JP2021120946A - Photosensitive resin composition for forming partition wall, partition wall, organic electroluminescent element, image display device and illumination - Google Patents

Abstract

To provide a photosensitive resin composition for forming a partition wall, which allows formation of a partition wall having a large taper angle.SOLUTION: The photosensitive resin composition for forming a partition wall comprises: (A) a photopolymerization initiator; (B) an ethylenically unsaturated compound; (C) an alkali-soluble resin, in which the (A) photopolymerization initiator comprises a hexaaryl biimidazole compound; and further (D) a sensitizer.SELECTED DRAWING: None

Description

The present invention relates to a partition wall forming photosensitive resin composition used for forming a partition wall, in particular, a partition wall composed of the partition wall forming photosensitive composition, an organic electroluminescent device provided with the partition wall, and the organic electroluminescent device. The present invention relates to an image display device and lighting including.

Conventionally, optical elements such as organic electroluminescent elements, color filters, and organic TFT arrays included in organic electroluminescent displays and organic field lighting have formed a partition wall (bank) on a substrate and then have a region surrounded by the partition wall. It is manufactured by laminating various functional layers inside. As a method for easily forming such a partition wall, a method of forming such a partition wall by a photolithography method using a photosensitive resin composition is known (see Patent Document 1).

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. There are known ways to do this. 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 ink injected between the adjacent regions from being mixed. Is required to do. As a method of imparting ink repellency to a partition wall, for example, a method of incorporating a fluororesin into the partition wall is known (see Patent Document 2).

On the other hand, 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 3 describes that a fine and highly accurate pattern can be formed by using a specific ultraviolet absorber and a polymerization inhibitor.

Further, Patent Documents 4 and 5 describe that by using a specific polymer, it is possible to form a pattern having high wettability on the substrate surface and high liquid repellency on the upper surface of the partition wall.

On the other hand, for example, Patent Document 6 describes that the taper shape of a coloring pattern is changed by using a sensitizer in a photosensitive coloring composition for a color filter.

JP-A-2010-262940 International Publication No. 2008/149498 Pamphlet Japanese Unexamined Patent Publication No. 2015-172742 JP 2015-161894 JP 2015-161895 Japanese Unexamined Patent Publication No. 2012-163769

In recent years, with the demand for improving the power consumption characteristics of organic electroluminescent devices using the inkjet method, there is a demand for improving the brightness of the functional layer surrounded by the partition wall.
When forming a functional layer using ink, the shape of the partition wall surrounding the functional layer is important. If the taper angle of the partition wall is low, the area of the light emitting portion is small, and if the taper angle of the partition wall is high, the area of the light emitting portion is large. Since it becomes large, it is required to increase the taper angle of the partition wall to improve the brightness.
When the present inventors examined the photosensitive resin compositions for forming a partition wall described in Patent Documents 3 to 5, it was found that the taper angle of the partition wall was low and the improvement in brightness was not sufficient.
On the other hand, the photosensitive resin composition described in Patent Document 6 contains a colorant, and there is no description about its use for partition wall formation, and it is unclear how the tapered shape changes.
Therefore, an object of the present invention is to provide a photosensitive resin composition for forming a partition wall capable of forming a partition wall having a large taper angle.
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. And.

As a result of diligent studies by the present inventors, a sensitizer using a specific photopolymerization initiator in a photosensitive resin composition for forming a partition wall containing a photopolymerization initiator, an ethylenically unsaturated compound, and an alkali-soluble resin. We have found that the above-mentioned problems can be solved by using the above-mentioned substances in combination with each other, and have completed the present invention.
That is, the gist of the present invention is as follows.

[1] A photosensitive resin composition for forming a partition wall containing (A) a photopolymerization initiator, (B) an ethylenically unsaturated compound, and (C) an alkali-soluble resin.
The (A) photopolymerization initiator contains a hexaarylbiimidazole compound, and the photopolymerization initiator is contained.
(D) A photosensitive resin composition for forming a partition wall, which comprises a sensitizer.
[2] The photosensitive resin composition for forming a partition wall according to [1], wherein the sensitizer (D) contains a thioxanthone-based compound.
[3] The photosensitive resin composition for forming a partition wall according to [1] or [2], which further contains (E) a liquid repellent.
[4] The photosensitive resin composition for forming a partition wall according to any one of [1] to [3], which further contains (F) a thiol compound.
[5] The photosensitive resin composition for forming a partition wall according to any one of [1] to [4], which further contains (G) a polymerization inhibitor.
[6] The photosensitive resin composition for forming a partition wall according to any one of [1] to [5], which further contains (H) an ultraviolet absorber.
[7] A partition wall composed of the photosensitive resin composition for forming a partition wall according to any one of [1] to [6].
[8] An organic electroluminescent device including the partition wall according to [7].
[9] An image display device including the organic electroluminescent device according to [8].
[10] Lighting including the organic electroluminescent device according to [8].

According to the photosensitive resin composition for forming a partition wall of the present invention, a partition wall having a large taper angle can be formed, and the brightness of the organic electroluminescent element can be improved.

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 in these unless the gist thereof is exceeded.
In the present invention, "(meth) acrylic" means "acrylic and / or methacryl", and "total solid content" means the total amount of the components of the photosensitive resin composition excluding the solvent. Shall mean. 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 homopolymer and a copolymer are included, and "(acid) anhydride" and "(acid) anhydride" and ". (Anhydrous) ... Acid "means that it contains both an acid and an anhydride thereof.
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.
In the present invention, the weight average molecular weight refers to the polystyrene-equivalent weight average molecular weight (Mw) obtained by GPC (gel permeation chromatography).

[1] Photosensitive resin composition for forming a partition wall The photosensitive resin composition for forming a partition wall of the present invention contains (A) a photopolymerization initiator, (B) an ethylenically unsaturated compound, and (C) an alkali-soluble resin. The photosensitive resin composition for forming a partition wall is characterized in that the (A) photopolymerization initiator contains a hexaarylbiimidazole compound and (D) a sensitizer. If necessary, other components may be further contained, and for example, (E) a liquid repellent, (F) a thiol compound, (G) a polymerization inhibitor, and (H) an ultraviolet absorber may be contained.

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

[1-1] Components and Composition of Photosensitive Resin Composition for Separation Form The components and composition thereof constituting the photosensitive resin composition for partition wall formation of the present invention 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) a photopolymerization initiator, (B) an ethylenically unsaturated compound and (C) an alkali. It contains a soluble resin and also contains (D) a sensitizer. Usually, it also contains 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 that the photosensitive resin composition contains (E) a liquid-repellent agent. As the components (A) to (D), those exhibiting an action as a liquid repellent may be used.

[1-1-1] Component (A); Photopolymerization Initiator The photosensitive resin composition for forming a partition wall of the present invention contains (A) a photopolymerization initiator, and the photopolymerization initiator is hexaarylbi. Contains imidazole compounds. Since the hexaarylbiimidazole compound has high absorbance and therefore has high surface curability, it is considered that a high taper angle can be obtained. In particular, since it has an energy rank that is susceptible to energy transfer, it is considered that the surface curability is increased and a high taper angle can be obtained by using the (D) sensitizer.
In addition, hexaarylbiimidazole tends to efficiently generate thiyl radicals from thiols when used with thiol compounds. Since the chile radical is not easily deactivated by oxygen, the taper angle tends to be large because it is sufficiently cured even on a surface that is normally susceptible to oxygen deactivation.

As the hexaarylbiimidazole compound, a hexaarylbiimidazole-based photoradical initiator represented by the following general formula (1-1) and / or the following general formula (1-2) is preferable from the viewpoint of increasing the taper angle.

In the above formula, R ^{1 to} R ³ are an alkyl group having 1 to 4 carbon atoms which may independently have a substituent, an alkoxy group having 1 to 4 carbon atoms which may have a substituent, or a halogen. Representing an atom, l, m and n each independently represent an integer of 0-5.

The ^{number of carbon atoms of the alkyl groups of R 1 to} R ³ is not particularly limited as long as it is in the range of 1 to 4, but from the viewpoint of increasing the taper angle, 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 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 1 to} R ³ may have, a group of a monovalent non-metal atomic group excluding hydrogen is used, and a halogen atom (-) is a preferable example. Examples thereof include F, -Br, -Cl, -I), a hydroxyl group and an alkoxy group.

The ^{number of carbon atoms of the alkoxy groups of R 1 to} R ³ is not particularly limited as long as it is within the range of 1 to 4, but is preferably 3 or less, more preferably 2 or less, from the viewpoint of increasing the taper angle. 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 that the alkoxy group having 1 to 4 carbon atoms of R ^{1 to R 3} may have include an alkyl group and an alkoxy group, and an alkyl group is preferable.

Examples of the halogen atoms of R ^{1 to} R ³ 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, R ^{1 to} R ³ are preferably halogen atoms independently, 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, at least one of m, n and l is preferably an integer of 1 or more, and m, n and l. It is more preferable that any two of them are 0 and the remaining one is 1.

Examples of the hexaarylbiimidazole compound represented by the general formula (1-1) and / or the general formula (1-2) include 2,2'-bis (o-chlorophenyl) -4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (o-methylphenyl) -4,5,4', 5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4, 4', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, 2,2'-bis (o, p-dichlorophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) ) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-fluorophenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4, 4', 5,5'-tetra (o, p-dibromophenyl) biimidazole, 2,2'-bis (o-bromophenyl) -4,4', 5,5'-tetra (o, p-dichlorophenyl) ) Biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-chloronaphthyl) biimidazole and the like. 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 replaced 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.

As the photopolymerization initiator (A), either a hexaarylbiimidazole compound represented by the general formula (1-1) or a hexaarylbiimidazole compound represented by the general formula (1-2) may be used. , Both may be used in combination. When used in combination, the ratio is not particularly limited. Note that (A-1) used in the examples has a structure satisfying the general formula (1-1).

The photopolymerization initiator (A) of the photosensitive resin composition for forming a partition wall of the present invention may contain other photopolymerization initiators other than the hexaarylbiimidazole compound.

As the other photopolymerization initiator, a photopolymerization initiator usually used in this field can be used. Examples of such photopolymerization initiators include acylphosphine oxide-based photoradical initiators, oxime-based photoradical initiators, triazine-based photoradical initiators, acetophenone-based photoradical initiators, benzophenone-based photoradical initiators, and hydroxy. Benzene-based photoinitiator, thioxanthone-based photoinitiator, anthraquinone-based photoradical initiator, ketal-based photoradical initiator, titanosen-based photoradical initiator, halogenated hydrocarbon derivative-based photoradical initiator, organic boronic acid salt Examples thereof include system photoradical initiators, onium salt-based photoradical initiators, sulfone compound-based photoradical initiators, carbamate derivative-based photoradical initiators, sulfonamide-based photoradical initiators, and triarylmethanol-based photoradical initiators. ..

Examples of the acylphosphine oxide-based photoradical initiator include the compounds shown below.

(In the above structural formula, Me represents a methyl group.)
Among the above compounds, a bisacylphosphine oxide derivative is preferable, a bisacylphenylphosphine oxide derivative is more preferable, and the compound shown in (a-1) having an absorption region at a long wavelength is most preferable.

Examples of the oxime-based photoinitiator include JP-A-2004-534797, JP-A-2000-80068, JP-A-2006-36750, JP-A-2008-179611, JP-A-2012-526185, and JP-A-2012-526185. Examples thereof include oxime ester compounds described in Table 2012-591191. Among them, from the viewpoint of sensitivity, N-acetoxy-N- {4-acetoxyimino-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-acetoxyimino-5- [9-Ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -methyl 5-oxopentanoate is also available as product names such as OXE-01, OXE-02 (manufactured by BASF), TR. -PBG-304, TR-PBG-305 (manufactured by Changshu Powerful Electronics New Materials Co., Ltd.), NCI-831, NCI-930 (manufactured by ADEKA) and the like can be mentioned as preferable ones.

As triazine-based photoradical initiators, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-methoxynaphthyl) -4,6-bis are used from the viewpoint of sensitivity. (Trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine and the like can be mentioned as preferable ones.

Examples of the acetophenone-based photoinitiator 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-methylphenylpropanone, α-aminoacetophenone, etc. Examples of the benzophenone-based photoinitiator include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and Michler ketone. As the hydroxybenzene-based photoinitiator, for example, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-benzylbenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 4 -Di-t-butylphenyl-3,5-di-t-butyl-4-hydroxybenzoate and the like, and examples of the thioxanthone-based photoinitiator are thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, and the like. 2,4-Dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone and the like, and examples of the anthraquinone-based photoradical initiator include 2-methylanthraquinone and the like. Examples of the ketal-based photoinitiator include benzyldimethyl ketal and the like.

Examples of the titanosen-based photoinitiator include dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis (2,4-difluorophenyl), and dicyclopentadienyltitanium. Bis (2,6-difluorophenyl), dicyclopentadienyltitanium bis (2,4,6-trifluorophenyl), dicyclopentadienyltitanium 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 photoradical 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 -Halomethylated s-triazine derivatives such as triazine can be mentioned, and among them, from the viewpoint of sensitivity, bi Su (trihalomethyl) -s-triazines are preferred.

Examples of the organic boronic acid salt-based photoradical 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-triphenylborone anion such as −pentafluorophenyl) boron anion, n-butyl-tris (p-chlorophenyl) boron anion, n-butyl-tris (2,6-difluoro-3-pyrrolylphenyl) 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 photoradical 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 photoradical 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 (t-butylsulfonyl) methane, phenylsulfonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (phenylsulfonyl) methane, naphthyl Carbonyl (phenylsulfonyl) methane, phenylcarbonyl (naphthylsulfonyl) methane, cyclohexylcarbonyl (phenylsulfonyl) methane, t-butylcarbonyl (phenylsulfonyl) methane, phenylcarbonyl (cyclohexylsulfonyl) methane, phenylcarbonyl (t-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 (t-butylsulfonyl) diazomethane, phenylsulfonyl (cyclohexylsulfonyl) diazomethane, bis (sulfonyl) diazomethane compound, phenylcarbonyl (phenylsulfonyl) diazomethane, naphthylcarbonyl (phenylsulfonyl) diazomethane , Phenylcarbonyl (naphthylsulfonyl) diazomethane, cyclohexylcarbonyl (phenylsulfonyl) diazomethane, t-butylcarbonyl (phenylsulfonyl) diazomethane, phenylcarbonyl (cyclohexylsulfonyl) diazomethane, phenylcarbonyl (t-butylcarbonyl) diazomethane and other carbonyl (sulfonyl) Examples include diazomethane compounds.

Examples of the carbamate derivative-based photoinitiator include benzoylcyclohexylcarbamate, 2-nitrobenzylcyclohexylcarbamate, 3,5-dimethoxybenzylcyclohexylcarbamate, 3-nitrophenylcyclohexylcarbamate, and the like. Examples of the photoradical initiator include N-cyclohexyl-4-methylphenylsulfone amide and N-cyclohexyl-2-naphthylsulfonamide, and examples of the triarylmethanol-based photoradical initiator thereof include triphenyl. Examples thereof include methanol, tri (4-chlorophenyl) methanol and the like.

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. Two or more kinds of hexaarylbiimidazole compounds may be used, and two or more kinds of other photopolymerization initiators may be used.

The content ratio of the (A) 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, still more preferably 1% by mass or more, particularly preferably 2% by mass or more, and usually 25% by mass or less, preferably 10% by mass or less, more preferably 8% by mass. Hereinafter, it is more preferably 5% by mass or less, and particularly preferably 4% by mass or less. When it is set to the lower limit value or more, the surface is sufficiently hardened and the taper angle tends to be high, and when it is set to the upper limit value or less, the internal curability is suppressed and the taper angle tends to be high.

The content ratio of the hexaarylbiimidazole compound in the photosensitive resin composition of the present invention is not particularly limited, but is usually 25% by mass or less, preferably 10% by mass or less, based on the total solid content of the photosensitive resin composition. It is more preferably 8% by mass or less, further preferably 5% by mass or less, particularly preferably 4% by mass or less, and usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0% by mass. It is 5% by mass or more, more preferably 1% by mass or more, and particularly preferably 2% by mass or more. When it is set to the lower limit value or more, the surface is sufficiently hardened and the taper angle tends to be high, and when it is set to the upper limit value or less, the internal curability is suppressed and the taper angle tends to be high.

The compounding ratio of the (A) photopolymerization initiator to the (B) ethylenically unsaturated compound in the photosensitive resin composition is 1 part by mass or more with respect to 100 parts by mass of the (B) ethylenically unsaturated compound. Is preferable, 2 parts by mass or more is more preferable, 4 parts by mass or more is further preferable, 200 parts by mass or less is preferable, 100 parts by mass or more 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. When it is set to the lower limit value or more, the surface is sufficiently hardened and the taper angle tends to be high, and when it is set to the upper limit value or less, the internal curability is suppressed and the taper angle tends to be high.

[1-1-2] Component (B); Ethylene Unsaturated Compound The photosensitive resin composition for forming a partition wall of the present invention contains (B) an ethylenically unsaturated compound. (B) 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, but it is polymerizable, crosslinkable, and a developing solution for exposed and non-exposed parts. 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 ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 3 or more, more preferably 4 or more, and preferably 15 or less. More preferably, the number is 10 or less. When it is set to the lower limit value or more, the polymerizable property tends to be improved and the sensitivity tends to be high, and when it is set to the upper limit value or less, the developability tends to be improved.
Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polys. Examples thereof include an ester obtained by an esterification reaction between a polyvalent hydroxy compound such as a hydroxy compound and an unsaturated carboxylic acid and a polybasic carboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethyl propantriacrylate, 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 exemplified compounds are replaced with methacrylates. Similarly, an itaconic acid ester in place of itaconate, a crotonic acid ester in place of clonate, a maleic acid ester in place of maleate, and the like can be mentioned.

Examples of the ester of the aromatic polyhydroxy compound and the unsaturated carboxylic acid include an acrylic acid ester and a methacrylic acid ester of an aromatic polyhydroxy compound such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. And so on.
The ester obtained by the esterification reaction of a polybasic carboxylic acid and an unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single ester, but typical specific examples include acrylic acid, phthalic acid, and Examples thereof include a condensate of ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester are reacted. 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 Chemical Co., Ltd.) and the like.

Among these, ester (meth) acrylates or urethane (meth) acrylates are preferably used as the (B) ethylenically unsaturated compound from the viewpoint of an appropriate taper angle and sensitivity, and dipentaerythritol hexa (meth) acrylate. , Dipentaerythritol penta (meth) acrylate, 2-trisacryloyloxymethylethylphthalic acid, pentaerythritol tetraacrylate, pentaerythritol triacrylate, dibasic acid anhydride adduct of dipentaerythritol pentaacrylate, pentaerythritol triacrylate It is more preferable to use a dibasic acid anhydride additive or the like.
One of these may be used alone, or two or more thereof may be used in combination.

In the present invention, the molecular weight of the (B) 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 (B) 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.
From the viewpoints of sensitivity, liquid repellency, and taper angle, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable, and among them, pentaerythritol tetraacrylate and dipentaerythritol hexa ( Meta) acrylates, dipentaerythritol penta (meth) acrylates and other tetrafunctional ester (meth) acrylates, 2-trisacryloyloxymethylethylphthalic acid, dipentaerythritol pentaacrylate dibasic acid anhydride adducts, etc. Additives of acid anhydrides to tetrafunctional or higher functional ester (meth) acrylates are more preferred in terms of sensitivity, liquid repellency and taper angle.

The content ratio of the (B) ethylenically unsaturated compound in the photosensitive resin composition of the present invention is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content. It is more 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. 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 improved, and when it is set to the upper limit value or less, the developability and the taper angle tend to be improved.

The content ratio of (B) 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. It is preferably parts by mass or more, particularly preferably 100 parts by mass or more, usually 150 parts by mass or less, preferably 140 parts by mass or less, more preferably 130 parts by mass or less, still more preferably 125 parts by mass or less. When it is set to the upper limit value or less, the taper angle becomes good, and there is a tendency that the occurrence of electrode disconnection when the organic EL element is used. Tends to be good.

[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 alkali 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, it is preferable to have a carboxyl group and to have an ethylenically unsaturated group because a partition wall having an appropriate taper angle can be obtained and the outflow of the partition wall due to thermal melting can be suppressed and the liquid repellency can be maintained. Is more preferable.
The following are (C-1) carboxyl group-containing (co) polymer, (C-2) carboxyl group-containing (co) polymer having an ethylenically unsaturated group in the side chain, (C-3) carboxyl group and ethylene. The sex unsaturated group-containing resin will be described in detail.

[1-1-3-a] (C-1) Carboxyl group-containing (co) polymer [1-1-3-a-1] Carboxyl group-containing (co) polymer (1)
Specific examples of the carboxyl group-containing (co) polymer include non-residuals such as (meth) acrylic acid, crotonic acid, isocrotonic acid, maleic acid, maleic anhydride, itaconic acid, and citraconic acid. Saturated carboxylic acid and styrenes such as styrene, α-methylstyrene and hydroxystyrene, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (Meta) acrylate, dodecyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, adamantyl (meth) acrylate, isobornyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) (Meta) acrylates, glycidyl (meth) acrylates, benzyl (meth) acrylates, N, N-dimethylaminoethyl (meth) acrylates, (meth) acrylic acid esters such as N- (meth) acryloylmorpholine, (meth) acrylonitrile, etc. (Meta) acrylonitriles, (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylamide and other (meth) acrylamides, acetic acid Examples thereof include copolymers with vinyl compounds such as vinyl.

Among these, (meth) acrylate- (meth) acrylic acid copolymer and styrene- (meth) acrylate- (meth) acrylic acid copolymer are preferable from the viewpoint of sensitivity. In the (meth) acrylate- (meth) acrylic acid copolymer, a copolymer composed of 5 to 80 mol% of (meth) acrylate and 20 to 95 mol% of (meth) acrylic acid is more preferable. A copolymer composed of 10 to 70 mol% of meta) acrylate and 30 to 90 mol% of (meth) acrylic acid is particularly preferable. The styrene- (meth) acrylate- (meth) acrylic acid copolymer is composed of 3 to 60 mol% of styrene, 10 to 70 mol% of (meth) acrylate, and 10 to 60 mol% of (meth) acrylic acid. Polymers are more preferred, and copolymers consisting of 5-50 mol% styrene, 20-60 mol% (meth) acrylates, and 15-55 mol% (meth) acrylic acid are particularly preferred.

[1-1-3-a-2] Carboxyl group-containing (co) polymer (2)
Further, instead of the unsaturated carboxylic acid, a compound obtained by adding a polybasic acid (anhydrous) to hydroxyalkyl (meth) acrylate, and the above-mentioned styrenes, (meth) acrylic acid esters, and (meth) acrylonitrile. Examples include copolymers with (meth) acrylamides, vinyl compounds, and the like.

Examples of the hydroxyalkyl (meth) acrylate include hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate, and hydroxybutyl (meth) acrylate, and examples of the polybasic acid (anhydrous) include succinic acid (succinic acid (meth) acrylate). (Esters), adipic acid (anhydrous), phthalic acid (anhydrous), tetrahydrophthalic acid (anhydrous), hexahydrophthalic acid (anhydrous), maleic acid (anhydrous), etc. Examples include succinic acid [2- (meth) acryloyl ethyl] ester, adipic acid [2- (meth) acryloyl ethyl] ester, phthalic acid [2- (meth) acryloyl ethyl] ester, and hexahydrophthalic acid [2-( Meta) acryloyl ethyl] ester, maleic acid [2- (meth) acryloyl ethyl] ester, succinic acid [2- (meth) acryloyl propyl] ester, adipic acid [2- (meth) acryloyl propyl] ester, phthalic acid [2 -(Meta) acryloylpropyl] ester, hexahydrophthalic acid [2- (meth) acryloylpropyl] ester, maleic acid [2- (meth) acryloylpropyl] ester, succinic acid [2- (meth) acryloylbutyl] ester, Adiponic acid [2- (meth) acryloyl butyl] ester, phthalic acid [2- (meth) acryloyl butyl] ester, hexahydrophthalic acid [2- (meth) acryloyl butyl] ester, maleic acid [2- (meth) acryloyl] Butyl] ester and the like can be mentioned.

From the viewpoint of development solubility, these carboxyl group-containing (co) polymers preferably have an acid value of 50 to 500 mg · KOH / g, and from the viewpoint of development solubility, the polystyrene-equivalent weight average molecular weight (Mw). ) Is preferably 1,000 to 300,000.

[1-1-3-b] (C-2) A carboxyl group-containing (co) polymer having an ethylenically unsaturated group in the side chain [1-1-3-b-1] Unsaturated carboxylic acid and two types Copolymer with the above compound having an ethylenically unsaturated group As a carboxyl group-containing (co) polymer having an ethylenically unsaturated group in the side chain, for example, allyl (meth) acrylate, 3-allyloxy-2-hydroxy. Compounds having two or more ethylenically unsaturated groups such as propyl (meth) acrylate, cinnamyl (meth) acrylate, crotonyl (meth) acrylate, metharyl (meth) acrylate, N, N-diallyl (meth) acrylamide, or Two or more unsaturated non-ethyles such as vinyl (meth) acrylate, 1-chlorovinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, vinyl crotonate, vinyl (meth) acrylamide The ratio of the compound having a saturated group, an unsaturated carboxylic acid such as (meth) acrylic acid, or an unsaturated carboxylic acid ester to the total of the former compound having an ethylenically unsaturated group is 10 to 90 mol. %, preferably a copolymer obtained by copolymerizing so as to be about 30 to 80 mol%.

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

[1-1-3-b-2] Epoxide group-containing unsaturated compound Modified carboxyl group-containing (co) polymer Further, as a carboxyl group-containing (co) polymer having an ethylenically unsaturated group in the side chain, for example, An epoxy group-containing unsaturated compound is reacted with a carboxyl group-containing (co) polymer, and an epoxy group of an epoxy group-containing unsaturated compound is added to a part of the carboxyl groups of the carboxyl group-containing (co) polymer to modify it. Examples thereof include modified carboxyl group-containing (co) polymers.
The carboxyl group-containing (co) copolymer includes the (meth) acrylate- (meth) acrylic acid copolymer of the above-mentioned carboxyl group-containing (co) polymer and styrene- (meth) acrylate from the viewpoint of sensitivity. -A (meth) acrylic acid copolymer or the like is preferable.
The epoxy group-containing unsaturated compounds include allyl glycidyl ether, glycidyl (meth) acrylate, α-ethyl glycidyl (meth) acrylate, glycidyl crotonate, glycidyl isocrotonate, crotonyl glycidyl ether, and monoalkyl monoalkyl itaconate. Unsaturated compounds containing aliphatic epoxy groups such as glycidyl ester, monoalkyl monoglycidyl ester of fumaric acid, molalkyl monoglycidyl ester of maleic acid, and 3,4-epoxide cyclohexylmethyl (meth) acrylate, 2,3-epoxide cyclopentylmethyl. Examples thereof include alicyclic epoxy group-containing unsaturated compounds such as (meth) acrylate and 7,8-epoxide [tricyclo [5.2.1.0] deci-2-yl] oxyethyl (meth) acrylate.
Then, it is obtained by reacting these epoxy group-containing unsaturated compounds with 5 to 90 mol%, preferably about 30 to 70 mol% of the carboxyl groups of the carboxyl group-containing (co) polymer. The reaction can be carried out by a known method.

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

[1-1-3-b-3] Unsaturated carboxylic acid-modified epoxy group and carboxyl group-containing (co) polymer Further, as a carboxyl group-containing (co) polymer having an ethylenically unsaturated group in the side chain, for example. , (Meta) acrylic acid and other unsaturated carboxylic acids, and the above-mentioned aliphatic epoxy group-containing unsaturated compounds or alicyclic epoxy group-containing unsaturated compounds, or further unsaturated carboxylic acid esters, styrene, etc. The copolymer obtained by copolymerizing the carboxyl group-containing unsaturated compound so as to account for 10 to 90 mol%, preferably about 30 to 80 mol%, in an unsaturated compound such as (meth) acrylic acid. Examples thereof include a modified epoxy group modified by reacting a saturated carboxylic acid and adding a carboxyl group of an unsaturated carboxylic acid to the epoxy group of the copolymer, and a carboxyl group-containing (co) polymer.

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

[1-1-3-b-4] Acid-modified epoxy group-containing (co) polymer Also, as a carboxyl group-containing (co) polymer having an ethylenically unsaturated group in the side chain, an epoxy group-containing (meth) acrylate To a copolymer of an ethylenically unsaturated compound and an ethylenically unsaturated compound, an ethylenically unsaturated monocarboxylic acid is added to at least a part of the epoxy group of the copolymer, and a large amount is added to at least a part of the hydroxyl groups generated by the addition. Examples thereof include an acid-modified epoxy group-containing (co) polymer obtained by adding a basic acid (anhydrous).
Specifically, a copolymer of 5 to 99 mol% of an epoxy group-containing (meth) acrylate such as glycidyl (meth) acrylate and 2 to 95 mol% of an ethylenically unsaturated compound such as a (meth) acrylic acid ester. Is added to an ethylenically unsaturated monocarboxylic acid in an amount of usually 10 to 100 mol% of the epoxy group contained in the copolymer, and a polybasic acid is added to an amount of usually 10 to 100 mol% of the hydroxyl group generated when the ethylenically unsaturated monocarboxylic acid is further added. Examples thereof include an acid-modified epoxy group-containing (co) polymer obtained by adding (anhydrous).

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

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

Here, as the ethylenically unsaturated compound, for example, it is preferable to use one or more mono (meth) acrylates having a partial structure represented by the following formula (II).

In formula (II), R ^{1d to} R ^4d independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and R ^5d and R ^6d independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, respectively. Represents the alkyl group of. Further, R ^5d and R ^6d may be connected to form a ring. The ^{ring formed by connecting R 5d} and R ^6d is preferably an aliphatic ring, which may be saturated or unsaturated, and the number of carbon atoms in the ring is preferably 5 to 6.

The ^{number of carbon atoms of the alkyl group in R 1d to} R ^4d is usually 1 or more, usually 10 or less, preferably 8 or less, and more preferably 5 or less. When it is set to the upper limit or less, the development solubility tends to be appropriate.
Among these, from the viewpoint of solubility, R ^{1d to} R ^4d are preferably hydrogen atoms.

The ^{number of carbon atoms of the alkyl group in R 5d} and R ^6d is usually 1 or more, and usually 10 or less, preferably 8 or less, and more preferably 5 or less. When it is at least the above lower limit value, it tends to show appropriate solubility, and when it is at least the above upper limit value, it tends to maintain hydrophilicity.
Among these, from the viewpoint of development solubility, ^{it is preferable that R 5d} and R ^6d are hydrogen atoms, or that R ^5d and R ^6d are linked to form an aliphatic ring having 5 to 6 carbon atoms. ..

Among the above formulas (II), mono (meth) acrylates having a structure represented by the following formulas (IIa), (IIb), or (IIc) are preferable. By introducing these partial structures, it is possible to increase the heat resistance and strength of the mono (meth) acrylate. As these mono (meth) acrylates, one type may be used, or two or more types may be used in combination in any combination and ratio.

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

In formula (III), R ^9d represents a hydrogen atom or a methyl group, and R ^10d represents a partial structure of the formula (II).
When a mono (meth) acrylate having a partial structure represented by the formula (II) is contained, the copolymerization ratio thereof is usually 1 mol% or more, preferably 2 mol% or more, and usually 70 mol% or less. It is preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 10 mol% or less, and particularly preferably 5 mol% or less. When it is set to the lower limit value or more, the residual film ratio tends to be high, and when it is set to the upper limit value or less, the residue tends to be reduced.

On the other hand, as the ethylenically unsaturated compound, an ethylenically unsaturated compound other than mono (meth) acrylate having a partial structure represented by the above-mentioned formula (II) (hereinafter, "other ethylenically unsaturated compound") is used. (Sometimes referred to as), for example, styrenes such as α-, o-, m-, p-alkyl, nitro, cyano, amide, ester derivatives of styrene, butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene and the like. Dienes, methyl (meth) acrylate, ethyl (meth) acrylate, -n-propyl (meth) acrylate, -iso-propyl (meth) acrylate, -n-butyl (meth) acrylate, (meth) Acrylic acid-sec-butyl, (meth) acrylate-tert-butyl, (meth) acrylate pentyl, (meth) acrylate neopentyl, (meth) acrylate isoamyl, (meth) acrylate hexyl, (meth) acrylate 2-ethylhexyl, lauryl (meth) acrylate, dodecyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclohexyl (meth) acrylate, ( Isobolonyl acrylate, (meth) adamantyl acrylate, allyl (meth) acrylate, propagil (meth) acrylate, phenyl (meth) acrylate, naphthyl (meth) acrylate, anthracelyl (meth) acrylate, (meth) ) Anthraninonyl acrylate, (meth) piperonyl acrylate, (meth) salicyl acrylate, (meth) acrylate frill, (meth) acrylate flufuryl, (meth) acrylate tetrahydrofuryl, (meth) acrylate pyranyl, Benzyl (meth) acrylate, phenethyl (meth) acrylate, cresyl (meth) acrylate, -1,1,1-trifluoroethyl (meth) acrylate, perfluorethyl (meth) acrylate, (meth) Perfluoro-n-propyl acrylate, perfluoro-iso-propyl (meth) acrylate, triphenylmethyl (meth) acrylate, cumyl (meth) acrylate, 3- (N, N-dimethyl) (meth) acrylate (Meta) acrylates such as amino) propyl, -2-hydroxyethyl (meth) acrylate, -2-hydroxypropyl (meth) acrylate, (meth) acrylate amide, (meth) acrylate N, N -Dimethylamide, (meth) acrylic (Meta) such as acid N, N-diethylamide, (meth) acrylic acid N, N-dipropylamide, (meth) acrylic acid N, N-di-iso-propylamide, (meth) acrylic acid anthracenylamide. Acrylic acid amides, (meth) acrylic acid anilide, (meth) acryloylnitrile, acrolein, vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, N-vinylpyrrolidone, vinylpyridine, vinyl acetate and other vinyl compounds, Unsaturated dicarboxylic acid diesters such as diethyl citraconate, diethyl maleate, diethyl fumarate, diethyl itacone, N-phenylmaleimide, N-cyclohexylmaleimide, N-laurylmaleimide, N- (4-hydroxyphenyl) maleimide and the like. Radical polymerizable compounds such as monomaleimides, N- (meth) acryloylphthalimide and the like can also be mentioned.

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

As the ethylenically unsaturated monocarboxylic acid to be added to the epoxy group contained in the copolymer of the epoxy group-containing (meth) acrylate and the ethylenically unsaturated compound, known ones can be used, and from the viewpoint of curability. Therefore, (meth) acrylic acid is preferable. The amount of the ethylenically unsaturated monocarboxylic acid added to the epoxy group contained in the copolymer is usually 10 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more of the epoxy group contained in the copolymer. It is mol% or more, more preferably 70 mol% or more, and usually 100 mol% or less. By setting the addition ratio of the ethylenically unsaturated monocarboxylic acid to the above lower limit value or more, the curability tends to be improved. A known method can be adopted as a method for adding an ethylenically unsaturated monocarboxylic acid to the copolymer.

The polybasic acid (anhydride) to be added to the hydroxyl group generated when the ethylenically unsaturated monocarboxylic acid is added to the copolymer is not particularly limited, and known ones can be used, for example, phthalic acid. Examples thereof include acid (anhydride), tetrahydrophthalic acid (anhydride), hexahydrophthalic acid (anhydride), succinic acid (anhydride), trimellitic acid (anhydride) and the like. From the viewpoint of reducing outgas, succinic acid (anhydride) is preferable, while from the viewpoint of improving the residual film ratio and reducing the residue, tetrahydrophthalic acid (anhydride) is preferable. One type of polybasic acid (anhydride) may be used alone, or two or more types may be used in combination in any combination and ratio. By adding such a component, alkali solubility can be imparted to the copolymer.

The amount of the polybasic acid (anhydrous) added is usually 5 mol% or more, preferably 10 mol% or more, of the hydroxyl group generated when the ethylenically unsaturated monocarboxylic acid is added to the copolymer. .. Further, it is usually 100 mol% or less, preferably 90 mol% or less, and more preferably 80 mol% or less. When it is set to the lower limit value or more, the developability tends to be imparted, and when it is set to the upper limit value or less, the development tends to proceed excessively and the film dissolution tends to be suppressed. As a method for adding a polybasic acid (anhydrous) to the hydroxyl group generated when the ethylenically unsaturated monocarboxylic acid is added to the copolymer, a known method can be arbitrarily adopted.

The above-mentioned modified products of the epoxy group-containing (co) polymer with ethylenically unsaturated monocarboxylic acid and polybasic acid (anhydrous) include a part of the carboxyl groups generated after the addition of the polybasic acid (anhydrous). The photosensitivity can be further improved by adding a glycidyl (meth) acrylate or a glycidyl ether compound having an ethylene unsaturated group. Further, the developability can be improved by adding a glycidyl ether compound having no ethylenically unsaturated group to a part of the carboxyl groups generated after the addition of the polybasic acid (anhydrous). Further, both of these may be added after the addition of the polybasic acid (anhydride).

Examples of the modified product of the epoxy group-containing (co) polymer described above with an ethylenically unsaturated monocarboxylic acid and a polybasic acid (anhydrous) include JP-A-8-297366 and JP-A-2001-89533. Examples thereof include the resins described in the publication.

The weight average molecular weight (Mw) of the acid-modified epoxy group-containing (co) polymer is not particularly limited, but is usually 3,000 or more, preferably 5,000 or more, and usually 100,000 or less, preferably 50. It is 000 or less, more preferably 30,000 or less, still more preferably 20,000 or less, still more preferably 15,000 or less, and particularly preferably 10,000 or less. The compatibility tends to be improved by setting the value to the lower limit value or more, and the solubility tends to be ensured by setting the value to the upper limit value or less. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 2.0 to 5.0 from the viewpoint of curability.
The acid value of the acid-modified epoxy group-containing (co) polymer is not particularly limited, but is preferably 5 mg · KOH / g or more, more preferably 10 mg · KOH / g or more, further preferably 20 mg · KOH / g or more. Further, 150 mg / KOH / g or less is preferable, 100 mg / KOH / g or less is more preferable, and 50 mg / KOH / g or less is further preferable. When it is at least the lower limit value, solubility tends to be ensured, and when it is at least the upper limit value, film thinning tends to be improved.

[1-1-3-c] (C-3) Carboxyl group and ethylenically unsaturated group-containing resin [1-1-3-c-1] Acid-modified epoxy resin As a carboxyl group and ethylenically unsaturated group-containing resin For example, a carboxyl group- and ethylenically unsaturated group-containing epoxy resin in which a polybasic acid (anhydrous) is added to an ethylenically unsaturated group monocarboxylic acid adduct of an epoxy resin, that is, a so-called epoxy (meth) acrylate resin. Can be mentioned. That is, by opening and adding a carboxy group of an ethylenically unsaturated monocarboxylic acid to the epoxy group of the epoxy resin, an ethylenically unsaturated bond is added to the epoxy resin via an ester bond (-COO-). At the same time, there is a case where one carboxy group of a polybasic acid (anhydrous) is added to the hydroxyl group generated at that time.

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. Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane. Epoxy resin, dihydrooxylfluorene type epoxy resin, dihydrooxylalkyleneoxylfluorene type epoxy resin, 9,9-bis (4'-hydroxyphenyl) fluorene diglycidyl etherified product, 1,1-bis (4'-hydroxy) Examples thereof include a diglycidyl etherified product of phenyl) adamantan. Among them, from the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and 9,9-bis (4'-hydroxyphenyl) fluorene. Diglycidyl etherified products and the like are preferable, and bisphenol A epoxy resin is more preferable.

Examples of the ethylenically unsaturated monocarboxylic acid include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid and the like, and pentaerythritol tri (meth) acrylate acrylate anhydride adduct. , Pentaerythritol tri (meth) acrylate tetrahydrophthalic acid anhydride adduct, dipentaerythritol penta (meth) acrylate acrylic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic acid anhydride adduct, dipentaerythritol penta (meth) Examples thereof include acrylate tetrahydrophthalic anhydride adducts, reaction products of (meth) acrylic acid and ε-caprolactone. Of these, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

Examples of the polybasic acid (anhydrous) include amber acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, and 3-ethyltetrahydrophthalic acid. , 4-Ethyltetrahydrophthalic acid, Hexahydrophthalic acid, 3-Methylhexahydrophthalic acid, 4-Methylhexahydrophthalic acid, 3-Ethylhexahydrophthalic acid, 4-Ethylhexahydrophthalic acid, Trimellitic acid, Pyro Examples thereof include merit acid, benzophenone tetracarboxylic acid, biphenyltetracarboxylic acid, and anhydrides thereof. Among them, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, and succinic anhydride or tetrahydrophthalic anhydride is more preferable from the viewpoint of image reproducibility and developability. Preferably, succinic anhydride is more preferred.

The acid value of the acid-modified epoxy resin in the present invention is not particularly limited, but is preferably 10 mg · KOH / g or more, more preferably 20 KOH / g or more, further preferably 30 mg · KOH / g or more, and 200 mg · KOH / g. The following is preferable, 180 mg / KOH / g or less is more preferable, 150 mg / KOH / g or less is further preferable, 100 mg / KOH / g or less is further preferable, and 80 mg / KOH / g or less is particularly preferable. 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 solubility tends to be improved.
The weight average molecular weight (Mw) of the acid-modified epoxy resin is not particularly limited, but is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, still more preferably 4,000 or more, and even more. It is preferably 5,000 or more, particularly preferably 6,000 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. Adhesion tends to be improved by setting the value to the lower limit value or more, and proper solubility tends to be maintained by setting the value to the upper limit value or less.

The acid-modified epoxy resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the coexistence of a catalyst and a thermal polymerization inhibitor, the ethylenically unsaturated monocarboxylic acid is added for an addition reaction, and a polybasic acid (anhydrous) is further added. A method of continuing 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 and trimethylbenzylammonium chloride. One or more kinds such as quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, and stibins such as triphenylstibin can be mentioned. Further, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone and the like.

The amount of the ethylenically unsaturated monocarboxylic acid used 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. Can be an amount. The temperature at the time of the addition reaction can be usually 60 to 150 ° C., preferably 80 to 120 ° C. Further, the amount of the polybasic acid (anhydrous) used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, relative to one chemical equivalent of the hydroxyl group generated in the addition reaction. It can be an amount that is a chemical equivalent.

Specific examples of the structural repetition unit of the acid-modified epoxy resin in the present invention are shown below.

[1-1-3-c-2] Modified phenol Resin As a resin containing a carboxyl group and an ethylenically unsaturated group, for example, a polybasic acid (anhydrous) is added to an ethylenically unsaturated group-containing epoxy compound adduct of a phenol resin. Examples thereof include a phenol resin containing a carboxyl group and an ethylenically unsaturated group to which the above is added. That is, by opening and adding the epoxy group of the ethylenically unsaturated group-containing epoxy compound to the phenolic hydroxyl group of the phenolic resin, an ethylenically unsaturated bond is added to the phenolic resin via an ester bond (-COO-). At the same time, a hydroxyl group generated at that time to which one carboxy group of a polybasic acid (anhydrous) is added can be mentioned.

Here, examples of the phenolic resin include phenol, o-cresol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, o-ethylphenol, m-ethylphenol, and p-ethylphenol. , Propropylphenol, n-butylphenol, t-butylphenol, 1-naphthol, 2-naphthol, 4,4'-biphenyldiol, bisphenol-A, pyrocatechol, resorcinol, hydroquinone, pyrogallol, 1,2,4-benzenetriol, At least one of the phenols such as benzoic acid, 4-hydroxyphenylacetic acid, salicylic acid, fluoroglucolcinol, etc. under acid catalyst, for example, formaldehyde, paraformaldehyde, acetaldehyde, paraaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, furfural, etc. In the same manner except that a novolak resin polycondensed with at least one of the aldehydes of the above or ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and an alkali catalyst is used instead of the acid catalyst in the polycondensation. Examples thereof include polycondensed resol resin. Here, the condensation reaction between the phenols and the aldehydes is carried out in the absence of a solvent or in a solvent.

The weight average molecular weight (Mw) of these novolak resins and resole resins is usually 1,000 to 20,000, preferably 1,000 to 10,000, and more preferably 1,000 to 8,000. .. When the weight average molecular weight is set to the lower limit value or more, the image intensity tends to be easily secured, and when the weight average molecular weight is set to the upper limit value or less, the developability tends to be easily secured.

Examples of the ethylenically unsaturated group-containing epoxy compound include glycidyl (meth) acrylate, (3,4-epoxycyclohexyl) methyl (meth) acrylate, glycidyloxy (poly) alkylene glycol (meth) acrylate, and methylglycidyl (meth). Acrylate, (3,4-epoxycyclohexyl) vinyl and the like can be mentioned. Of these, glycidyl (meth) clearate and (3,4-epoxycyclohexyl) methyl (meth) acrylate are particularly preferable.

A known method can be used for the reaction of the novolak resin, the resole resin and the like with the ethylenically unsaturated group-containing epoxy compound. For example, tertiary amines such as triethylamine and benzylmethylamine, quaternary ammonium salts such as dodecyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride and benzyltriethylammonium chloride, and one or more such as pyridine and triphenylphosphine. An ethylenically unsaturated group-containing epoxy compound can be added to a novolak resin, a resole resin, or the like by reacting with an organic solvent at a reaction temperature of 50 to 150 ° C. for several to several tens of hours.

The amount of the catalyst used is preferably 0.01 to 10% by mass, particularly preferably 0.3 to 5%, based on the reaction raw material mixture (total of novolak resin, resole resin and ethylenically unsaturated group-containing epoxy compound). It is mass%. In addition, in order to prevent polymerization during the reaction, a polymerization inhibitor (for example, one or more of methquinone, hydroquinone, methylhydroquinone, p-methoxyphenol, pyrogallol, tert-butylcatechol, dibutylhydroxytoluene, phenothiazine, etc.) is used. It is preferably used, and the amount used is preferably 0.01 to 10% by mass, particularly preferably 0.03 to 5% by mass, based on the reaction raw material mixture.
The preferable ratio of adding the ethylenically unsaturated group-containing epoxy compound to the phenolic hydroxyl group of the novolak resin, the resole resin, etc. is 1 to 99 mol%. This ratio can be adjusted by the amount of the ethylenically unsaturated group-containing epoxy compound added to the phenolic hydroxyl group.

As the polybasic acid (anhydride), for example, known ones can be used, and maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methylendomethylenetetrahydrophthalic acid, and chlorend. Dibasic carboxylic acids such as acids, methyltetrahydrophthalic acid, 5-norbornene-2,3-dicarboxylic acid, methyl-5-norbornen-2,3-dicarboxylic acid or anhydrides thereof, trimellitic acid, pyromellitic acid, Examples thereof include polybasic carboxylic acids such as benzophenone tetracarboxylic acid and biphenyl tetracarboxylic acid, or anhydrides thereof. Of these, tetrahydrophthalic anhydride or succinic anhydride is preferred. One of these may be used alone, or two or more thereof may be mixed and used.

The addition rate of the polybasic acid (anhydrous) is usually 10 to 100 mol%, preferably 20 to 100 mol%, more than the hydroxyl group of the reaction product of the novolak resin, the resole resin and the like and the ethylenically unsaturated group-containing epoxy compound. It is preferably 30 to 100 mol%. By setting this addition rate within the above range, developability tends to be easily ensured.

[1-1-3-d] Other alkali-soluble resins In addition, when it is intended to provide a partition wall on an organic electric field element of a substrate that is easily deteriorated by an alkaline developing solution, a developing solution of a weakly alkaline alkaline compound. Alternatively, when a developing solution containing no alkaline compound is used, polyvinyl alcohol or the above-mentioned [1-1-3-a-1] carboxyl group-containing (co) polymer (1) is mentioned as the alkali-soluble resin. A vinyl alcohol copolymer obtained by copolymerizing 0.1 to 40 mol%, preferably 1 to 30 mol% of a comonomer (preferably vinyl acetate or the like), or the above-mentioned [1-1-3-a]. -1] Carboxyl group-containing (co) polymer A modified polyvinyl alcohol in which the copolymer described in (1) is introduced by an esterification reaction in an amount of 0.1 to 40 mol%, preferably 1 to 30 mol% is preferably used.
Further, for the purpose of forming an appropriate taper angle and maintaining liquid repellency, the ethylenically unsaturated monocarboxylic acid mentioned in the above-mentioned [1-1-3-c-1] acid-modified epoxy resin (as a preferable example). , (Meta) acrylic acid, (meth) acrylic acid and ε-caprolactone reaction, etc.), or even polybasic acids (anhydrous) (preferably tetrahydrophthalic acid anhydride, etc.) by esterification reaction. A modified polyvinyl alcohol introduced in an amount of 0.1 to 30 mol%, preferably 0.5 to 20 mol%, or a (meth) acryloyl (oxy) group or a (meth) acrylamide group described in JP-A-2008-45047. A compound having an aldehyde group having a A modified polyvinyl alcohol in which 0.1 to 30 mol%, preferably 0.5 to 20 mol% of the above is introduced by a formal reaction is preferably used.

Among the above-mentioned alkali-soluble resins as the (C) alkali-soluble resin, a carbosyl group-containing (co) polymer having an ethylenically unsaturated group in the (C-2) side chain or a (C-3) carboxyl group from the viewpoint of the taper angle. And an ethylenically unsaturated group-containing resin are preferable, a carbosyl group-containing (co) polymer having an ethylenically unsaturated group in the (C-2) side chain is more preferable, and an acid-modified epoxy group-containing (co) polymer is further preferable. preferable.

The weight average molecular weight (Mw) of the alkali-soluble resin of the above component (C) is not particularly limited, but is preferably 2,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and 7,000 or more. Is particularly preferable, 50,000 or less is preferable, 30,000 or less is more preferable, 20,000 or less is further preferable, and 10,000 or less is particularly preferable. When it is set to the lower limit value or more, the development tends to proceed excessively and the film dissolution tends to be suppressed, and when it is set to the upper limit value or less, an appropriate development solubility tends to be exhibited.
The acid value of the alkali-soluble resin of the component (C) is not particularly limited, but is preferably 10 mg · KOH / g or more, more preferably 20 mg · KOH / g or more, more preferably 30 mg · KOH / g or more, and 200 mg · KOH / g or more. KOH / g or less is preferable, 150 mg / KOH / g or less is more preferable, 100 mg / KOH / g or less is further preferable, 70 mg / KOH / g or less is further preferable, and 50 mg / KOH / g or less is particularly preferable. When it is set to the lower limit value or more, appropriate development solubility tends to be obtained, and when it is set to the upper limit value or less, the development tends to proceed excessively and the film dissolution tends to be suppressed.
In particular, an acrylate resin having a polycyclic alicyclic skeleton such as the above formulas (IIa), (IIb) and (IIc) having excellent rigidity, high heat resistance and hydrophobicity and having an ethylenically unsaturated group in the side chain, specifically Specifically, a monomethacrylate copolymer having a styrene / glycidyl methacrylate / tricyclodecane skeleton [alkaline-soluble binder (C-1) described in Examples below] is preferable.

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 at least the above lower limit value, it tends to be possible to obtain appropriate development solubility and sensitivity, and when it is at least the above upper limit value, it tends to be possible to obtain appropriate development solubility and sensitivity.

The content of the (B) 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. It is 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, and usually 99% by mass or less, preferably 97% by mass or less, more preferably. It is 95% by mass or less. When it is at least the above lower limit value, it tends to be possible to obtain appropriate development solubility and sensitivity, and when it is at least the above upper limit value, it tends to be possible to obtain appropriate development solubility and sensitivity.

[1-1-4] Component (D); Sensitizer The photosensitive resin composition for forming a partition wall of the present invention contains (D) a sensitizer. 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. In particular, since the photosensitive resin composition for forming a partition wall of the present invention contains a hexaarylbiimidazole compound, it is considered that the surface curability is increased and the taper angle is increased.

In the photosensitive resin composition of the present invention, a sensitizer usually used in this field can be used as the (D) sensitizer. 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. Systems 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, aclysin compounds, azine compounds, thiazine compounds, oxazine compounds, indolin compounds, azulene compounds, azurenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane 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, spirooxazine compounds, thiospiropirane compounds, metal arene complexes, organic ruthenium complexes, benzophenone compounds and the like.
One of these may be used alone, or two or more thereof may be used in combination.

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, a desired pattern tends to be easily formed.

[1-1-5] Component (E); Liquid Repellent The photosensitive resin composition for forming a partition wall of the present invention may contain (F) a liquid repellent. In particular, when an organic electroluminescent device is produced by an inkjet method, it is preferable to contain (E) a liquid repellent, and by containing (E) a liquid repellent, it can impart liquid repellency to the surface of the partition wall. It is considered that the obtained partition wall can prevent color mixing for each pixel of the organic layer.
Examples of the liquid repellent include silicone-containing compounds and fluorine-based compounds, and preferably, a liquid repellent containing 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 a liquid-repellent component of a 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 during the development 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 on 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, perfluoroalkyl sulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, and perfluoroalkyltrialkylammonium salt. , Oligomers containing perfluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and base 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", "F120", "F142D", "F144D", "F150", "F160", and "F171" manufactured by DIC. "Same F172", "Same F173", "Same F177", "Same F178A", "Same F178K", "Same F179", "Same F183", "Same F184", "Same F191", "Same F812", "Same F815", "Same F824", "Same F833", "Same FENSAMCF300", "Same MCF310", "Same MCF312", "Same MCF323", "Same RS72K", "Same RS304", "Same RS202", "Same RS202" RS201, RS102, RS101, RS105, RS401, RS402, RS501, RS502, RS301, RS303, 3M Japan's "Fluorard FC430", "FC431", "Novec FC-4430", "FC4432", Asahi Glass's "Asahi Guard AG710", "Surflon S-382", "SC-101", "Same" Commercially available under trade names such as "SC-102", "SC-103", "SC-104", "SC-105", "SC-106", and "Obtool DAC-HP" manufactured by Daikin Industries, Ltd. Fluorine-containing organic compounds that have been used can be used.

As described above, when a fluorine-based compound is used as the liquid repellent, the F atom content in the liquid repellent is not particularly limited, but the fluorine atom content is preferably 1% by mass or more, 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 substance. A high molecular weight liquid repellent is preferable because the fluidity of the liquid repellent due to firing 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. Preferably, 500 or more is more preferable, 100,000 or less is preferable, and 10,000 or less is more preferable.

The content ratio of the liquid repellent (E) in the photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.2% 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 0.35% 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 (E) liquid repellent, and a surfactant may be used instead of the (E) liquid repellent. 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 exhibiting wettability during development, and a polyether-modified silicone-based one is preferable. Surfactants are even 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-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-decafluorodecane, 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, "Mega Fvck F142D", "Mega Fvck F17 F172", "Mega Fvck F173" and "Mega Fvck F183" manufactured by DIC Corporation. , "Mega Fvck F470", "Mega Fvck F475", "FC430" manufactured by 3M Japan Ltd., "DFX-18" manufactured by Neos Co., Ltd., and the like.

Examples of the silicone-based surfactant include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Adaptive", "SH8400", manufactured by Toray Dow Corning Co., Ltd. Commercially available products such as "BYK323" and "BYK330" manufactured by Big Chemie can be mentioned.
The surfactant may contain a surfactant other than the fluorine-based surfactant and the silicone-based surfactant, and other surfactants include nonionic, anionic, cationic, amphoteric surfactants and the like. 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, pentaerythlit fatty acid esters, polyoxyethylene pentaerythlit fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy Examples thereof include ethylene 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, alkyl benzene sulfonates, alkyl naphthalene 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 alkyl phenyl ether sulfates, alkyl phosphate esters, 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, for alkyl sulfates, "Emar 10" manufactured by Kao Corporation, and for alkylnaphthalene sulfonates, "Perex NB-L" manufactured by Kao Corporation. 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. 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 "Kotamin 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 types, 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. Of these, 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.

[1-1-6] Component (F); Thiol Compound The photosensitive resin composition for forming a partition wall of the present invention may contain a (F) thiol compound. Since the SH bond of a thiol compound has a small energy, bond cleavage is likely to occur, and a hydrogen abstraction transfer or a chain transfer reaction is likely to occur, so that the sensitivity and surface curability tend to be high.

Examples of thiol compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4 (3H) -quinazoline, and β-mercaptonaphthalene. , 1,4-dimethylmercaptobenzene, hexanedithiol, decandithiol, butanediol bis (3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis Thioglycolate, trimethylolpropanetris (3-mercaptopropionate), trimethylolpropanetris thioglycolate, trishydroxyethyltristhiopropionate, pentaerythritoltetrakis (3-mercaptopropionate), pentaerythritoltris ( 3-Mercaptopropionate), Butanediolbis (3-Mercaptobutyrate), Ethethyleneglycolbis (3-Mercaptobutyrate), Trimethylol Propantris (3-Mercaptobutyrate), Pentaerythritol Tetrakiss (3-Mercaptobutyrate) Rate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trion, etc.

Of these, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferable among the compounds having an aromatic ring from the viewpoint of increasing the taper angle and sensitivity, and trimethylpropanthritol (3) is preferable among the aliphatic compounds. -Mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercapto) Butyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) ) -Trione is preferred.

From the viewpoint of sensitivity, aliphatic polyfunctional compounds are more preferable, and specifically, trimethylolpropanthris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), and pentaerythritol tris (3). -Mercaptopropionate), Trimethylolpropanthris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritoltris (3-mercaptobutyrate), 1,3,5-tris (3) -Mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -Trione is preferred, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3- Mercaptobutyrate) is more preferred.
These can be used alone or in admixture of two or more.

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

The content ratio of the (F) thiol compound in the photosensitive composition of the present invention is usually 0.01% by mass or more, preferably 0.1% by mass or more, based on the total solid content of the photosensitive resin composition. , More preferably 0.5% by mass or more, further preferably 1% by mass or more, particularly preferably 1.5% by mass or more, usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass. It is as follows. 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, it tends to be easy to form a desired pattern.

The blending ratio of the (F) thiol compound to the (A) photopolymerization initiator in the photosensitive resin composition is preferably 10 parts by mass or more, preferably 25 parts by mass or more, based on 100 parts by mass of the (A) photopolymerization initiator. More than parts by mass is more preferable, 50 parts by mass or more is further preferable, 500 parts by mass or less is preferable, 400 parts by mass or more is more preferable, 300 parts by mass or less is further preferable, and 200 parts by mass 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, it tends to be easy to form a desired pattern.

[1-1-7] Component (G); Polymerization Inhibitor The photosensitive resin composition for forming a partition wall of the present invention may contain (G) a polymerization inhibitor. It is considered that the taper angle of the obtained partition wall can be increased because the inclusion of the (G) polymerization inhibitor inhibits radical polymerization.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, hydroquinone or methoxyphenol is preferable, 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 producing (C) an alkali-soluble resin, a polymerization inhibitor may be contained in the resin, which may be used as the (G) polymerization inhibitor of the present invention, or polymerized in the resin. In addition to the banning agent, the same or different polymerization banning agent 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.

[1-1-8] Component (H); Ultraviolet absorber The photosensitive resin composition for forming a partition wall of the present invention may contain (H) 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 by 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, a benzotriazole compound and / or a hydroxyphenyltriazine compound is preferable, and a benzotriazole compound is particularly preferable, from the viewpoint of increasing the taper angle.

Examples of the benzotriazole compound include 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-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) -Phenyl-benzotriazole-2-yl) phenyl] propionate mixture, 2- [2-hydroxy-3,5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl- 5-Methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole, 2- (2'-hydroxy-5'-t- Octylphenyl) benzotriazole, benzenepropanoic acid, 3- (2H-benzotriazole-2-yl)-(1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl ester compound, 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.

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, TINUVIN 326, TINUVIN900, "TINUVIN 928", TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80 , EVERSORB81 (manufactured by Taiwan Yongkou Chemical Co., Ltd.), Tomisorb 100, Tomisorb 600 (manufactured by AP Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Otsuka Chemical Co., Ltd.), RUV And so on.

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 AP Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, SEESORB102. Benzophenone compounds such as SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Cipro Chemicals); benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.), phenyl salicylate; , Chorusic acid derivatives such as isoamyl methoxycinnamate; α-naphthal, β-naphthol, α-naphthal methyl 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-dihydroxy Naphthalene derivatives such as naphthalene; anthracene such as anthracene and 9,10-dihydroxyanthracene and their derivatives; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes , Dyes such as p-aminobenzoic acid dyes; 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 (H) 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 or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, still more preferable. Is 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 (A) to the photopolymerization initiator is usually 1 part by mass or more, preferably 10 parts by mass or more, as the blending amount of (H) ultraviolet absorber to 100 parts by mass of (A) photopolymerization initiator. More preferably 30 parts by mass or more, further preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, still more preferably. It is 150 parts 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.

[1-1-9] 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 the thermal polymerization initiator, the degree of cross-linking of the film tends to be increased. Specific examples of such a thermal polymerization initiator include azo compounds, organic peroxides, hydrogen peroxide and the like. One of these may be used alone, or two or more thereof may be used in combination.

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 in the above-mentioned photosensitive resin composition is calculated. The content ratio of the photopolymerization initiator is preferably such that the content ratio of the photopolymerization initiator and the thermal polymerization initiator is such that, from the viewpoint of sensitivity, the thermal polymerization initiator is used with respect to 100 parts by mass of the photopolymerization initiator. It is preferably 5 to 300 parts by mass.

[1-1-10] Amino Compound The photosensitive resin composition for forming a partition wall of the present invention may contain an amino compound in order to promote thermosetting. In this case, the content of the amino compound in the photosensitive resin composition is usually 40% by mass or less, preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. 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 glycoluryl resin obtained by polycondensing glycoluryl and formaldehyde; urea and formaldehyde are combined. Polycondensation urea resin; resin obtained by polycondensation of two or more kinds such as melamine, benzoguanamine, glycoluryl, or urea and formaldehyde; modified resin obtained by alcohol condensation modification of the methylol group of the above-mentioned resin and the like. One of these may be used alone, or two or more thereof may be used in combination. 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 "Nikalac" (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.

[1-1-11] 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 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 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% by mass with respect to the total solid content of the photosensitive resin composition. % Or less, more preferably 5% by mass or less.

[1-1-12] 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. The content thereof 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.

[1-1-13] 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.

[1-1-14] 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 integers of 1 to 10, and s is 1, 2 or 3.

[1-1-15] Inorganic filler In addition, 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 the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter or the like. 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.

[1-1-16] 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 a 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 , Glycol dialkyl ethers such as dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-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 ketone, methylnonyl ketone, methoxymethylpentanone; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxy Monovalent or polyhydric 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; amylformate, ethylformate, ethyl acetate, butyl acetate, Ppropyl 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 acid, ethyl 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 amilk loride; ether ketones such as methoxymethylpentanone; acetonitrile, benzonitrile. Una nitriles: tetrahydrofurans such as tetrahydrofuran, dimethyl tetrahydrofuran, dimethoxytetrahydrofuran and the like.

Commercially available solvents corresponding to the above include Mineral Spirit, Barsol # 2, Apco # 18 Solvent, Apco Thinner, Socal Solvent No. 1 and No. 2. Solbesso # 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 using 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. 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. 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 set to the lower limit value or more, an appropriate coating uniformity tends to be obtained, and when it is set to the upper limit value or less, an appropriate coating uniformity tends to be obtained.

[1-2] 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] Partition and partition wall forming method The photosensitive resin composition of the present invention can be suitably used for forming a partition wall, particularly a partition wall for partitioning an organic layer of an organic electroluminescent device.
The method of 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. Examples of the method for forming the partition wall include 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. Specific examples of such a bank forming method include an inkjet method and a photolithography method.

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

In the photolithography method, the photosensitive resin composition for forming a partition wall is applied to the entire surface of the region where the partition wall of the substrate is formed to form the 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 a substrate in the photolithography method, a contact transfer type coating device such as a roll coater, a reverse coater, or a bar coater or a spinner (rotary type) is applied on the substrate on which a 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 divided according to the bank pattern. To expose 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 element 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 polyesters such as polyethylene terephthalate; polyethylene and polyolefins such as polypropylene; polycarbonates; poly (meth) metaacrylic resins; polysulfones; polyimides. 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 composed 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 pattern of the partition wall 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.

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

As the solvent used when forming the ink for forming the organic layer, water, an organic solvent, and a mixed solvent thereof can be used. The organic solvent is not particularly limited as long as it can be removed from the film formed after the injection of the ink. Specific examples of the organic solvent include toluene, xylene, anisole, mesityrene, 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 to form the organic layer is appropriately selected according to the type of 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 modifier, and the like.

[4] Image Display Device The image display device of the present invention includes the above-mentioned organic electroluminescent element. As long as it includes an organic electroluminescent element, the model and structure of the image display device are not particularly limited, and for example, an active drive type organic electroluminescent element can be used for assembly according to a conventional method. 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 device. 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 element 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 device that emits white light may be used. Further, organic electroluminescent elements having different emission colors may be combined so that each color is 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 Separation Forming Propylene glycol monomethyl ether so that each component is used in the blending ratio (parts by mass) shown in Table 1 and the content ratio of the total solid content is 25% by mass. Each component was stirred with acetate until uniform to prepare photosensitive resin compositions for partition wall formation in Examples and Comparative Examples.
The symbols in the table represent the following.

A-1: 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd.)

A-2: 2-Methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (IRGACURE907) (manufactured by BASF)
B-1: Dipentaerythritol hexaacrylate (DPHA) (manufactured by Nippon Kayaku Co., Ltd.)

C-1: The following acrylic copolymer resin Dicyclopentanyl methacrylate / styrene / glycidyl methacrylate (molar ratio 0.02 / 0.05 / 0.93) is a copolymer resin containing the constituent monomer, and acrylic acid is glycidyl methacrylate. An alkali-soluble acrylic copolymer resin obtained by adding an equal amount of the above-mentioned tetrahydrophthalic anhydride to 1 mol of the above-mentioned copolymer resin so as to have a molar ratio of 0.1. The weight average molecular weight is 7,700, and the solid acid value is 28.5 mg-KOH / g.

D-1: 2,4-Diethylthioxanthone (DETX-S) (manufactured by Nippon Kayaku Co., Ltd.)

E-1: RS72K (manufactured by DIC, fluorine-based, oligomer having an ethylenic double bond)
F-1: 2-Mercaptobenzimidazole (manufactured by Tokyo Kasei Co., Ltd.)
F-2: Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Yodo Kagaku Co., Ltd.)
G-1: Methyl hydroquinone (manufactured by Seiko Kagaku Co., Ltd.)
H-1: TINUVIN 384-2 (manufactured by BASF)
I-1: PM21 (manufactured by Nippon Kayaku Co., Ltd.)

[2] Formation and evaluation of partition walls The method of performance evaluation will be described below.

(Creation of substrate for contact angle measurement)
A coating liquid (the photosensitive resin composition for forming a partition wall) was applied to a thickness of 2.0 μm after firing using a spinner on the ITO film of a glass substrate having an ITO film formed on its surface. Then, it was heated and dried on a hot plate at 100 ° C. for 2 minutes, and the obtained coating film was ^{exposed by shaking the exposure amount in the range of 50 to 1150 mJ / cm 2} without using a mask (every 10 mJ for less than 100 mJ). 100-500mJ is every 20mJ, and over 500mJ is every 50mJ). At this time, the intensity at a wavelength of 365 nm was 25 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 in an oven at 230 ° C. for 30 minutes to obtain various contact angle measuring substrates on which a cured product was formed.

(Evaluation of contact angle)
Since the curability differs depending on the sensitivity of the composition, the amount of exposure that causes liquid repellency differs depending on the composition of the composition. Here, the exposure amount at which liquid repellency is generated means an exposure amount at which the contact angle is 10 degrees or more. The contact angle with respect to propylene glycol monomethyl ether acetate was measured using various contact angle measuring substrates having different exposure amounts, and the minimum exposure amount at which liquid repellency was generated was determined and is shown in Table 1. The contact angle was measured by a Drop Master 500 contact angle measuring device manufactured by Kyowa Interface Science Co., Ltd. under the conditions of 23 ° C. and 50% humidity.

(Creation of partition wall)
A coating liquid (the photosensitive resin composition for forming a partition wall) was applied to a thickness of 2.0 μm after firing using a spinner on the ITO film of a glass substrate having an ITO film formed on its surface. Then, it was heated and dried on a hot plate at 100 ° C. for 2 minutes. The obtained coating film was exposed using a photomask. The exposure amount was set to the minimum exposure amount at which liquid repellency was generated, and the exposure gap was set to 16 μm. As the photomask, a mask having a grid-like opening (a mask having a plurality of 80 μm × 280 μm covering portions at 40 μm intervals) was used. Then, in the same manner as in preparing the substrate for measuring the contact angle, development was carried out with an aqueous solution of TMAH and then heat curing was carried out to obtain a grid-like partition wall.

(Measurement of bulkhead taper angle)
An SEM observation sample for cross-sectional observation was prepared, the cross-sectional shape of the partition wall was observed using a scanning electron microscope (SEM, manufactured by KEYENCE CORPORATION), and the taper angle thereof was measured. The results are shown in Table 1.
In this cross section, 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. A point at a height that is 1/2 of H on the hypotenuse of the partition wall is defined as A, a tangent line with the hypotenuse at point A is defined as T, and the angle formed by the tangent line T and the boundary surface S is measured and used as a taper angle.

From Table 1, the partition wall obtained from the photosensitive resin composition of the example in which the hexaarylbiimidazole compound was used as the photopolymerization initiator and further used the sensitizer was good with a large taper angle. It is considered that this is because the high surface curability of the hexahexaarylbiimidazole compound is combined with the low internal curability of the photosensitive resin composition due to the reduction of the light transmittance inside the photosensitive resin composition. Be done. On the other hand, each photosensitive resin composition of the comparative example had a low taper angle, which was due to the use of an initiator having low surface curability and the fact that internal curing was not suppressed without using a sensitizer. Is thought to be the cause.

1: Partition 2: ITO film 3: Glass substrate A: Point of height that is 1/2 of H on the hypotenuse of partition wall H: Height of partition wall S: Boundary surface between partition wall and ITO film T: Hypotenuse at point A Tangent with

Claims (10)

A photosensitive resin composition for forming a partition wall containing (A) a photopolymerization initiator, (B) an ethylenically unsaturated compound, and (C) an alkali-soluble resin.
The (A) photopolymerization initiator contains a hexaarylbiimidazole compound, and the photopolymerization initiator is contained.
A photosensitive resin composition for forming a partition wall, which further contains (D) a sensitizer and (E) a liquid repellent. The photosensitive resin composition for forming a partition wall according to claim 1, wherein the liquid repellent (E) contains a cross-linking group. The photosensitive resin composition for forming a partition wall according to claim 1 or 2, wherein the sensitizer (D) contains a thioxanthone-based compound. The photosensitive resin composition for forming a partition wall according to any one of claims 1 to 3, further containing (F) a thiol compound. The photosensitive resin composition for forming a partition wall according to any one of claims 1 to 4, further containing (G) a polymerization inhibitor. The photosensitive resin composition for forming a partition wall according to any one of claims 1 to 5, further comprising (H) an ultraviolet absorber. A partition wall composed of the photosensitive resin composition for forming a partition wall according to any one of claims 1 to 6. The organic electroluminescent device having the partition wall according to claim 7. An image display device including the organic electroluminescent element according to claim 8. Lighting including the organic electroluminescent device according to claim 8.

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