyl group, and RG is} an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a hydroxyl group, and the like. Represents a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent. t represents an integer from 0 to 5.

( ^RG )
In the above formula (I''), ^RG is an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, a hydroxyl group, and the like. Represents a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
Examples of the alkyl group in ^RG include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, and even more preferably 18 or less. It is more preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

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

Examples of the alkenyl group in ^RG include linear, branched or cyclic alkenyl groups. The carbon number is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, still more preferably 16 or less. , 14 or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

Specific examples of the alkenyl group include an ethenyl group, a propenyl group, a butylenel group, a cyclohexenyl group and the like. Among these, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable, from the viewpoint of curability.
The substituents that the alkenyl group may have include a methyl group, an ethyl group, a propyl group, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group and an oligo. 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 ^RG include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of liquid repellency.

Examples of the alkoxy group in ^RG include linear, branched or cyclic alkoxy groups. The carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

The substituents that the alcohol group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

Examples of the alkyl sulfide group in ^RG include linear, branched or cyclic alkyl sulfide groups. The carbon number is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

Specific examples of the alkyl sulfide group include a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group and the like. Among these, a methyl sulfide group or an ethyl sulfide group is preferable from the viewpoint of developability.
The substituents that the alkyl group in the alkyl sulfide group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group and a phenyl group. Examples thereof include a group, a carboxyl group, an acryloyl group and a methacryloyl group, and a hydroxy group and an oligoethylene glycol group are preferable from the viewpoint of developability.

As described above, ^RG has 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, and the like. Alternatively, it represents an alkyl sulfide group which may have a substituent, and among these, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable, from the viewpoint of developability.

(T)
In the above equation (I''), t represents an integer of 0 to 5. From the viewpoint of developability, 2 or less is preferable, 1 or less is more preferable, and 0 is further 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 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 further preferable, and 20 mol is more preferable. % Or less is particularly preferable, and 10 mol% or less is most preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

(Partial structure represented by the general formula (I'''))
(C2) When the acrylic copolymer resin contains the partial structure represented by the general formula (I), it is represented by the following general formula (I''') as the other partial structure contained from the viewpoint of developability. It is preferable that a partial structure is included.

In the above formula (I'''), ^RH represents a hydrogen atom or a methyl group.

(C2) The content ratio of the partial structure represented by the general formula (I''') contained in the acrylic copolymer resin is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, and 30 mol. % Or more is further preferable, 90 mol% or less is preferable, 80 mol% or less is more preferable, 70 mol% or less is further preferable, and 50 mol% or less is particularly preferable. When it is at least the lower limit value, the residue tends to be reduced, and when it is at least the upper limit value, the development adhesion tends to be improved. On the other hand, from the viewpoint of outgas, it is preferable that it does not contain 0%, that is, the partial structure represented by the general formula (I ″ ″).

(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, further preferably 40 mgKOH / g or more, and even more preferably 50 mgKOH / g. G or more is particularly preferable, 100 mgKOH / g or less is preferable, 90 mgKOH / g or less is more preferable, 70 mgKOH / g or less is further preferable, and 60 mgKOH / g or less is further preferable. When it is at least the lower limit value, the residue tends to be reduced, and when it is at least the upper limit value, 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. Also, it is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, still more preferably 10,000 or less. Especially preferably, it is 7000 or less. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the residue tends to be reduced.

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

In the (C) alkali-soluble resin, either (c1) epoxy (meth) acrylate resin or (c2) acrylic copolymer resin may be contained alone, or both may be contained. Further, a resin other than (c1) and (c2) may be contained. For example, the (C) alkali-soluble resin itself may be imparted with liquid repellency by containing 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, and further, with respect to 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 it is set to the lower limit value or more, the developability tends to be improved, and when it is set to the upper limit value or less, the outgas at the time of light emission of the element tends to be reduced.

The content ratio 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, and further, with respect to 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 it is set to the lower limit value or more, the outgas at the time of light emission of the element tends to be reduced, and when it is set to the upper limit value or less, the film reduction tends to be suppressed.

The content ratio of the alkali-soluble resin (c) in the (C) 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, and particularly preferably. Is 90% by mass or more, and usually 100% by mass or less. By setting the value to the lower limit or more, the developability tends to be improved and the outgas at the time of light emission of the element tends to be reduced.

The content of the (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 10% by mass or more, 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. It is preferably 97% by mass or less, more preferably 95% by mass or less. When it is set to the lower limit value or more, the curability tends to be improved, and when it is set to the upper limit value or less, the outgas during light emission of the device tends to be reduced.

The compounding ratio of the (C) alkali-soluble resin to the (A) ethylenically unsaturated compound in the photosensitive resin composition is 50 parts by mass or more with respect to 100 parts by mass of the (A) ethylenically unsaturated compound. Preferably, 60 parts by mass or more is more preferable, 70 parts by mass or more is further 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 further preferable. , 100 parts by mass or less is particularly preferable. When it is set to the lower limit value or more, the development adhesion tends to be improved, and when it is set to the upper limit value or less, the curability tends to be improved.

[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 element is produced by an inkjet method, it is preferable to contain (D) a liquid repellent agent, and by containing (D) a liquid repellent agent, it is possible to impart liquid repellent property 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 silicone-containing compounds and fluorine-based compounds, and preferable examples thereof include a liquid repellent having a cross-linking group (hereinafter, may be referred to as a “cross-linking group-containing liquid repellent”). Examples of the cross-linking group include an epoxy group and 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 developing solution.
When a cross-linking group-containing liquid repellent is used, the cross-linking reaction on the surface of the formed coating film can be accelerated when the coating film is exposed, and the liquid repellent is less likely to flow out in the developing process, resulting in a partition wall. Is considered to be able to exhibit high liquid repellency.

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

Specific examples of the cross-linking group-containing liquid repellent, particularly the ethylenically unsaturated group-containing fluorine-based compound, include, for example, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, and perfluoroalkyltrialkylammonium salt. , Oligomers containing perfluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and parent oil groups, oligomers containing perfluoroalkyl groups and hydrophilic groups and new oil groups, urethanes containing perfluoroalkyl and hydrophilic groups, per Examples thereof include 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", and "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 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" , "Mega Fuck RS201", "Mega Fuck RS202", "Mega Fuck RS301", "Mega Fuck RS303", "Mega Fuck RS304", "Mega Fuck RS401", "Mega Fuck RS402", "Mega Fuck RS501", "Mega" "Fuck RS502", "Mega Fuck RS-72-K", "DEFENSA MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", "Fluorard FC430", "Fluorard FC431", "FC" -4430, FC-4432, Asahi Guard AG710, Surflon S-382, Surflon SC-101, Surflon SC-102, Surflon SC-103, Surflon SC Fluorine-containing organic compounds commercially available under trade names such as "-104", "Surflon SC-105", "Surflon SC-106", and "Optur DAC-HP" manufactured by Daikin Industries, Ltd. can be used.

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

The molecular weight of the liquid repellent is not particularly limited, and it may be a low molecular weight compound or a high molecular weight compound. A high molecular weight liquid repellent is preferable because the fluidity of the liquid repellent due to post-baking can be suppressed and the outflow of the liquid repellent can be suppressed from the bank. 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, and 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, and more preferably 0.3% by mass or less. When it is set to the lower limit value or more, it tends to show high liquid repellency, and when it is set to the upper limit value or less, it tends to suppress outflow to the pixel portion.

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 the (D) liquid repellent agent, or a surfactant may be used instead of the (D) liquid repellent agent. The surfactant can be used for the purpose of improving the coatability of the photosensitive resin composition for forming a partition wall as a coating liquid and the developability of the coating film, and among them, a fluorine-based or silicone-based surfactant is preferable. ..
In particular, a silicone-based surfactant is preferable because it has an action of removing the residue of the photosensitive resin composition from the unexposed portion and a function of developing wettability during development, and a polyether-modified silicone-based material is preferable. Surfactants are more preferred.

As the fluorine-based surfactant, a compound having a fluoroalkyl or fluoroalkylene group at 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-tetrafluorooctylhexyl ether, octaethylene glycol di (1,1,2,2-tetrafluoropropyl) ether, octaethylene glycol di (1,1,2,2-tetrafluorooctylhexyl ether). 1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di (1,1,2,2- Tetrafluorobutyl) ether, hexapropylene glycol di (1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9, 9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane and the like can be mentioned. 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. , "Mega Fuck F470", "Mega Fuck F475", "FC430" manufactured by 3M Japan Ltd., "DFX-18" manufactured by Neos, and the like.

Examples of the silicone-based surfactant include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Adaptive", and "SH8400" manufactured by Toray Dow Corning. Commercially available products such as "BYK323" and "BYK330" manufactured by Big Chemie can be mentioned.
The surfactant may contain other than a fluorine-based surfactant and a silicone-based surfactant, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants. Be done.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, and polyoxyethylene fatty acid esters. Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrit fatty acid esters, polyoxyethylene pentaerythrit fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy Examples thereof include polyethylene sorbit fatty acid esters. Examples of these commercially available products include polyoxyethylene-based surfactants such as "Emargen 104P" and "Emargen A60" manufactured by Kao Corporation.

Examples of the anionic surfactant include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate esters, and higher alcohol sulfates. Ester salts, aliphatic alcohol sulfate esters, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special Examples include high molecular weight surfactants. Of these, special polymer-based surfactants are preferable, and special polycarboxylic acid-type polymer-based surfactants are even more preferable. Commercially available products can be used as such anionic surfactants. For example, Kao's "Emar 10" is used for alkyl sulfate esters, and Kao's "Perex NB-L" is used for alkylnaphthalene sulfonates. Examples of the special polymer-based surfactant include "Homogenol L-18" and "Homogenol L-100" manufactured by Kao Corporation.

Further, as the above-mentioned cationic surfactant, quaternary ammonium salts, imidazoline derivatives, alkylamine salts and the like are used, and as amphoteric surfactants, betaine-type compounds, imidazolium salts, imidazolines, amino acids and the like are used. And so on. Of these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are even more preferred. Examples of commercially available products include "Acetamine 24" manufactured by Kao Corporation for alkylamine salts, and "Cotamin 24P" and "Cotamin 86W" manufactured by Kao Corporation for quaternary ammonium salts.
Further, the surfactant may be used in a combination of two or more kinds, for example, a silicone-based surfactant / fluorine-based surfactant, a silicone-based surfactant / special polymer-based surfactant, and a fluorine-based surfactant. / Examples include a combination of special polymer-based surfactants. Above all, a combination of a silicone-based surfactant / a fluorine-based surfactant is preferable. In this combination of silicone-based surfactant / fluorine-based surfactant, for example, / Neos's "DFX-18", Big Chemie's "BYK-300" or "BYK-330" / AGC Seimi Chemical's "S" -393 ", Shinetsu Silicone" KP340 "/ DIC" F-478 "or" F-475 ", Toray Dow Corning" SH7PA "/ Daikin" DS-401 ", NUC" Examples include "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 the inclusion of the polymerization inhibitor inhibits the 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, and methylhydroquinone is more preferable, from the viewpoint of polymerization inhibitory ability.

The polymerization inhibitor preferably contains one kind or two or more kinds. Usually, when (C) an 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. Alternatively, the same or different polymerization inhibitor may be added at the time of producing the photosensitive resin composition.

The content ratio 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.% by mass, based on the total solid content of the photosensitive resin composition. It is 01% by mass or more, and usually 0.3% by mass or less, preferably 0.2% by mass or less, and more preferably 0.1% by mass or less. When it is set to the lower limit value or more, the taper angle tends to be increased, and when it is set to the upper limit value or less, high sensitivity tends to be maintained.

[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 the light source used for exposure with the ultraviolet absorber. By adding the ultraviolet absorber, effects such as improving the taper angle shape after development and eliminating the residue remaining in the unexposed portion after development can be obtained. As the ultraviolet absorber, for example, a compound having an absorption maximum between the wavelengths of 250 nm and 400 nm can be used from the viewpoint of inhibiting the light absorption of the initiator.
Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, dyes and the like.
These UV absorbers can be used alone or in combination of two or more.

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

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

In the above formula (Z1), R ^1e and R ^2e are independently hydrogen atoms, 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. R ^3e represents a hydrogen atom or a halogen atom.

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

In the above formula (Z3), R ^6e represents an alkylene group which may have a substituent, and R ^7e represents a hydrogen atom or a methyl group.

(R ^1e and R ^2e )
In the above formula (Z1), R ^1e and R ^2e are independently represented by a hydrogen atom, an alkyl group which may have a substituent, a group represented by the general formula (Z2), or a general formula (Z3). Represents the group represented.
Examples of the alkyl group include linear, branched or cyclic alkyl groups. The carbon number is preferably 1 or more, more preferably 2 or more, further preferably 4 or more, preferably 10 or less, and even more preferably 6 or less. It is more preferably 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, a tert-butyl group and the like. Of these, the tert-butyl group is preferred.
The substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like.

(R ^3e )
In the above 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, it is preferable that R ^3e is 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 a linear, branched or cyclic alkylene group. The carbon number is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a propylene group, a butylene group and the like. Of these, an ethylene group is preferable.
The substituents that the alkylene group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like.

Among these, it is preferable that R ^4e is an ethylene group.

(R ^5e )
In the above formula (Z2), it represents an alkyl group which may have a substituent.
Examples of the alkyl group include linear, branched or cyclic alkyl groups. The carbon number is preferably 4 or more, more preferably 5 or more, further preferably 7 or more, preferably 15 or less, and even more preferably 10 or less. It is more preferably 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 hepsy group, an octyl group, a nonyl group and the like.
The substituents that the alkyl group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like.
Among these, from the viewpoint of the tapered shape, it is preferable that R ^5e is 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 a linear, branched or cyclic alkylene group. The carbon number is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, still more preferably 3 or less.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a propylene group, a butylene group and the like. Of these, an ethylene group is preferable.
The substituents that the alkylene group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group and a carboxyl group. , Acryloyl group, methacryloyl group and the like.

Among these, from the viewpoint of the tapered shape, R ^1e is a tert-butyl group, R ^2e is a group represented by the above formula (Z 2) (however, 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 and R ^7e is a methyl group), and R ^3e is a hydrogen atom. 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 and R ^5e is an alkyl group having 7 to 9 carbon atoms), R ^3e . A compound in which is a hydrogen atom is more preferable.

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-benzotriazole-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5) -Chloro-2H-benzotriazole-2-yl) phenyl] propionate mixture, 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 direct Compound of chain alkyl ester, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole-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-benzotriazole-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl Ester compounds are preferred.

Examples of commercially available benzotriazole compounds include Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Industry Co., Ltd.), and TINUVIN PS. , TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (Taiwan Yongguang chemical (Industrial), Tomisorb 100, Tomisorb 600 (manufactured by AP Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (Cipro Chemical Co., Ltd.), RUVA-93 (Otsuka Chemical Co., Ltd.) and the like.

Examples of triazine compounds include 2- [4,6-di (2,4-kisilyl) -1,3,5-triazine-2-yl] -5-octyloxyphenol, 2- [4,6-bis (4,6-bis). 2,4-dimethylphenyl) -1,3,5-triazine-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-glycidate ester reaction product, 2,4-bis "2-hydroxy-4-butoxyphenyl"- Examples thereof include 6- (2,4-dibutoxyphenyl) -1,3-5-triazine. Among these, a hydroxyphenyltriazine compound is preferable from the viewpoint of taper angle and exposure sensitivity.
Examples of commercially available triazine compounds include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).

Examples of other ultraviolet absorbers include Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eiko Chemical Industry Co., Ltd.), Tomisorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESOR. Benzophenone compounds such as SEESORB105, SEESORB106, SEESORB107, SEESORB151 (Cipro Chemical); benzoate compounds such as Sumisorb 400 (Sumitomo Chemical Co., Ltd.), phenyl salicylate; , Cycillic acid derivatives such as isoamyl methoxycinnamate; α-naphthal, β-naphthal, α-naphthalmethyl ether, α-naphthal ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4- Dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxyl Naphthalene derivatives such as naphthalene; anthracene such as anthracene and 9,10-dihydroxyanthracene and its derivatives; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthracinone dyes, diphenylcyanoacrylate dyes, triazine dyes , P-Aminobenzoic acid dyes and the like; and the like. Among these, from the viewpoint of exposure sensitivity, it is preferable to use a cinnamic acid derivative and a naphthalene derivative, and it is particularly preferable to use a cinnamic acid derivative.

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, based on the total solid content. The above is 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, still more preferably 3% by mass. % Or less. When it is at least the lower limit value, the taper angle tends to be large, and when it is at least the upper limit value, the sensitivity tends to be high.

The blending ratio of (B) to the photopolymerization initiator is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 10 parts by mass or more, as the blending amount of the ultraviolet absorber with respect to 100 parts by mass of (B) the photopolymerization initiator. 30 parts by mass or more, more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably 150 parts by mass. It is as follows. When it is at least the lower limit value, the taper angle tends to be large, and when it is at least the upper limit value, the sensitivity tends to be high.

[1-1-7] Thermal Polymerization Initiator Further, the photosensitive resin composition for forming a partition wall of the present invention may contain a thermal polymerization initiator. By containing a thermal polymerization initiator, there is a tendency that the degree of cross-linking of the film can be increased. Specific examples of such a thermal polymerization initiator include azo compounds, organic peroxides, hydrogen peroxide and the like. 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 anticipation of an increase in sensitivity and a crosslink density of the film, the total content of these photopolymerization initiators is the total of the above-mentioned photopolymerization initiator in the photosensitive resin composition. The content ratio of the photopolymerization initiator is preferably such that the content ratio of the photopolymerization initiator is 100 parts by mass of the photopolymerization initiator from the viewpoint of sensitivity. It is preferably 5 to 300 parts by mass.

[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. Further, it is usually 0.5% by mass or more, preferably 1% by mass or more. When it is set to the upper limit value or less, the storage stability tends to be maintained, and when it is set to the lower limit value or more, sufficient thermosetting property tends to be secured.

Examples of the amino compound include an amino compound having a methylol group as a functional group and at least two alkoxymethyl groups obtained by alcohol condensation modification having 1 to 8 carbon atoms thereof. Specifically, for example, a melamine resin obtained by polycondensing melamine and formaldehyde; a benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde; a glycol uryl resin obtained by polycondensing glycoluryl and formaldehyde; urea and formaldehyde. Polycondensation urea resin; resin obtained by polycondensation of two or more kinds such as melamine, benzoguanamine, glycol uryl, or urea and formaldehyde; modified resin obtained by alcohol condensation modification of the methylol group of the above-mentioned resin and the like. These may be used alone or in combination of two or more. Among the amino compounds, a melamine resin and a modified resin thereof are preferable, a modified resin having a methylol group modification ratio of 70% or more is more preferable, and a modified resin having a modification ratio of 80% or more is particularly preferable.

As specific examples of the above amino compounds, examples of the melamine resin and its modified resin include "Simel" (registered trademark) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327 manufactured by Cytec. 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nicarac" (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 its modified resin include "Simel" (registered trademark) 1123, 1125, 1128 manufactured by Cytec. Examples of the glycoluril resin and its modified resin include "Simel" (registered trademark) 1170, 1171, 1174, 1172 manufactured by Cytec Co., Ltd. and "Nicarac" (registered trademark) MX manufactured by Sanwa Chemical Co., Ltd. -270 and the like. Examples of the urea resin and its modified resin include "UFR" (registered trademark) 65 and 300 manufactured by Cytec Co., Ltd. and "Nicarac" (registered trademark) MX-290 manufactured by Sanwa Chemical Co., Ltd. Be 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. Further, for example, when a pigment is used, a known dispersant or dispersion aid may be used in combination so that the pigment can stably exist in the photosensitive resin composition without agglomeration. In particular, coloring the liquid-repellent partition wall in black has the effect of obtaining a clear pixel display. As the black colorant, in addition to black dyes, black pigments, carbon black, titanium black, etc., mixing organic pigments to color black is also effective as an effect of imparting low conductivity. The content ratio 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 viewpoint of plate-making property and color characteristics.
On the other hand, for the purpose of reducing the outgas from the partition wall, it is desirable to make the partition wall transparent, and the content ratio of the colorant in that case is preferably 10 mass by 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] Coatability improver and development improver The photosensitive resin composition for forming a partition wall of the present invention contains a coatability improver and a development improver in order to improve coatability and development solubility. It may be. As the coatability improver or the development improver, for example, known cationic, anionic, nonionic, fluorine-based, and silicone-based surfactants can be used. Further, as the development improving agent, a known substance such as an organic carboxylic acid or an anhydride thereof can also be used. Further, the content ratio is usually 20% by mass or less, preferably 10% by mass or less, based on the total solid content of the photosensitive resin composition from the viewpoint of sensitivity.

[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 the adhesion to the substrate. Various types of silane coupling agents such as epoxy-based, methacrylic-based, amino-based, and imidazole-based agents can be used, but from the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferable. The content thereof 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] Phosphoric acid-based adhesion improver It is also preferable to add a phosphoric acid-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 phosphoric acid-based adhesion improver, (meth) acryloyloxy group-containing phosphates are preferable, and among them, those represented by the following general formulas (Va), (Vb) and (Vc) are preferable.

In the above general formulas (Va), (Vb) and (Vc), R ⁸ represents a hydrogen atom or a methyl group, r and r'are independently integers 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. 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. It is more preferably 3% by mass or less, and particularly preferably 1% by mass or less. When it is at least the above lower limit value, the adhesion tends to be good, and when it is at least the above upper limit value, the storage stability of the photosensitive composition tends to be maintained.

[1-1-13] Inorganic Filler Further, the photosensitive resin composition for forming a partition wall of the present invention further improves the strength as a cured product and has an appropriate interaction with an alkali-soluble resin (formation of a matrix structure). ) May contain an inorganic filler for the purpose of improving the flatness of the coating film and improving the taper angle. Examples of such an inorganic filler include talc, silica, alumina, barium sulfate, magnesium oxide, and those surface-treated 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 size referred to in this embodiment is a value measured by a laser diffraction / scattering particle size distribution measuring device manufactured by Beckman Coulter. Among these inorganic fillers, silica sol and silica sol modified product are 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. It is 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, contains a solvent). The photosensitive resin composition may be referred to as "photosensitive resin composition solution"). The solvent is not particularly limited, and examples thereof include the organic solvents described below.

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 Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, 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 , Glycoldialkyl ethers such as dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate Glycolalkyl ether acetates such as triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate; ethylene glycol diacetate, 1 , 3-butylene glycol diacetate, glycol diacetates such as 1,6-hexanol diacetate; alkyl acetates such as cyclohexanol acetate; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether , Ethylisobutyl ethers, ethers such as dihexyl ethers; acetone, methylethylketone, methylamylketone, methylisopropylketone, methylisoamylketone, diisopropylketone, diisobutylketone, methylisobutylketone, cyclohexanone, ethylamylketone, methylbutylketone, methyl Ketones such as hexyl ketones, methylnonyl ketones, methoxymethylpentanones; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxy Monovalent or polyvalent alcohols such as methylpentanol, glycerin, benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene, cumene; amylformates, ethylformates, ethyl acetate, butyl acetate, Propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprilate, butyl stearate, ethyl benzoate, 3-ethoxypropion Chain or cyclic esters such as methyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amilkloride; ether ketones such as methoxymethylpentanone; acetonitrile, benzonitrile. Una nitriles: Tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran and the like.

Examples of commercially available solvents corresponding to the above include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, and Sokal Solvent No. 1 and No. 2. Solvento # 150, shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, jiglime (all trade names) and the like can be mentioned.

The solvent can dissolve or disperse each component in the photosensitive resin composition, and is selected according to the method of use of the photosensitive resin composition of the present invention, but is large from the viewpoint of coatability. 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, and 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 may be used alone or in admixture of two or more. Further, in these solvents, the ratio of the total solid content in the photosensitive resin composition solution is usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, and usually 90% by mass or less, preferably 90% by mass or less. Is preferably used so as to be 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less. When it is at least the above lower limit value, a coating film tends to be obtained even for a high film thickness, and when it is at least the above upper limit value, an appropriate coating uniformity tends to be obtained.

[1-2] Physical characteristics of the photosensitive resin composition for forming a partition wall As a physical property of the photosensitive resin composition for forming a partition wall of the present invention, an acid value can be mentioned. The photosensitive resin composition for forming a partition wall of the present invention has an acid value of 20 mgKOH / g or more with respect to the total solid content. By setting the photosensitive resin composition for partition wall formation to the above lower limit value or more, the solubility in a developing solution is increased, the unexposed portion can be sufficiently dissolved and removed, and the taper angle of the obtained partition wall is increased. Conceivable.

The acid value of the photosensitive resin composition for forming a partition wall with respect to the total solid content 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 more preferably 26 mgKOH / g or more. Preferably, 28 mgKOH / g or more is particularly preferable, and usually 60 mgKOH / g or less, 55 mgKOH / g or less is preferable, 50 mgKOH / g or less is more preferable, 40 mgKOH / g or less is further preferable, and 35 mgKOH / g or less is particularly preferable. When it is set to the lower limit value or more, the solubility in the developing solution is high, and the taper angle tends to be high because the unexposed portion can be sufficiently dissolved and removed. Tends to be good.

[1-3] Method for preparing a photosensitive resin composition for forming a partition wall The photosensitive resin composition for forming a partition wall of the present invention is prepared by mixing each of the above components with a stirrer. In addition, you may filter using a membrane filter or the like so that the prepared photosensitive resin composition becomes uniform.

[2] Septum and method for forming a partition The photosensitive resin composition of the present invention can be suitably used for forming a partition for partitioning a partition, particularly an organic layer (light emitting portion) of an organic electroluminescent device.
The method for forming a partition wall (bank) using the photosensitive resin composition for forming a partition wall described above is not particularly limited, and a conventionally known method can be adopted. As a method for forming the partition wall, for example, a coating step of applying a photosensitive resin composition for forming a partition wall on a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer. , Including methods. A specific example of such a bank forming 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 region where a partition wall is formed on a substrate 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 a partition wall on the substrate.

In the coating process of applying the photosensitive resin composition on the substrate in the 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 placed on the substrate on which the partition wall should be formed. The photosensitive resin composition is applied using a non-contact coating device such as a coating device) or a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.

Next, in the exposure step, the photosensitive resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative mask, and the photosensitive resin composition layer is partially formed according to the bank pattern. To be exposed to. 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, and 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 partition wall is formed by developing the photosensitive resin composition layer exposed according to the pattern of the partition wall with a developing solution. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developing solution 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. Further, an antifoaming agent or a surfactant can be added to the developing solution.

Then, the partition wall after development is post-baked and heat-cured. Post-baking is preferably at 150-250 ° C. for 15-60 minutes.

The substrate used for forming the partition wall is not particularly limited, and is appropriately selected according to the type of the organic electroluminescent device manufactured by using the substrate on which the partition wall is formed. Suitable substrate materials include glass and various resin materials. Specific examples of the resin material include polyester such as polyethylene terephthalate; polyethylene and polyolefin such as polypropylene; polycarbonate; poly (meth) methacrylic resin; polysulfone; polyimide. Among these substrate materials, glass and polyimide are preferable because they have excellent heat resistance. Further, depending on the type of the organic electroluminescent element to be manufactured, a transparent electrode layer such as ITO or ZnO may be provided in advance on the surface of the substrate on which the partition wall is formed.

[3] Organic electroluminescent device The organic electroluminescent device of the present invention includes a partition wall made of the above-mentioned photosensitive resin composition for forming a partition wall.
Various optical elements are manufactured using the substrate having the partition wall pattern manufactured by the method described above. The method for forming the organic electroluminescent element is not particularly limited, but preferably, after forming the partition wall pattern on the substrate by the above method, ink is injected into the region surrounded by the partition wall on the substrate to form a pixel or the like. By forming the organic layer, an organic electroluminescent device is manufactured.
Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.
In the bottom emission type, for example, a partition wall is formed on a glass substrate on which transparent electrodes are laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. To. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall. Is created.
Examples of the light emitting layer include an organic electroluminescent layer as described in Japanese Patent Application Laid-Open No. 2009-146691 and Japanese Patent No. 5734681. Further, quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.

When the taper angle of the partition wall is low and the lower portion of the partition wall has a skirt shape as shown in FIG. 1, even if a thin-film deposition layer is formed on the upper portion of the partition wall, light emission is not performed, so that the light emission area becomes small. When the light emitting layer is created by the inkjet method, the ink for forming the organic layer is repelled at the skirt of the partition wall, so that the area surrounded by the partition wall may not be uniformly covered with the ink for forming the organic layer. be. On the other hand, by having a good shape with a high taper angle and no skirting, it is possible to emit light in the area surrounded by the partition wall, and in the inkjet method, the ink for forming the organic layer makes it uniform. Can be covered. 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, tetraline, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate, and butyl acetate, 3-phenoxytoluene. And so on. Further, a surfactant, an antioxidant, a viscosity modifier, an ultraviolet absorber and the like can be added to the ink.

As a method of injecting ink into the region surrounded by the partition wall, an inkjet method is preferable because a small amount of ink can be easily injected into a predetermined place. The ink used for forming the organic layer is appropriately selected according to the type of the organic electroluminescent device to be manufactured. When the ink is injected by the inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be satisfactorily ejected from the inkjet head, but 4 to 20 mPa · s is preferable, and 5 to 10 mPa · s is more preferable. The viscosity of the ink can be adjusted by adjusting the solid content in the ink, changing the solvent, adding a viscosity adjusting agent, and the like.

[4] Image Display Device The image display device of the present invention includes the above-mentioned organic electroluminescent element. The type and structure of the image display device are not particularly limited as long as they include an organic electroluminescent element, and can be assembled according to a conventional method using, for example, 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" (Ohmsha, published on August 20, 2004, by Shizushi Tokito, Chihaya Adachi, 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 an organic electroluminescent element having a different emission color such as RGB may be combined to display an image.

[5] Lighting The lighting of the present invention includes the above-mentioned organic electroluminescent element. The model and structure are not particularly limited, and the organic electroluminescent device of the present invention can be used for assembly according to a conventional method. The organic electroluminescent device may be a simple matrix drive system or an active matrix drive system.
In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. Further, organic electroluminescent elements having different emission colors may be combined so that the colors are mixed to be white, or the color mixing ratio may be adjusted to provide a toning function.

Hereinafter, the photosensitive resin composition for forming a partition wall of the present invention will be described with reference to specific examples, but the present invention is not limited to the following examples as long as the gist of the present invention is not exceeded.

[1] Preparation of photosensitive resin composition for partition wall formation Propylene glycol monomethyl ether so that each component is used in the blending ratio (part by mass) shown in Table 1 and the content ratio of the total solid content is 25% by mass. Using acetate, each component was stirred until uniform to prepare a photosensitive resin composition for forming a partition wall of Examples and Comparative Examples. The numerical values in Table 1 mean the values of solid content.
The symbols in the table represent 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: Megafuck RS-72-K (manufactured by DIC, fluorine-based, oligomer having an ethylenic double bond)
e-1: 2-Mercaptobenzimidazole (manufactured by Tokyo Kasei Co., Ltd.)
e-2: Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Yodo Kagaku Co., Ltd.)
f-1: TINUVIN384-2 (made by BASF, UV 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 the general formula (1) and partial structure represented by the general formula (iii). Equivalent to the resin contained)
100 parts by mass of bisphenol A type epoxy compound represented by the following formula (epoxy equivalent 186 g / eq, mixture of compounds having n of 1 to 20 in the formula), 40 parts by mass of acrylic acid, 0.06 parts by mass of p-methoxyphenol, 2.4 parts by mass of triphenylphosphine and 126 parts by mass of propylene glycol monomethyl ether acetate were charged in a reaction vessel, and the mixture was 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, 4.5 parts by mass of anhydrous succinic acid was added, and the mixture was reacted at 95 ° C. for 3 hours to have a solid acid value of 60 mgKOH. An alkali-soluble resin (c-1) solution having a polystyrene-equivalent weight average molecular weight (Mw) of / g and a polystyrene-equivalent weight average molecular weight (Mw) of 8000 was obtained.

c-2: The following ethylenically unsaturated group-containing resin ((c1) epoxy (meth) acrylate resin / partial structure represented by the general formula (1) and partial structure represented by the general formula (iii). Equivalent to the resin contained)
Similar to c-1, 100 parts by mass of bisphenol A type epoxy compound (epoxy equivalent 186 g / eq, mixture of 1 to 20 n in the formula) represented by the above formula, 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 in a reaction vessel, and the mixture was 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 anhydrous succinic acid was added, and the mixture was reacted at 95 ° C. for 3 hours to have a solid acid value of 30 mgKOH. An alkali-soluble resin (c-2) solution having a polystyrene-equivalent weight average molecular weight (Mw) of 8300 at / g and measured by GPC was obtained.

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

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

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

The physical characteristics of the photosensitive resin composition for forming a partition wall were evaluated by the method described below.

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

(Creation of substrate for gas amount measurement)
The photosensitive resin composition for forming a partition wall was applied onto a glass substrate using a spinner so as to have a thickness of 1.7 μm after heat curing (post-baking). Then, it was heated and dried on a hot plate at 95 ° C. for 2 minutes, and the obtained coating film was entirely exposed to 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 . Then, it 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 10 seconds. This substrate was heat-cured (post-baked) at 230 ° C. for 30 minutes in an oven to obtain a substrate for measuring the amount of gas with a cured product.

(Measurement of gas amount)
The outgas when the prepared gas quantity measuring substrate (40 mm × 8 mm, 4 sheets) was heated in a heating furnace at 230 ° C. for 20 minutes was analyzed by GC / MS (manufactured by Agilent Technologies, trade name “5973N”). , The sum of the areas of all detected peak components was calculated. However, the calculation was performed excluding the peak corresponding to tetramethylammonium derived from the TMAH (tetramethylammonium hydroxide) aqueous solution. Next, the sum of the detected peak areas was converted into the amount of toluene using a calibration curve, divided by the measured substrate area, and the amount of outgas in terms of toluene per unit area (ng / cm ² ) was calculated. The results are shown in Table 1. The calibration curve was created by measuring GC / MS using toluene having a known concentration and plotting the amount of toluene and the peak area value of the detected gas.

(Creation of substrate for contact angle measurement)
The photosensitive resin composition for forming a partition wall was applied onto a glass substrate using a spinner so as to have a thickness of 1.7 μm after heat curing (post-baking). Then, it was heated and dried on a hot plate at 95 ° C. for 2 minutes, and the obtained coating film was entirely exposed to 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 . Then, it 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 10 seconds. This substrate was heat-cured (post-baked) at 230 ° C. for 30 minutes in an oven to obtain a substrate for measuring the contact angle with a cured product.

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

[2] Formation and evaluation of partition walls The method of performance evaluation will be described below.
(Formation of partition wall)
Using a spinner on the ITO film of the glass substrate having the ITO film formed on the surface, the photosensitive resin composition for forming a partition wall was applied so as to have a thickness of 1.7 μm after heat curing (post-baking). Then, it was heated and dried on a hot plate at 95 ° C. for 2 minutes, and a photomask (a mask having a plurality of 80 μm × 280 μm coating films at 40 μm intervals) was used for the obtained coating film at an exposure gap of 16 μm and a wavelength of 365 nm. Exposure was performed with an exposure amount of 100 mJ / cm ² using ultraviolet rays having an intensity of 7.5 mW / cm ² . The ultraviolet irradiation at this time was performed under air. Then, it 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, the substrate on which the pattern was formed by removing unnecessary portions was heat-cured (post-baked) at 230 ° C. for 30 minutes in an oven to form a grid-like partition wall.

(Evaluation of taper angle and line width of partition wall, area of opening)
The above-mentioned lattice-shaped partition wall was cut to prepare a sample for cross-sectional observation, the cross-sectional shape of the partition wall was observed using a scanning electron microscope (SEM, manufactured by KEYENCE), and the taper angle and line width were measured. .. The cross-sectional shape of the partition wall was observed to be substantially trapezoidal.
In this cross-sectional view, as shown in FIG. 1, the boundary surface between the partition wall 1 and the ITO film 2 is S, and the height of the partition wall is H. On the hypotenuse of the partition wall, the tangent line of the hypotenuse in contact with the boundary surface S was defined as T, and the angle formed by the tangent line T and the boundary surface S was measured and used as a taper angle. The higher the taper angle, the better the developability and the tendency for residue to be less likely to occur, and the more likely it is to get wet and spread in inkjet coating.
In addition, the opening width (horizontal width, vertical width) at the bottom of the partition wall was measured, and the area of the opening was calculated by multiplying them. Table 1 shows the results of the taper angle, the line width at the bottom of the taper, and the area of the opening. The area of the opening is a relative value to the area of the corresponding mask shielding portion. 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 amount of outgas generated on the substrate obtained by using the photosensitive resin composition containing the resins (c-1) to (c-4) to which succinic acid was added was the resin to which tetrahydrophthalic acid was added ( It was found that the amount was significantly less than that of the substrate obtained by using the photosensitive resin composition containing c-5).
From this, the photosensitive resin composition containing a resin having a short carbon chain added such as succinic acid is a photosensitive resin composition containing a resin having a long carbon chain added such as tetrahydrophthalic acid. It was confirmed that the amount of outgas generated was smaller under the gas measurement conditions of heating at 230 ° C. after heating and curing by post-baking at 230 ° C. for 30 minutes. It is considered that this is because most of the acids having a short carbon chain such as succinic acid are desorbed and removed at the time of post-baking, and no gas is generated at the time of subsequent heating at 230 ° C.

From Table 1, when the photosensitive resin compositions of Comparative Examples 1 and 2 having a low acid value are used, the taper angle is low, while when the photosensitive resin compositions of Examples 1 and 2 having a high acid value are used, the taper angle is low. It turned out to be higher. Further, it was confirmed that when a photosensitive resin composition having a low acid value was used, the area of the opening was small, and when a photosensitive resin composition having a high acid value was used, the area of the opening was large. .. When the acid value of the photosensitive resin composition is low, the solubility of the unexposed portion in the developer becomes low, the deep part of the coating film becomes difficult to develop sufficiently, and the taper angle becomes low. It is considered that by increasing the acid value of the unexposed portion, the solubility of the unexposed portion in the developing solution can be increased, the unexposed portion can be sufficiently dissolved and removed, and the taper angle becomes high.

1: Partition 2: ITO film 3: Glass substrate T: Tangent line with the hypotenuse in contact with the boundary surface S H: Height of the partition wall S: Boundary surface between the partition wall and the ITO film

Claims (12)

A photosensitive resin composition for forming a partition wall containing (A) an ethylenically unsaturated compound, (B) a photopolymerization initiator , (C) an alkali-soluble resin and a colorant .
The acid value of the photosensitive resin composition for forming a partition wall is 20 mgKOH / g or more with respect to the total solid content, and the acid value is 20 mgKOH / g or more.
The alkali-soluble resin (C) contains an alkali-soluble resin (c) having a partial structure represented by the following general formula (1) .
The alkali-soluble resin (c) contains (c1) epoxy (meth) acrylate resin.
The (c1) epoxy (meth) acrylate resin is a resin obtained by adding an acid or an ester compound having an ethylenically unsaturated bond to the epoxy resin and further adding a polybasic acid or an anhydride thereof.
A photosensitive resin composition for forming a partition wall , wherein the content ratio of the colorant is 5% by mass or less with respect to the total solid content of the photosensitive resin composition.

(In the above 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 forming a partition wall according to claim 1, wherein the content ratio of the colorant is 0% by mass with respect to the total solid content of the photosensitive resin composition. The photosensitive resin composition for forming a partition wall according to claim 1 or 2 , wherein the alkali-soluble resin (c) is a resin having a carboxyl group and an ethylenically unsaturated group. The (c1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin containing a repeating unit structure represented by the following general formula (i), and an epoxy containing a partial structure represented by the following general formula (ii). The partition wall forming according to claim 1 or 2 , which contains at least one selected from the group consisting of a meta) acrylate resin and an epoxy (meth) acrylate resin containing a partial structure represented by the following general formula (iii). Photosensitive resin composition.

(In the formula (i), Ra 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) further represents. It may be substituted with any substituent. * Represents a bond.)

(In formula (ii), 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), ^Re represents a hydrogen atom or a methyl group, and γ may have a single bond, —CO—, an alkylene group which may have a substituent, or a substituent. Represents a cyclic hydrocarbon group of valence. The benzene ring in formula (iii) may be further substituted with any substituent. * Represents a bond.) The photosensitive resin composition for forming a partition wall according to any one of claims 1 to 4 , further comprising (D) a liquid repellent. The photosensitive resin composition for forming a partition wall according to claim 5 , wherein the liquid repellent (D) contains a liquid repellent having a cross-linking group. The photosensitive resin composition for forming a partition wall according to any one of claims 1 to 6 , further comprising a chain transfer agent. The photosensitive resin composition for forming a partition wall according to any one of claims 1 to 7 , further comprising an ultraviolet absorber. A partition wall made of the photosensitive resin composition for forming a partition wall according to any one of claims 1 to 8 . The organic electroluminescent device comprising the partition wall according to claim 9 . An image display device including the organic electroluminescent element according to claim 10 . Lighting including the organic electroluminescent device according to claim 10 .

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