TW202132359A - Photosensitive resin composition, partition wall, organic electroluminescent element and image display device - Google Patents

Abstract

The present invention provides a photosensitive resin composition which is capable of achieving a good balance between level difference control and inkjet coatability. A photosensitive resin composition according to the present invention contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound and (D) a liquid repellent agent, and is characterized in that: the photopolymerization initiator (A) contains a photopolymerization initiator represented by general formula (I); and the liquid repellent agent (D) contains an acrylic resin (D1) that contains a fluorine atom and a repeating unit represented by general formula (II).

Description

Photosensitive resin composition, barrier ribs, organic electroluminescence element, and image display device

The present invention relates to a photosensitive resin composition, a barrier wall formed by curing the photosensitive resin composition, an organic electroluminescence element provided with the barrier rib, and an image display device including the organic electroluminescence element.

In the past, organic electroluminescent elements included in organic electroluminescent displays and the like are manufactured by laminating various functional layers in the area surrounded by the barrier ribs after forming barrier ribs (barrier ribs) on the substrate. As a method of easily forming such barrier ribs, a method of forming by photolithography using a photosensitive resin composition is known.

In addition, as a method of laminating various functional layers in an area surrounded by barrier walls, the following method is known: firstly, an ink containing the material constituting the functional layer is prepared, and then the prepared ink is injected into the area surrounded by the barrier wall Inside. Among these methods, the inkjet method is often used in terms of the ease of accurately injecting a specific amount of ink into a specific location.

Furthermore, in the case of using ink to form a functional layer, there are cases where it is required to impart ink repellency (liquid repellency) to the barrier wall in order to prevent the ink from adhering to the barrier wall, or to prevent the ink injected into adjacent areas from mixing with each other. ).

When the organic light-emitting layer is formed by the inkjet method, it is difficult to control the film thickness of the organic light-emitting layer. Since the film thickness of the organic light-emitting layer is formed so that the end adjacent to the barrier wall is thicker than the central part, there are problems such as uneven light emission, reduced light-emitting efficiency, and shorter life span of the organic electroluminescent display. In order to solve this problem, Patent Document 1 proposes the following method: fabricating barrier ribs having first barrier ribs and second barrier ribs with different heights as barrier ribs (barriers) dividing pixel regions, and linearly on the second barrier ribs The organic light-emitting layer is coated on the ground, thereby controlling the film thickness of the pixel area arranged in the second barrier wall to be uniform. In addition, as a method of forming the first barrier wall and the second barrier wall, it is also proposed to use masks (halftone masks) with different transmittances to form first barrier walls and second barrier walls with different heights at once. method.

On the other hand, Patent Document 2 describes that by using a photosensitive resin composition containing a specific alkali-soluble resin, it is possible to form barrier walls having both fine line patterns and minute contact holes, especially by using specific photopolymerization. The initiator can impart sufficient ink repellency to the barrier wall. In addition, Patent Document 3 describes that by using a photosensitive resin composition containing a specific polymer and a specific photopolymerization initiator, a spacer with desired elastic properties can be formed. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] International Publication No. 2009/147838 [Patent Document 2] International Publication No. 2013/069789 [Patent Document 3] Japanese Patent Laid-Open No. 2015-184411

[The problem to be solved by the invention]

When barrier ribs with different heights are used and the organic light-emitting layer is formed by an inkjet method, it is required to control the height difference (step difference) between the first barrier rib and the second barrier rib or the inkjet coatability. Although Patent Document 1 describes that by controlling the liquid repellency of the first barrier wall and the second barrier wall, an organic light-emitting layer having a uniform film thickness can be coated, but there is no description of a specific method for controlling the level difference. There is no description about the balance between the level difference and the inkjet coating property. In addition, as a result of studies conducted by the inventors of the present invention, it is clear that the photosensitive resin composition described in Patent Document 2 is difficult to balance the control of the step difference and the inkjet coatability. There is no description about the liquid repellent in Patent Document 3, and it is not clear what kind of characteristics it exhibits when the liquid repellent is used.

Therefore, the object of the present invention is to provide a photosensitive resin composition that can balance the control of the step difference and inkjet coating properties. In addition, the present invention provides a barrier rib formed by curing a photosensitive resin composition, an organic electroluminescence element provided with the barrier rib, and an image display device including the organic electroluminescence element. [Technical means to solve the problem]

The inventors of the present invention conducted diligent studies, and found that a combination of a specific photopolymerization initiator and a photosensitive resin composition containing a photopolymerization initiator, an alkali-soluble resin, a photopolymerizable compound, and a liquid repellent The specific liquid repellent can solve the above-mentioned problems, thereby completing the present invention. That is, the gist of the present invention is as follows.

(式(I)中，R^1a 表示可具有取代基之烷基、或可具有取代基之芳香族環基； R^2a 表示烷基； R^3a 表示1價取代基； n表示0或1； h表示0～2之整數) [化2]

(式(II)中，R¹¹ 分別獨立地表示氫原子或甲基，R¹² 表示可具有取代基之碳數2～6之烷基，可被-O-、-C(=O)-、-S-、-NH-之任一者以上中斷； *表示鍵結部) [2]如[1]中記載之感光性樹脂組合物，其中於上述式(I)中，R^3a 為R^4a -O-(其中，R^4a 表示可具有取代基之烷基、或可具有取代基之芳香族環基)，h為1。 [3]如[1]或[2]中記載之感光性樹脂組合物，其中上述通式(I)所表示之光聚合起始劑之含量相對於總光聚合起始劑為80～100質量%。 [4]如[1]至[3]中任一項記載之感光性樹脂組合物，其中(B)鹼可溶性樹脂相對於上述(C)光聚合性化合物100質量份之含量為200質量份以下。 [5]如[1]至[4]中任一項記載之感光性樹脂組合物，上述丙烯酸系樹脂(D1)具有氟烷基及/或氟伸烷基。 [6]如[1]至[5]中任一項記載之感光性樹脂組合物，其中上述(B)鹼可溶性樹脂包含具有下述通式(i)或(iii)所表示之部分結構之樹脂。 [化3]

(式(i)中，R^a 表示氫原子或甲基，R^b 表示可具有取代基之2價烴基； 式(i)中之苯環可進而被任意取代基取代； *表示鍵結鍵) [化4]

(式(iii)中，R^e 表示氫原子或甲基，γ表示單鍵、-CO-、可具有取代基之伸烷基、或可具有取代基之2價環狀烴基；  式(iii)中之苯環可進而被任意取代基取代；  *表示鍵結鍵)  [7]如[1]至[6]中任一項記載之感光性樹脂組合物，其用於形成阻隔壁。 [8]如[7]中記載之感光性樹脂組合物，其用於藉由光微影法一次性形成具有階差之阻隔壁。 [9]一種阻隔壁，其係使如[1]至[8]中任一項記載之感光性樹脂組合物硬化而成。 [10]一種有機電致發光元件，其具備如[9]中記載之阻隔壁。 [11]一種圖像顯示裝置，其包含如[10]中記載之有機電致發光元件。 [發明之效果][1] A photosensitive resin composition characterized in that it contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a liquid repellent, And the above (A) photopolymerization initiator contains the photopolymerization initiator represented by the following general formula (I), and the above (D) liquid repellent contains the repeating unit represented by the following general formula (II) and fluorine Atomic acrylic resin (D1). [化1]

(In formula (I), R ^1a represents an optionally substituted alkyl group or an optionally substituted aromatic cyclic group; R ^2a represents an alkyl group; R ^3a represents a monovalent substituent; n represents 0 or 1; h Represents an integer from 0 to 2) [化2]

(In formula (II), R ¹¹ each independently represents a hydrogen atom or a methyl group, and R ¹² represents an optionally substituted alkyl group having 2 to 6 carbon atoms, which may be substituted by -O-, -C(=O)-, Any one or more of -S- and -NH- is interrupted; * indicates a bonding portion) [2] The photosensitive resin composition as described in [1], wherein in the above formula (I), R ^3a is R ^4a -O- (wherein R ^4a represents an optionally substituted alkyl group or an optionally substituted aromatic ring group), h is 1. [3] The photosensitive resin composition as described in [1] or [2], wherein the content of the photopolymerization initiator represented by the general formula (I) is 80-100 mass relative to the total photopolymerization initiator %. [4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of (B) alkali-soluble resin relative to 100 parts by mass of the above-mentioned (C) photopolymerizable compound is 200 parts by mass or less . [5] The photosensitive resin composition according to any one of [1] to [4], wherein the acrylic resin (D1) has a fluoroalkyl group and/or a fluoroalkylene group. [6] The photosensitive resin composition according to any one of [1] to [5], wherein the above-mentioned (B) alkali-soluble resin comprises a partial structure represented by the following general formula (i) or (iii) Resin. [化3]

(In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group that may have a substituent; the benzene ring in formula (i) may be further substituted with any substituent; * represents a bonding bond) [化4]

(In formula (iii), R ^e represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a bivalent cyclic hydrocarbon group which may have a substituent; formula (iii) The benzene ring in may be further substituted with any substituent; * represents a bonding bond) [7] The photosensitive resin composition as described in any one of [1] to [6], which is used to form a barrier rib. [8] The photosensitive resin composition as described in [7], which is used to form barrier ribs having a step difference at one time by a photolithography method. [9] A barrier rib obtained by curing the photosensitive resin composition as described in any one of [1] to [8]. [10] An organic electroluminescence device including the barrier rib as described in [9]. [11] An image display device comprising the organic electroluminescence element as described in [10]. [Effects of Invention]

According to the present invention, it is possible to provide a photosensitive resin composition capable of achieving both step control and inkjet coating properties.

Hereinafter, the present invention will be described in detail. The following description is an example of the embodiment of the present invention, and as long as it does not exceed the gist, the present invention is not limited to these. In the present invention, "(meth)acrylic acid" means "acrylic acid and/or methacrylic acid". In the present invention, the "total solid content" means all the components in the photosensitive resin composition excluding the solvent. In the present invention, the numerical range represented by "~" means a range that includes the numerical values described before and after "~" as the lower limit and the upper limit. In the present invention, the so-called "A and/or B" means one or both of A and B, and specifically means A, B, or A and B. In the present invention, the so-called "(co)polymer" means both homopolymer and copolymer (copolymer), and the so-called "polyacid (anhydride)" means "polyacid and /Or polybasic acid anhydride". In the present invention, the weight average molecular weight means the weight average molecular weight (Mw) in terms of polystyrene obtained by GPC (Gel Permeation Chromatography). In the present invention, the so-called acid value means the acid value converted from effective solid content, which is calculated by neutralization titration.

In the present invention, the so-called barrier wall material refers to barrier wall material, wall material, and wall material. Similarly, the so-called barrier wall refers to barrier wall, wall, and wall. In the present invention, the so-called light-emitting portion (pixel portion) refers to a portion that emits light when electric energy is applied.

[1] Photosensitive resin composition The photosensitive resin composition of the present invention contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a liquid repellent, and (A) a photopolymerization initiator Contains the photopolymerization initiator represented by the general formula (I) described below, (D) the liquid repellent contains the acrylic resin (D1) containing the repeating unit represented by the general formula (II) described below and fluorine atoms ). The photosensitive resin composition of the present invention may further include other components as necessary, for example, an ultraviolet absorber or a polymerization inhibitor may also be included.

In the present invention, the so-called barrier ribs are, for example, those used to divide functional layers (organic layers, light-emitting parts) in active matrix organic electroluminescence devices, and for example, are used as materials for forming the functional layers by using The ink is ejected to the divided area (pixel area) and dried to form a pixel that includes a functional layer and barrier ribs.

[1-1] Components and composition of photosensitive resin composition The components and composition of the photosensitive resin composition of the present invention will be described. The photosensitive resin composition of the present invention contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a liquid repellent.

[1-1-1] Component (A): photopolymerization initiator The photosensitive resin composition of the present invention contains (A) a photopolymerization initiator. The photopolymerization initiator is a compound that polymerizes the ethylenically unsaturated bond of the (C) photopolymerizable compound with active light.

The (A) photopolymerization initiator in the photosensitive resin composition of the present invention contains a photopolymerization initiator represented by the following general formula (I) (hereinafter, sometimes referred to as "photopolymerization initiator (a1)" ").

[化5]

(In formula (I), R ^1a represents an optionally substituted alkyl group or an optionally substituted aromatic cyclic group; R ^2a represents an alkyl group; R ^3a represents a monovalent substituent; n represents 0 or 1; h Represents an integer from 0 to 2)

Since the photopolymerization initiator (a1) has a sulfide skeleton, the surface hardenability is moderate and the desired step is easily formed. Therefore, it is considered that it becomes easy to apply the organic light-emitting layer uniformly and linearly on the second barrier wall adjacent to the pixel region. ^{In addition, R 2a} , which is a radical generating site, is an alkyl group, and the mobility of the generated radicals is large. It is considered that the linear first barrier wall adjacent to the second barrier wall can be sufficiently maintained The liquid repellent can prevent the ink from covering the first barrier wall during application.

(R ^{1a ) The alkyl group in R 1a} in the above formula (I) may be linear, branched, cyclic, or bonded. The carbon number of the alkyl group is not particularly limited, and is usually 1 or more, and is preferably 20 or less, more preferably 10 or less, still more preferably 6 or less, and still more preferably 2 or less. For example, it is preferably 1-20, more preferably 1-10, still more preferably 1-6, and particularly preferably 1-2. Moreover, by setting it as below the said upper limit, there exists a tendency for internal hardenability to become high.

As the alkyl group, for example, methyl, ethyl, propyl, butyl, pentyl, isopentyl, hexyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, cyclopentylethyl, cyclopentyl Hexylmethyl and cyclohexylethyl, among them, methyl, hexyl, isopentyl, cyclopentylmethyl, cyclohexylmethyl are preferred from the viewpoint of internal hardening, and methyl is more preferred .

Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, and a carboxyl group. From the viewpoint of ease of synthesis, it is preferably unsubstituted.

^{Examples of the aromatic ring group in R 1a} in the above formula (I) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is not particularly limited, but is preferably 4 or more, more preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 4-30 are preferable, 5-20 are more preferable, and 5-12 are still more preferable. By setting it as the above-mentioned lower limit or more, the solubility in a solvent tends to become favorable. Moreover, by setting it as below the said upper limit, there exists a tendency for internal hardenability to become high.

The aromatic ring group may, for example, be a phenyl group, a naphthyl group, a pyridyl group, and a furyl group. Among them, from the viewpoint of developability, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable. Examples of the substituent that the aromatic ring group may have include a hydroxyl group and an alkyl group, and from the viewpoint of developability, an alkyl group is preferred. Among these, from the viewpoint of internal curability, it is preferable that R ^1a is an alkyl group which may have a substituent.

(R ^{2a ) The alkyl group in R 2a} in the above formula (I) may be linear, branched, cyclic, or bonded. The carbon number of the alkyl group is not particularly limited, but is usually 1 or more, and is preferably 5 or less, more preferably 3 or less, and still more preferably 2 or less. For example, it is preferably 1 to 5, more preferably 1 to 3, and still more preferably 1 to 2. By setting it as the upper limit or less mentioned above, there exists a tendency for internal hardenability to become high.

As the alkyl group, for example, a methyl group, an ethyl group, a propyl group, and a pentyl group may be mentioned. Among them, a methyl group is preferred from the viewpoint of internal hardenability.

(R ^{3a ) The monovalent substituent in R 3a} in the above formula (I) is not particularly limited, but from the viewpoint of developability, R ^4a -O-, R ^4a -(C=O)- .

Examples of R ^4a include an optionally substituted alkyl group and an optionally substituted aromatic ring group. The alkyl group of R ^4a may be linear, branched, cyclic, or bonded. The carbon number of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 8 or less, more preferably 5 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-8 are preferred, 1-5 are more preferred, 1-3 are more preferred, and 2-3 are particularly preferred. By setting it as the above-mentioned lower limit or more, there exists a tendency for synthesis to become easy. Moreover, by setting it as the said upper limit or less, developability tends to become favorable.

The alkyl group may, for example, be a methyl group, an ethyl group, a propyl group, or a pentyl group. Among these, from the viewpoint of developability, a methyl group and an ethyl group are preferable, and an ethyl group is more preferable. Examples of the substituent that the alkyl group may have include a hydroxyl group and a carboxyl group, and from the viewpoint of developability, a hydroxyl group is preferred.

The aromatic ring group of R ^4a may, for example, be an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 4-30 are preferable, 5-20 are more preferable, and 5-12 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for synthesis to become easy. Moreover, by setting it as the said upper limit or less, developability tends to become favorable. As an aromatic ring group, a phenyl group, a naphthyl group, a thienyl group, a furyl group, a benzothienyl group, and a benzofuryl group are mentioned, for example. Among them, from the viewpoint of sensitivity, benzothienyl and benzofuranyl are preferred, and benzofuranyl is more preferred. As the substituent which the aromatic ring group may have, for example, an alkyl group, a hydroxyl group, and a carboxyl group may be mentioned, and from the viewpoint of synthesis properties, it is preferably unsubstituted.

^{As the monovalent substituent of R 3a} in the above formula (I), from the viewpoint of moderate internal hardenability, R ^4a in which R 4a is an ethyl group substituted with a hydroxyl group and R ^4a -O- and R ^4a are preferably benzene benzofuranyl of ^{R 4a - (C = O)} -, more preferably R ^4a is hydroxy substituted ethyl of the R ^4a -O-.

(n) In the above formula (I), n represents 0 or 1. From the viewpoint of moderate internal hardenability, n is 1 preferably. From the viewpoint of ease of synthesis, n is preferably zero.

(h) In the above formula (I), h represents an integer of 0-2. From the viewpoint of developability, h is preferably 0 or 1, more preferably 1. When h is an integer of 1 or more, ^{the substitution position of R 3a} is not particularly limited. From the viewpoint of synthesis, it is preferably an ortho position or a para position, and more preferably a para position.

As specific examples of known compounds of the photopolymerization initiator (a1), the following compounds may be mentioned.

[化6]

Among them, the compound represented by the formula (a1-3) is preferred from the viewpoint of moderate internal hardenability.

The (A) photopolymerization initiator in the photosensitive resin composition of the present invention may further include photopolymerization initiators other than the photopolymerization initiator (a1) (hereinafter, sometimes referred to as "other photopolymerization initiators"). Starter (a2)”). As the other photopolymerization initiator (a2), photopolymerization initiators generally used in this field can be used. As such a photopolymerization initiator, for example, a hexaarylbiimidazole-based photopolymerization initiator, an phosphine oxide-based photopolymerization initiator, and an oxime ester other than the photopolymerization initiator (a1) It is a photopolymerization initiator, a three-series photopolymerization initiator, an acetophenone-based photopolymerization initiator, and a benzophenone-based photopolymerization initiator.

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

[化7]

In the above formula, R ¹¹ to R ¹³ represent an alkyl group having 1 to 4 carbons, an alkoxy group having 1 to 4 carbons, or a halogen atom, and m, n, and l each independently represent an integer of 0 to 5.

The carbon number of the alkyl group of R ¹¹ to R ¹³ is not particularly limited as long as it is 1 to 4. From the viewpoint of sensitivity, it is preferably 1 to 3, and more preferably 1 to 2. The alkyl group may be chain-like or cyclic. As the alkyl group, for example, a methyl group, an ethyl group, a propyl group, and an isopropyl group may be mentioned, and among them, a methyl group and an ethyl group are preferable.

The carbon number of the alkoxy group of R ¹¹ to R ¹³ is not particularly limited as long as it is 1 to 4. From the viewpoint of sensitivity, it is preferably 1 to 3, and more preferably 1 to 2. The alkyl part of the alkoxy group may be chain-like or cyclic. As the alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropyloxy group, and a butoxy group may be mentioned. Among them, a methoxy group and an ethoxy group are preferable.

Moreover, as ^{the halogen atom of R 11} to R ¹³ , for example, a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom can be exemplified. Among them, from the viewpoint of ease of synthesis, a chlorine atom and a fluorine atom are preferred, and more preferred are Chlorine atom. Among these, from the viewpoint of sensitivity and ease of synthesis, R ¹¹ to R ^{13 are} preferably each independently a halogen atom, and more preferably a chlorine atom.

m, n, and l are each independently 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, more preferably m, n, and l Either one is 1 and the other two are 0.

As the hexaarylbiimidazole compound represented by the general formula (1-1) and/or the general formula (1-2), for example, 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-chloro Naphthyl) biimidazole. Among them, hexaphenylbiimidazole compounds are preferred, and the ortho position of the benzene ring bonded to the 2,2'-position on the imidazole ring is substituted with a methyl group, a methoxy group, or a halogen atom, and the imidazole ring The above 4,4',5,5'-bonded benzene ring is unsubstituted, or substituted with a halogen atom or a methoxy group.

As the other photopolymerization initiator (a2), any of the hexaarylbiimidazole-based compound represented by the general formula (1-1) and the hexaarylbiimidazole-based compound represented by the general formula (1-2) can be used One or both can be used together. In the case of combined use, the ratio is not particularly limited.

As the phosphine oxide-based photopolymerization initiator, for example, 2,4,6-trimethylbenzyl diphenyl phosphine oxide, bis(2,4,6-trimethylbenzyl) Group) phenyl phosphine oxide.

As the oxime ester-based photopolymerization initiator other than the photopolymerization initiator (a1), for example, 1,2-octanedione-1-[4-(phenylthio)phenyl]-2- (O-benzyl oxime) ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl)-1-(O-acetyl Oxime), the compound described in Japanese Patent Application Publication No. 2004-534797, the compound described in Japanese Patent Application Publication No. 2000-80068, the compound described in International Publication No. 2012/45736, Japanese Patent Application Publication No. 2006- The compound described in No. 36750, the compound described in Japanese Patent Laid-Open No. 2008-179611, the compound described in International Publication No. 2009/131189, the compound described in Japanese Patent Publication No. 2012-526185, and the Japanese Patent The compound described in JP 2012-519191, the compound described in International Publication No. 2006/18973, and the compound described in International Publication No. 2008/78678.

As the tris-based photopolymerization initiator, for example, 2,4,6-tris(monochloromethyl)-symmetric tris, 2,4,6-tris(dichloromethyl)-symmetrical tris , 2,4,6-tris(trichloromethyl)-symmetrical tris, 2-methyl-4,6-bis(trichloromethyl)-symmetrical, 2-n-propyl-4,6- Bis(trichloromethyl)-symmetric tris, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-phenyl-4, 6-Bis(trichloromethyl)-symmetric tris, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-(3,4-epoxy Phenyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-(1- (P-Methoxyphenyl)-2,4-butadienyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-styryl-4,6-bis(trichloromethyl) Group)-symmetric three 𠯤, 2-(p-methoxystyryl)-4,6-bis (trichloromethyl)-symmetric three 𠯤, 2-(p-methoxy-m-hydroxystyryl)- 4,6-Bis(trichloromethyl)-symmetric tris, 2-(p-isopropyloxystyryl)-4,6-bis(trichloromethyl)-symmetric tris, 2-(p Tolyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-(p-methoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-( P-ethoxynaphthyl)-4,6-bis(trichloromethyl)-symmetric tris, 2-(p-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-symmetric tris 𠯤, 2-phenylthio-4,6-bis(trichloromethyl)-symmetric tris, 2-benzylthio-4,6-bis(trichloromethyl)-symmetric tris, 2,4, 6-Tris(Dibromomethyl)-Symmetric Tris, 2,4,6-Tris(Tribromomethyl)-Symmetric Tris, 2-Methyl-4,6-Bis(Tribromomethyl)-Symmetry Tris, 2-methoxy-4,6-bis(tribromomethyl)-symmetric tris, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-symmetry Among them, from the viewpoint of sensitivity, bis(trihalomethyl)-symmetric tris derivatives are preferred.

As an acetophenone-based photopolymerization initiator, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl Phenyl ketone, 1-hydroxy-1-(p-dodecylphenyl) ketone, 1-hydroxy-1-methylethyl-(p-isopropylphenyl) ketone, 1-trichloromethyl-( P-Butylphenyl) ketone, α-hydroxy-2-methylphenylacetone, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2 -Benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylamine 2-ethylhexyl-1,4-dimethylaminobenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzylidene)cyclohexanone, 4-(diethylamino)chalcone. As the benzophenone-based photopolymerization initiator, for example, benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2 -Carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, Michele ketone.

The content of the (A) photopolymerization initiator in the photosensitive resin composition of the present invention is not particularly limited. In the total solid content of the photosensitive resin composition, it is preferably 0.5% by mass or more, more preferably 1 % By mass or more, more preferably 1.5% by mass or more, more preferably 2% by mass or more, more preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6 mass% or less, particularly preferably It is 4% by mass or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 0.5-10% by mass, more preferably 1-8% by mass, still more preferably 1.5-6% by mass, and particularly preferably 2-4% by mass. By setting it to be more than the above lower limit value, there is a tendency that film reduction does not occur during development, a coating film can be formed, and sufficient ink repellency can be produced. Moreover, by setting it as the above upper limit or less, there exists a tendency for the desired pattern shape to be easily formed.

The content of the photopolymerization initiator (a1) in the photosensitive resin composition of the present invention is also not particularly limited. In the total solid content of the photosensitive resin composition, it is preferably 0.5% by mass or more, more preferably 1 % By mass or more, more preferably 1.5% by mass or more, more preferably 2% by mass or more, more preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 6 mass% or less, particularly preferably It is 4% by mass or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 0.5-10% by mass, more preferably 1-8% by mass, still more preferably 1.5-6% by mass, and particularly preferably 2-4% by mass. By setting it as the above-mentioned lower limit value or more, there exists a tendency which becomes easy to suppress a collapse, and to form a 2nd barrier wall. In addition, there is a tendency to easily control the level difference by setting it to the upper limit or less.

(A) The content of the photopolymerization initiator (a1) in the photopolymerization initiator is also not particularly limited, but is preferably 20% by mass or more, more preferably 40% by mass or more, and still more preferably 60% by mass or more, Still more preferably 70% by mass or more, particularly preferably 80% by mass or more, and usually 100% by mass or less. For example, it is preferably from 20 to 100% by mass, more preferably from 40 to 100% by mass, still more preferably from 60 to 100% by mass, still more preferably from 70 to 100% by mass, and particularly preferably from 80 to 100% by mass. By setting it as the above-mentioned lower limit value or more, there exists a tendency which becomes easy to suppress a collapse, and to form a 2nd barrier wall.

As a compounding ratio of the (A) photopolymerization initiator to (C) the photopolymerizable compound in the photosensitive resin composition, it is preferably 1 part by mass or more with respect to 100 parts by mass of the (C) photopolymerizable compound, More preferably 2 parts by mass or more, still more preferably 3 parts by mass or more, more preferably 200 parts by mass or less, more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, and even more preferably 20 parts by mass Parts or less, particularly preferably 10 parts by mass or less, most preferably 8 parts by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1 to 200 parts by mass, more preferably 1 to 100 parts by mass, still more preferably 2 to 50 parts by mass, and still more preferably 2 to 20 parts by mass, particularly preferably It is 3-10 parts by mass, most preferably 3-8 parts by mass. By setting it as the above-mentioned lower limit value or more, there exists a tendency to become a suitable sensitivity. Moreover, by setting it as the above upper limit or less, there exists a tendency for the desired pattern shape to be easily formed.

A sensitizer and a photopolymerization initiator can also be used in combination. With the sensitizer, the sensitivity is improved, and at the same time, the light transmittance inside the photosensitive resin composition is reduced, so there is a tendency for the taper angle to increase.

系化合物、9-氧硫𠮿

系化合物、𠮿酮系化合物、9-氧硫𠮿

系化合物、香豆素系化合物、酮香豆素系化合物、花青系化合物、部花青系化合物、氧喏衍生物等聚次甲基色素、吖啶系化合物、𠯤系化合物、噻𠯤系化合物、㗁 𠯤系化合物、吲哚啉系化合物、薁系化合物、薁鎓系化合物、方酸鎓系化合物、卟啉系化合物、四苯基卟啉系化合物、三芳基甲烷系化合物、四苯并卟啉系化合物、四吡𠯤并四氮雜卟啉系化合物、酞菁系化合物、四氮雜卟啉系化合物、四喹㗁啉并四氮雜卟啉系化合物、萘酞菁系化合物、亞酞菁系化合物、吡喃鎓系化合物、噻喃鎓系化合物、新西蘭雞蛋果青苷系化合物、輪烯系化合物、螺哌喃系化合物、螺㗁 𠯤系化合物、硫代螺哌喃系化合物、金屬芳烴錯合物、有機釕錯合物、二苯甲酮系化合物。 該等可單獨使用1種，亦可將2種以上併用。As the sensitizer, sensitizers commonly used in this field can be used. The sensitizer has the characteristic of transferring energy obtained by absorption to the photopolymerization initiator or electron transfer with the photopolymerization initiator to efficiently promote the radical polymerization reaction. As such a sensitizer, for example, chalcone derivatives or unsaturated ketones such as dibenzylidene acetone; 1,2-diketone compounds such as Benzil or camphorquinone; Benzoin Series compounds, 茀 series compounds, naphthoquinone series compounds, anthraquinone series compounds, 𠮿

Series compounds, 9-oxysulfur 𠮿

Series compounds, ketone series compounds, 9-oxysulfur𠮿

Based compounds, coumarin-based compounds, keto-coumarin-based compounds, cyanine-based compounds, merocyanine-based compounds, oxo derivatives, and other polymethine pigments, acridine-based compounds, 𠯤-based compounds, thionin-based compounds Compounds, indoline-based compounds, indoline-based compounds, azulene-based compounds, azulenium-based compounds, squaraine-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds, tetrabenzo Porphyrin-based compounds, tetrapyrazine-tetraazaporphyrin-based compounds, phthalocyanine-based compounds, tetraazaporphyrin-based compounds, tetraquinophyrin-tetraazaporphyrin-based compounds, naphthalocyanine-based compounds, sub- Phthalocyanine-based compounds, pyrylium-based compounds, thiopyrylium-based compounds, New Zealand egg fructinoside-based compounds, anemone-based compounds, spiropyran-based compounds, spiropyran-based compounds, thiosiropiperane-based compounds, Metal arene complexes, organic ruthenium complexes, benzophenone compounds. These may be used individually by 1 type, and may use 2 or more types together.

系化合物、二苯甲酮系化合物。Among them, from the viewpoint of increased sensitivity and increased cone angle, 9-oxysulfur is preferred.

Series compounds, benzophenone series compounds.

系化合物，例如可例舉：9-氧硫𠮿

、2-甲基9-氧硫𠮿

、4-甲基9-氧硫𠮿

、2,4-二甲基9-氧硫𠮿

、2-乙基9-氧硫𠮿

、4-乙基9-氧硫𠮿

、2,4-二乙基9-氧硫𠮿

、2-異丙基9-氧硫𠮿

、4-異丙基9-氧硫𠮿

、2,4-二異丙基9-氧硫𠮿

、2-氯9-氧硫𠮿

、4-氯9-氧硫𠮿

、2,4-二氯9-氧硫𠮿

。該等中，就感度提昇及錐角增大之觀點而言，較佳為2,4-二乙基9-氧硫𠮿

。As 9-oxysulfur 𠮿

Series compounds, for example: 9-oxysulfur 𠮿

, 2-Methyl 9-oxysulfur 𠮿

, 4-Methyl 9-oxysulfur 𠮿

, 2,4-Dimethyl 9-oxysulfur 𠮿

, 2-ethyl 9-oxysulfur 𠮿

, 4-ethyl 9-oxysulfur 𠮿

, 2,4-Diethyl 9-oxysulfur 𠮿

, 2-isopropyl 9-oxysulfur 𠮿

, 4-isopropyl 9-oxysulfur 𠮿

, 2,4-Diisopropyl 9-oxysulfur 𠮿

, 2-chloro-9-oxysulfur 𠮿

, 4-Chloro 9-oxysulfur 𠮿

, 2,4-Dichloro 9-oxysulfur 𠮿

. Among them, 2,4-diethyl 9-oxysulfur 𠮿 is preferred from the viewpoint of increased sensitivity and increased cone angle.

.

As the benzophenone compound, for example, benzophenone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone Methyl ketone, 4,4'-bis(ethylmethylamino)benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of sensitivity improvement and cone angle increase.

When the photosensitive resin composition contains a sensitizer, the content of the sensitizer in the photosensitive resin composition in the total solid content of the photosensitive resin composition is preferably 0.1% by mass or more, more preferably 0.3 Mass% or more, more preferably 0.5 mass% or more, still more preferably 0.8 mass% or more, particularly preferably 1 mass% or more, most preferably 1.2 mass% or more, and more preferably 10 mass% or less, more preferably It is 7% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 0.1-10% by mass, more preferably 0.3-10% by mass, still more preferably 0.5-7% by mass, still more preferably 0.8-7% by mass, particularly preferably It is 1 to 5% by mass, and most preferably 1.2 to 3% by mass. By setting it as the above lower limit value or more, there is a tendency for the sensitivity to be improved and the taper angle can be increased. In addition, by setting it below the above upper limit value, there is a tendency to easily form a desired pattern.

[1-1-2] (B) Component: Alkali-soluble resin The photosensitive resin composition of this invention contains (B) alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it can be developed with an alkaline developer. As the alkali-soluble resin, various resins containing a carboxyl group and/or a hydroxyl group may be mentioned. Among them, a resin having a carboxyl group is preferable from the viewpoints of obtaining a barrier wall with a moderate taper angle and suppressing the outflow of the liquid repellent caused by the thermal melting of the barrier wall surface during post-baking, thereby maintaining ink repellency.

[Alkali-soluble resin with ethylenic double bond (b)] In the photosensitive resin composition of the present invention, (B) the alkali-soluble resin preferably contains an alkali-soluble resin (b) having an ethylenic double bond (hereinafter, it may be abbreviated as "alkali-soluble resin (b)"). The inclusion of the alkali-soluble resin (b) having an ethylenic double bond increases the sensitivity and suppresses the outflow of the liquid repellent during development, thereby tending to increase the ink repellency of the obtained barrier wall.

The specific structure of the alkali-soluble resin (b) having an ethylenic double bond is not particularly limited. From the viewpoint of developing solubility, epoxy (meth)acrylate resin (b1) and/or acrylic copolymer are preferred. The resin (b2) is more preferably an epoxy (meth)acrylate resin (b1) from the viewpoint of reducing outgassing. Hereinafter, the epoxy (meth)acrylate resin (b1) will be described in detail.

[Epoxy (meth)acrylate resin (b1)] The epoxy (meth)acrylate resin (b1) is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond (ethylenic double bond) to an epoxy resin and further adding a polybasic acid or an anhydride thereof. For example, the carboxyl group of an acid having an ethylenically unsaturated bond is added to the epoxy group of the epoxy resin by ring-opening, and the ethylenic unsaturated bond is added to the epoxy resin through the ester bond (-COO-), and The hydroxyl group produced at this time is obtained by adding one of the carboxyl groups of polybasic acid anhydrides. Moreover, when adding a polybasic acid anhydride, a polyhydric alcohol is added simultaneously for addition. Furthermore, the epoxy (meth)acrylate resin (b1) also includes a resin obtained by reacting the resin obtained by the above reaction with a compound having a functional group capable of further reacting with the carboxyl group of the resin. Therefore, the epoxy (meth)acrylate resin does not substantially have an epoxy group in the chemical structure, and is not limited to "(meth)acrylate", but because the epoxy compound (epoxy resin) is a raw material, and "(Meth)acrylate" is a representative example, so it is named as usual.

Here, the term “epoxy resin” refers to a raw material compound before forming a resin by thermosetting, and as the epoxy resin, it can be appropriately selected from among known epoxy resins and used. In addition, as the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or higher phenolic hydroxyl group, and it may be a monomer or a polymer. Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, biphenol Aldehyde epoxy resin, triphenol epoxy resin, epoxide of polymer of phenol and dicyclopentane, dihydroalkylene oxide type epoxy resin, dihydroalkylene alkylene oxide type ring Oxygen resin, 9,9-bis(4'-hydroxyphenyl) diglycidyl etherate, 1,1-bis(4'-hydroxyphenyl)adamantane diglycidyl etherate, preferably Use those with aromatic rings on the main chain.

Among them, from the viewpoint of the strength of the cured film, bisphenol A type epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, epoxy resin of a polymer of phenol and dicyclopentadiene are preferred. The epoxide of 9,9-bis(4'-hydroxyphenyl) sulfide, and more preferably bisphenol A type epoxy resin.

Examples of the acid having an ethylenically unsaturated bond include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, pentaerythritol tri(meth)acrylate succinate Acid anhydride adduct, pentaerythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalate Dicarboxylic acid anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride adduct, reaction product of (meth)acrylic acid and ε-caprolactone. Among them, from the viewpoint of sensitivity, (meth)acrylic acid is preferred.

As the polybasic acid (anhydride), for example, succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4- Methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4 -Methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, Biphenyltetracarboxylic acid, and anhydrides of these. These may be used individually by 1 type, and may use 2 or more types together. Among them, from the viewpoint of reduction of residues in the pixel portion after development, succinic anhydride, maleic anhydride, and itaconic anhydride are preferred, and succinic anhydride is more preferred.

By using polyols, the molecular weight of the epoxy (meth)acrylate resin (b1) is increased, branches can be introduced into the molecule, and there is a tendency that a balance between molecular weight and viscosity can be achieved. In addition, it is possible to increase the rate of introduction of the acid into the molecule, and there is a tendency to easily achieve a balance of sensitivity, adhesion, and the like. Examples of polyols include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propane triol. These may be used individually by 1 type, and may use 2 or more types together.

The acid value of the epoxy (meth)acrylate resin (b1) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more, still more preferably 40 mgKOH/g or more, and still more It is preferably 60 mgKOH/g or more, more preferably 200 mgKOH/g or less, more preferably 180 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and still more preferably 120 mgKOH/g or less, particularly preferably Less than 100 mgKOH/g. The above upper and lower limits can be combined arbitrarily, for example, preferably 10 to 200 mgKOH/g, more preferably 10 to 180 mgKOH/g, still more preferably 20 to 150 mgKOH/g, and even more preferably 40 to 120 mgKOH/g g, particularly preferably 60-100 mgKOH/g. By setting it as the above-mentioned lower limit or more, residue is easy to reduce. In addition, by setting it below the above upper limit value, outgassing when the device emits light tends to decrease.

The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b1) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, still more preferably 3000 or more, and still more preferably 4000 or more, It is particularly preferably 5,000 or more, particularly preferably 6,000 or more, most preferably 7,000 or more, more preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, and particularly preferably 10,000 or less. The above upper limit and lower limit can be combined arbitrarily, preferably 1,000 to 30,000, more preferably 2,000 to 30,000, still more preferably 3,000 to 20,000, still more preferably 4,000 to 20,000, particularly preferably 5,000 to 15,000, particularly preferably 6000 to 15000, preferably 7000 to 10000. By setting it above the above lower limit value, outgassing when the device emits light tends to decrease. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

When (B) alkali-soluble resin contains epoxy (meth)acrylate resin (b1), the content of epoxy (meth)acrylate resin (b1) contained in (B) alkali-soluble resin is not particularly Limited, preferably 30% by mass or more, more preferably 50% by mass or more, still more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and usually 100% by mass %the following. The above upper limit and lower limit can be combined arbitrarily. For example, it is preferably from 30 to 100% by mass, more preferably from 50 to 100% by mass, still more preferably from 70 to 100% by mass, still more preferably from 80 to 100% by mass, and particularly preferably from 90 to 100% by mass. By setting it as above the above lower limit value, outgassing tends to decrease.

The epoxy (meth)acrylate resin (b1) can be synthesized by a previously known method. Specifically, the following method can be used: the above epoxy resin is dissolved in an organic solvent, in the coexistence of a catalyst and a thermal polymerization inhibitor, the above-mentioned acid or ester compound having an ethylenically unsaturated bond is added to add the above-mentioned acid or ester compound. Then, the polybasic acid or its anhydride is added to continue the reaction.

Examples of the organic solvent include methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. As the catalyst, for example, tertiary amines such as triethylamine, dimethylbenzylamine, and tribenzylamine; tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, Quaternary ammonium salts such as tetrabutylammonium chloride and trimethylbenzylammonium chloride; phosphorus compounds such as triphenylphosphine; antimony such as triphenyl antimony. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone. These may be used individually by 1 type, and may use 2 or more types together.

The acid or ester compound having an ethylenically unsaturated bond can be used in an amount that is preferably 0.7 to 1.3 stoichiometry, and more preferably 0.9 to 1.1 stoichiometry with respect to 1 stoichiometric weight of the epoxy group of the epoxy resin. The temperature during the addition reaction is preferably 60 to 150°C, more preferably 80 to 120°C. The polybasic acid (anhydride) can be used in an amount that is preferably 0.1 to 1.2 stoichiometry, more preferably 0.2 to 1.1 stoichiometry with respect to 1 stoichiometric weight of the hydroxyl group generated in the addition reaction.

Regarding the epoxy (meth)acrylate resin (b1), from the viewpoint of outgassing when the device emits light, it preferably contains an epoxy (former) selected from the group consisting of a partial structure represented by the following general formula (i) Base) acrylate resin (b1-1) (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (b1-1)"), a ring containing a partial structure represented by the following general formula (ii) Oxygen (meth)acrylate resin (b1-2) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (b1-2)"), and includes those represented by the following general formula (iii) Partially structured epoxy (meth)acrylate resin (b1-3) (hereinafter, sometimes referred to as "epoxy (meth)acrylate resin (b1-3)") at least one of the group consisting of .

Regarding the epoxy (meth)acrylate resin (b1), among these, from the viewpoint of reducing outgassing when the device emits light, it is preferable to contain a ring including a partial structure represented by the following general formula (i) The oxygen (meth)acrylate resin (b1-1) is more preferably an epoxy (meth)acrylate resin (b1-1) containing a partial structure represented by the following general formula (i). It is speculated that one of the reasons is: due to the rigid main skeleton, it is not easy to decompose when heated.

[化8]

In the formula (i), R ^a represents a hydrogen atom or a methyl group, R ^b represents a divalent hydrocarbon group of substituents. The benzene ring in formula (i) may be further substituted with any substituent. * Indicates a bonding key.

(R ^b ) In the above formula (i), R ^b represents a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group may, for example, be a divalent aliphatic group, a divalent aromatic ring group, and a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups.

The divalent aliphatic group may, for example, be linear, branched, or cyclic. Among them, from the standpoint of development solubility, the linear form is preferable, and on the other hand, the cyclic form is preferable from the standpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The above upper limit and lower limit can be combined arbitrarily, and for example, 1-20 are preferable, 3-15 are more preferable, and 6-10 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

Examples of the bivalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexyl, and n-heptyl. Among these, the methylene group is more preferable from the viewpoint of residue reduction. As the bivalent branched aliphatic group, for example, the above-mentioned bivalent linear aliphatic group has a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a second group. Butyl and tertiary butyl are the side chain structures. The number of rings possessed by the bivalent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 10 or less, more preferably 5 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-5 are still more preferable. By setting it to the above lower limit or more, there is a tendency for the residual film rate to increase. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. As the bivalent cyclic aliphatic group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a nordane ring, an isobornane ring, and an adamantane ring can be exemplified. The ring is formed by removing two hydrogen atoms. Among these, from the viewpoint of development adhesiveness, a group obtained by removing two hydrogen atoms from an adamantane ring is preferred.

As the substituent that the divalent aliphatic group may have, for example, alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups are easy to synthesize From a viewpoint, it is preferable to be unsubstituted.

The divalent aromatic ring group may, for example, be a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 4-20 are preferable, 5-15 are more preferable, and 6-10 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

環、聯三伸苯環、乙烷合萘環、螢蒽環、茀環。 作為2價芳香族雜環基中之芳香族雜環，可為單環亦可為縮合環。作為2價芳香族雜環基，例如可例舉：具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環。該等中，就光硬化性之觀點而言，較佳為具有2個自由原子價之苯環、萘環，更佳為具有2個自由原子價之苯環。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic hydrocarbon ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetrabenzene ring, pyrene ring, benzopyrene ring,

Ring, bis-terphenylene ring, ethane naphthalene ring, fluoranthene ring, pyrene ring. The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, and oxadiazole having 2 free valences. Ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring , Benzisothiazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyridine ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, oxoline ring, Quinoline ring, phenanthridine ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring. Among these, from the viewpoint of photocurability, a benzene ring and a naphthalene ring having 2 free valences are preferred, and a benzene ring having 2 free valences is more preferred.

Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and a glycidyl ether group. Among these, from the viewpoint of hardening properties, it is preferable to be unsubstituted.

As a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, there can be mentioned one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic groups. The base formed by the connection of the ring base. The number of divalent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

As a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, for example, groups represented by the following formulas (i-A) to (i-F) can be mentioned. Among these, the group represented by the following formula (i-A) is preferred from the viewpoint of the rigidity of the skeleton and the hydrophobization of the film. The * in the chemical formula represents a bonding bond.

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As mentioned above, the benzene ring in formula (i) may be further substituted with any substituent. As the substituent of the benzene ring in the formula (i), for example, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group may be mentioned. The number of substituents is also not particularly limited, as long as it is chemically permissible, it may be one or two or more. From the viewpoint of hardening properties, it is preferably unsubstituted.

The partial structure represented by the above formula (i) is preferably a partial structure represented by the following formula (i-1) from the viewpoint of development solubility.

[化10]

Of formula (i-1), R ^a is and R ^b in the above formula (i) of R ^a and R ^b are synonymous. R ¹ represents a divalent hydrocarbon group having 1 to 4 carbon atoms which may have a substituent. * Indicates a bonding key. The benzene ring in formula (i-1) may be further substituted with any substituent.

(R ¹ ) In the above general formula (i-1), R ¹ represents an optionally substituted divalent hydrocarbon group with 1 to 4 carbon atoms. The divalent hydrocarbon group may, for example, be an alkylene group and an alkenylene group.

The alkylene group may be a straight chain or a branched chain, and from the viewpoint of development solubility, a straight chain is preferred. The carbon number is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 4 or less, more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, and for example, 1 to 4 are preferred, 1 to 3 are more preferred, and 2 to 3 are still more preferred. By setting it as the above-mentioned lower limit or more, there exists a tendency for the residual film rate to become high. In addition, by setting it below the above upper limit value, there is a tendency that the amount of outgassing generated when the device emits light is reduced.

Specific examples of alkylene include methylene, ethylene, propylene, and butylene. From the viewpoint of reducing outgassing, methylene or ethylene is preferred, and more preferred is Ethylene.

The alkenylene group may be a straight chain or a branched chain, and from the viewpoint of development solubility, a straight chain is preferred. The carbon number is not particularly limited, but it is usually 2 or more, more preferably 4 or less, and more preferably 3 or less. For example, it is preferably 2 to 4, more preferably 2 to 3. By setting it as the above-mentioned lower limit or more, there exists a tendency for the residual film rate to become high. In addition, by setting it below the above upper limit value, there is a tendency that the amount of outgassing generated when the device emits light is reduced.

Specific examples of the alkenylene group include an ethylene group, an propylene group, and a butenylene group. From the viewpoint of outgassing, an ethylene group is preferable.

The substituents that the divalent hydrocarbon group having 1 to 4 carbons may have are not particularly limited, and examples thereof include a halogen atom, an alkoxy group, a benzyl group, and a hydroxyl group. From the viewpoint of ease of synthesis, it is preferably Not replaced.

Among these, from the viewpoint of reducing outgassing, R ¹ is preferably a divalent alkylene group having 1 to 4 carbon atoms, more preferably a methylene group or an ethylene group, and still more preferably an ethylene group.

The partial structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-1) may be one type or two or more types.

The number of the partial structure represented by the above formula (i) contained in 1 molecule of the epoxy (meth)acrylate resin (b1-1) is not particularly limited, and is preferably 1 or more, more preferably 2 or more, and further It is preferably 3 or more, more preferably 10 or less, and still more preferably 8 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 2-10 are more preferable, and 3-8 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

The number of the partial structures represented by the above formula (i-1) contained in 1 molecule of the epoxy (meth)acrylate resin (b1-1) is not particularly limited, and is preferably 1 or more, more preferably 2 or more , More preferably 3 or more, more preferably 10 or less, and still more preferably 8 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 2-10 are more preferable, and 3-8 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

Specific examples of epoxy (meth)acrylate resin (b1-1) are given below.

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[化12]

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[化16]

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As another aspect, the epoxy (meth)acrylate resin (b1) is preferably an epoxy (meth)acrylate containing a partial structure represented by the following formula (ii) from the viewpoint of developing adhesiveness Resin (b1-2).

[化18]

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

(R ^d ) In the above formula (ii), R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain. The cyclic hydrocarbon group may, for example, be an aliphatic ring group or an aromatic ring group.

The number of rings possessed by the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less . The above upper limit and lower limit can be combined arbitrarily, for example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, and 8-15 are especially preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. As the aliphatic ring in the aliphatic ring group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring may be mentioned. . Among these, an adamantane ring is preferable from the viewpoint of development adhesiveness.

環、聯三伸苯環、乙烷合萘環、螢蒽環、茀環。該等中，就圖案化特性之觀點而言，較佳為茀環。The number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, more preferably 10 or less, more preferably 5 or less, and still more preferably 4 the following. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 2-5 are more preferable, and 3-4 are still more preferable. By setting it to be more than the above lower limit value, there is a tendency for residue to decrease. Moreover, by setting it as below the said upper limit, there exists a tendency for development adhesiveness to improve. The aromatic ring group may, for example, be an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, more preferably 40 or less, more preferably 30 or less , More preferably 20 or less, and particularly preferably 15 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 4-40 is preferable, 6-40 is more preferable, 8-30 is still more preferable, 10-20 is still more preferable, and 12-15 is especially preferable. By setting it to be more than the above lower limit value, there is a tendency for residue to decrease. Moreover, by setting it as below the said upper limit, there exists a tendency for development adhesiveness to improve. As the aromatic ring in the aromatic ring group, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetrabenzene ring, a pyrene ring, a benzopyrene ring,

Ring, bis-terphenylene ring, ethane naphthalene ring, fluoranthene ring, pyrene ring. Among them, from the viewpoint of patterning characteristics, a chrysanthemum ring is preferable.

The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples include: a divalent aliphatic group, a divalent aromatic ring group, and a combination of one or more divalent aliphatic groups with 1 A group formed by linking two or more divalent aromatic ring groups.

The divalent aliphatic group may, for example, be linear, branched, or cyclic. Among them, from the standpoint of development solubility, the linear form is preferable, and on the other hand, the cyclic form is preferable from the standpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, more preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-25 are preferable, 3-20 are more preferable, and 6-15 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

Examples of the bivalent linear aliphatic group include methylene, ethylene, n-propyl, n-butyl, n-hexyl, and n-heptyl. Among these, from the viewpoint of residue, methylene is preferred. As the bivalent branched aliphatic group, for example, the above-mentioned bivalent linear aliphatic group has a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, an isobutyl group, and a third group. Dibutyl and tertiary butyl are the side chain structures. The number of rings possessed by the bivalent cyclic aliphatic group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. As the bivalent cyclic aliphatic group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a nordecane ring, an isobornane ring, and adamantane ring can be cited. The base formed by 2 hydrogen atoms. Among these, from the viewpoint of development adhesiveness, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.

As the substituent that the divalent aliphatic group may have, for example, alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups are easy to synthesize From a viewpoint, it is preferable to be unsubstituted.

The divalent aromatic ring group may, for example, be a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. The above upper limit and lower limit can be arbitrarily combined, for example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

環、聯三伸苯環、乙烷合萘環、螢蒽環、茀環。 作為2價芳香族雜環基中之芳香族雜環，可為單環亦可為縮合環。作為2價芳香族雜環基，例如可例舉具有2個自由原子價之呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環。該等中，就光硬化性之觀點而言，較佳為具有2個自由原子價之苯環、萘環，更佳為具有2個自由原子價之苯環。The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. As the divalent aromatic hydrocarbon ring group, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetraphenyl ring, a pyrene ring, a benzopyrene ring and

Ring, bis-terphenylene ring, ethane naphthalene ring, fluoranthene ring, pyrene ring. The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. As the divalent aromatic heterocyclic group, for example, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadiazole ring having two free valences can be mentioned. , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, Benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyridine ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquinoline ring, quinoline ring, quinoline Acetyl ring, phenanthridine ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring. Among these, from the viewpoint of photocurability, a benzene ring and a naphthalene ring having 2 free valences are preferred, and a benzene ring having 2 free valences is more preferred.

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

As a group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, there can be mentioned one or more of the above-mentioned divalent aliphatic groups and one or more of the above-mentioned divalent aromatic groups. The base formed by the connection of the ring base. The number of divalent aliphatic groups is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 10 or less, more preferably 5 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 1-5 are more preferable, and 2-3 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

As the group formed by linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, for example, the groups represented by the above-mentioned formulas (i-A) to (i-F) and the like can be mentioned. Among these, the group represented by the above-mentioned formula (i-C) is preferable from the viewpoint of reduction of residue.

As the side chain cyclic hydrocarbon group, the bonding form of the divalent hydrocarbon group is not particularly limited. For example, a form in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted on the side chain, or a form containing an aliphatic group can be mentioned. One carbon atom of the group constitutes the form of a cyclic hydrocarbon group as a side chain.

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

[化19]

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

(R ^α ) In the above formula (ii-1), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent. The cyclic hydrocarbon group may, for example, be an aliphatic ring group or an aromatic ring group.

The number of rings possessed by the aliphatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-6 are preferable, 1-4 are more preferable, and 2-3 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly preferably 15 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, and 8-15 are especially preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. As the aliphatic ring in the aliphatic ring group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring may be mentioned. . Among these, an adamantane ring is preferable from the viewpoint of development adhesiveness.

The number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and more preferably 10 or less, more preferably 5 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferred, 2-10 are more preferred, and 3-5 are still more preferred. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. The aromatic ring group may, for example, be an aromatic hydrocarbon ring group and an aromatic heterocyclic group. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, more preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. The above upper limit and lower limit can be arbitrarily combined, for example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a sulphur ring. Among these, from the viewpoint of development adhesiveness, a sage ring is preferable.

Examples of substituents that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, etc. Alkyl groups with 1 to 5 carbons; alkoxy groups with 1 to 5 carbons such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; carboxyl groups. From the viewpoint of ease of synthesis, preferably Not replaced.

n represents an integer of 1 or more, preferably 2 or more, and more preferably 3 or less. For example, 1-3 are preferable, and 1-2 are more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

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

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

The following is a specific example of the partial structure represented by the above formula (ii-1).

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

[化25]

In the formula (ii-2), R ^c has the same meaning as in the above formula (ii). R ^β represents a bivalent cyclic hydrocarbon group which may have a substituent. The benzene ring in formula (ii-2) may be further substituted with any substituent. * Indicates a bonding key.

(R ^β ) In the above formula (ii-2), R ^β represents a bivalent cyclic hydrocarbon group which may have a substituent. The cyclic hydrocarbon group may, for example, be an aliphatic ring group or an aromatic ring group.

The number of rings possessed by the aliphatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 10 or less, and more preferably 5 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, and 2-5 are more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 4-40 are preferable, 6-35 are more preferable, and 8-30 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. The aliphatic ring in the aliphatic ring group may, for example, be a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a nordecane ring, an isobornane ring, and an adamantane ring. Among these, an adamantane ring is preferable from the viewpoint of development adhesiveness.

The number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and more preferably 10 or less, and preferably 5 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferred, 2-10 are more preferred, and 3-5 are still more preferred. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. The aromatic ring group may, for example, be an aromatic hydrocarbon ring group and an aromatic heterocyclic group. In addition, the carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, more preferably 40 or less, more preferably 30 or less, and still more preferably It is 20 or less, particularly preferably 15 or less. The above upper limit and lower limit can be arbitrarily combined, for example, 4-40 are preferred, 6-30 are more preferred, 8-20 are more preferred, and 10-15 are particularly preferred. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a sulphur ring. Among these, from the viewpoint of development adhesiveness, a sage ring is preferable.

Examples of substituents that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, etc. Alkyl with 1 to 5 carbons; Alkoxy with 1 to 5 carbons such as methoxy and ethoxy; hydroxy; nitro; cyano; carboxyl. Among them, from the viewpoint of ease of synthesis, it is preferable to be unsubstituted.

Among these, from the viewpoint of hardening properties, R ^β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group. As another aspect, from the viewpoint of development adhesiveness, R ^β is preferably a divalent aromatic ring group, and more preferably a divalent fluorine ring group.

As described above, the benzene ring in formula (ii-2) may be further substituted with any substituent. As the substituent of the benzene ring in the formula (ii-2), for example, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group may be mentioned. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of hardening properties, it is preferably unsubstituted.

The following is a specific example of the partial structure represented by the above formula (ii-2).

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[化27]

[化28]

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The partial structure represented by the above formula (ii) is preferably the partial structure represented by the following formula (ii-3) from the viewpoint of curability.

[化30]

In the formula (ii-3), R ^c and R ^d have the same meaning as in the above formula (ii). R ^{1 is} synonymous with the above formula (i-1). * Indicates a bonding key.

The partial structure represented by the above formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (b1-2) may be one type or two or more types.

The number of the partial structure represented by the above formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (b1-2) is not particularly limited, and is preferably 1 or more, more preferably 3 or more, and , Preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-20 are preferable, 1-15 are more preferable, and 3-10 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

As yet another aspect, the epoxy (meth)acrylate resin (b1) is preferably an epoxy containing a partial structure represented by the following general formula (iii) from the viewpoint of reducing outgassing when the device emits light (Meth)acrylate resin (b1-3).

[化31]

In the formula (iii), R ^e represents a hydrogen atom or a methyl group, gamma] represents a single bond, CO-, it may have a substituent group of the alkylene group, or a divalent radical of a cyclic hydrocarbon substituent. The benzene ring in formula (iii) may be further substituted with any substituent. * Indicates a bonding key.

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

The alkylene group may be linear or branched. From the viewpoint of development solubility, it is preferably linear, and from the viewpoint of development adhesion, it is preferably branched. The carbon number is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 6 or less, more preferably 4 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1 to 6 are preferable, and 2 to 4 are more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

As the alkylene group, for example, methylene, ethylene group, propylene group, butylene group, hexylene group, and heptylene group may be mentioned. From the viewpoint of compatibility of development adhesion and development solubility, preferred is Methylene, ethylene, and propylene, more preferably dimethylmethylene (2,2-propylene).

The substituents that the alkylene group may have include, for example, alkoxy groups with 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; From the viewpoint of solubility, it is preferably unsubstituted.

The divalent cyclic hydrocarbon group may, for example, be a divalent aliphatic ring group or a divalent aromatic ring group.

The number of rings possessed by the aliphatic ring group is not particularly limited, but it is usually 1 or more, preferably 2 or more, more preferably 10 or less, and more preferably 5 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, and 2-5 are more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. In addition, the carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, more preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 4-40 are preferable, 6-35 are more preferable, and 8-30 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. As the aliphatic ring in the aliphatic ring group, for example, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, and an adamantane ring may be mentioned. . Among these, an adamantane ring is preferable from the viewpoint of development adhesiveness.

The number of rings possessed by the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and more preferably 10 or less, more preferably 5 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferred, 2-10 are more preferred, and 3-5 are still more preferred. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. The aromatic ring group may, for example, be an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, more preferably 40 or less, more preferably 30 or less, and still more preferably 20 Below, 15 or less is particularly preferable. The above upper limit and lower limit can be arbitrarily combined, for example, 4-40 are preferred, 6-30 are more preferred, 8-20 are more preferred, and 10-15 are particularly preferred. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a sulphur ring. Among these, from the viewpoint of development adhesiveness, a sage ring is preferable.

Examples of substituents that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, isopentyl, etc. Alkyl groups with 1 to 5 carbons; alkoxy groups with 1 to 5 carbons such as methoxy and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; Not replaced.

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

As mentioned above, the benzene ring in formula (iii) may be further substituted with any substituent. As the substituent of the benzene ring in formula (iii), for example, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group may be mentioned. The number of substituents is also not particularly limited, and may be one or two or more. From the viewpoint of hardening properties, it is preferably unsubstituted.

The partial structure represented by the above formula (iii) is preferably the partial structure represented by the following formula (iii-1) from the viewpoint of development solubility.

[化32]

Of formula (iii-1) in a, R ^e, and γ is synonymous with the above-described formula (iii). R ¹ and R the formula (i-1) of ¹ synonymous. * Indicates a bonding key. The benzene ring in formula (iii-1) may be further substituted with any substituent.

The number of the partial structure represented by the above formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (b1-3) is not particularly limited, and is preferably 1 or more, more preferably 5 or more, and further It is preferably 10 or more, more preferably 18 or less, and more preferably 15 or less. The above upper limit and lower limit can be arbitrarily combined, for example, 1-18 are preferable, 5-18 are more preferable, and 10-15 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

The number of the partial structures represented by the above formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-3) is not particularly limited, and is preferably 1 or more, more preferably 3 or more , More preferably 5 or more, more preferably 18 or less, and still more preferably 15 or less. The above upper limit and lower limit can be arbitrarily combined, for example, 1-18 are preferable, 3-18 are more preferable, and 5-15 are still more preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

Specific examples of epoxy (meth)acrylate resin (b1-3) are given below.

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[化34]

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[Acrylic copolymer resin (b2)] From the viewpoint of curability, the acrylic copolymer resin (b2) preferably has an ethylenic double bond in the side chain.

Among the acrylic copolymer resins (b2), from the viewpoint of development solubility, an acrylic copolymer resin (b2-1) containing a partial structure represented by the following general formula (I) is preferred.

[化36]

In formula (I), R ^A and R ^B each independently represent a hydrogen atom or a methyl group. * Indicates a bonding key.

The partial structure represented by the above formula (I) is preferably a partial structure represented by the following general formula (I-1) from the viewpoint of developability.

[化37]

In the formula (I-1), ^{R A} and R ^{B have the} same meaning as ^{R A} and R ^B of the above formula (I). R ¹ and R the formula (i-1) of ¹ synonymous.

The partial structure represented by the above formula (I) is preferably the partial structure represented by the following formula (I-2) from the viewpoint of sensitivity.

[化38]

In the formula (I-2), ^{R A} and R ^{B have the} same meaning as ^{R A} and R ^B in the above formula (I).

When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I), the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I) The content is not particularly limited, and is preferably 5 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, still more preferably 50 mol% or more, and particularly preferably 70 mol% % Or more, preferably 80 mol% or more, more preferably 99 mol% or less, more preferably 97 mol% or less, and still more preferably 95 mol% or less. The above upper and lower limits can be combined arbitrarily, for example, preferably 5 to 99 mol%, more preferably 20 to 99 mol%, still more preferably 30 to 97 mol%, and even more preferably 50 to 97 mol% Ear%, particularly preferably 70 to 95 mol%, most preferably 80 to 95 mol%. By setting it to be more than the above lower limit value, there is a tendency for residue to decrease. Moreover, by setting it as below the said upper limit, there exists a tendency for development adhesiveness to improve.

When the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I-1), the acrylic copolymer resin (b2-1) is represented by the general formula (I-1) The content of the partial structure is not particularly limited, and is preferably 1 mol% or more, more preferably 5 mol% or more, still more preferably 8 mol% or more, and still more preferably 10 mol% or more, and, It is preferably 99 mol% or less, more preferably 60 mol% or less, further preferably 40 mol% or less, still more preferably 30 mol% or less, and particularly preferably 20 mol% or less. The above upper limit and lower limit can be arbitrarily combined, for example, preferably 1 to 99 mol%, more preferably 1 to 60 mol%, still more preferably 5 to 40 mol%, and even more preferably 8 to 30 mol% %, particularly preferably 10-20 mol%. By setting it to the above lower limit or more, the sensitivity increases and the residue tends to decrease. Moreover, by setting it as below the said upper limit, there exists a tendency for development adhesiveness to improve.

When the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I-2), the acrylic copolymer resin (b2-1) is represented by the general formula (I-2) The content of the part of the structure is not particularly limited, preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 30 mol% or more, and still more preferably 40 mol% or more, especially 50 mol% or more, preferably 70 mol% or more, more preferably 99 mol% or less, more preferably 95 mol% or less, further preferably 90 mol% or less, and particularly preferably 85 mol% Mole% or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 10 to 99 mol%, more preferably 20 to 99 mol%, still more preferably 30 to 95 mol%, and even more preferably 40 to 95 mol% %, particularly preferably 50-90 mol%, most preferably 70-85 mol%. By setting it as the above-mentioned lower limit or more, there exists a tendency for sensitivity to become high. Moreover, by setting it as below the said upper limit, there exists a tendency for developability to improve.

When the acrylic copolymer resin (b2-1) includes the partial structure represented by the general formula (I), other partial structures that can be included are not particularly limited. From the viewpoint of development adhesion, for example, it is preferably The partial structure represented by the following general formula (I') is included.

[化39]

In the above formula (I'), R ^D represents a hydrogen atom or a methyl group, and ^RE represents an optionally substituted alkyl group, an optionally substituted aryl group (aromatic ring group), or an optionally substituted alkenyl group .

(R ^E ) In the above formula (I'), ^RE represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group. As R ^E in the group include linear, branched or cyclic alkyl group of. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less, Particularly preferably, it is 12 or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 1-18, still more preferably 3-16, still more preferably 3-14, and particularly preferably 5-12. By setting it as the above-mentioned lower limit value or more, there exists a tendency for film strength to become high, and development adhesiveness improves. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

As the alkyl group, for example, a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group may be mentioned. Among these, from the viewpoint of film strength, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred. Examples of substituents that the alkyl group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amino, epoxy, oligoethylene glycol, phenyl, From the viewpoint of developability, the carboxyl group, acryl group, and methacryl group are preferably a hydroxyl group or an oligoethylene glycol group.

環、聯三伸苯環、乙烷合萘環、螢蒽環、茀環。 作為芳香族雜環基中之芳香族雜環基，為單環或縮合環均可，例如可例舉：呋喃環、苯并呋喃環、噻吩環、苯并噻吩環、吡咯環、吡唑環、咪唑環、㗁二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、呋喃并吡咯環、呋喃并呋喃環、噻吩并呋喃環、苯并異㗁唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡𠯤環、嗒𠯤環、嘧啶環、三𠯤環、喹啉環、異喹啉環、㖕啉環、喹㗁啉環、啡啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環。該等中，就硬化性之觀點而言，較佳為苯環基、萘環基，更佳為苯環基。 作為芳基可具有之取代基，例如可例舉：甲基、乙基、丙基、甲氧基、乙氧基、氯基、溴基、氟基、羥基、胺基、環氧基、低聚乙二醇基、苯基、羧基，就顯影性之觀點而言，較佳為羥基、低聚乙二醇基。As R ^E of the aryl group (aromatic ring group), include: a monovalent aromatic hydrocarbon ring group, a monovalent aromatic heterocyclic group. The carbon number is preferably 4 or more, more preferably 6 or more, more preferably 24 or less, more preferably 22 or less, still more preferably 20 or less, and particularly preferably 18 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 4-24 are preferable, 4-22 are more preferable, 6-20 are still more preferable, and 6-18 are particularly preferable. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit. The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, for example, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a fused tetraphenyl ring, a pyrene ring, Benzopyrene ring,

Ring, bis-terphenylene ring, ethane naphthalene ring, fluoranthene ring, pyrene ring. The aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, for example: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring , Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furo Furan ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrimidine ring, pyrimidine ring, pyrimidine ring, tricyclic ring, quinoline ring, isoquine A quinoline ring, a oxoline ring, a quinoline ring, a phenanthridine ring, a piperidine ring, a quinazoline ring, a quinazolinone ring, and a azulene ring. Among these, from the viewpoint of curability, a benzene ring group and a naphthalene ring group are preferable, and a benzene ring group is more preferable. As the substituent that the aryl group may have, for example, methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amino, epoxy, low A polyethylene glycol group, a phenyl group, and a carboxyl group are preferably a hydroxyl group or an oligoethylene glycol group from the viewpoint of developability.

As the alkenyl group of R ^E, include: linear, branched or cyclic alkenyl group of. The carbon number is preferably 2 or more, more preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. For example, it is preferably 2-22, more preferably 2-20, still more preferably 2-18, still more preferably 2-16, particularly preferably 2-14. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

Examples of alkenyl groups include vinyl groups, propenyl groups, butenyl groups, and cyclohexenyl groups. Among these, from the viewpoint of curability, vinyl group and acrylic group are preferred, and vinyl group is more preferred. Examples of substituents that the alkenyl group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amino, epoxy, oligoethylene glycol, phenyl, The carboxyl group is preferably a hydroxyl group or an oligoethylene glycol group from the viewpoint of developability.

Among these, from the viewpoint of developability, R ^{E is} preferably an alkyl group and an alkenyl group, more preferably an alkyl group, and still more preferably a dicyclopentyl group.

When the acrylic copolymer resin (b2-1) contains the partial structure represented by the general formula (I'), the acrylic copolymer resin (b2-1) contains the part represented by the general formula (I') The content of the structure is not particularly limited, and is preferably 0.5 mol% or more, more preferably 1 mol% or more, further preferably 1.5 mol% or more, particularly preferably 2 mol% or more, and more preferably 90 mol% or less, more preferably 70 mol% or less, still more preferably 50% mol% or less, still more preferably 30 mol% or less, particularly preferably 10 mol% or less. The above upper limit and lower limit can be combined arbitrarily, for example, 0.5 to 90 mol% is preferred, 0.5 to 70 mol% is more preferred, 1 to 50% mol is more preferred, and 1.5 to 30 mol% is more preferred %, particularly preferably 2-10 mol%. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

When the acrylic copolymer resin (b2-1) includes the partial structure represented by the above general formula (I), it is preferable to further include the following general formula (I'' from the viewpoint of heat resistance and film strength. ) Part of the structure.

[化40]

In the above formula (I''), R ^F represents a hydrogen atom or a methyl group, and R ^G represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, and an optionally substituted alkyl group. An oxy group, a thiol group, or an alkyl sulfide group which may have a substituent. t represents an integer of 0-5.

(R ^G ) In the above formula (I''), R ^G represents an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an optionally substituted alkoxy group, sulfur Alcohol group or alkyl sulfide group which may have a substituent. As R ^G of the group include: a linear, branched or cyclic alkyl group of. The carbon number is preferably 1 or more, more preferably 3 or more, still more preferably 5 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 14 or less, Particularly preferably, it is 12 or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1-20, more preferably 1-18, still more preferably 3-16, still more preferably 3-14, and particularly preferably 5-12. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

As the alkyl group, for example, a methyl group, an ethyl group, a cyclohexyl group, a dicyclopentyl group, and a dodecyl group may be mentioned. Among these, from the viewpoint of development adhesiveness, dicyclopentyl and dodecyl are preferred, and dicyclopentyl is more preferred. Examples of substituents that the alkyl group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amino, epoxy, oligoethylene glycol, phenyl, From the viewpoint of developability, the carboxyl group, acryl group, and methacryl group are preferably a hydroxyl group or an oligoethylene glycol group.

As the alkenyl group of R ^G, include: linear, branched or cyclic alkenyl group of. The carbon number is preferably 2 or more, more preferably 22 or less, more preferably 20 or less, still more preferably 18 or less, still more preferably 16 or less, and particularly preferably 14 or less. For example, it is preferably 2-22, more preferably 2-20, still more preferably 2-18, still more preferably 2-16, particularly preferably 2-14. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

Examples of alkenyl groups include vinyl groups, propenyl groups, butenyl groups, and cyclohexenyl groups. Among these, from the viewpoint of curability, vinyl group and acrylic group are preferred, and vinyl group is more preferred. Examples of substituents that the alkenyl group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amino, epoxy, oligoethylene glycol, phenyl, The carboxyl group is preferably a hydroxyl group or an oligoethylene glycol group from the viewpoint of developability.

As the halogen atom in R ^G, include: a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, those in the ink will be allocated in terms of viewpoint, preferably fluorine atom.

As ^{the alkoxy group in R G} , a linear, branched or cyclic alkoxy group may be mentioned. The carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. For example, it is preferably 1-20, more preferably 1-18, still more preferably 1-16, still more preferably 1-14, particularly preferably 1-12. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

As the substituent that the alkoxy group may have, for example, a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, and a phenyl group From the viewpoint of developability, carboxyl group, acryl group, and methacryl group are preferably a hydroxyl group or an oligoethylene glycol group.

The alkyl sulfide group in R ^G may, for example, be a linear, branched or cyclic alkyl sulfide group. The carbon number is preferably 1 or more, more preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, still more preferably 14 or less, and particularly preferably 12 or less. For example, it is preferably 1-20, more preferably 1-18, still more preferably 1-16, still more preferably 1-14, particularly preferably 1-12. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

As an alkyl sulfide group, a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, and a butyl sulfide group are mentioned, for example. Among these, from the viewpoint of developability, a methyl sulfide group and an ethyl sulfide group are preferred. As the substituent that the alkyl group in the alkyl sulfide group may have, for example, a methoxy group, an ethoxy group, a chlorine group, a bromine group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, and an oligoethylene group may be mentioned. From the viewpoint of developability, the glycol group, phenyl group, carboxyl group, acryl group, and methacryl group are preferably a hydroxyl group or an oligoethylene glycol group.

Among these, from the viewpoint of developability, R ^{G is} preferably a hydroxyl group or a carboxyl group, and more preferably a carboxyl group.

(t) In the above formula (I''), t represents an integer of 0-5. From the viewpoint of developability, 0-2 is preferable, 0-1 is more preferable, and 0 is still more preferable.

When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I''), the acrylic copolymer resin (b2-1) is represented by the above general formula (I'') The content of the part of the structure is not particularly limited, and is preferably 1 mol% or more, more preferably 2 mol% or more, further preferably 3 mol% or more, particularly preferably 5 mol% or more, and more It is preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, still more preferably 30 mol% or less, particularly preferably 20 mol% or less, and most preferably 10 mol% Mole% or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1 to 90 mol%, more preferably 1 to 70 mol%, still more preferably 2 to 50 mol%, and even more preferably 2 to 30 mol% %, particularly preferably 3-20 mol%, most preferably 5-10 mol%. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

When the acrylic copolymer resin (b2-1) includes the partial structure represented by the above general formula (I), it is preferable to further include the following general formula (I''') from the viewpoint of developability Represents part of the structure.

[化41]

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

When the acrylic copolymer resin (b2-1) contains the partial structure represented by the above general formula (I'''), the above general formula (I''') contained in the acrylic copolymer resin (b2-1) The content of the partial structure shown is not particularly limited, and is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 30 mol% or more, and more preferably 90 mol% or less , More preferably 80 mol% or less, further preferably 70 mol% or less, and particularly preferably 50 mol% or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5 to 90 mol%, more preferably 5 to 80 mol%, further preferably 10 to 70 mol%, and particularly preferably 30 to 50 mol% . By setting it to be more than the above lower limit value, there is a tendency for residue to decrease. Moreover, by setting it as below the said upper limit, there exists a tendency for development adhesiveness to improve.

The acid value of the acrylic copolymer resin (b2) is not particularly limited, but is preferably 5 mgKOH/g or more, more preferably 10 mgKOH/g or more, still more preferably 20 mgKOH/g or more, and still more preferably 25 mgKOH/g g or more, more preferably 100 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 60 mgKOH/g or less, and still more preferably 40 mgKOH/g or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5-100 mgKOH/g, more preferably 10-80 mgKOH/g, still more preferably 20-60 mgKOH/g, and still more preferably 25-40 mgKOH/g g. By setting it to be more than the above lower limit value, there is a tendency for residue to decrease. Moreover, by setting it as below the said upper limit, there exists a tendency for development adhesiveness to improve.

The weight average molecular weight (Mw) of the acrylic copolymer resin (b2) is not particularly limited, but is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, still more preferably 4,000 or more, and particularly preferably 5,000 or more Also, it is preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, and still more preferably 10,000 or less. Especially preferably, it is below 8000. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 1,000 to 30,000, more preferably 2,000 to 20,000, still more preferably 3,000 to 15,000, still more preferably 4,000 to 10,000, and particularly preferably 5,000 to 8,000. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, there is a tendency for residue to decrease by setting it below the above upper limit.

When (B) the alkali-soluble resin contains the acrylic copolymer resin (b2), the content of the acrylic copolymer resin (b2) contained in the (B) alkali-soluble resin is not particularly limited, but is preferably 5 mass% or more, It is more preferably 10% by mass or more, still more preferably 15% by mass or more, particularly preferably 20% by mass or more, and generally preferably 100% by mass or less, more preferably 80% by mass or less, and still more preferably 50% by mass %the following. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably from 5 to 100% by mass, more preferably from 10 to 100% by mass, still more preferably from 15 to 80% by mass, and particularly preferably from 20 to 50% by mass. By setting it as the above-mentioned lower limit or more, there exists a tendency for developing solubility to become favorable. By setting it below the above upper limit value, the taper angle tends to increase.

In (B) alkali-soluble resin, either epoxy (meth)acrylate resin (b1) and acrylic copolymer resin (b2) may be contained individually, and both may be contained. Furthermore, (B) alkali-soluble resin may contain alkali-soluble resin other than alkali-soluble resin (b).

Regarding the content of (B) alkali-soluble resin in the photosensitive resin composition of the present invention, in the total solid content of the photosensitive resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further It is preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, more preferably 90% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass Below, it is especially preferable that it is 50 mass% or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5 to 90 mass%, more preferably 10 to 90 mass%, still more preferably 20 to 70 mass%, still more preferably 30 to 60 mass%, particularly preferably It is 40-50% by mass. By setting it as the above-mentioned lower limit or more, there exists a tendency for developability to improve. In addition, by setting it below the above upper limit value, there is a tendency to reduce outgassing when the device emits light.

When the photosensitive resin composition of the present invention contains the epoxy (meth)acrylate resin (b1), the content of the epoxy (meth)acrylate resin (b1) is not particularly limited, and is used in the photosensitive resin combination The total solid content of the substance is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more, Furthermore, it is preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5 to 90 mass%, more preferably 10 to 90 mass%, still more preferably 20 to 70 mass%, still more preferably 30 to 60 mass%, particularly preferably It is 40-50% by mass. By setting it as the above-mentioned lower limit or more, there exists a tendency for developability to improve. In addition, by setting it below the above upper limit value, there is a tendency to reduce outgassing when the device emits light.

In addition, when the photosensitive resin composition of the present invention contains the acrylic copolymer resin (b2), the content of the acrylic copolymer resin (b2) is not particularly limited, and is based on the total solid content of the photosensitive resin composition. It is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and more preferably 90% by mass Hereinafter, it is more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 50% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5 to 90 mass%, more preferably 10 to 90 mass%, still more preferably 20 to 70 mass%, still more preferably 30 to 60 mass%, particularly preferably It is 40-50% by mass. By setting it as the above-mentioned lower limit or more, there exists a tendency for developability to improve. In addition, by setting it below the above upper limit value, there is a tendency to reduce outgassing when the device emits light.

In addition, the total content of (B) alkali-soluble resin and (C) photopolymerizable compound in the total solid content of the photosensitive resin composition is preferably 5% by mass or more, more preferably 10% by mass or more, and more It is preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 70% by mass or more, still more preferably 80% by mass or more, most preferably 90% by mass or more, and more preferably 99% by mass or less , More preferably 97% by mass or less, and still more preferably 95% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5 to 99 mass%, more preferably 10 to 99 mass%, still more preferably 30 to 99 mass%, still more preferably 50 to 97 mass%, especially It is preferably 70 to 97% by mass, particularly preferably 80 to 95% by mass, and most preferably 90 to 95% by mass. By setting it as the above lower limit value or more, there exists a tendency for hardenability to improve. In addition, by setting it below the above upper limit value, outgassing when the device emits light tends to decrease.

The blending ratio of (B) alkali-soluble resin to (C) photopolymerizable compound in the photosensitive resin composition is preferably 50 parts by mass or more with respect to 100 parts by mass of (C) photopolymerizable compound, more preferably 60 parts by mass or more, more preferably 70 parts by mass or more, particularly preferably 80 parts by mass or more, more preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 200 parts by mass or less, Particularly preferably, it is 120 parts by mass or less. All upper and lower limits can be combined arbitrarily, for example, preferably 50-400 parts by mass, more preferably 60-300 parts by mass, still more preferably 70-200 parts by mass, and particularly preferably 80-120 parts by mass. By setting it as the above-mentioned lower limit or more, there exists a tendency for development adhesiveness to improve. In addition, by setting it below the above upper limit value, there is a tendency for the curability to improve.

[1-1-3] (C) Component: Photopolymerizable compound The photosensitive resin composition of this invention contains (C) a photopolymerizable compound. It is thought that by containing (C) a photopolymerizable compound, it will become high sensitivity. As the photopolymerizable compound used here, it means a compound having one or more ethylenically unsaturated bonds (ethylenic double bond) in the molecule, and can expand the exposure area and the exposure area in terms of polymerizability, crosslinking properties, and the accompanying In terms of the difference in the solubility of the developer in the non-exposed part, etc., a compound having two or more ethylenic unsaturated bonds in the molecule is preferred. In addition, the unsaturated bond is more preferably derived from a (meth)acryloyloxy group, that is, a (meth)acrylate compound.

In the photosensitive resin composition of the present invention, it is particularly desirable to use a multifunctional ethylenic monomer having two or more ethylenic unsaturated bonds in one molecule. The number of ethylenically unsaturated groups possessed by the multifunctional ethylenic monomer is not particularly limited, and is preferably 2 or more, more preferably 3 or more, more preferably 4 or more, particularly preferably 5 or more, and , Preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 7 or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 2-15, more preferably 3-10, still more preferably 4-8, and particularly preferably 5-7. By setting it as the above-mentioned lower limit or more, polymerizability will improve, and there exists a tendency to become high sensitivity. By setting it as the above upper limit or less, there exists a tendency for developability to become more favorable. As the photopolymerizable compound, for example, an aliphatic polyhydroxy compound and an unsaturated carboxylic acid ester; an aromatic polyhydroxy compound and an unsaturated carboxylic acid ester; an aliphatic polyhydroxy compound, an aromatic polyhydroxy compound It is an ester obtained by the esterification reaction of a polyvalent hydroxyl compound with an unsaturated carboxylic acid and a polyvalent carboxylic acid.

As esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate may be mentioned. Acrylates of aliphatic polyhydroxy compounds such as acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc.; Methacrylate obtained by substituting methacrylate for the acrylate of these compounds; Iconate obtained by substituting the acrylate of these compounds with itconate; Substituting the acrylate of these compounds with Crotonic acid ester derived from crotonate; maleic acid ester derived from replacing the acrylate of these compounds with maleic acid ester.

As esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, for example, hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol diacrylate, Acrylate and methacrylate of aromatic polyhydroxy compounds such as methacrylate and pyrogallol triacrylate. The ester obtained by the esterification reaction of a polyhydric hydroxy compound such as aliphatic polyhydroxy compound and aromatic polyhydric compound with unsaturated carboxylic acid and polycarboxylic acid is not necessarily a single substance. For example, acrylic acid, ortho Condensate of phthalic acid and ethylene glycol; Condensate of acrylic acid, maleic acid, and diethylene glycol; Condensate of methacrylic acid, terephthalic acid and pentaerythritol; Acrylic acid, adipic acid, butane Condensate of glycol and glycerin.

As examples of the photopolymerizable compound used in the photosensitive resin composition of the present invention other than the above, for example, it is useful to combine polyols and hydroxyl-containing (meth)acrylates with polyisocyanate compounds and hydroxyl-containing (methyl) ) Urethane (meth)acrylates obtained by reacting acrylate or polyisocyanate compounds; among the addition reactants of polyepoxy compounds and hydroxyl-containing (meth)acrylate or (meth)acrylic acid Class epoxy acrylates; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl-containing compounds such as divinyl phthalate. As urethane (meth)acrylates, for example, 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 Shinnakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (Kyoeisha Chemical Company manufacture), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.).

Among them, from the viewpoint of suitable taper angle and sensitivity, as (C) the photopolymerizable compound, it is preferable to use ester-based (meth)acrylates or urethane (meth)acrylates It is more preferable to use dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-tri(meth)acryloyloxymethyl phthalate, and pentaerythritol tetra(meth)acrylate. Base) acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate dibasic anhydride adduct, pentaerythritol tri(meth)acrylate dibasic anhydride adduct. These may be used individually by 1 type, and may use 2 or more types together.

In the photosensitive resin composition of the present invention, the molecular weight of the (C) photopolymerizable compound is not particularly limited, but from the viewpoints of sensitivity, ink repellency, and taper angle, it is preferably 100 or more, more preferably 150 or more , More preferably 200 or more, still more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 100-1000, more preferably 150-1000, still more preferably 200-1000, still more preferably 300-700, particularly preferably 400-700, most preferably 500～700. (C) The carbon number of the photopolymerizable compound is not particularly limited. From the viewpoints of sensitivity, ink repellency, and taper angle, it is preferably 7 or more, more preferably 10 or more, still more preferably 15 or more, and still more It is preferably 20 or more, particularly preferably 25 or more, more preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, and particularly preferably 30 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 7-50 are preferable, 10-50 are more preferable, 15-40 are still more preferable, 20-35 are still more preferable, and 25-30 are especially preferable. From the viewpoints of sensitivity, ink repellency, and taper angle, ester-based (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred Among them, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, etc. are more preferred Series of (meth)acrylates, 2,2,2-tris(meth)acryloxymethyl ethyl phthalate, dipentaerythritol penta(meth)acrylate dibasic acid anhydride adducts, etc. An adduct obtained by adding an acid anhydride to a trifunctional or higher ester-based (meth)acrylate.

Regarding the content of the (C) photopolymerizable compound in the photosensitive resin composition of the present invention, in the total solid content of the photosensitive resin composition, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further It is preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, more preferably 80% by mass or less, more preferably 70% by mass or less, and still more preferably 60% by mass Hereinafter, it is more preferably 55% by mass or less, and particularly preferably 50% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, still more preferably 30 to 55% by mass, particularly preferably It is 40-50% by mass. By setting it as the above-mentioned lower limit or more, there exists a tendency to become a suitable internal hardening property. By setting it as the said upper limit or less, developability tends to become favorable.

[1-1-4] (D) Component: Liquid repellent The (D) liquid repellent in the photosensitive resin composition of the present invention contains an acrylic resin (D1) containing a repeating unit represented by the following general formula (II) and a fluorine atom.

[化42]

(In formula (II), R ¹¹ each independently represents a hydrogen atom or a methyl group, and R ¹² represents an optionally substituted alkyl group having 2 to 6 carbon atoms, which may be substituted by -O-, -C(=O)-, Any one of -S-, -NH- is interrupted; * indicates the bonding part)

The carbon number of the alkyl group of R ¹² is usually 2 or more, preferably 4 or more carbon atoms, and usually 6 or less, preferably 5 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 2-6 are preferable, and 4-5 are more preferable. By setting it as the above lower limit or more, synthesis becomes easy. Moreover, by setting it to the above upper limit or less, the degree of freedom of the ethylenic unsaturated bond becomes high, and there exists a tendency for hardenability and liquid repellency to improve. In addition, ^{the alkyl group of R 12} may be interrupted by any one or more of -O-, -C(=O)-, -S-, and -NH-; as another form, it may be interrupted by -O-, -C(= O)- or -NH- interruption, as yet another form, can be interrupted by -OC(=O)-NH-.

When R ¹² has a substituent, examples of the substituent include a hydroxyl group and an alkoxy group having 1 to 3 carbon atoms. It is preferably unsubstituted or substituted with a hydroxyl group, more preferably unsubstituted.

As R ¹² , in terms of liquid repellency, -(C ₂ H ₄ ) ₂ -NHCOO-(C ₂ H ₄ ) ₂ -, -(CH) ₂ -CHOH-(CH ₂ )- The group represented is more preferably the group represented by -(C ₂ H ₄ ) ₂ -NHCOO-(C ₂ H ₄ ) ₂ -.

Since it is possible to impart ink repellency (liquid repellency) to the surface of the barrier wall obtained by containing acrylic resin (D1), it is believed that when the organic electroluminescent element is produced by inkjet, the ink can be prevented from adhering to the barrier. The wall, in addition, can prevent the ink injected into the adjacent areas from mixing with each other.

It is believed that by using a liquid repellent having an ethylenically unsaturated group as the general formula (II), the crosslinking reaction on the surface of the formed coating film can be accelerated when the formed coating film is exposed, and the liquid repellent is not easy to develop It flows out during processing, and as a result, the obtained barrier wall can exhibit high ink repellency.

Since it is a resin containing fluorine atoms, the resin containing fluorine atoms is aligned on the surface of the barrier wall, and there is a tendency to play a role in preventing blooming or color mixing of the ink. In more detail, the radicals having fluorine atoms repel the ink and tend to play a role in preventing the blooming or color mixing of the ink caused by the ink crossing the barrier wall and entering the adjacent area.

The acrylic resin (D1) preferably has either or both of a fluoroalkyl group and a fluoroalkylene group, and more preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. By having either or both of the fluoroalkyl group and the fluoroalkylene group, or either or both of the perfluoroalkyl group and the perfluoroalkylene ether chain, there is a tendency that the resin containing a fluorine atom is more It is easy to align on the surface of the barrier wall, showing higher ink repellency, and further preventing ink blooming or color mixing.

Examples of perfluoroalkyl groups include perfluorobutyl, perfluorohexyl, and perfluorooctyl. As the perfluoroalkylene ether chain, for example, -CF ₂ -O-, -(CF ₂ ) ₂ -O-, -(CF ₂ ) ₃ -O-, -CF ₂ -C(CF ₃ )O -, -C(CF ₃ )-CF ₂ -O- and divalent groups having these repeating units.

The acrylic resin (D1) may have structural units other than the repeating unit represented by the general formula (II) or the structural unit containing a fluorine atom. For example, a structural unit containing an epoxy group, a structural unit containing a carboxyl group, and a structural unit having an alkylene oxide chain can be exemplified.

As a commercial product of acrylic resin (D1), fluorine-containing products commercially available under the trade names of "MEGAFAC (registered trademark; the same below) RS-72-K" and "MEGAFAC RS-90" manufactured by DIC can be used Organic compounds.

The content of fluorine atoms in the acrylic resin (D1) is not particularly limited. In the acrylic resin (D1), it is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more, Furthermore, it is more preferable that it is 25 mass% or more. Furthermore, it is preferably 50% by mass or less, and more preferably 35% by mass or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 1-50% by mass, more preferably 10-50% by mass, still more preferably 20-35% by mass, and still more preferably 25-35% by mass. By setting it as above the lower limit value, it is easy to ensure a high contact angle, and by setting it as below the upper limit value, there is a tendency that outflow to the pixel portion can be suppressed.

The molecular weight of the acrylic resin (D1) is not particularly limited, and it may be a low-molecular-weight compound or a high-molecular-weight compound. A high-molecular-weight body is preferred because it can suppress fluidity caused by post-baking and can suppress outflow from the barrier wall. From this point of view, the weight average molecular weight of the acrylic resin (D1) is preferably 100 or more , More preferably 500 or more, more preferably 100,000 or less, more preferably 10,000 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 100 to 100,000 are preferred, and 500 to 10,000 are more preferred.

Acrylic resin (D1) may be used individually by 1 type, and may use 2 or more types together.

In the present invention, a liquid repellent other than the acrylic resin (D1) may be used in combination as the (D) liquid repellent.

The content of the (D) liquid repellent in the photosensitive resin composition of the present invention is not particularly limited. In the total solid content of the photosensitive resin composition, it is preferably 0.01% by mass or more, more preferably 0.05% by mass Above, it is more preferably 0.1% by mass or more, particularly preferably 0.2% by mass or more, more preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, 0.01 to 5 mass% is preferred, 0.05 to 5 mass% is more preferred, 0.1 to 3 mass% is still more preferred, and 0.2 to 1 mass% is particularly preferred. By setting it to be higher than the above lower limit value, there is a tendency for the ink repellency to improve. In addition, by setting it to the upper limit or less, when the ink is applied to the pixel portion after the barrier ribs are formed, there is a tendency that a uniform coating film is easily obtained.

The content of the acrylic resin (D1) in the photosensitive resin composition of the present invention is not particularly limited, but in the total solid content of the photosensitive resin composition, it is preferably 0.01% by mass or more, more preferably 0.1% by mass Above, it is more preferably 0.2% by mass or more, more preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less. The above upper limit and lower limit can be arbitrarily combined, for example, 0.01 to 5 mass% is preferred, 0.1 to 3 mass% is more preferred, and 0.2 to 1 mass% is still more preferred. By setting it to be higher than the above lower limit value, there is a tendency for the ink repellency to improve. In addition, by setting it to the upper limit or less, when the ink is applied to the pixel portion after the barrier ribs are formed, there is a tendency that a uniform coating film is easily obtained.

[1-1-5] (E) Chain transfer agent The photosensitive resin composition of this invention may contain (E) a chain transfer agent. By including a chain transfer agent, the deactivation of free radicals caused by oxygen suppression near the surface can be improved, the surface hardenability can be improved, and the taper angle tends to increase. In addition, by improving the surface hardenability, the outflow of the liquid repellent can be suppressed, and the liquid repellent can be easily fixed near the surface of the barrier wall, and the contact angle tends to increase. As the chain transfer agent, for example, a mercapto group-containing compound or carbon tetrachloride can be exemplified, and a mercapto group-containing compound is more preferable because the chain transfer effect tends to be higher. The mercapto group-containing compound has a small S-H bonding energy, which tends to cause bond scission and chain transfer reaction. Therefore, there is a tendency to improve the surface hardenability.

Among chain transfer agents, from the viewpoints of taper angle and surface hardening properties, mercapto group-containing compounds having aromatic rings and aliphatic mercapto group-containing compounds are preferred.

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

[化43]

In formula (E-1), Z represents -O-, -S- or -NH-, and R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ each independently represent a hydrogen atom or a monovalent substituent. Among them, from the viewpoint of the taper angle, Z is preferably -S- or -NH-, and more preferably -NH-. Furthermore, from the viewpoint of the cone angle, R ⁶¹ , R ⁶² , R ⁶³ and R ^{64 are} preferably each independently a hydrogen atom, an alkyl group having 1 to 4 carbons, or an alkoxy group having 1 to 4 carbons, More preferably, it is a hydrogen atom.

As the mercapto group-containing compound having an aromatic ring, for example, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene, and other mercapto group-containing compounds having an aromatic ring, from the viewpoint of cone angle, 2- Mercaptobenzothiazole, 2-mercaptobenzimidazole.

As the aliphatic mercapto group-containing compound, from the viewpoint of surface hardening properties, hexamethylene dithiol, decane dithiol, or a compound represented by the following general formula (E-2) can be preferably used.

[化44]

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

In the above general formula (E-2), m is preferably 1 or 2 from the viewpoint of ease of synthesis. In addition, from the viewpoint of surface hardenability, n is preferably 3 or 4. The alkyl group of R ⁷¹ and R ⁷² preferably has 1 to 3 carbon atoms from the viewpoint of surface hardenability. From the viewpoint of surface hardenability, it is preferable ^{that at least one of R 71} and R ⁷² , for example, R ⁷² is a hydrogen atom. In this case, R ^{71 is} preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. .

When n is 2, from the viewpoint of surface hardenability, X is preferably an ether bond and a C1-C6 alkylene group which may have a branch. Among them, from the viewpoint of surface hardenability and ease of synthesis, the alkylene group having 1 to 6 carbon atoms is more preferred, and the alkylene group having 4 carbon atoms is more preferred.

When n is 3, X is preferably a structure represented by the following general formula (E-2-1) or (E-2-2) from the viewpoint of surface hardenability and ease of synthesis.

[化45]

In the formula (E-2-1), R ⁷³ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxymethyl group. Among R ⁷³ , an ethyl group is preferred from the viewpoint of a taper angle.

[化46]

In the formula (E-2-2), R ⁷⁴ represents an alkylene group having 1 to 4 carbon atoms. Among R ⁷⁴ , from the viewpoint of the taper angle, an ethylene group is preferred.

When n is 4, X is preferably a structure represented by the following general formula (E-2-3).

[化47]

As the aliphatic mercapto group-containing compound, for example, butanediol bis(3-mercaptopropionate), butanediol bismercaptoacetate, ethylene glycol bis(3-mercaptopropionate), ethyl Glycol dimercaptoacetate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane trimercaptoacetate, trihydroxyethyl trithiopropionate, pentaerythritol tetra(3-mercapto) Propionate), pentaerythritol tris(3-mercaptopropionate), butanediol bis(3-mercaptobutyrate), ethylene glycol bis(3-mercaptobutyrate), trimethylolpropane tris(3 -Mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1, 3,5-Three 𠯤-2,4,6(1H,3H,5H)-trione.

Among these, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tris(3-mercaptopropionate), trimethylolpropane tris(3-mercaptopropionate) are preferred. (3-mercaptobutyrate), pentaerythritol tetra(3-mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)- 1,3,5-tris-2,4,6(1H,3H,5H)-trione, more preferably pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyrate).

These may be used individually by 1 type, and may use 2 or more types together.

Among them, from the viewpoint of improving ink repellency, it is preferable to select at least one member selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoazole In combination with a photopolymerization initiator, it is used as a photopolymerization initiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may also be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination. As yet another aspect, from the viewpoint of surface hardening, it is preferable to use 1 or 2 selected from the group consisting of pentaerythritol tetra(3-mercaptopropionate) and pentaerythritol tetra(3-mercaptobutyrate) Above.

When the photosensitive resin composition of the present invention contains (E) a chain transfer agent, its content is not particularly limited. In the total solid content of the photosensitive resin composition, it is preferably 0.01% by mass or more, more preferably 0.025% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, more preferably 5% by mass or less, more preferably 4% by mass or less, More preferably, it is 3% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, 0.01 to 5 mass% is preferred, 0.025 to 5 mass% is more preferred, 0.05 to 4 mass% is still more preferred, and 0.1 to 4 mass% is even more preferred. It is 1 to 3% by mass. By setting it to more than the above-mentioned lower limit value, there exists a tendency for the taper angle to become high, surface hardening property becomes high, and ink repellency becomes high. In addition, by setting it below the above upper limit value, there is a tendency to easily form a desired pattern.

As the content when a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used together as a chain transfer agent, relative to 100 parts by mass of a mercapto group-containing compound having an aromatic ring, the aliphatic mercapto group-containing compound is more It is preferably 10 parts by mass or more, more preferably 50 parts by mass or more, still more preferably 80 parts by mass or more, more preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and still more preferably 200 parts by mass or less , Particularly preferably 150 parts by mass or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 10 to 400 parts by mass, more preferably 10 to 300 parts by mass, still more preferably 50 to 200 parts by mass, and particularly preferably 80 to 150 parts by mass. By setting it to more than the above-mentioned lower limit value, there exists a tendency for ink repellency to become high. In addition, by setting it below the above upper limit value, the sensitivity tends to increase.

As a compounding ratio of the (E) chain transfer agent to the (D) photopolymerization initiator in the photosensitive resin composition, it is preferably 10 parts by mass or more with respect to 100 parts by mass of the (D) photopolymerization initiator, More preferably 25 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, more preferably 500 parts by mass or less, more preferably 400 parts by mass or less, and still more preferably 300 parts by mass Hereinafter, it is more preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, preferably 10 to 500 parts by mass, more preferably 10 to 400 parts by mass, still more preferably 25 to 300 parts by mass, still more preferably 50 to 200 parts by mass, especially It is 80 to 150 parts by mass. By setting it to more than the above-mentioned lower limit value, there exists a tendency for the taper angle to become high, surface hardening property becomes high, and ink repellency becomes high. In addition, by setting it below the above upper limit value, there is a tendency to easily form a desired pattern.

[1-1-6]Ultraviolet absorber The photosensitive resin composition of this invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the following purpose: the ultraviolet absorber absorbs the specific wavelength of the light source used for exposure, thereby controlling the light hardening distribution. By including the ultraviolet absorber, there is a tendency that effects such as improvement of the cone angle shape after development or reduction of residue remaining in the non-exposed part after development can be obtained. As the ultraviolet absorber, from the viewpoint of suppressing light absorption by the photopolymerization initiator, for example, it can be used for a compound having a maximum absorption between 250 nm and 400 nm. As the ultraviolet absorber, for example, benzotriazole-based compounds, tris-based compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, two Naphthalene compounds, phenanthroline compounds, dyes. These ultraviolet absorbers may be used individually by 1 type, and may use 2 or more types together.

Among them, from the viewpoint of increasing the cone angle, benzotriazole compounds and/or hydroxyphenyltriazole compounds are preferred, and benzotriazole compounds are particularly preferred.

Among the benzotriazole-based compounds, the benzotriazole compound described in the following general formula (Z1) is preferred in terms of the cone shape.

[化48]

In the above formula (Z1), R ^1e and R ^2e each independently represent a hydrogen atom, an optionally substituted alkyl group, a group represented by the following general formula (Z2), or a group represented by the following general formula (Z3) base. R ^3e represents a hydrogen atom or a halogen atom.

[化49]

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

[化50]

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

(R ^1e and R ^2e ) In the above formula (Z1), R ^1e and R ^2e each independently represent a hydrogen atom, an optionally substituted alkyl group, a group represented by the general formula (Z2), or a general formula (Z3 ) Represents the base. As the alkyl group, a linear, branched or cyclic alkyl group may be mentioned. The carbon number is preferably 1 or more, more preferably 2 or more, still more preferably 4 or more, more preferably 10 or less, more preferably 6 or less, and still more preferably 4 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-10 are preferable, 2-6 are more preferable, and 4-6 are still more preferable.

As the alkyl group, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, and a tertiary butyl group may be mentioned. Among them, the tertiary butyl group is preferred. Examples of substituents that the alkyl group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amino, epoxy, oligoethylene glycol, phenyl, Carboxyl, acryloyl, and methacryloyl.

(R ^3e ) In the above formula (Z1), R ^3e represents a hydrogen atom or a halogen atom. The halogen atom may, for example, be a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Among them, from the viewpoint of synthesis, R ^3e is preferably a hydrogen atom.

(R ^4e ) In the above formula (Z2), R ^4e represents an alkylene group which may have a substituent. As the alkylene group, a linear, branched or cyclic alkylene group may be mentioned. The carbon number is usually 1 or more, preferably 2 or more, more preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-6 are preferable, 1-4 are more preferable, and 2-3 are still more preferable.

As the alkylene group, for example, a methylene group, an ethylene group, a propylene group, a propylene group, and a butylene group may be mentioned. Among them, ethylene is preferred. As the substituent that the alkylene group may have, for example, a methoxy group, an ethoxy group, a chlorine group, a bromine group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, and a phenyl group , Carboxyl, acryloyl, methacryloyl.

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

(R ^5e ) In the above formula (Z2), it represents an alkyl group which may have a substituent. As the alkyl group, a linear, branched or cyclic alkyl group may be mentioned. The carbon number is preferably 4 or more, more preferably 5 or more, still more preferably 7 or more, more preferably 15 or less, more preferably 10 or less, and still more preferably 9 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 5-15 are preferable, 5-10 are more preferable, and 7-9 are still more preferable.

Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and nonyl. Examples of substituents that the alkyl group may have include: methoxy, ethoxy, chloro, bromo, fluoro, hydroxyl, amino, epoxy, oligoethylene glycol, phenyl, Carboxyl, acryloyl, and methacryloyl. Among these, from the viewpoint of the cone shape, R ^5e is preferably heptyl, octyl, or nonyl.

(R ^6e ) In the above formula (Z3), R ^6e represents an alkylene group which may have a substituent. As the alkylene group, a linear, branched or cyclic alkylene group may be mentioned. The carbon number is usually 1 or more, preferably 2 or more, more preferably 6 or less, more preferably 4 or less, and still more preferably 3 or less. The above upper limit and lower limit can be combined arbitrarily, for example, 1-6 are preferable, 1-4 are more preferable, and 2-3 are still more preferable.

As the alkylene group, for example, a methylene group, an ethylene group, a propylene group, a propylene group, and a butylene group may be mentioned. Among them, ethylene is preferred. As the substituent that the alkylene group may have, for example, a methoxy group, an ethoxy group, a chlorine group, a bromine group, a fluoro group, a hydroxyl group, an amino group, an epoxy group, an oligoethylene glycol group, and a phenyl group , Carboxyl, acryloyl, methacryloyl.

Among them, from the viewpoint of the cone shape, it is preferable that R ^1e is a tertiary butyl group, and R ^2e is a group represented by the above formula (Z2) (wherein, R ^4e is an ethylene group, and R ^5e is a carbon The number 7-9 alkyl), R ^3e is a hydrogen atom compound, or R ^1e is a hydrogen atom, R ^2e is the group represented by the above formula (Z3) (wherein, R ^6e is an ethylene group, and R ^7e is A compound in which R ^3e is a hydrogen atom, more preferably R ^1e is a tertiary butyl group, and R ^2e is a group represented by the above formula (Z2) (wherein, R ^4e is an ethylene group, and R ^5e is a carbon A compound having an alkyl group of 7 to 9) and R ^3e is a hydrogen atom.

As the benzotriazole-based compound, for example, 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H- Benzotriazole, 3[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl] octyl propionate and 3-[3-third Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionic acid 2-ethylhexyl mixture, 2-[2-hydroxy-3,5- Bis(α,α-dimethylbenzyl)phenyl)-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzo Triazole, 2-(3,5-di-tertiary pentyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5'-tertiary octylphenyl)benzotriazole , 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionic acid heptyl ester, 3-[3-tert-butyl-5-( 2H-benzotriazol-2-yl)-4-hydroxyphenyl]octyl propionate, 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyl Phenyl) nonyl propionate, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzo Triazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol. Among them, 3-[3-tertiarybutyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl]propane is preferred from the viewpoint of taper angle and exposure sensitivity. Heptyl acrylate, 3-[3-tert-butyl-5-(2H-benzotriazol-2-yl)-4-hydroxyphenyl] octyl propionate, 3-[3-tert-butyl-5 -(2H-Benzotriazol-2-yl)-4-hydroxyphenyl]nonyl propionate, and mixtures thereof.

As commercially available benzotriazole compounds, for example, SUMISORB (registered trademark, the same hereinafter) 200, SUMISORB250, SUMISORB300, SUMISORB340, SUMISORB350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 ( Seonghoku Chemical Industry Co., Ltd.), TINUVIN (registered trademark, the same below) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN326, TINUVIN900, TINUVIN928, TINUVIN1130 (manufactured by BASF Corporation), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Everlight Chemical Industry Co., Ltd.), TOMISORB (registered trademark, the same below) 100, TOMISORB 600 (manufactured by API Corporation), SEESORB (registered trademark, the same below) 701 , SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Shipro Kasei), RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

Examples of the tris-based compound include: 2-[4,6-bis(2,4-xylenyl)-1,3,5-tris-2-yl]-5-octyloxyphenol , 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-tris-2-yl]-5-[3-(dodecyloxy)-2- (Hydroxypropoxy)phenol, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triglyceric acid The reaction product of (2-ethylhexyl) ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3, 5-Three 𠯤. Among these, from the viewpoint of taper angle and exposure sensitivity, a hydroxyphenyl triphenyl compound is preferred. As a commercially available tri-series compound, for example, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (manufactured by BASF Corporation), etc. may be mentioned.

As other ultraviolet absorbers, for example, SUMISORB130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Everlight Chemical Industry Co., Ltd.), TOMISORB 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, Benzophenone compounds such as SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Shipro Kasei); SUMISORB400 (manufactured by Sumitomo Chemical Co., Ltd.), benzoic acid ester compounds such as phenyl salicylate; 2-ethylhexyl cinnamate , 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, isoamyl methoxycinnamate and other cinnamic acid derivatives; α-naphthol, β-naphthol, α-naphthalene Phenol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene Hydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and other naphthalene derivatives; anthracene, 9 , 10-Dihydroxyanthracene and other anthracene and its derivatives; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes , Three 𠯤 series dyes, p-aminobenzoic acid series dyes and other dyes. Among them, 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.

When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the photosensitive resin composition is preferably 0.01% by mass in the total solid content of the photosensitive resin composition Above, more preferably 0.05% by mass or more, still more preferably 0.1% by mass or more, still more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, more preferably 15% by mass or less, more preferably 10 Mass% or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The above upper limit and lower limit can be combined arbitrarily, for example, 0.01 to 15% by mass is preferable, 0.05 to 15% by mass is more preferable, 0.1 to 10% by mass is still more preferable, and 0.5 to 5% by mass is still more preferable, particularly It is 1 to 3% by mass. By setting it to be equal to or higher than the above lower limit value, the taper angle tends to increase. Moreover, by setting it as below the said upper limit, there exists a tendency for high sensitivity.

When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the blending ratio with respect to (D) photopolymerization initiator is preferably 1 with respect to 100 parts by mass of (D) photopolymerization initiator Parts by mass or more, more preferably 10 parts by mass or more, still more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, and more preferably 500 parts by mass or less, more preferably It is 300 parts by mass or less, more preferably 200 parts by mass or less, and particularly preferably 150 parts by mass or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 10 to 500 parts by mass, more preferably 30 to 300 parts by mass, still more preferably 50 to 200 parts by mass, and particularly preferably 80 to 150 parts by mass. By setting it to be equal to or higher than the above lower limit value, the taper angle tends to increase. Moreover, by setting it as below the said upper limit, there exists a tendency for high sensitivity.

[1-1-7] Polymerization inhibitor The photosensitive resin composition of this invention may contain a polymerization inhibitor. Since radical polymerization can be suppressed by containing a polymerization inhibitor, it is considered that the taper angle of the obtained barrier wall can be increased. As the polymerization inhibitor, for example, hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-methylphenol (BHT). Among these, from the viewpoint of polymerization inhibitory ability, methylhydroquinone and methoxyphenol are preferred, and methylhydroquinone is more preferred.

A polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together. Generally, in the production of (B) alkali-soluble resin, there is a case where the resin contains a polymerization inhibitor. It can be used as the polymerization inhibitor contained in the photosensitive resin composition of the present invention, and it can also be used in the production of a photosensitive resin composition. In addition to the polymerization inhibitor contained in the resin, a polymerization inhibitor that is the same or different from it is added.

When the photosensitive resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor in the photosensitive resin composition is preferably 0.0005 mass% in the total solid content of the photosensitive resin composition Above, it is more preferably 0.001% by mass or more, still more preferably 0.01% by mass or more, more preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and still more preferably 0.1% by mass or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 0.0005 to 0.3% by mass, more preferably 0.001 to 0.2% by mass, and still more preferably 0.01 to 0.1% by mass. By setting it as the above lower limit or more, there is a tendency that the taper angle can be increased. In addition, there is a tendency that high sensitivity can be maintained by setting it below the above upper limit value.

[1-1-8] Amino compound The photosensitive resin composition of the present invention may also contain an amino compound to promote thermal curing. When the photosensitive resin composition of the present invention contains an amine-based compound, the content of the amine-based compound in the photosensitive resin composition is preferably 40% by mass in the total solid content of the photosensitive resin composition Below, it is more preferably 30% by mass or less. Moreover, it is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 0.5 to 40% by mass, and more preferably 1 to 30% by mass. By setting it as the upper limit or less mentioned above, there exists a tendency which can maintain storage stability. By setting it as the above-mentioned lower limit or more, there exists a tendency which can ensure sufficient thermosetting property.

As the amino compound, for example, an amino compound having at least two methylol groups or an alkoxymethyl group obtained by condensation-modifying a methylol group with an alcohol having 1 to 8 carbon atoms as a functional group can be mentioned. Specifically, for example, a melamine resin obtained by polycondensing melamine and formaldehyde; a benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde; and a sweetened resin obtained by polycondensing glycoluril and formaldehyde. Urea resin; urea resin obtained by polycondensation of urea and formaldehyde; resin obtained by copolycondensation of two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde; the methylol of the above resin Modified resin obtained by alcohol condensation modification. These may be used individually by 1 type, and may use 2 or more types together. As the amine-based compound, among them, melamine resin and its modified resins are preferred, modified resins with a methylol modification ratio of 70% or more are more preferred, and modified resins with 80% or more of them are particularly preferred.

Regarding the melamine resin and its modified resin as an amino compound, for example, CYMEL (registered trademark, the same below) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327 manufactured by Cytec Corporation , 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and NIKALAC manufactured by SANWA CHEMICAL (registered trademark, the same below) MW-390, MW-100LM , MX-750LM, MW-30M, MX-45, MX-302. As the benzoguanamine resin and its modified resin, for example, CYMEL 1123, 1125, and 1128 manufactured by Cytec Corporation can be mentioned. As the glycoluril resin and its modified resin, for example, CYMEL 1170, 1171, 1174, 1172 manufactured by Cytec Corporation, and NIKALAC MX-270 manufactured by SANWA CHEMICAL Corporation may be mentioned. As the urea resin and its modified resin, for example, UFR (registered trademark, the same below) 65 and 300 manufactured by Cytec Corporation, and NIKALAC MX-290 manufactured by SANWA CHEMICAL Corporation may be mentioned.

[1-1-9] Coloring agent The photosensitive resin composition of the present invention may contain a coloring agent to color the barrier ribs. As the coloring agent, known coloring agents such as pigments and dyes can be used. When a pigment is used, a well-known dispersant or dispersion aid may be used in combination so that the pigment can stably exist in the photosensitive resin composition without aggregation. In particular, by coloring the ink repellent barrier wall into black, it has the effect of obtaining a clear pixel display. As a black coloring agent, in addition to black dyes, black pigments, carbon black, titanium black, etc., it is also effective to maintain low conductivity by mixing organic pigments to color black. The content of the colorant is preferably 60% by mass or less, and more preferably 40% by mass or less in the total solid content of the photosensitive resin composition from the viewpoint of plate-making properties and color characteristics. As another aspect, if the photosensitive resin composition contains a coloring agent, there is a tendency that the curability of the barrier ribs is reduced, the liquid repellency of the barrier ribs is reduced, and outgassing is likely to occur. Therefore, it is desirable that the content of the coloring agent in the photosensitive resin composition is relatively low. For example, relative to the total solid content of the photosensitive resin composition, it is preferably 20% by mass or less, more preferably 10% by mass or less, especially It is 5% by mass or less, preferably 0% by mass.

[1-1-10] Coatability improver, development improver The photosensitive resin composition of the present invention may also contain a coatability improver or a development modifier to improve coatability or development solubility. As the coatability improver or the development improver, for example, a well-known surfactant can be used. Surfactants can be used for the purpose of improving the coatability of the photosensitive resin composition as a coating liquid and the developability of the coating film. Among them, a fluorine-based surfactant or a silicone-based surfactant is preferred. . Especially in terms of having the function of removing the residue of the photosensitive resin composition from the unexposed part during development and having the function of expressing wettability, a silicone-based surfactant is preferred, and a polyether is more preferred. Modified silicone surfactants.

The fluorine-based surfactant is preferably a compound having a fluoroalkyl group or a fluoroalkylene group in at least any one of the terminal, main chain, and side chain. Specifically, examples include: 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, Octaethylene glycol bis(1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol bis(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol bis( 1,1,2,2-tetrafluorobutyl) ether, hexapropylene glycol bis(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecyl sulfonate, 1, 1,2,2,8,8,9,9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, etc. Examples of these commercially available products include: "BM-1000" and "BM-1100" manufactured by BM Chemie, "MEGAFACF 470", "MEGAFACF 475", "MEGAFACF 554", and "MEGAFACF 470" manufactured by DIC. MEGAFACF 559", "FC430" manufactured by 3M Japan, and "DFX-18" manufactured by NEOS.

As the silicone-based surfactant, for example, "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", "SH8400" manufactured by Dow Corning Toray ", "BYK (registered trademark, the same below) 323" and "BYK330" manufactured by BYK-Chemie. Other surfactants other than fluorine-based surfactants and silicone-based surfactants can also be included as surfactants. As other surfactants, for example, nonionic, anionic, cationic, and amphoteric interfaces can be mentioned. Active agent.

As nonionic surfactants, for example, polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, Polyoxyethylene fatty acid esters, glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters Class, sorbitol fatty acid esters, polyoxyethylene sorbitol fatty acid esters. Examples of these commercially available products include polyoxyethylene-based surfactants such as "EMULGEN (registered trademark; the same hereinafter) 104P" and "EMULGEN A60" manufactured by Kao Corporation.

Examples of anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkyl naphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, and alkyl sulfates. Type, alkyl sulfate ester salts, higher alcohol sulfate ester salts, aliphatic alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphates Salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special polymer surfactants. Among them, a special polymer surfactant is preferred, and a special polycarboxylic acid polymer surfactant is more preferred. As an anionic surfactant, for example, alkyl sulfate ester salts may include "EMAL (registered trademark) 10" manufactured by Kao Corporation, and alkyl naphthalene sulfonates may include "Pelex (registered trademark) manufactured by Kao Corporation. ) NB-L" and so on. The special polymer-based surfactants include "HOMOGENOL (registered trademark, the same below) L-18" and "HOMOGENOL L-100" manufactured by Kao Corporation.

Examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts. As an amphoteric surfactant, for example, betaine-type compounds, imidazolium salts, imidazolines, and amino acids may be mentioned. Among them, quaternary ammonium salts are preferred, and stearyl trimethyl ammonium salts are more preferred. As the cationic surfactant or amphoteric surfactant, for example, the alkylamine salt may be "Acetamin (registered trademark) 24" manufactured by Kao Corporation, and the quaternary ammonium salt may be manufactured by Kao Corporation. "Quartamin (registered trademark, the same below) 24P" and "Quartamin 86W". Surfactant may be used individually by 1 type, and may use 2 or more types together. For example, a combination of silicone-based surfactant/fluorine-based surfactant, a combination of silicone-based surfactant/special polymer-based surfactant, fluorine-based surfactant/special polymer-based interface A combination of active agents. Among them, a combination of polysiloxane-based surfactant/fluorine-based surfactant is preferred. Regarding the combination of the polysiloxane-based surfactant/fluorine-based surfactant, for example, "BYK-300" or "BYK-330" manufactured by BYK-Chemie / "DFX-18" manufactured by NEOS , BYK-Chemie company "BYK-300", "BYK-330"/AGC SEIMI CHEMICAL company "S-393", BYK-Chemie company "BYK-300" or "BYK-330"/DIC "F-554" or "F-559" manufactured by the company, "KP340" manufactured by Shin-Etsu Silicones, "F-478" or "F-475" manufactured by DIC, and "SH7PA" manufactured by Dow Corning Toray "/"DS-401" made by Daikin Company, "L-77" made by NUC Company/3 "FC4430" made by M Japan Company. As the development modifier, for example, a well-known development modifier containing an organic carboxylic acid or an anhydride thereof can also be used. When the photosensitive resin composition of the present invention contains a coatability improver or a development modifier, the content of the coatability improver or the development modifier is in terms of sensitivity from the viewpoint of sensitivity. The total solid content is preferably 20% by mass or less, and more preferably 10% by mass or less.

[1-1-11] Silane coupling agent The photosensitive resin composition of the present invention may also contain a silane coupling agent to improve the adhesion to the substrate. As the silane coupling agent, for example, epoxy-based, methacrylic-based, amino-based, and imidazole-based silane coupling agents can be used. From the viewpoint of improving adhesion, epoxy-based and imidazole-based silane coupling agents are particularly preferred. When the photosensitive resin composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 20% by mass or less in the total solid content of the photosensitive resin composition from the viewpoint of adhesion , More preferably 15% by mass or less.

[1-1-12] Phosphoric acid based adhesion improver The photosensitive resin composition of the present invention may also contain a phosphoric acid-based adhesion improver to improve the adhesion to the substrate. The phosphoric acid-based adhesion improving agent is preferably a (meth)acryloyloxy-containing phosphoric acid ester, and among these, those represented by the following general formulas (Va), (Vb), and (Vc) are preferred.

[化51]

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 1-10, and s is 1, 2, or 3.

When the photosensitive resin composition of the present invention contains a phosphoric acid-based adhesion improver, its content is not particularly limited. In the total solid content of the photosensitive resin composition, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, more preferably 0.3% by mass or more, more preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 0.1 to 5% by mass, more preferably 0.2 to 3% by mass, and still more preferably 0.3 to 1% by mass. By setting it to the above lower limit or more, there is a tendency for the adhesion to the substrate to improve. In addition, by setting it to the upper limit or less, the surface hardenability tends to be improved.

[1-1-13] Inorganic filler The photosensitive resin composition of the present invention may also contain an inorganic filler to increase the strength of the hardened product, and to improve the superiority of the coating film obtained by the moderate interaction with the alkali-soluble resin (formation of the matrix structure) The flatness and cone angle. As the inorganic filler, for example, talc, silica, alumina, barium sulfate, magnesium oxide, and those obtained by surface-treating these with various silane coupling agents.

The average particle diameter of the inorganic filler is preferably 0.005 to 20 μm, more preferably 0.01 to 10 μm. Here, the average particle size refers to the value measured by a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter, etc. Among the inorganic fillers, the silica sol and the modified silica sol are preferable because of the tendency of the dispersion stability and the improvement effect of the cone angle to be excellent. When the photosensitive resin composition of the present invention contains an inorganic filler, as its content, from the viewpoint of sensitivity, it is preferably 5% by mass or more in the total solid content of the photosensitive resin composition, and more It is preferably 10% by mass or more, more preferably 80% by mass or less, and more preferably 70% by mass or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.

[1-1-14] Solvent The photosensitive resin composition of the present invention usually contains a solvent, and is used in a state where the above-mentioned components are dissolved or dispersed in the solvent. The solvent is not particularly limited, and for example, the organic solvents described below can be mentioned.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol tertiary butyl ether, diethyl 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-methoxy Glycol monoalkyl ethers such as butyl butanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether; ethylene glycol dimethyl ether, Diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether and other glycol dialkyl ethers ; Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether Acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, acetic acid 3 -Methyl-3-methoxybutyl ester, 3-methoxy-1-butyl acetate and other glycol alkyl ether acetates; ethylene glycol diacetate, 1,3-butanediol diethyl Ester, 1,6-hexanol diacetate and other glycol diacetates; cyclohexyl acetate and other alkyl acetates; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether , Dipentyl ether, ethyl isobutyl ether, dihexyl ether and other ethers; acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone Methyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol Monohydric or polyhydric alcohols such as alcohol, glycerin, and benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutene, n-hexane, hexene, isoprene, dipentene, dodecane, etc.; cyclohexane Alkane, methylcyclohexane, methylcyclohexene, bicyclohexane and other alicyclic hydrocarbons; benzene, toluene, xylene, cumene and other aromatic hydrocarbons; pentyl formate, ethyl formate, acetic acid Ethyl acetate, butyl acetate, propyl acetate, pentyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, isobutyl Methyl butyrate, ethyl octanoate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, Ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone and other chain or cyclic esters; 3-methoxypropionate Alkoxycarboxylic acids such as acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as chlorobutane and chloropentane; ether ketones such as methoxymethylpentanone; nitriles such as acetonitrile and benzonitrile; Tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, etc. Nan class and so on.

As a commercially available solvent equivalent to the above-mentioned solvent, for example, mineral spirits, Varsol #2, Apco #18 solvent, Apco diluent, Socal solvent No. 1 and No. 2, Solvesso #150, Shell TS28 solvent, Carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol Dimethyl ether (all trade names).

The solvent can dissolve or disperse the components in the photosensitive resin composition, and can be selected according to the method of using the photosensitive resin composition of the present invention. From the viewpoint of coatability, it is preferably under atmospheric pressure (1013.25 hPa) The boiling point is 60 to 280°C, more preferably 70 to 260°C. For example, propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, and 3-methoxy-1-butyl acetate are preferable.

A solvent may be used individually by 1 type, and may use 2 or more types together. Regarding the solvent, it is preferable that the total solid content in the photosensitive resin composition is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 18% by mass or more, and more preferably 90%. It is used in a mass% or less, more preferably 50 mass% or less, still more preferably 40 mass% or less, and particularly preferably 30 mass% or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 10 to 90% by mass, more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, and particularly preferably 18 to 30% by mass. By setting it as the above-mentioned lower limit or more, there exists a tendency for a coating film to be obtained even for a high film thickness. Moreover, by setting it as the above upper limit or less, there exists a tendency to obtain moderate coating uniformity.

[1-2] Preparation method of photosensitive resin composition The photosensitive resin composition of the present invention is prepared by mixing the above-mentioned components with a mixer. Furthermore, it is also possible to perform filtration using a membrane filter etc. so that the prepared photosensitive resin composition may become uniform.

[2] Barrier wall and its forming method The photosensitive resin composition of the present invention can be suitably used to form barrier ribs, especially barrier ribs for dividing the organic layer (light emitting part) of an organic electroluminescent device. The barrier rib of the present invention is obtained by curing the photosensitive resin composition of the present invention. The method of forming barrier ribs using the photosensitive resin composition of the present invention is not particularly limited, and a previously known method can be used. As a method of forming the barrier ribs, for example, a method including the following steps: a coating step, which is to coat a photosensitive resin composition on a substrate to form a photosensitive resin composition layer; and an exposure step, which is to The photosensitive resin composition layer is exposed. As a specific example of the method of forming such barrier ribs, photolithography may be mentioned.

In the photolithography method, the photosensitive resin composition is applied to the entire surface of the substrate where the barrier ribs are formed to form a photosensitive resin composition layer. Expose the formed photosensitive resin composition layer according to the pattern of the specific barrier rib, and then develop the exposed photosensitive resin composition layer to form barrier ribs on the substrate.

In the coating step of applying the photosensitive resin composition on the substrate in the photolithography method, a roll coater, a reverse coater, and a bar coater are used on the substrate where the barrier wall should be formed. The photosensitive resin composition is applied by contact transfer coating equipment such as a machine, or a non-contact coating equipment such as a spin coater (rotary coating equipment), a curtain-type flat coater, etc., and if necessary The solvent is removed by drying, and a photosensitive resin composition layer is formed.

Then, 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 exposed according to the pattern of the barrier ribs. During exposure, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, carbon arc lamps and other light sources that emit ultraviolet light can be used. The exposure amount varies depending on the composition of the photosensitive resin composition, and for example, it is preferably about 10 to 400 mJ/cm ² .

Then, in the developing step, the photosensitive resin composition layer that has been exposed according to the pattern of the barrier ribs is developed with a developer, thereby forming the pattern of the barrier ribs. The development method is not particularly limited, and a dipping method, spray method, etc. can be used. Specific examples of the developer include organic developer such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. And other aqueous solutions. In addition, a defoamer or a surfactant may be added to the developer.

Afterwards, post-baking is performed on the developed barrier rib pattern to be cured by heat, thereby obtaining the barrier rib. The post-baking is preferably performed at 150-250°C for 15-60 minutes.

After forming the barrier ribs, a cleaning process can also be performed to clean the unexposed areas. The cleaning method is not particularly limited, and examples thereof include plasma irradiation, excimer light irradiation, and UV (ultraviolet) irradiation. In excimer light irradiation or UV irradiation, the active oxygen can decompose and remove organic matter attached to the pixel portion by light irradiation.

The substrate used for the formation of the barrier ribs is not particularly limited, and can be appropriately selected according to the type of organic electroluminescence element manufactured using the substrate on which the barrier ribs are formed. As a preferable material for the substrate, glass or various resin materials can be cited. Specific examples of the resin material include: polyester such as polyethylene terephthalate; polyolefin such as polyethylene and polypropylene; polycarbonate; poly(meth)acrylic resin; Imine. Among the materials of these substrates, glass and polyimide are preferred in terms of excellent heat resistance. In addition, according to the type of organic electroluminescent element to be manufactured, a transparent electrode layer such as ITO (Indium Tin Oxides) or ZnO (Zinc Oxide) can also be pre-arranged on the surface of the substrate for forming the barrier ribs. .

Since the photosensitive resin composition of the present invention is excellent in the controllability of surface curability and internal curability, it can be suitably used to form barrier ribs having a step difference. Here, the barrier wall with a step difference refers to a barrier wall having a first barrier wall and a second barrier wall with different heights, for example, it means a barrier wall having a height of the first barrier wall greater than that of the second barrier wall. By using barrier ribs with a step difference, there is a tendency that the film thickness of the organic layer (light-emitting part) can be made uniform. In addition, since the second barrier ribs are provided between the pixels, the insulation between the pixels can be ensured, and light emission other than the pixel portion can be suppressed.

The height of the step difference, that is, the height difference between the upper surface of the first barrier wall and the upper surface of the second barrier wall is preferably 0.7 μm or more, more preferably 0.8 μm or more, and still more preferably 0.9 μm or more. Furthermore, it is preferably 1.3 μm or less, more preferably 1.2 μm or less, and still more preferably 1.1 μm or less. The above upper limit and lower limit can be combined arbitrarily, and for example, it is preferably 0.7 to 1.3 μm, more preferably 0.8 to 1.2 μm, and still more preferably 0.9 to 1.1 μm. By setting it as the above-mentioned lower limit or more, there exists a tendency which can ensure linear inkjet coatability. In addition, there is a tendency that insulation between pixels can be ensured by setting it below the above upper limit value.

Fig. 1 and Fig. 2 show an example of a substrate provided with barrier ribs having a step difference. Fig. 1 is a top view, and Fig. 2 is a cross-sectional view taken along the line X-X of Fig. 1. The substrate 1 is provided with barrier ribs 2 with a step difference, and the opening area in the barrier rib 2, that is, the area divided by the barrier rib 2 becomes the pixel portion 3. The barrier wall 2 has a first barrier wall upper surface 11 and a second barrier wall upper surface, and a step 13 is formed by the height difference between the first barrier wall upper surface 11 and the second barrier wall upper surface 12.

As a method of forming a barrier rib with a step difference, for example, a method of using a negative halftone mask in the exposure step of the above-mentioned forming method by photolithography can be exemplified. As a negative halftone mask, for example, the portion corresponding to the pixel portion 3 is a light-shielding portion (light transmittance 0%), and the portion corresponding to the upper surface 11 of the first barrier rib is an opening with the highest average light transmittance. The portion (completely through the opening) and the portion corresponding to the upper surface 12 of the second barrier wall becomes a mask with an average light transmittance lower than that of the completely through opening (middle through opening). According to this method, the difference in the residual film rate can be caused by the difference in the average light transmittance between the complete transmission opening and the intermediate transmission opening, that is, the difference in the exposure amount, thereby forming a step difference. By using the halftone mask in this way, it is possible to form a barrier wall with a step difference at one time by the photolithography method. In the case of one-time formation in this way, a continuous barrier wall with no clear boundary between the first barrier wall and the second barrier wall can be formed.

[3] Organic electroluminescence element The organic electroluminescence element of the present invention is equipped with the barrier ribs of the present invention. Various organic electroluminescent devices can be manufactured using a substrate provided with a barrier rib pattern manufactured by the method described above. The method of forming the organic electroluminescent device is not particularly limited. It is preferable to manufacture the organic electroluminescent device by the following method: after forming a pattern of barrier ribs on the substrate by the above method, the ink is injected onto the substrate. Organic layers such as pixels are formed in the area surrounded by the barrier ribs. As the type of the organic electroluminescence element, a bottom emission type or a top emission type can be mentioned. The bottom-emission type organic electroluminescence element is produced, for example, as follows: a barrier wall is formed on a glass substrate laminated with transparent electrodes, and a hole transport layer, a light-emitting layer, an electron transport layer, and a metal are laminated in the opening surrounded by the barrier wall. Electrode layer. The top-emission organic electroluminescence element is produced, for example, as follows: a barrier wall is formed on a glass substrate laminated with a metal electrode layer, and an electron transport layer, a light-emitting layer, and a hole transport layer are stacked on the opening surrounded by the barrier wall. Transparent electrode layer. As the light-emitting layer, an organic electroluminescent layer as described in Japanese Patent Laid-Open No. 2009-146691 or Japanese Patent No. 5736681 can be mentioned. It is also possible to use quantum dots as described in Japanese Patent No. 5653387 or Japanese Patent No. 5653101.

As the solvent used when forming the ink for forming the organic layer, water, organic solvents, and mixed solvents of these can be used. The organic solvent is not particularly limited as long as it can be removed from the film formed after the ink is injected. As the organic solvent, for example, toluene, xylene, anisole, symmetric trimethylbenzene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, Ethanol, isopropanol, ethyl acetate, butyl acetate, 3-phenoxytoluene. In addition, for example, surfactants, antioxidants, viscosity modifiers, and ultraviolet absorbers can be added to the ink.

As a method of injecting ink into the area surrounded by the barrier wall, in terms of being able to easily inject a small amount of ink to a specific position, the inkjet method is preferred. The ink used for the formation of the organic layer can be appropriately selected according to the type of the organic electroluminescence 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 ejected from the inkjet head well. It is preferably 4-20 mPa·s, more preferably 5～ 10 mPa·s. The viscosity of the ink can be adjusted by the adjustment of the solid content of the ink, the change of the solvent, the addition of the viscosity regulator, etc.

[4] Image display device The image display device of the present invention includes the organic electroluminescence element of the present invention. As long as it is an image display device containing the organic electroluminescence element of the present invention, there is no particular limitation on the style or structure of the image display device. For example, an active matrix organic electroluminescence element can be used and assembled according to a conventional method. . For example, the image display device of the present invention can be formed by the method described in "Organic EL Display" (Ohmsha, issued on August 20, 2004, by Shishi Shi, Chinami Adachi, Hideyuki Murata). For example, organic electroluminescence elements that emit white light can be combined with color filters for image display, or organic electroluminescence with different luminous colors such as RGB (Red-Green-Blue) The components are combined for image display. [Example]

Hereinafter, the present invention will be described with specific examples, but the present invention is not limited to the following examples as long as it does not exceed the gist. The constituent components of the photosensitive resin composition used in the following examples and comparative examples are as follows.

＜Photopolymerization initiator＞ a-1: Compounds with the following chemical structures

[化52]

a-2: IRGACURE OXE-01 manufactured by BASF a-3: IRGACURE OXE-02 manufactured by BASF a-4: PBG-305 manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd. a-5: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole manufactured by Hodogaya Chemical Industry Co., Ltd.

＜Alkali-soluble resin＞ b-1: Alkali-soluble resin with the following structural units (epoxy (meth)acrylate resin (solid content acid value 80 mgKOH/g, weight average molecular weight converted from polystyrene measured by GPC) ( Mw) is 8000, which is a mixture of m and n between 1 and 20)

[化53]

* In the above formula represents a bond with a monovalent group or a hydrogen atom represented by the following formula.

b-2：具有以下結構單元之鹼可溶性樹脂(環氧(甲基)丙烯酸酯樹脂(日本化藥公司製造之「ZCR-8029H」(重量平均分子量Mw＝7000，酸值＝62 mgKOH/g)；具有下述式(C1)所表示之部分結構))[化54]

b-2: Alkali-soluble resin with the following structural units (epoxy (meth)acrylate resin ("ZCR-8029H" manufactured by Nippon Kayaku Co., Ltd.)" (weight average molecular weight Mw = 7000, acid value = 62 mgKOH/g) ; Has the partial structure represented by the following formula (C1)))

[化55]

＜Photopolymerizable compound＞ c-1: Dipentaerythritol hexaacrylate (DPHA) manufactured by Nippon Kayaku Co., Ltd.

＜Liquid repellent agent＞ d-1: MEGAFAC RS-72-K manufactured by DIC Corporation (acrylic resin containing the repeating unit represented by the general formula (II) and fluorine atom) d-2: MEGAFAC RS-78 manufactured by DIC Corporation (acrylic resin that does not contain the repeating unit represented by the general formula (II) but contains an ethylenically unsaturated group and a fluorine atom) d-3: MEGAFAC F-559 manufactured by DIC (Stock) ＜Additives＞ e-1: KAYAMER PM-21 manufactured by Nippon Kayaku Corporation ＜Chain transfer agent＞ f-1: 2-Mercaptobenzimidazole (manufactured by Tokyo Chemical Co., Ltd.)

<Preparation of photosensitive resin composition> Each component was used in the blending ratio described in Table 1, and propylene glycol monomethyl ether acetate was used so that the content of the total solid component of the photosensitive resin composition became 19% by mass, and the components were stirred to be uniform to prepare The photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5 are shown. Furthermore, the blending ratio (mass %) of each component in Table 1 means the value of the solid component of each component in the total solid component of the photosensitive resin composition.

[Table 1] Example Comparative example 1 2 3 1 2 3 4 5 Allocation ratio (A) Photopolymerization initiator a-1 3.0 3.0 2.25 3.0 3.0 a-2 3.0 a-3 3.0 a-4 0.75 a-5 2.0 (B) Alkali-soluble resin b-1 48.1 24.1 20.1 48.1 48.1 48.1 48.1 20.1 b-2 24.1 (C) Photopolymerizable compound c-1 48.1 48.1 30.1 48.1 48.1 48.1 48.1 30.1 (D) Liquid repellent d-1 0.3 0.3 0.3 0.3 0.3 0.3 d-2 0.3 d-3 0.3 (E) Additives e-1 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 (F) Chain transfer agent f-1 1.0 Evaluation results Step difference The first barrier ①[μm] 1.5 1.5 1.5 1.5 1.5 Unable to form a barrier 1.5 1.5 The second barrier ②[μm] 0.5 0.7 0.3 0.0 1.0 0.5 0.2 ΔH(①－②)[μm] 1.0 A 0.8 B 1.2 B 1.5 C 0.5 C 1.0 A 1.3 C Contact angle [degrees] 42 41 42 42 41 36 29 Inkjet coatability Ruin A A A B A B B Linear coating A A A A B B B

Using the photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 to 5, performance evaluation was performed by the method described below.

<Production and evaluation of a substrate for contact angle measurement> Using a spin coater, each photosensitive resin composition was applied to a glass substrate so that it would have a thickness of 1.5 μm after heat curing. Thereafter, it was heated and dried on a hot plate at 95°C for 2 minutes to obtain a coated film substrate. Then, the exposure machine MA-1100 manufactured by Dainippon Scientific Research Co., Ltd. was used to expose the entire surface of the obtained coating film ^{with an exposure amount of 60 mJ/cm 2 without using a mask.} The intensity at the wavelength of 365 nm at this time is 40 mW/cm ² . Then, spray development was performed for 60 seconds with a 2.38% by mass TMAH (Tetramethylammonium Hydroxide) aqueous solution at 24° C., and thereafter, it was washed with pure water for 10 seconds. This substrate was heat-cured in an oven at 230°C for 30 minutes to obtain a coated substrate for contact angle measurement on the entire surface.

The measurement of the contact angle was carried out under the conditions of 23°C and 50% humidity using the contact angle measurement device Drop Master 500 manufactured by Kyowa Interface Science Co., Ltd. 0.7 μL of propylene glycol methyl ether acetate was dropped on the substrate for contact angle measurement, and the contact angle after 1 second was measured. The measurement results are shown in Table 1. The larger the contact angle, the higher the ink repellency.

＜Barrier with step difference and evaluation＞ Using each photosensitive resin composition, a barrier rib was formed by the method described below, and performance evaluation was performed.

(Formation of barrier ribs) On the ITO film of the glass substrate with the ITO film formed on the surface, each photosensitive resin composition was applied using a spin coater so as to have a thickness of 1.5 μm after heating and curing. Thereafter, it was heated and dried on a hot plate at 95°C for 2 minutes to obtain a coated substrate. Use a photomask (the linear fully transparent openings with an opening width of 20 μm and the linear middle transmission openings with an opening width of 60 μm are arranged alternately adjacent to each other, and are arranged at an interval of 70 μm in the middle transmission opening A mask with a covering part of 60 μm×240 μm), with an exposure gap of 10 μm, using an exposure machine MA-1100 manufactured by Dainippon Scientific Co., Ltd. to expose the obtained coating film. The middle transmission opening is a thin film of Cr oxide that has a light transmittance of 5% at a wavelength of 365 nm. During the exposure, the intensity at a wavelength of 365 nm was 40 mW/cm ² , and the exposure was 60 mJ/cm ² , and it was carried out in air. Next, spray development was performed for 60 seconds with a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 24° C., and thereafter, it was washed with pure water for 1 minute. Through these operations, the useless part is removed, and the patterned substrate is heated and cured in an oven at 230° C. for 30 minutes to obtain a barrier rib substrate with a step difference.

(Measurement of film thickness of barrier wall) With respect to the barrier rib substrate having a step, the thickness of the cured film (first barrier rib) corresponding to the complete transmission opening and the cured film (second barrier rib) corresponding to the intermediate transmission opening was measured. In the measurement, the three-dimensional non-contact surface shape measurement system Micromap MM3500-M100 manufactured by Ryoka Systems was used.

(Evaluation of level difference) The film thickness difference (step difference, ΔH) between the first barrier rib and the second barrier rib was calculated and evaluated in accordance with the following criteria. The results are shown in Table 1. A: The step difference ΔH is 0.9 μm or more and 1.1 μm or less B: The step difference ΔH is 0.7 μm or more and less than 0.9 μm, or more than 1.1 μm and less than 1.3 μm C: The step difference ΔH is less than 0.7 μm or more than 1.3 μm Furthermore, the range of the level difference is preferably A and B, more preferably A.

(Evaluation of inkjet coating suitability) For the barrier rib substrate with the step difference, DMP-2831 manufactured by Fuji Film is used for inkjet coating on the pixel area corresponding to the covered portion. As the ink, a solvent (isoamyl benzoate) is used alone, and 180 pL is applied to each pixel area. According to the following criteria, whether the ink is broken (the phenomenon that the ink crosses the first barrier wall) and whether the ink is linear The coating is evaluated. The higher the ink repellency of the barrier wall, the more likely it is to suppress the tendency of collapse. In addition, the more suitable the level difference is, the better the linear coatability tends to be.

(Route evaluation) A: The ink can be applied to the pixel area without overflowing outside the first barrier wall. B: Ink overflows from the pixel area over the first barrier wall (collapse).

(Linear inkjet coating properties) A: The ink can be applied linearly without interrupting the second barrier wall across a plurality of pixel regions. B: The ink is interrupted between a plurality of pixel regions and cannot be applied linearly.

From the comparison of Examples 1 to 3 in Table 1 and Comparative Examples 1 to 2, it can be seen that in Examples 1 to 3, the height difference between the first barrier wall and the second barrier wall, that is, the level difference, is within an appropriate range. After being clothed, the thread-like spreadability is also good, and there is no collapse. In Comparative Example 1, the second barrier wall could not be formed, and it could be applied linearly during inkjet application, but collapse occurred. In Comparative Example 2, the film thickness of the second barrier rib became thick, and the linear ink coatability was insufficient. In Comparative Example 3, the barrier ribs could not be formed. In Comparative Examples 4 to 5, the contact angle of the surface of the first barrier wall was low, and collapse occurred during inkjet coating, and the coating could not be applied in a line.

In order to prevent the ink from collapsing outside the first barrier wall when the ink is applied by the inkjet method, it is important to fix the liquid repellent on the surface of the barrier wall to ensure the liquid repellency of the barrier wall surface. However, when the curing degree of the coating film after UV exposure is insufficient, a part of the film surface will be dissolved during the subsequent development process, and the liquid repellent will flow out into the developer, thereby blocking the liquid repellency of the surface of the barrier wall. Getting worse. Since the use of an oxime ester photopolymerization initiator that mainly utilizes i-rays as a photopolymerization initiator increases the surface hardening of the coating film, it is effective as a method to ensure the liquid repellency of the barrier wall surface. However, when the first barrier wall and the second barrier wall are exposed at the same time by using a mask with openings with different transmittances, that is, a so-called halftone mask, and each barrier wall is formed through the process of development and thermal curing , There is a tendency that the surface hardening degree of the second barrier wall becomes too high, and it is difficult to control the step difference with the first barrier wall.

Since the photopolymerization initiator contained in the photosensitive resin composition of Comparative Example 2 has a carbazole skeleton, the surface hardening degree of the second barrier rib becomes too high, and the film thickness thereof becomes thick. Therefore, during inkjet coating, a certain amount of ink stays in the pixel area and cannot flow onto the second barrier wall, and the linear coating performance is insufficient. In Comparative Example 3, a biimidazole-based initiator was used as the photopolymerization initiator, and a chain transfer agent was used in combination to improve the curability of the surface, but the photocurability was insufficient, so the barrier ribs were developed during the development step The liquid washed away and failed to form a barrier wall.

Since the photopolymerization initiators contained in the photosensitive resin compositions of Example 1 and Comparative Example 1 all have a sulfide skeleton, the curability of the surface is not so high. However, in the photopolymerization initiator contained in the photosensitive resin composition of Comparative Example 1, the radical generation site is a phenylcarbonyl group, and it is considered that the mobility of the generated radicals is low, and the internal curability is also weakened. Therefore, it is inferred that during development, the portion corresponding to the side wall of the first barrier wall is excessively developed by the developer, and the side wall cannot hold the liquid repellent, and thus collapse occurs during inkjet coating. In addition, it is considered that since the internal hardenability is low, the second barrier wall cannot be formed.

In the photopolymerization initiator contained in the photosensitive resin composition of Example 1, the radical generating site is a methyl carbonyl group, and it is considered that the mobility of the generated radical is relatively high, and the internal curability is also high. Therefore, it is presumed that during development, the developability of the portion corresponding to the side wall of the first barrier wall also becomes moderate, and the side wall can also sufficiently retain the liquid repellent, thereby suppressing collapse. In addition, it is considered that since the internal curability is moderately high, it is possible to form the second barrier rib of a desired thickness, and the linear coatability is also good. As in Example 3, even when the photopolymerization initiator represented by the general formula (I) and other photopolymerization initiators are used, the height of the first barrier wall and the second barrier wall can be ensured The difference, that is, the level difference, is within an appropriate range, and the contact angle of the surface of the first barrier wall and linear coatability are also good. However, the step difference of Example 1 is a more preferable range. It is believed that the reason is that in the photosensitive resin composition of Example 1, the photopolymerization initiator represented by the general formula (I) accounts for a higher proportion of the total photopolymerization initiator, and therefore the internal curability is higher. .

The use of an acrylic resin containing the repeating unit represented by the general formula (II) and a fluorine atom as a liquid repellent is also important for ensuring the liquid repellency of the barrier wall surface. When there is no repeating unit represented by the general formula (II), it is difficult for the liquid repellent to be fixed on the surface of the coating film after ultraviolet exposure and flow into the developing solution of the development process, so that the liquid repellency of the barrier wall surface is changed. Poor tendency. In Comparative Example 4, an acrylic resin containing ethylenically unsaturated groups and fluorine atoms was used as the liquid repellent, but the number of crosslinking groups was small, so it was considered that the liquid repellent was difficult to fix on the surface of the coating film after UV exposure However, it will flow into the developing solution of the development process, and the contact angle of the barrier wall surface becomes low, and the liquid repellency cannot be ensured. In Comparative Example 5, since the liquid repellent did not have the repeating unit represented by the general formula (II) and did not have an ethylenically unsaturated group, the contact angle of the barrier wall surface became low, and the liquid repellency could not be ensured.

1: substrate 2: barrier wall with step difference 3: Pixel section 11: The upper surface of the first barrier wall 12: The upper surface of the second barrier wall 13: step difference

Fig. 1 is a plan view showing an example of a substrate provided with barrier ribs having a step. Fig. 2 is a cross-sectional view showing an example of a substrate provided with barrier ribs having a step.

Claims (11)

A photosensitive resin composition characterized in that it contains (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a liquid repellent, and the above ( A) The photopolymerization initiator contains a photopolymerization initiator represented by the following general formula (I), and the above (D) liquid repellent contains acrylic acid containing a repeating unit represented by the following general formula (II) and a fluorine atom Series resin (D1); [化1]

(In formula (I), R ^1a represents an optionally substituted alkyl group or an optionally substituted aromatic cyclic group; R ^2a represents an alkyl group; R ^3a represents a monovalent substituent; n represents 0 or 1; h Represents an integer from 0 to 2) [化2]

(In formula (II), R ¹¹ each independently represents a hydrogen atom or a methyl group, and R ¹² represents an optionally substituted alkyl group having 2 to 6 carbon atoms, which may be substituted by -O-, -C(=O)-, Any one or more of -S- and -NH- is interrupted; * indicates the bonding part). The photosensitive resin composition of claim 1, wherein in the above formula (I), R ^3a is R ^4a -O- (wherein, R ^4a represents an alkyl group which may have a substituent or an aromatic group which may have a substituent Cyclic group), h is 1. The photosensitive resin composition according to claim 1 or 2, wherein the content of the photopolymerization initiator represented by the general formula (I) is 80-100% by mass relative to the total photopolymerization initiator. The photosensitive resin composition according to any one of claims 1 to 3, wherein the content of the (B) alkali-soluble resin with respect to 100 parts by mass of the (C) photopolymerizable compound is 200 parts by mass or less. The photosensitive resin composition according to any one of claims 1 to 4, wherein the acrylic resin (D1) has a fluoroalkyl group and/or a fluoroalkylene group. The photosensitive resin composition according to any one of claims 1 to 5, wherein the above-mentioned (B) alkali-soluble resin comprises a resin having a partial structure represented by the following general formula (i) or (iii); [化3]

(In formula (i), R ^a represents a hydrogen atom or a methyl group, and R ^b represents a divalent hydrocarbon group that may have a substituent; the benzene ring in formula (i) may be further substituted with any substituent; * represents a bonding bond) [化4]

(In formula (iii), R ^e represents a hydrogen atom or a methyl group, and γ represents a single bond, -CO-, an alkylene group which may have a substituent, or a bivalent cyclic hydrocarbon group which may have a substituent; formula (iii) The benzene ring in can be further substituted by any substituent; * represents a bonding bond). The photosensitive resin composition according to any one of claims 1 to 6, which is used to form a barrier wall. The photosensitive resin composition according to claim 7, which is used to form a barrier wall with a step difference at a time by a photolithography method. A barrier wall formed by curing the photosensitive resin composition according to any one of claims 1 to 8. An organic electroluminescence element provided with a barrier wall as claimed in claim 9. An image display device comprising the organic electroluminescence element as claimed in claim 10.

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