JP7205089B2 - Photosensitive resin composition, partition wall, organic electroluminescence device, image display device and lighting - Google Patents

Description

TECHNICAL FIELD The present invention relates to a photosensitive resin composition, a partition made of the photosensitive resin composition, an organic electroluminescence device comprising the partition, an image display device and illumination comprising the organic electroluminescence device.

Conventionally, organic electroluminescence elements included in organic electric field displays and organic electric field lighting have been formed by forming partitions (banks) on a substrate and then laminating various functional layers in the region surrounded by the partitions. manufactured. As a method for easily forming such partition walls, a method of forming them by photolithography using a photosensitive resin composition is known.

In addition, as a method of laminating various functional layers in the region surrounded by the partition walls, first, an ink containing the materials constituting the functional layers is prepared, and then the prepared ink is injected into the region surrounded by the partition walls. It is known how to Among these methods, the inkjet method is often adopted because it is easy to accurately inject a predetermined amount of ink into a predetermined location.

Furthermore, when the functional layer is formed using ink, the partition wall should be made ink-repellent ( liquid repellency) may be required. As a method of imparting ink repellency to the partition walls, for example, a method of incorporating a fluorine-based compound into the partition walls is known (see Patent Documents 1 and 2).

Further, Patent Document 3 describes that a cured product having high ink repellency can be formed by using a specific fluororesin, and Patent Document 4 describes the use of a specific fluororesin. It is described that a cured product having good antifouling properties, scratch resistance, and smoothness can be formed by this.

WO2013/161829 JP 2017-227771 A JP 2012-092308 A JP 2018-025687 A

When a partition wall is formed using a photosensitive resin composition, if residue of the composition is generated in a pixel portion surrounded by the partition wall, part of the pixel portion may not emit light. For this reason, UV cleaning treatment is sometimes performed for the purpose of removing residues after forming the partition walls. However, the present inventors have investigated and found that while UV cleaning treatment removes residues, the ink repellency of the partition walls is reduced. It was found that there is a problem that
As a result of investigation by the present inventors, it was found that the photosensitive resin compositions described in Patent Documents 1 and 2 do not have sufficient ink repellency after UV cleaning treatment.
In addition, it was found that the photosensitive resin compositions described in Patent Documents 3 and 4 do not have sufficient ink repellency.

Accordingly, an object of the present invention is to provide a photosensitive resin composition capable of forming a pattern having good ink repellency even after UV irradiation.
Another object of the present invention is to provide a partition made of the photosensitive resin composition, an organic electroluminescence element including the partition, and an image display device and lighting including the organic electroluminescence element.

As a result of intensive studies by the present inventors, it was found that the above problems can be solved by using a liquid-repellent agent having a specific structure in the photosensitive resin composition and by setting the content ratio of the alkali-soluble resin to the photopolymerizable compound within a specific range. and completed the present invention.
That is, the gist of the present invention is as follows.

[1] A photosensitive resin composition containing (A) a liquid repellent agent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator,
The (A) liquid repellent agent contains a fluorine atom-containing acrylic resin (a) having an adamantane skeleton and an ethylenic double bond,
A photosensitive resin composition, wherein the content ratio of the alkali-soluble resin (B) is 500 parts by mass or less relative to 100 parts by mass of the photopolymerizable compound (C).

[2] The photosensitive resin composition according to [1], wherein the fluorine atom-containing acrylic resin (a) has a partial structure represented by the following general formula (2).

(In Formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group.
^X4 represents a perfluoroalkylene group. A plurality of X ⁴ contained in formula (2) may be the same or different, and in the case of different ones, they may exist randomly or in blocks.
Each X ⁵ independently represents a direct bond or any divalent linking group.
n is an integer of 1 or more.
* represents a bond. )

[3] The photosensitive resin composition according to [1] or [2], wherein the alkali-soluble resin (B) contains an epoxy (meth)acrylate resin (b1).
[4] The photosensitive resin composition according to any one of [1] to [3], wherein the content of (A) the liquid repellent agent is 2% by mass or less in the total solid content.
[5] The photosensitive resin composition according to any one of [1] to [4], which is used for forming partition walls.

[6] A partition made of the photosensitive resin composition according to any one of [1] to [5].
[7] An organic electroluminescence device comprising the partition according to [6].
[8] An image display device comprising the organic electroluminescence device of [7].
[9] Lighting including the organic electroluminescent device according to [7].

ADVANTAGE OF THE INVENTION By this invention, the photosensitive resin composition which can form a pattern with favorable ink repellency after UV irradiation can be provided.

The present invention will be described in detail below. It should be noted that the following description is an example of the embodiment of the present invention, and the present invention is not specified as long as it does not exceed the gist thereof.
In the present invention, "(meth)acrylic" means "acrylic and/or methacrylic", and "total solid content" means all components other than the solvent in the photosensitive resin composition. shall mean. Furthermore, in the present invention, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
Further, in the present invention, "(co)polymer" means including both a single polymer (homopolymer) and a copolymer (copolymer), and "polybasic acid (anhydride)" means "polybasic acid and/or polybasic acid anhydride".
In the present invention, the weight average molecular weight refers to the polystyrene equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography).
In the present invention, the acid value represents an acid value in terms of effective solid content, and is calculated by neutralization titration.

In the present invention, a partition wall material means a bank material, a wall material, and a wall material, and similarly, a partition wall means a bank, a wall, and a wall.
In the present invention, the light-emitting portion means a portion that emits light when electrical energy is applied.

[1] Photosensitive resin composition The photosensitive resin composition of the present invention contains (A) a liquid repellent agent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator. , The (A) liquid repellent agent has an adamantane skeleton and an ethylenic double bond, and the content ratio of the (B) alkali-soluble resin with respect to 100 parts by mass of the (C) photopolymerizable compound is 500 parts by mass or less. characterized by If necessary, it may further contain other components such as a chain transfer agent, an ultraviolet absorber, a polymerization inhibitor, and the like.

In the present invention, the partition is, for example, for partitioning the functional layers (organic layer, light-emitting portion) in the active drive type organic electroluminescent device, and for configuring the functional layer in the partitioned region (pixel region). It is used to form pixels and the like including functional layers and partition walls by ejecting and drying the ink, which is the material of .

[1-1] Components and Composition of Photosensitive Resin Composition Components constituting the photosensitive resin composition of the present invention and their composition will be described.
The photosensitive resin composition of the present invention contains (A) a liquid-repellent agent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator, and usually also contains a solvent.

[1-1-1] Component (A); Liquid Repellent The photosensitive resin composition of the present invention contains (A) a liquid repellent. (A) By containing a liquid-repellent agent, it is possible to impart ink repellency (liquid repellency) to the surface of the resulting partition walls. is prevented, and mixing of inks injected between adjacent regions can be prevented.

(A) the liquid repellent agent in the photosensitive resin composition of the present invention contains a fluorine atom-containing acrylic resin having an adamantane skeleton and an ethylenic double bond (hereinafter sometimes referred to as "acrylic resin (a)"). . Due to UV irradiation, the surface temperature of the cured product tends to increase due to the heat generated by the absorption of the resin, etc. in the cured product, but the acrylic resin (a) contains fluorine atoms and segregates more on the surface layer, so the effect of heat generation is suppressed. easy to receive. The acrylic resin (a) has an adamantane skeleton, which is an aliphatic polycyclic structure with high heat resistance, so that the thermal decomposition of the acrylic resin (a) during UV irradiation is suppressed, and even after UV irradiation, fluorine atoms on the partition wall surface can be maintained, the rate of decrease in the contact angle after UV irradiation is low, and the IJ coating suitability is considered to be good. In addition, by having an ethylenic double bond, the acrylic resin (a) is fixed on the surface of the coating film when it is exposed to light. It is thought that the ink repellency of the resulting partition walls can be enhanced.
In addition, since the acrylic resin (a) has an acrylic resin structure, the compatibility with (B) the alkali-soluble resin and (C) the photopolymerizable compound can be improved, and the storage stability of the photosensitive resin composition is also improved. In addition, it is thought that the generation of residues in the pixel portion can be suppressed, and the wetting and spreading property can be improved.

The acrylic resin (a) has an adamantane skeleton, and the adamantane skeleton may be a monovalent group or a divalent or higher group. Further, it may be unsubstituted or may have a substituent.
The adamantane skeleton can be anywhere in the chemical structure of acrylic resin (a), for example, it can be in the main chain or side chain of the acrylic resin. From the viewpoint of ease of synthesis, it is preferably in the side chain.

The content of the adamantane ring in the acrylic resin (a) is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, particularly preferably 30% by mass or more, and 50% by mass or less is preferable, 45% by mass or less is more preferable, 40% by mass or less is even more preferable, and 35% by mass or less is particularly preferable. When the content is at least the above lower limit, the contact angle tends to be suppressed from decreasing during UV irradiation. When the adamantane skeleton has a substituent, the adamantane ring when calculating the content of the adamantane ring is calculated by excluding the substituent, that is, by replacing the substituent with a hydrogen atom. In addition, when the adamantane skeleton is a monovalent group, the calculation is performed by replacing one bond with a hydrogen atom, and in the case of a divalent group, similarly, the calculation is performed by replacing two bonds with a hydrogen atom. .

The double bond equivalent of the acrylic resin (a) is not particularly limited, but is preferably 700 or less, more preferably 600 or less, further preferably 550 or less, particularly preferably 500 or less, and preferably 200 or more, more preferably 300 or more. It is preferably 400 or more, more preferably 450 or more. When the upper limit value or less is used, the outflow of the liquid-repellent agent to the pixel portion during development is suppressed, and the applicability of the inkjet liquid tends to be improved. tends to be higher.
The double bond equivalent of acrylic resin (a) can be calculated from the following formula.
(Double bond equivalent of acrylic resin (a))
= (molecular weight of acrylic resin (a))/(number of ethylenically unsaturated double bonds per molecule of acrylic resin (a))

The acrylic resin (a) contains fluorine atoms. The content of fluorine atoms in the acrylic resin (a) is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, particularly preferably 8% by mass or more, and 30% by mass or less is preferable, 20% by mass or less is more preferable, 15% by mass or less is even more preferable, and 12% by mass or less is particularly preferable. When the content is equal to or higher than the lower limit, the ink repellency tends to be enhanced, and when the content is equal to or lower than the upper limit, resin synthesis tends to be facilitated.

Although the chemical structure of the acrylic resin (a) is not particularly limited, it preferably has a partial structure represented by the following general formula (1) as a partial structure containing an adamantane skeleton from the viewpoint of ink repellency after UV irradiation. .

In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents a monovalent adamantyl group which may have a substituent.

( ^R2 )
In formula (1), R ² represents a monovalent adamantyl group which may have a substituent.
Examples of the substituent that the adamantyl group in R ² may have include a hydroxyl group, an alkoxy group, a halogen atom, and a monovalent group having an ethylenic double bond.

When the acrylic resin (a) has a partial structure represented by the general formula (1), the content is not particularly limited, but is preferably 60 mol% or more, more preferably 80 mol% or more, and 90 mol% or more. is more preferable, 93 mol% or more is particularly preferable, 99 mol% or less is preferable, 98 mol% or less is more preferable, 97 mol% or less is more preferable, and 96 mol% or less is particularly preferable. When it is at least the above lower limit, the decrease in ink repellency after UV irradiation tends to be sufficiently suppressed, and when it is at most the above upper limit, the ink repellency tends to increase.

Among the partial structures represented by the general formula (1), from the viewpoint of suppressing the outflow of the liquid-repellent agent to the pixel portion during development and improving the coatability of the inkjet liquid, the following general formula (1-1) It is preferable that the partial structure represented by is included.

In formula (1-1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group.
X ¹ represents an adamantylene group optionally having a substituent.
^X2 represents a urethane bond or an ester bond.
^X3 represents a divalent hydrocarbon group.
* represents a bond.

( ^X1 )
In formula (1-1) above, X ¹ represents an adamantylene group which may have a substituent.
Examples of the substituent that the adamantylene group in X ¹ may have include a hydroxyl group, an alkoxy group, and a halogen atom. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

⁽ X2)
In the formula (1-1), X ² represents a urethane bond (--O--CO--NH--) or an ester bond (--O--CO--). Among these, a urethane bond is preferable from the viewpoint of suppressing a decrease in ink repellency after UV irradiation.

⁽ X3)
In formula (1-1) above, X ³ represents a divalent hydrocarbon group.
Divalent hydrocarbon groups include divalent aliphatic groups and divalent aromatic ring groups.

Divalent aliphatic groups include linear, branched, or cyclic alkylene groups and linear, branched, or cyclic alkenylene groups.
Although the number of carbon atoms in the divalent aliphatic group is not particularly limited, it is generally preferably 1 or more and 2 or more, preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less. When it is at least the above lower limit, there is a tendency to suppress the decrease in ink repellency after UV irradiation, and when it is at most the above upper limit, the ink repellency tends to increase.
Specific examples of divalent aliphatic groups include methylene, ethylene, ethenylene, propylene, propenylene, butylene, butenylene, cyclohexylene and adamantylene groups.
A hydroxyl group, an alkoxy group, a halogen atom, etc. are mentioned as a substituent which the divalent aliphatic group may have.

The divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
Although the number of carbon atoms in the divalent aromatic ring group is not particularly limited, it is generally preferably 4 or more, 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is at least the above lower limit, there is a tendency to suppress the decrease in ink repellency after UV irradiation.
The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
Further, the divalent aromatic heterocyclic group includes, 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. , indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine groups such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring; mentioned.
Examples of substituents that the divalent aromatic ring group may have include hydroxyl groups, alkyl groups, alkoxy groups, and halogen atoms.

Among these, a divalent aliphatic group is preferable, a methylene group and an ethylene group are more preferable, and an ethylene group is further preferable, from the viewpoint of ensuring ink repellency and suppressing the residual liquid repellent agent in the pixel portion during development. preferable.

When the acrylic resin (a) has a partial structure represented by the general formula (1-1), the content is not particularly limited, but is preferably 50 mol% or more, more preferably 60 mol% or more, and 70 mol. % or more, particularly preferably 80 mol % or more, preferably 95 mol % or less, more preferably 93 mol % or less, and even more preferably 92 mol % or less. When the value is at least the above lower limit, there is a tendency to suppress the decrease in ink repellency after UV irradiation. It tends to suppress the outflow and improve the applicability of the inkjet liquid.

On the other hand, from the viewpoint of ink repellency after UV irradiation, the acrylic resin (a) preferably contains a partial structure represented by the following general formula (2) as a partial structure containing a fluorine atom. In the following general formula (2), since the poly(perfluoroalkylene ether) chain is bonded to two or more main chains, the poly(perfluoroalkylene ether) chain is difficult to detach from the acrylic resin (a) even by UV washing, and the partition wall It is believed that a sufficient amount of fluorine atoms can be present on the surface, resulting in good ink repellency even after UV cleaning treatment.

In formula ( ² ), ^R4 and R5 each independently represent a hydrogen atom or a methyl group. ^X4 represents a perfluoroalkylene group. A plurality of X ⁴ contained in formula (2) may be the same or different, and in the case of different ones, they may exist randomly or in blocks. Each X ⁵ independently represents a direct bond or any divalent linking group. n is an integer of 1 or more. * represents a bond.

( ^X4 )
In Formula (2) above, X ⁴ represents a perfluoroalkylene group.
Although the number of carbon atoms in the perfluoroalkylene group is not particularly limited, it is generally preferably 1 or more and 2 or more, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, there is a tendency to exhibit sufficient ink repellency, and when the content is equal to or lower than the upper limit, compatibility with other materials tends to be good.
Specific examples of perfluoroalkylene groups include groups represented by the following general formulas (2-a) to (2-e).

In formulas (2-a) to (2-e), * represents a bond.

Among the above formulas (2-a) to (2-e), from the viewpoint of obtaining high ink repellency, the group represented by the above formula (2-a) and the group represented by the above formula (2-b) are preferred.

Moreover, from the viewpoint of ink repellency, both the group represented by the formula (2-a) and the group represented by the formula (2-b) should be included as X ⁴ in the formula (2). is more preferred. Although the molar ratio between the group represented by the formula (2-a) and the group represented by the formula (2-b) contained in the formula (2) is not particularly limited, from the viewpoint of ink repellency, 1:10 to 10:1 is preferred, 1:4 to 4:1 is more preferred, and 1:2 to 2:1 is even more preferred.

( ^X5 )
In formula (2), X ⁵ represents a direct bond or any divalent linking group.
The optional divalent linking group includes -O-, -CO-O-, -CO-NH-, -O-CO-NH-, and a divalent hydrocarbon group which may have a substituent. mentioned. at least one selected from the group consisting of -O-, -CO-O-, -CO-NH-, and -O-CO-NH-, at least one of -CH ₂ - contained in the hydrocarbon group; may be replaced with

Divalent hydrocarbon groups include divalent aliphatic groups and divalent aromatic ring groups.
Divalent aliphatic groups include linear, branched, or cyclic alkylene groups and linear, branched, or cyclic alkenylene groups.
Although the number of carbon atoms in the divalent aliphatic group is not particularly limited, it is generally preferably 1 or more and 5 or less, more preferably 3 or less, and even more preferably 2 or less. The ink repellency tends to be enhanced by making it equal to or less than the above upper limit.
Specific examples of the divalent aliphatic group include methylene group, ethylene group, ethenylene group, propylene group, propenylene group, butylene group and butenylene group.
A hydroxyl group, an alkoxy group, etc. are mentioned as a substituent which the divalent aliphatic group may have.

The divalent aromatic ring group includes a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group.
Although the number of carbon atoms in the divalent aromatic ring group is not particularly limited, it is generally preferably 4 or more, 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is at least the above lower limit, compatibility with other materials tends to be improved, and when the content is at most the above upper limit, ink repellency tends to be enhanced.
The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
Further, the divalent aromatic heterocyclic group includes, 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. , indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine groups such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, and azulene ring; mentioned.
Examples of the substituent that the divalent aromatic ring group may have include a hydroxyl group, an alkyl group, and an alkoxy group.

Specific examples of X ⁵ include the following.

Among these, a divalent aliphatic group is preferable, a methylene group and an ethylene group are more preferable, and a methylene group is further preferable, from the viewpoint of ensuring ink repellency and suppressing the residual liquid repellent agent in the pixel portion during development. preferable.

(n)
In the formula (2), n is an integer of 1 or more, but from the viewpoint of ink repellency, it is preferably an integer of 3 to 40, more preferably an integer of 6 to 30, and 10 to 20. is more preferably an integer of

When the acrylic resin (a) has a partial structure represented by the general formula (2), the content is not particularly limited, but is preferably 0.1 mol% or more, more preferably 0.5 mol% or more, 1 mol % or more is more preferable, 2 mol % or more is particularly preferable, 50 mol % or less is preferable, 30 mol % or less is more preferable, and 10 mol % or less is even more preferable. When it is above the lower limit, there is a tendency to suppress the deterioration of the liquid-repellent ink property after UV cleaning treatment, and when it is below the above-mentioned upper limit, it is possible to suppress the outflow of the liquid-repellent agent to the pixel portion during development. There is a tendency for the coatability of the inkjet liquid to be improved.

When the acrylic resin (a) contains two or more partial structures selected from the group consisting of the general formulas (1) and (2), the acrylic resin (a) may be a random copolymer or a block copolymer. It may be a polymer. When it is a block copolymer, from the viewpoint of ink repellency, the A block containing the partial structure represented by the general formula (1) and the B block containing the partial structure represented by the general formula (2) It is preferably an AB block copolymer containing.

The weight average molecular weight of the acrylic resin (a) is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound. The weight average molecular weight of the acrylic resin (a) is preferably 1,000 or more, more preferably 5,000 or more, even more preferably 8,000 or more, still more preferably 9,000 or more, and preferably 100,000 or less. , is more preferably 50,000 or less, more preferably 30,000 or less, even more preferably 25,000 or less, particularly preferably 20,000 or less, and most preferably 15,000 or less. Within the above range, the fluidity of the liquid-repellent agent due to post-baking is suppressed, and there is a tendency to suppress the outflow of the liquid-repellent agent from the partition walls.

The content of (A) the liquid repellent agent in the photosensitive resin composition of the present invention is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, in the total solid of the photosensitive resin composition. It is preferably 0.2% by mass or more, more preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.7% by mass or less. When the concentration is equal to or higher than the lower limit, high ink repellency tends to be exhibited.

The content of the acrylic resin (a) in the photosensitive resin composition of the present invention is not particularly limited, but it is preferably 0.01% by mass or more in the total solid content of the photosensitive resin composition, and 0.1% by mass or more. It is more preferably 0.2% by mass or more, more preferably 2% by mass or less, more preferably 1% by mass or less, and even more preferably 0.7% by mass or less. There is a tendency that the decrease in ink repellency after UV irradiation can be sufficiently suppressed, and by making it equal to or less than the above upper limit, there is a tendency that the outflow of the acrylic resin (a) into the pixel portion can be suppressed.

The (A) liquid repellent agent in the photosensitive resin composition of the present invention may contain a liquid repellent agent other than the acrylic resin (a).

Specific examples of other liquid-repellent agents include perfluoroalkylsulfonic acids, perfluoroalkylcarboxylic acids, perfluoroalkylalkylene oxide adducts, perfluoroalkyltrialkylammonium salts, perfluorocarboxylic acid esters, and perfluoroalkylphosphoric acid esters. , perfluoroalkyl group-containing oligomers, and perfluoroalkylene group-containing fluorine atom-containing organic compounds.

Commercially available products of these fluorine atom-containing organic compounds include "Megafac F116", "Megafac F120", "Megafac F142D", "Megafac F144D", "Megafac F150" and "Megafac F160" manufactured by DIC. ”, “Megafuck F171”, “Megafuck F172”, “Megafuck F173”, “Megafuck F177”, “Megafuck F178A”, “Megafuck F178K”, “Megafuck F179”, “Megafuck F183”, "Megafuck F184", "Megafuck F191", "Megafuck F812", "Megafuck F815", "Megafuck F824", "Megafuck F833", "Megafuck RS101", "Megafuck RS102", "Megafuck" RS105", "Megafuck RS201", "Megafuck RS202", "Megafuck RS301", "Megafuck RS303", "Megafuck RS304", "Megafuck RS401", "Megafuck RS402", "Megafuck RS501", "Megafac RS502", "Megafac RS-56", "Megafac RS-72-K", "DEFENSA MCF300", "DEFENSA MCF310", "DEFENSA MCF312", "DEFENSA MCF323", 3M Japan's "Florado" FC-430", "Florado FC-431", "FC-4430", "FC-4432", AGC Seimi Chemical Co., Ltd. "Asahiguard AG-710", "Surflon S-382", "Surflon SC-101" , "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105", "Surflon SC-106", and "Optool DAC-HP" manufactured by Daikin Industries, Ltd. Fluorine atom-containing organic compounds commercially available from

(A) The content of the acrylic resin (a) in the liquid repellent agent is not particularly limited, but it is preferably 50% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and usually 100% by mass. It is below. When the content is equal to or higher than the lower limit, there is a tendency that the decrease in ink repellency after UV irradiation is suppressed.

When (A) the liquid repellent agent contains another liquid repellent agent, the content ratio of the other liquid repellent agent in (A) the liquid repellent agent is not particularly limited, but is preferably 10% by mass or more, more preferably 15% by mass or more, 20% by mass or more is more preferable, 50% by mass or less is preferable, 40% by mass or less is more preferable, and 30% by mass or less is even more preferable. When it is at least the above lower limit, there is a tendency to suppress residue in the pixel portion, and when it is at most the above upper limit, there is a tendency to suppress a decrease in ink repellency after UV irradiation.

[1-1-2] Component (B): Alkali-Soluble Resin The photosensitive resin composition of the present invention contains (B) an alkali-soluble resin. The alkali-soluble resin is not particularly limited as long as it is a resin that can be developed with an alkali developer. Alkali-soluble resins include various resins containing carboxyl groups and/or hydroxyl groups. Among them, a resin containing a carboxyl group is preferable from the viewpoint of obtaining partition walls with an appropriate taper angle and suppressing the outflow of the liquid-repellent agent due to thermal melting of the partition wall surface during post-baking and maintaining the ink repellency. .

(B) Among the alkali-soluble resins, from the viewpoint of sensitivity and ink repellency, an alkali-soluble resin (b) having an ethylenic double bond (hereinafter sometimes abbreviated as "alkali-soluble resin (b)"). is preferably included.

[Alkali-soluble resin (b) having an ethylenic double bond]
Although the specific structure of the alkali-soluble resin (b) having an ethylenic double bond is not particularly limited, from the viewpoint of development solubility, epoxy (meth)acrylate resin (b1) and/or acrylic copolymer resin (b2) Preferably, the epoxy (meth)acrylate resin (b1) is more preferable from the viewpoint of reducing outgassing.
The epoxy (meth)acrylate resin (b1) is described in detail below.

[Epoxy (meth)acrylate resin (b1)]
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 its anhydride. be. For example, an ethylenically unsaturated bond is added to the epoxy resin via an ester bond (-COO-) by ring-opening addition of a carboxyl group of an acid having an ethylenically unsaturated bond to the epoxy group of the epoxy resin. In addition, one carboxyl group of the polybasic acid anhydride is added to the hydroxyl group generated at that time. Moreover, when adding a polybasic acid anhydride, the thing added by adding a polyhydric alcohol simultaneously is mentioned. Furthermore, the epoxy (meth)acrylate resin (b1) also includes a resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a reactive functional group.
Thus, the epoxy (meth)acrylate resin has substantially no epoxy group due to its chemical structure, and is not limited to "(meth)acrylate", but an epoxy compound (epoxy resin) is a raw material. and "(meth)acrylate" is a typical example, so it is named in this way according to common practice.

Here, the term "epoxy resin" includes raw material compounds before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. As the epoxy resin, a compound obtained by reacting a phenolic compound and epihalohydrin can be used. The phenolic compound is preferably a compound having a divalent or more divalent phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, biphenyl novolak epoxy resin, trisphenol epoxy resin, phenol and dicyclopentane. epoxidized polymer with dihydroxylfluorene type epoxy resin, dihydroxylalkyleneoxylfluorene type epoxy resin, 9,9-bis(4'-hydroxyphenyl)fluorene diglycidyl etherate, 1,1-bis Diglycidyl etherified products of (4′-hydroxyphenyl)adamantane and the like can be mentioned, and those having an aromatic ring in the main chain can be preferably used.

Among them, from the viewpoint of cured film strength, bisphenol A type epoxy resin, phenol novolak epoxy resin, cresol novolak epoxy resin, epoxidized polymer of phenol and dicyclopentadiene, 9,9-bis(4'-hydroxyphenyl) Fluorene epoxidized products are preferred, and bisphenol A type epoxy resins are more preferred.

Acids having an ethylenically unsaturated bond include, for example, (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, pentaerythritol tri (Meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydrophthalic anhydride Examples include acid adducts and reaction products of (meth)acrylic acid and ε-caprolactone. Among them, (meth)acrylic acid is preferable from the viewpoint of sensitivity.

Examples of polybasic acids (anhydrides) include succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4 - ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid , benzophenonetetracarboxylic acid, biphenyltetracarboxylic acid, and their anhydrides. These may be used singly or in combination of two or more. Among these, succinic anhydride, maleic anhydride, and itaconic anhydride are preferred, and succinic anhydride is more preferred, from the viewpoint of reducing residues on pixel portions after development.

The use of a polyhydric alcohol tends to increase the molecular weight of the epoxy (meth)acrylate resin (b1), introduce branches into the molecule, and balance the molecular weight and viscosity. In addition, the rate of introduction of acid groups into the molecule can be increased, and there is a tendency to easily balance sensitivity, adhesion, and the like.
The polyhydric alcohol is, for example, one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. Preferably.

The acid value of the epoxy (meth)acrylate resin (b1) is not particularly limited, but is preferably 10 mg-KOH/g or more, more preferably 20 mg-KOH/g or more, still more preferably 40 mg-KOH/g or more, and 50 mg-KOH. / g or more is more preferable, 200 mg-KOH/g or less is preferable, 180 mg-KOH/g or less is more preferable, 150 mg-KOH/g or less is more preferable, 120 mg-KOH/g or less is even more preferable, 100 mg-KOH/g or less is particularly preferred. When the content is equal to or higher than the lower limit, the amount of residue tends to be reduced and the taper angle tends to increase.

Although the weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (b1) is not particularly limited, it is usually 1,000 or more, preferably 2,000 or more, more preferably 3,000 or more, and still more preferably 4,000 or more. , More preferably 5,000 or more, particularly preferably 6,000 or more, most preferably 7,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less , more preferably 10,000 or less. When the concentration is equal to or higher than the above lower limit, outgassing during light emission of the device tends to be reduced, and when the concentration is equal to or lower than the upper limit, there is a tendency to reduce residue.

(B) The content of the epoxy (meth)acrylate resin (b1) contained in the alkali-soluble resin is not particularly limited, but is preferably 30% by mass or more, more preferably 50% by mass or more, and further preferably 70% by mass or more. More preferably 80% by mass or more, particularly preferably 90% by mass or more, and usually 100% by mass or less. Outgassing tends to be reduced by making it equal to or higher than the lower limit.

The epoxy (meth)acrylate resin (b1) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and in the presence of a catalyst and a thermal polymerization inhibitor, the acid or ester compound having the ethylenically unsaturated bond is added for an addition reaction, and further polybasic acid or its A method of continuing the reaction by adding anhydride can be used.

Here, the organic solvent used for the reaction includes one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine; One or more of quaternary ammonium salts, phosphorus compounds such as triphenylphosphine, and stibines such as triphenylstibine can be used. Furthermore, the thermal polymerization inhibitor includes one or more of hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, and the like.

The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the epoxy group of the epoxy resin. It can be an amount that becomes The temperature during the addition reaction is usually 60 to 150°C, preferably 80 to 120°C. Furthermore, the amount of polybasic acid (anhydride) used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the hydroxyl groups generated in the addition reaction. It can be an amount that provides a chemical equivalent.

The epoxy (meth)acrylate resin (b1) is an epoxy (meth)acrylate resin (b1-1) containing a partial structure represented by the following general formula (i), from the viewpoint of reducing outgassing when the device emits light. From an epoxy (meth)acrylate resin (b1-2) containing a partial structure represented by (ii) and an epoxy (meth)acrylate resin (b1-3) containing a partial structure represented by the following general formula (iii) It is preferable to contain at least one selected from the group consisting of:

Among these, the epoxy (meth)acrylate resin (b1) is an epoxy (meth)acrylate resin (b1-1) containing a partial structure represented by the following general formula (i) from the viewpoint of reducing outgassing when the device emits light. Preferably. One of the reasons is presumed that it is difficult to decompose by heat due to having a rigid main skeleton.

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

(R ^b )
In formula (i) above, R ^b represents a divalent hydrocarbon group which may have a substituent.
The divalent hydrocarbon group includes a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. mentioned.

The divalent aliphatic group includes linear, branched and cyclic ones. Among these, linear ones are preferable from the viewpoint of developing solubility, while cyclic ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene and n-heptylene groups. Among these, a methylene group is preferable from the viewpoint of residue reduction.
Specific examples of the divalent branched aliphatic group include the divalent straight-chain aliphatic group described above and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl as a side chain. groups, iso-butyl groups, sec-butyl groups, tert-butyl groups, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is generally preferably 1 or more and 2 or more, and generally 10 or less and 5 or less. When the concentration is equal to or higher than the lower limit, the residual film ratio tends to be improved, and when the concentration is equal to or lower than the upper limit, the amount of residue tends to be reduced. Specific examples of divalent cyclic aliphatic groups include a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring in which two hydrogen atoms are removed. The group which carried out is mentioned. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of development adhesion.

Substituents which the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
In addition, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring; . Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

Examples of substituents that the divalent aromatic ring group may have include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group, propoxy group, glycidyl ether group and the like. Among these, unsubstituted is preferred from the viewpoint of curability.

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is generally preferably 1 or more and 2 or more, generally 10 or less and 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of groups in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (iA) to (iF), etc. is mentioned. Among these, a group represented by the following formula (iA) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane. * in the chemical formula represents a bond.

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

Further, the partial structure represented by the formula (i) is preferably a partial structure represented by the following general formula (i-1) from the viewpoint of developing solubility.

In formula (i-1), R ^a and R ^b have the same definitions as in formula (i) above. R ^X represents a hydrogen atom or a polybasic acid residue. * represents a bond. The benzene ring in formula (i-1) may be further substituted with any substituent.

( ^RX )
In (i-1), the polybasic acid residue of R ^x means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned. Among them, from the viewpoint of reducing outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and succinic acid Anhydrides are more preferred.

The partial structure represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-1) may be one type or two or more types. For example, one in which R ^X is a hydrogen atom and one in which R ^X is a polybasic acid residue may be mixed.

The number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, 3 or more is more preferable, 10 or less is preferable, and 8 or less is more preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

The number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more. It is preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

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

On the other hand, the epoxy (meth)acrylate resin (b1) is an epoxy (meth)acrylate resin (b1-2) containing a partial structure represented by the following general formula (ii) from the viewpoint of development adhesion. is preferred.

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

( ^Rd )
In formula (ii) above, R ^d represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is usually preferably 1 or more and 2 or more, and is usually 10 or less and 5 or less, preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and more preferably 4 or less. When the concentration is equal to or higher than the lower limit, the amount of residue tends to be reduced, and when the concentration is equal to or lower than the upper limit, the development adhesion tends to be improved.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, and 30 or less. It is more preferably 20 or less, and particularly preferably 15 or less. When the concentration is equal to or higher than the lower limit, the amount of residue tends to be reduced, and when the concentration is equal to or lower than the upper limit, the development adhesion tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, A fluorene ring and the like can be mentioned. Among these, a fluorene ring is preferable from the viewpoint of patterning properties.

In addition, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited. and a group in which a divalent aliphatic group and one or more divalent aromatic ring groups are linked.

The divalent aliphatic group includes linear, branched and cyclic ones. Among these, linear ones are preferable from the viewpoint of developing solubility, while cyclic ones are preferable from the viewpoint of reducing permeation of the developer into the exposed area. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of divalent linear aliphatic groups include methylene, ethylene, n-propylene, n-butylene, n-hexylene and n-heptylene groups. Among these, a methylene group is preferable from the viewpoint of residue.
Specific examples of the divalent branched aliphatic group include the divalent straight-chain aliphatic group described above and a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and n-butyl as a side chain. groups, iso-butyl groups, sec-butyl groups, tert-butyl groups, and the like.
Although the number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, it is generally preferably 1 or more and 2 or more, and generally 10 or less and 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced. Specific examples of divalent cyclic aliphatic groups include a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring in which two hydrogen atoms are removed. The group which carried out is mentioned. Among these, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable from the viewpoint of development adhesion.

Substituents which the divalent aliphatic group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; and carboxyl group. Among these, unsubstituted groups are preferred from the viewpoint of ease of synthesis.

Moreover, a bivalent aromatic-hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. The divalent aromatic hydrocarbon ring group includes, for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Groups such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring can be mentioned.
In addition, the aromatic heterocycle in the divalent aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of divalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring and azulene ring; . Among these, from the viewpoint of photocurability, a benzene ring or a naphthalene ring having two free valences is preferred, and a benzene ring having two free valences is more preferred.

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

Further, as the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic Groups in which one or more cyclic groups are linked can be mentioned.
Although the number of divalent aliphatic groups is not particularly limited, it is generally preferably 1 or more and 2 or more, generally 10 or less and 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the groups represented by the above formulas (iA) to (iF), etc. is mentioned. Among these, the group represented by the above formula (iC) is preferable from the viewpoint of reducing residues.

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

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

In formula (ii-1), R ^c has the same meaning as in formula (ii) above. 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.

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

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is generally preferably 1 or more and 2 or more, and generally 6 or less and 4 or less, and more preferably 3 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly 15 or less. preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, although the number of rings possessed by the aromatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.

Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as iso-amyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; Among these, unsubstituted is preferred from the viewpoint of ease of synthesis.

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

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

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

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

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

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

( ^Rβ )
In formula (ii-2) above, R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is generally preferably 1 or more and 2 or more, and is generally preferably 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
The number of carbon atoms in the aliphatic ring group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, although the number of rings possessed by the aromatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Examples of the aromatic ring group include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and 10 40 or less is more preferable, 30 or less is more preferable, 20 or less is more preferable, and 15 or less is particularly preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.

Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as iso-amyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; Among these, non-substituted groups are preferred from the viewpoint of ease of synthesis.

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

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

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

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

In formula (ii-3), R ^c and R ^d have the same definitions as in formula (ii) above. R ^X represents a hydrogen atom or a polybasic acid residue.

In (ii-3), the polybasic acid residue of R ^X means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. In addition, one more OH group may be removed and shared with R ^X in another molecule represented by formula (ii-3), that is, a plurality of formula (ii ^- 3 ) may be linked.
Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned. Among them, from the viewpoint of reducing outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and succinic acid Anhydrides are more preferred.

The partial structure represented by the 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 partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (b1-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less are preferable, 15 or less are more preferable, and 10 or less are more preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

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

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

(γ)
In the above formula (iii), γ represents a single bond, —CO—, an optionally substituted alkylene group, or an optionally substituted divalent cyclic hydrocarbon group.

The alkylene group may be linear or branched, but from the viewpoint of development solubility, it is preferably linear, and from the viewpoint of development adhesion, it is preferably branched. Although the number of carbon atoms is not particularly limited, it is usually preferably 1 or more and 2 or more, and usually 6 or less and 4 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group and a heptylene group. group is preferred, and dimethylmethylene group is more preferred.

Examples of substituents which the alkylene group may have include alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Among these, non-substitution is preferred from the viewpoint of compatibility between development adhesion and development solubility.

The divalent cyclic hydrocarbon group includes a divalent aliphatic ring group or a divalent aromatic ring group.

Although the number of rings possessed by the aliphatic ring group is not particularly limited, it is generally preferably 1 or more and 2 or more, and is generally preferably 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
The number of carbon atoms in the aliphatic ring group is generally 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and even more preferably 30 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of development adhesion.

On the other hand, although the number of rings possessed by the aromatic ring group is not particularly limited, it is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less and 5 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. In addition, the number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, preferably 40 or less, more preferably 30 or less, and further preferably 20 or less. It is preferred, and 15 or less is particularly preferred. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, a fluorene ring is preferable from the viewpoint of development adhesion.

Examples of substituents that the cyclic hydrocarbon group may have include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, Alkyl groups having 1 to 5 carbon atoms such as iso-amyl groups; alkoxy groups having 1 to 5 carbon atoms such as methoxy groups and ethoxy groups; hydroxyl groups; nitro groups; cyano groups; Among these, non-substituted groups are preferred from the viewpoint of ease of synthesis.

Among these, from the viewpoint of reducing residues, γ is preferably an optionally substituted alkylene group, more preferably a dimethylmethylene group.

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

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

In formula (iii-1), R ^e and γ have the same definitions as in formula (iii) above. R ^X represents a hydrogen atom or a polybasic acid residue. * represents a bond. The benzene ring in formula (iii-1) may be further substituted with any substituent.

In formula (iii-1), the polybasic acid residue of R ^X means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned. Among them, from the viewpoint of reducing outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and succinic acid Anhydrides are more preferred.

The number of partial structures represented by the formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more, 10 or more is more preferable, 18 or less is preferable, and 15 or less is more preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

In addition, the number of partial structures represented by the formula (iii-1) contained in one molecule of the epoxy (meth)acrylate resin (b1-3) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 5 or more, more preferably 18 or less, and still more preferably 15 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

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

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

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

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

From the viewpoint of developability, the partial structure represented by formula (I) is preferably a partial structure represented by general formula (I-1) below.

In formula (I-1), R ^A and R ^B have the same definitions as in formula (I) above. R ^Z represents a hydrogen atom or a polybasic acid residue.

In (I-1), the polybasic acid residue of R ^Z means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydrophthalic acid. One or more selected from acids, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid can be mentioned. Among them, from the viewpoint of reducing outgassing, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, succinic anhydride or tetrahydrophthalic anhydride is more preferable, and succinic acid Anhydrides are more preferred.

The content ratio of the partial structure represented by the general formula (I) contained in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 5 mol% or more, more preferably 20 mol% or more, and 30 mol. % or more, more preferably 50 mol% or more, particularly preferably 70 mol% or more, most preferably 80 mol% or more, preferably 99 mol% or less, more preferably 97 mol% or less, 95 mol % or less is more preferable. When the concentration is equal to or higher than the lower limit, the amount of residue tends to be reduced, and when the concentration is equal to or lower than the upper limit, the development adhesion tends to be improved.

The content of the partial structure represented by the general formula (I-1) contained in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, More preferably 10 mol% or more, still more preferably 15 mol% or more, particularly preferably 20 mol% or more, preferably 99 mol% or less, more preferably 60 mol% or less, further preferably 40 mol% or less, 30 mol % or less is particularly preferred. When the concentration is equal to or higher than the lower limit, the sensitivity tends to increase and the amount of residue tends to be reduced.

When the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I), the other partial structure that may be contained is not particularly limited, but from the viewpoint of development adhesion, for example, It preferably contains a partial structure represented by the following general formula (I').

In the above formula (I'), ^R represents a hydrogen atom or a methyl group, and R represents an ^optionally substituted alkyl group, an optionally substituted aryl group, or a substituent. represents an alkenyl group which may be present.

( ^RE )
In formula (I′) above, R ^E represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group.
Examples of the alkyl group for R ^E include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. When the content is equal to or higher than the lower limit, the film strength tends to increase and the development adhesion tends to be improved.

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

The aryl group for R ^E includes a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 4 or more, more preferably 6 or more, preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and 18 The following are particularly preferred. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring. Examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
Further, the aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. , imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furfuran ring, thienofuran ring, benzoisoxazole ring, benzoiso thiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, and the like. Among these, from the viewpoint of curability, a benzene ring group or a naphthalene ring group is preferred, and a benzene ring group is more preferred.
Examples of substituents that the aryl group may have include methyl, ethyl, propyl, methoxy, ethoxy, chloro, bromo, fluoro, hydroxy, amino, epoxy, oligo An ethylene glycol group, a phenyl group, a carboxyl group and the like can be mentioned, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Alkenyl groups for R ^E include linear, branched and cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkenyl groups include ethenyl, propenyl, butylenyl, cyclohexenyl and the like. Among these, from the viewpoint of curability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.
Examples of substituents that the alkenyl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo An ethylene glycol group, a phenyl group, a carboxyl group and the like can be mentioned, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

Thus, R ^E represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkenyl group. From the viewpoint of developability, an alkyl group or an alkenyl group is preferred, an alkyl group is more preferred, and a dicyclopentanyl group is even more preferred.

The content of the partial structure represented by the general formula (I′) contained in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 0.5 mol % or more, more preferably 1 mol % or more. , more preferably 1.5 mol% or more, particularly preferably 2 mol% or more, preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50% mol or less, more preferably 30 mol% or less More preferably, 10 mol % or less is particularly preferable. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

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

In the above formula (I''), ^R represents a hydrogen atom or a methyl group, R represents an ^optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, represents a carboxyl group, a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkylsulfide group which may have a substituent; t represents an integer of 0 to 5;

( ^RG )
In the above formula (I''), R ^G is an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, or a substituted group. represents an optionally substituted alkoxy group, a thiol group, or an optionally substituted alkylsulfide group.
Alkyl groups for R ^G include linear, branched and cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, preferably 20 or less, more preferably 18 or less, It is more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

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

Alkenyl groups for R ^G include linear, branched and cyclic alkenyl groups. The number of carbon atoms is preferably 2 or more, preferably 22 or less, more preferably 20 or less, further preferably 18 or less, and even more preferably 16 or less. , 14 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkenyl groups include ethenyl, propenyl, butylenyl, cyclohexenyl and the like. Among these, from the viewpoint of curability, an ethenyl group or a propenyl group is preferable, and an ethenyl group is more preferable.
Examples of substituents that the alkenyl group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligo An ethylene glycol group, a phenyl group, a carboxyl group and the like can be mentioned, and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferable.

The halogen atom in ^RG includes a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of ink repellency.

The alkoxy group for R ^G includes linear, branched or cyclic alkoxy groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Examples of substituents that the alkoxy group may have include a methoxy group, an ethoxy group, a chloro group, a bromo group, a fluoro group, a hydroxy group, an amino group, an epoxy group, an oligoethylene glycol group, a phenyl group, and a carboxyl group. , an acryloyl group, a methacryloyl group, etc., and from the viewpoint of developability, a hydroxy group and an oligoethylene glycol group are preferred.

The alkylsulfide group for R ^G includes linear, branched or cyclic alkylsulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, further preferably 16 or less, and even more preferably 14 or less. , 12 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

Specific examples of alkylsulfide groups include methylsulfide, ethylsulfide, propylsulfide, and butylsulfide groups. Among these, a methylsulfide group or an ethylsulfide group is preferable from the viewpoint of developability.
Substituents that the alkyl group in the alkylsulfide group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, acryloyl group, methacryloyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferred.

Thus, R ^G is an optionally substituted alkyl group, an optionally substituted alkenyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkyl sulfide group, but among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

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

The content ratio of the partial structure represented by the general formula (I'') contained in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, More preferably 3 mol% or more, particularly preferably 5 mol% or more, preferably 90 mol% or less, more preferably 70 mol% or less, further preferably 50 mol% or less, and even more preferably 30 mol% or less, 20 mol % or less is particularly preferred, and 10 mol % or less is most preferred. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

When the acrylic copolymer resin (b2-1) contains a partial structure represented by the general formula (I), it further contains a partial structure represented by the following general formula (I''') from the viewpoint of developability. is preferred.

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

The content of the partial structure represented by the general formula (I''') contained in the acrylic copolymer resin (b2-1) is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more. , more preferably 30 mol % or more, preferably 90 mol % or less, more preferably 80 mol % or less, even more preferably 70 mol % or less, and particularly preferably 50 mol % or less. When the concentration is equal to or higher than the lower limit, the amount of residue tends to be reduced, and when the concentration is equal to or lower than the upper limit, the development adhesion tends to be improved. On the other hand, from the viewpoint of reducing outgassing, it is preferable that the partial structure represented by the general formula (I''') is not contained at 0%.

The acid value of the acrylic copolymer resin (b2) is not particularly limited, but is preferably 5 mg-KOH/g or more, more preferably 10 mg-KOH/g or more, still more preferably 20 mg-KOH/g or more, and 25 mg-KOH/g. The above is more preferable, and 100 mg-KOH/g or less is preferable, 80 mg-KOH/g or less is more preferable, 60 mg-KOH/g or less is more preferable, and 40 mg-KOH/g or less is even more preferable. When the concentration is equal to or higher than the lower limit, the amount of residue tends to be reduced, and when the concentration is equal to or lower than the upper limit, the development adhesion tends to be improved.

Although the weight average molecular weight (Mw) of the acrylic copolymer resin (b2) is not particularly limited, it is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 3,000 or more, and even more preferably 4,000. More preferably, it is 5,000 or more, and usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, and still more preferably 10,000 or less. Especially preferably, it is 8,000 or less. When the content is equal to or higher than the lower limit, the development adhesion tends to be improved, and when the content is equal to or lower than the upper limit, the residue tends to be reduced.

(B) When the alkali-soluble resin contains the acrylic copolymer resin (b2), the content of the acrylic copolymer resin (b2) in the alkali-soluble resin (B) is not particularly limited, but is preferably 5% by mass or more. It is 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 even more preferably 50% by mass or less. When the content is equal to or higher than the lower limit, the solubility in development tends to be improved, and when the content is equal to or lower than the upper limit, the taper angle tends to increase.

The (B) alkali-soluble resin may contain either one of the epoxy (meth)acrylate resin (b1) and the acrylic copolymer resin (b2) alone, or both of them. Furthermore, the alkali-soluble resin (B) may contain an alkali-soluble resin other than the alkali-soluble resin (b).

The content of (B) the alkali-soluble resin in the photosensitive resin composition of the present invention is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 20% by mass or more, in the total solid content. It is 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less. When the concentration is equal to or higher than the lower limit, the developability tends to be improved, and when the concentration is equal to or lower than the upper limit, outgassing during device light emission tends to be reduced.

Further, 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) in the total solid content is not particularly limited, but is usually 5 mass. % or more, preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, and more It is preferably 60% by mass or less, particularly preferably 50% by mass or less. When the concentration is equal to or higher than the lower limit, the developability tends to be improved, and when the concentration is equal to or lower than the upper limit, outgassing during device light emission tends to be reduced.

Further, when the photosensitive resin composition of the present invention contains the acrylic copolymer resin (b2), the content of the acrylic copolymer resin (b2) in the total solid content is not particularly limited, but usually 5% by mass or more, preferably is 10% by mass or more, more preferably 20% by mass or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 90% by mass or less, preferably 70% by mass or less, more preferably 60% by mass % or less, particularly preferably 50 mass % or less. When the concentration is equal to or higher than the lower limit, the developability tends to be improved, and when the concentration is equal to or lower than the upper limit, outgassing during device light emission tends to be reduced.

In addition, the total content of (B) the alkali-soluble resin and (C) the photopolymerizable compound in the total solid content is usually 5% by mass or more, preferably 10% by mass or more, more preferably 30% by mass or more, and further It is preferably 50% by mass or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, most preferably 90% by mass or more, and usually 99% by mass or less, preferably 97% by mass or less. , more preferably 95% by mass or less. When the content is at least the lower limit, curability tends to improve, and when the content is at most the upper limit, outgassing during device light emission tends to be reduced.

In the photosensitive resin composition of the present invention, the content of (B) alkali-soluble resin is 500 parts by mass or less relative to 100 parts by mass of (C) photopolymerizable compound. By setting the content ratio of the alkali-soluble resin (B) to the photopolymerizable compound (C) to be equal to or less than the above upper limit, the photocurability can be increased, and a sufficient amount of the liquid repellent agent can be fixed to the pattern surface during exposure. It is thought that the outflow of the liquid-repellent agent can be suppressed during subsequent development processing, and sufficient ink repellency can be obtained before and after UV irradiation.
(C) The content of the alkali-soluble resin (B) with respect to 100 parts by mass of the photopolymerizable compound is not particularly limited as long as it is 500 parts by mass or less, preferably 400 parts by mass or less, more preferably 300 parts by mass or less, and 200 parts by mass. The amount is more preferably 150 parts by mass or less, more preferably 50 parts by mass or more, more preferably 60 parts by mass or more, still more preferably 70 parts by mass or more, and particularly preferably 80 parts by mass or more. Curability tends to be improved by setting the upper limit value or less, and residue tends to be less likely to occur when the value is set to the lower limit value or more.

[1-1-3] Component (C); Photopolymerizable Compound The photosensitive resin composition of the present invention contains (C) a photopolymerizable compound. (C) It is considered that the inclusion of the photopolymerizable compound results in high sensitivity.
The photopolymerizable compound used here means a compound having one or more ethylenically unsaturated bonds (ethylenic double bonds) in the molecule, and has polymerizability, crosslinkability, and the accompanying exposure area. A compound having two or more ethylenically unsaturated bonds in the molecule is preferred, and the unsaturated bond is a (meth)acryloyloxy derived from a group, that is, a (meth)acrylate compound is more preferred.

In the photosensitive resin composition of the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, still more preferably 4 or more, and particularly preferably 5 or more. , and preferably 15 or less, more preferably 10 or less, still more preferably 8 or less, and particularly preferably 7 or less. When the content is at least the above lower limit, the polymerizability tends to be improved and the sensitivity tends to be high, and when the content is at most the above upper limit, the developability tends to be better.
Specific examples of photopolymerizable compounds include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic polyhydroxy compounds, and the like. and esters obtained by an esterification reaction of polyhydric hydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids.

Esters of the aliphatic polyhydroxy compounds and unsaturated carboxylic acids include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, and methacrylic acid esters obtained by replacing the acrylates of these exemplary compounds with methacrylates Similarly, itaconate instead of itaconate, crotonate instead of clonate, maleate instead of maleate, and the like.

Esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, and pyrogallol triacrylate. etc.
Esters obtained by the esterification reaction of polyhydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single substances, but are representative. Specific examples include condensates of acrylic acid, phthalic acid and ethylene glycol, condensates of acrylic acid, maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, acrylic acid, adipic acid, Examples include condensates of butanediol and glycerin.

Other examples of the photopolymerizable compound used in the photosensitive resin composition of the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic acid ester or a polyisocyanate compound and a polyol and a hydroxyl group-containing (meth)acrylic acid ester. urethane (meth)acrylates such as those obtained by reacting them; epoxy acrylates such as addition reaction products of polyepoxy compounds and hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; Allyl esters such as diallyl phthalate; and vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth)acrylates include, 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 Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV -7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.) and the like.

Among these, it is preferable to use ester (meth)acrylates or urethane (meth)acrylates as the (C) photopolymerizable compound from the viewpoint of an appropriate taper angle and sensitivity, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-tris(meth)acryloyloxymethylethyl phthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate dibasic It is more preferable to use an acid anhydride adduct, a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate, or the like.
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 photopolymerizable compound (C) is not particularly limited, but is preferably 100 or more, more preferably 150 or more, and It is preferably 200 or more, more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less. The number of carbon atoms in (A) the ethylenically unsaturated compound is not particularly limited, but from the viewpoint 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 preferably 15 or more. It is preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, even more preferably 35 or less, particularly preferably 30 or less.
From the viewpoint of sensitivity, ink repellency, and taper angle, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferred. Among them, pentaerythritol tetra (meth)acrylate and pentaerythritol tri(meth)acrylate dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate and other trifunctional or higher ester (meth)acrylates, 2,2,2-tris(meth)acryloyloxymethylethyl phthal Acid anhydride adducts to trifunctional or higher ester (meth)acrylates such as dibasic acid anhydride adducts of dipentaerythritol penta(meth)acrylate improve sensitivity, ink repellency, and taper angle. is more preferable.

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

The content of (C) the photopolymerizable compound relative to 100 parts by mass of the (B) alkali-soluble resin is 20 parts by mass or more, preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 80 parts by mass. It is at least 150 parts by mass, preferably at most 130 parts by mass, more preferably at most 120 parts by mass, and even more preferably at most 110 parts by mass. When it is at least the above lower limit, sensitivity during exposure tends to be good, and the taper angle and ink repellency tend to be good, and when it is at most the upper limit, developability tends to be good.

[1-1-4] Component (D); Photopolymerization Initiator The photosensitive resin composition of the present invention contains (D) a photopolymerization initiator. The photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the ethylenically unsaturated bond of the (C) photopolymerizable compound by actinic rays, and a known photopolymerization initiator can be used. can.

In the photosensitive resin composition of the present invention, a photopolymerization initiator commonly used in this field can be used as (D) the photopolymerization initiator. Examples of such photopolymerization initiators include hexaarylbiimidazole-based photopolymerization initiators, acylphosphine oxide-based photopolymerization initiators, oxime ester-based photopolymerization initiators, triazine-based photopolymerization initiators, and acetophenone-based photopolymerization initiators. Initiators, benzophenone-based photopolymerization initiators, and the like.

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

In the above formula, each of R ¹¹ to R ¹³ is independently an optionally substituted alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms which may be substituted, or halogen represents an atom, and m, n and l each independently represents an integer of 0 to 5;

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

The number of carbon atoms in the alkoxy groups of R ¹¹ to R ¹³ is not particularly limited as long as it is within the range of 1 to 4, but from the viewpoint of sensitivity, it is preferably 3 or less, more preferably 2 or less. The alkyl group portion of the alkoxy group may be chain or cyclic. Specific examples of alkoxy groups include methoxy, ethoxy, propoxy, isopropyloxy, and butoxy groups, with methoxy and ethoxy groups being preferred. An alkoxy group can be mentioned as a substituent which the alkoxy group having 1 to 4 carbon atoms represented by R ¹¹ to R ¹³ may have.

Further, the halogen atoms represented by R ¹¹ to R ¹³ include, for example, a chlorine atom, an iodine atom, a bromine atom, and a fluorine atom. Among them, from the viewpoint of ease of synthesis, a chlorine atom or a fluorine atom is preferable, and a chlorine atom is more preferable. preferable.
Among these, from the viewpoint of sensitivity and ease of synthesis, each of R ¹¹ to R ¹³ is preferably independently a halogen atom, more preferably a chlorine atom.

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

Examples of hexaarylbiimidazole compounds represented by general formula (1-1) and/or general formula (1-2) include 2,2'-bis(o-chlorophenyl)-4,5,4' ,5′-tetraphenylbiimidazole, 2,2′-bis(o-methylphenyl)-4,5,4′,5′-tetraphenylbiimidazole, 2,2′-bis(o-chlorophenyl)-4 ,4′,5,5′-tetra(o,p-dichlorophenyl)biimidazole, 2,2′-bis(o,p-dichlorophenyl)-4,4′,5,5′-tetra(o,p- dichlorophenyl)biimidazole, 2,2′-bis(o-chlorophenyl)-4,4′,5,5′-tetra(p-fluorophenyl)biimidazole, 2,2′-bis(o-chlorophenyl)-4 ,4′,5,5′-tetra(o,p-dibromophenyl)biimidazole, 2,2′-bis(o-bromophenyl)-4,4′,5,5′-tetra(o,p- dichlorophenyl)biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(p-chloronaphthyl)biimidazole and the like. Among them, hexaphenylbiimidazole compounds are preferred, and those in which the o-position of the benzene ring bonded to the 2,2'-position on the imidazole ring is substituted with a methyl group, a methoxy group, or a halogen atom are more preferred. Preferred are those in which the benzene rings bonded to the 4,4',5,5'-positions on the imidazole ring are unsubstituted or substituted with halogen atoms or methoxy groups.

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

Preferable acylphosphine oxide photopolymerization initiators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide. .

The oxime ester photopolymerization initiator preferably contains an oxime ester compound having a carbazole skeleton or a diphenyl sulfide skeleton, and more preferably an oxime ester compound having a diphenyl sulfide skeleton. By including an oxime ester compound having a diphenyl sulfide skeleton, short-wavelength light absorption is strong and surface curability is improved.

The chemical structure of the oxime ester compound having a diphenyl sulfide skeleton is not particularly limited, but from the viewpoint of sensitivity, it is preferable to use one represented by the following general formula (DI).

In general formula (DI) above, R ²³ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ²⁴ represents an optionally substituted alkyl group or an optionally substituted aromatic ring group.
R ²⁵ represents a hydroxyl group, a carboxyl group or a group represented by the following general formula (D-II), and h represents an integer of 0-5.
The benzene ring shown in formula (DI) may further have a substituent.

In formula (D-II), R ^25a represents -O-, -S-, -OCO- or -COO-.
R ^25b represents an optionally substituted alkylene group.
The alkylene portion of R ^25b may be interrupted 1 to 5 times by -O-, -S-, -COO- or -OCO-. The alkylene portion of R ²⁵ may have a branched side chain and may be cyclohexylene.
R ^25c represents a hydroxyl group or a carboxyl group.

Although the number of carbon atoms in the alkyl group in R ²³ is not particularly limited, it is preferably 1 or more from the viewpoint of solubility in solvents. From the viewpoint of developability, it is preferably 20 or less, more preferably 10 or less, even more preferably 8 or less, even more preferably 5 or less, and particularly preferably 3 or less. preferable.

Specific examples of the alkyl group include a methyl group, a hexyl group, a cyclopentylmethyl group, etc. Among these, from the viewpoint of developability, a methyl group or a hexyl group is preferable, and a methyl group is more preferable.
Examples of the substituent that the alkyl group may have include an aromatic ring group, a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and the like. From the viewpoint of alkali developability, a hydroxyl group and a carboxyl group are preferred. A carboxyl group is more preferred. Moreover, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

The aromatic ring group for R ²³ includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. Although the number of carbon atoms in the aromatic ring group is not particularly limited, it is preferably 5 or more from the viewpoint of solubility in solvents. From the viewpoint of developability, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less.

Specific examples of the aromatic ring group include a phenyl group, a naphthyl group, a pyridyl group, a furyl group, and the like. Among these, from the viewpoint of developability, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.
Examples of substituents that the aromatic ring group may have include a hydroxyl group, a carboxyl group, a halogen atom, an amino group, an amide group, and an alkyl group. groups are more preferred.
Among these, from the viewpoint of developability, R ²³ is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and even more preferably a methyl group. .

Although the number of carbon atoms in the alkyl group in R ²⁴ is not particularly limited, it is preferably 1 or more from the viewpoint of sensitivity. From the viewpoint of sensitivity, it is preferably 20 or less, more preferably 10 or less, even more preferably 5 or less, and particularly preferably 3 or less.

Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, etc. Among these, from the viewpoint of sensitivity, a methyl group or an ethyl group is preferable, and a methyl group is more preferable.
Examples of the substituent that the alkyl group may have include a halogen atom, a hydroxyl group, a carboxyl group, an amino group, an amide group, etc. From the viewpoint of alkali developability, a hydroxyl group and a carboxyl group are preferred, and a carboxyl group is more preferred. On the other hand, it is preferably unsubstituted from the viewpoint of ease of synthesis.

The aromatic ring group for R ²⁴ includes aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms is preferably 30 or less, more preferably 12 or less, usually 4 or more, preferably 6 or more. The sensitivity tends to be high when the concentration is equal to or less than the upper limit, and the sublimability tends to be low when the concentration is equal to or more than the lower limit.

The aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring group. groups such as ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring.
In addition, the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. , pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline Groups such as rings, quinazolinone rings, and azulene rings can be mentioned.
Examples of substituents that the aromatic ring group may have include an alkyl group, a halogen atom, a hydroxyl group, and a carboxyl group.
Among these, from the viewpoint of sensitivity, R ²⁴ is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group, and even more preferably a methyl group.
On the other hand, from the viewpoint of plate-making properties, R ²⁴ is preferably an optionally substituted aromatic ring group, more preferably an optionally substituted aromatic hydrocarbon group. , more preferably an unsubstituted aromatic hydrocarbon group, and particularly preferably a phenyl group.

R ²⁵ is a hydroxyl group, a carboxyl group, or a group represented by the general formula (D-II). It is preferably a group.
In the general formula (D-II), as described above, R ^25a represents -O-, -S-, -OCO- or -COO-. O- or -OCO- is preferred, and -O- is more preferred.

As described above, R ^25b represents an optionally substituted alkylene group.
Although the number of carbon atoms in the alkylene group in R ^25b is not particularly limited, it is preferably 1 or more, more preferably 2 or more, and 20 or less from the viewpoint of solubility in the photosensitive resin composition. is preferred, 10 or less is more preferred, 5 or less is even more preferred, and 3 or less is particularly preferred.
The alkylene group may be linear or branched, and may contain an aliphatic ring. Among these, from the viewpoint of solubility in the photosensitive resin composition, a linear chain is preferred.

Specific examples of the alkylene group include a methylene group, an ethylene group, a propylene group and the like, and among these, an ethylene group is more preferable from the viewpoint of solubility in the photosensitive resin composition.

As mentioned above, R ^25c is a hydroxyl group or a carboxyl group. From the viewpoint of development adhesion, R ^25c is preferably a hydroxyl group.

In the general formula (DI), h represents an integer of 0-5. In particular, from the viewpoint of developability, h is preferably 1 or more, preferably 4 or less, more preferably 3 or less, further preferably 2 or less, and 1. Most preferred.
On the other hand, h is preferably 0 from the viewpoint of ease of synthesis.

Triazine-based photopolymerization initiators include halomethylated s-triazine derivatives such as 2,4,6-tris(monochloromethyl)-s-triazine, 2,4,6-tris(dichloromethyl)- s-triazine, 2,4,6-tris(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 2-n-propyl-4,6-bis( trichloromethyl)-s-triazine, 2-(α,α,β-trichloroethyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s -triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-epoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine , 2-(p-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[1-(p-methoxyphenyl)-2,4-butadienyl]-4,6-bis(trichloromethyl) )-s-triazine, 2-styryl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-( p-methoxy-m-hydroxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(pi-propyloxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p- ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-phenylthio-4,6- Bis(trichloromethyl)-s-triazine, 2-benzylthio-4,6-bis(trichloromethyl)-s-triazine, 2,4,6-tris(dibromomethyl)-s-triazine, 2,4,6- tris(tribromomethyl)-s-triazine, 2-methyl-4,6-bis(tribromomethyl)-s-triazine, 2-methoxy-4,6-bis(tribromomethyl)-s-triazine, 2 Halomethyl such as -(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine and bis(trihalomethyl)-s-triazine derivatives are preferred from the viewpoint of sensitivity.

Acetophenone-based photopolymerization initiators include, for example, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexylphenylketone, 1-hydroxy-1-(p-dodecylphenyl)ketone. , 1-hydroxy-1-methylethyl-(p-isopropylphenyl)ketone, 1-trichloromethyl-(p-butylphenyl)ketone, α-hydroxy-2-methylphenylpropanone, 2-methyl-1[4- (Methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1-one, 2-benzyl-2-dimethylamino-1 -(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethyl aminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 4-(diethylamino)chalcone and the like.
Examples of benzophenone-based photopolymerization initiators include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-carboxybenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, and Michler's ketone.

One of these photopolymerization initiators may be contained alone in the photosensitive resin composition, or two or more thereof may be contained. Among these photopolymerization initiators, it is preferable to contain at least one selected from the group consisting of hexaarylbiimidazole-based photopolymerization initiators, oxime ester-based photopolymerization initiators, and acetophenone-based photopolymerization initiators. Hexaarylbiimidazole compounds are particularly preferable because they have high absorbance and therefore have high surface curability, as well as high ink repellency and a high taper angle. In addition, oxime ester compounds are particularly preferable in that they have high sensitivity and exhibit ink repellency even at low exposure doses. Acetophenone-based photopolymerization initiators are particularly preferred because they have high internal curability, high ink repellency, and high taper angles.

The content of (D) the photopolymerization initiator in the photosensitive resin composition of the present invention is not particularly limited, but usually 0.01% by mass or more, preferably 0.1% by mass in the total solid content of the photosensitive resin composition % or more, more preferably 0.5 mass % or more, more preferably 1 mass % or more, particularly preferably 1.5 mass % or more, usually 25 mass % or less, preferably 10 mass % or less, more preferably 8 % by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less. When it is at least the above lower limit, a coating film is formed without causing film reduction during development, and there is a tendency for sufficient ink repellency to occur. tends to be easier.

Further, the mixing ratio of the (D) photopolymerization initiator to the (C) photopolymerizable compound in the photosensitive resin composition is preferably 1 part by weight or more with respect to 100 parts by weight of the (C) photopolymerizable compound. , More preferably 2 parts by mass or more, more preferably 3 parts by mass or more, preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, and even more preferably 20 parts by mass or less , 10 parts by mass or less is particularly preferred, and 5 parts by mass or less is most preferred. Setting it to the above lower limit or more tends to provide an appropriate sensitivity, and setting it to the above upper limit or less tends to facilitate formation of a desired pattern shape.

A sensitizer may be used in combination with the photopolymerization initiator. The sensitizer improves the sensitivity and at the same time decreases the light transmittance into the photosensitive resin composition, which tends to increase the taper angle.

As a sensitizer, a sensitizer commonly used in this field can be used. The sensitizer has the characteristic of transferring the energy obtained by absorption to the photopolymerization initiator, or causing transfer of electrons with the photopolymerization initiator, thereby efficiently promoting the reactive radical polymerization reaction. Examples of such sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone; 1,2-diketone compounds such as benzyl and camphorquinone; benzoin compounds; compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonol derivatives, etc. Polymethine dyes, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds , tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium tetraphyllin-based compounds, annulene-based compounds, spiropyran-based compounds, spirooxazine-based compounds, thiospiropyran-based compounds, metal arene complexes, organic ruthenium complexes, benzophenone-based compounds, and the like.
These may be used individually by 1 type, and may use 2 or more types together.

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

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

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

When the photosensitive resin composition contains a sensitizer, the content of the sensitizer in the total solid content of the photosensitive resin composition is not particularly limited, but is usually 0.1% by mass or more, preferably 0.3. % by mass or more, more preferably 0.5% by mass or more, still more preferably 0.8% by mass or more, even more preferably 1% by mass or more, particularly preferably 1.2% by mass or more, and usually 10% by mass Below, it is preferably 7% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less. When it is equal to or higher than the lower limit, there is a tendency that sensitivity can be improved and the taper angle can be increased, and when it is equal to or lower than the upper limit, it tends to be easier to form a desired pattern.

[1-1-5] Chain Transfer Agent The photosensitive resin composition of the present invention may further contain a chain transfer agent. By containing a chain transfer agent, radical deactivation due to oxygen inhibition or the like in the vicinity of the surface can be improved, surface curability can be improved, and the taper angle tends to increase. In addition, by increasing the surface curability, the outflow of the liquid-repellent agent can be suppressed, and the liquid-repellent agent tends to be easily fixed in the vicinity of the surface of the partition, increasing the contact angle.
Examples of chain transfer agents include mercapto group-containing compounds, carbon tetrachloride, and the like, and it is more preferable to use compounds having a mercapto group because they tend to have a high chain transfer effect. Since bond cleavage is likely to occur due to the small SH bond energy, and chain transfer reaction is likely to occur, surface curability tends to be enhanced.

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

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

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 these, from the viewpoint of the taper angle, Z is preferably -S- or -NH-, and more preferably -NH-.
From the viewpoint of the taper angle, R ⁶¹ , R ⁶² , R ⁶³ and R ⁶⁴ are each independently preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms, and more preferably a hydrogen atom. preferable.

Specifically, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, 2-mercapto-4(3H)-quinazoline, β-mercaptonaphthalene , 1,4-dimethylmercaptobenzene and the like, and 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred from the viewpoint of the taper angle.

On the other hand, as the aliphatic mercapto group-containing compound, hexanedithiol, decanedithiol, or a compound represented by the following general formula (E-2) is preferably used from the viewpoint of surface curability.

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

In general formula (E-2), m is preferably 1 or 2 from the viewpoint of ease of synthesis. Moreover, n is preferably 3 or 4 from the viewpoint of surface curability.
The alkyl groups for R ⁷¹ and R ⁷² preferably have 1 to 3 carbon atoms from the viewpoint of surface curability. From the viewpoint of surface curability, at least one of R ⁷¹ and R ⁷² , for example, R ⁷² is preferably a hydrogen atom, in which case R ⁷¹ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. is preferred.

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

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

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

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

On the other hand, when n is 4, X preferably has a structure represented by general formula (E-2-3) below.

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

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

These various things can be used individually by 1 type, or in mixture of 2 or more types.

Among these, from the viewpoint of enhancing ink repellency, one or more selected from the group consisting of 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, and 2-mercaptobenzoxazole are combined with a photopolymerization initiator, It is preferred for use as a photoinitiator system. For example, 2-mercaptobenzothiazole may be used, 2-mercaptobenzimidazole may be used, or 2-mercaptobenzothiazole and 2-mercaptobenzimidazole may be used in combination.
From the viewpoint of surface curability, it is preferable to use one or more selected from the group consisting of pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate).

The content of the chain transfer agent in the photosensitive resin composition of the present invention is not particularly limited. It is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, particularly preferably 1% by mass or more, and is usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less. be. When it is at least the above lower limit, the taper angle tends to be high, the surface curability is high, and the ink repellency tends to be high. be.

Further, when a mercapto group-containing compound having an aromatic ring and an aliphatic mercapto group-containing compound are used in combination as a chain transfer agent, the content ratio is 100 parts by mass of the mercapto group-containing compound having an aromatic ring. On the other hand, the aliphatic mercapto group-containing compound is usually 10 parts by mass or more, preferably 50 parts by mass or more, more preferably 80 parts by mass or more, usually 400 parts by mass or less, preferably 300 parts by mass or less, and more It is preferably 200 parts by mass or less, more preferably 150 parts by mass or less. When the content is at least the lower limit, the ink repellency tends to be enhanced, and when the content is at or below the upper limit, the sensitivity tends to be enhanced.

Further, the compounding ratio of the chain transfer agent to (C) the photopolymerizable compound in the photosensitive resin composition is preferably 10 parts by mass or more, and 25 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (C). More preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, preferably 500 parts by mass or less, more preferably 400 parts by mass or less, further preferably 300 parts by mass or less, 200 parts by mass The following is more preferable, and 150 parts by mass or less is particularly preferable. When it is at least the above lower limit, the taper angle tends to be high, the surface curability is high, and the ink repellency tends to be high. be.

[1-1-6] Ultraviolet Absorber The photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the photocuring distribution by absorbing a specific wavelength of the light source used for exposure by the ultraviolet absorber. By including an ultraviolet absorber, there is a tendency to obtain effects such as improving the taper angle shape after development and reducing residues remaining in non-exposed areas after development. As the ultraviolet absorber, for example, a compound having an absorption maximum between 250 nm and 400 nm can be used from the viewpoint of inhibiting light absorption by the photopolymerization initiator.
Examples of UV absorbers include benzotriazole compounds, triazine compounds, benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, and dyes.
These ultraviolet absorbers can be used singly or in combination of two or more.

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

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

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

In formula (Z2) above, R ^4e represents an optionally substituted alkylene group, and R ^5e represents an optionally substituted alkyl group.

In formula (Z3) above, R ^6e represents an optionally substituted alkylene group, and R ^7e represents a hydrogen atom or a methyl group.

(R ^1e and R ^2e )
In formula (Z1), R ^1e and R ^2e are each independently a hydrogen atom, an optionally substituted alkyl group, a group represented by general formula (Z2), or a group represented by general formula (Z3) represents the group represented.
Alkyl groups include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 2 or more, further preferably 4 or more, preferably 10 or less, more preferably 6 or less, It is more preferably 4 or less.

Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl and tert-butyl groups. Among these, a tert-butyl group is preferred.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group. , an acryloyl group, a methacryloyl group, and the like.

( ^R3e )
In formula (Z1), R ^3e represents a hydrogen atom or a halogen atom.
Halogen atoms include fluorine, chlorine, bromine, and iodine atoms.
Among these, from the viewpoint of synthesis, R ^3e is preferably a hydrogen atom.

( ^R4e )
In formula (Z2) above, R ^4e represents an optionally substituted alkylene group.
Alkylene groups include linear, branched and cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

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

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

( ^R5e )
In the formula (Z2), represents an optionally substituted alkyl group.
Alkyl groups include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 4 or more, more preferably 5 or more, further preferably 7 or more, preferably 15 or less, more preferably 10 or less, It is more preferably 9 or less.

Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and nonyl groups.
Examples of substituents that the alkyl group may have include methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, and carboxyl group. , an acryloyl group, a methacryloyl group, and the like.
Among these, R ^5e is preferably a heptyl group, an octyl group, or a nonyl group from the viewpoint of a tapered shape.

( ^R6e )
In formula (Z3), R ^6e represents an optionally substituted alkylene group.
Alkylene groups include linear, branched and cyclic alkylene groups. The number of carbon atoms is usually 1 or more, preferably 2 or more, preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

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

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

Specific examples of benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, octyl-3[3- tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5- A mixture of chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3- t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-5' -t-octylphenyl)benzotriazole, benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl esters of compound, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1- methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol. Among these, from the viewpoint of taper angle and exposure sensitivity, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester Compounds are preferred.

Examples of commercially available benzotriazole compounds include Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by Johoku Chemical Co., Ltd.), ＴＩＮＵＶＩＮ ＰＳ、ＴＩＮＵＶＩＮ９９－２、ＴＩＮＵＶＩＮ１０９、ＴＩＮＵＶＩＮ３８４－２、ＴＩＮＵＶＩＮ ３２６、ＴＩＮＵＶＩＮ９００、「ＴＩＮＵＶＩＮ ９２８」、ＴＩＮＵＶＩＮ９２８、ＴＩＮＵＶＩＮ１１３０（ＢＡＳＦ社製）、ＥＶＥＲＳＯＲＢ７０、ＥＶＥＲＳＯＲＢ７１、ＥＶＥＲＳＯＲＢ７２、ＥＶＥＲＳＯＲＢ７３、ＥＶＥＲＳＯＲＢ７４、ＥＶＥＲＳＯＲＢ７５、ＥＶＥＲＳＯＲＢ７６、ＥＶＥＲＳＯＲＢ２３４、ＥＶＥＲＳＯＲＢ７７、 EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Eikoh Chemical Co., Ltd.), Tomisorb 100, Tomisorb 600 (manufactured by API Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB70SEE (manufactured by PROC) (manufactured by Otsuka Chemical Co., Ltd.).

Triazine compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl)-4 2,4-bis "2-hydroxy-4-butoxyphenyl"- 6-(2,4-dibutoxyphenyl)-1,3-5-triazine, etc. Among these, hydroxyphenyltriazine compounds are preferred from the viewpoint of taper angle and exposure sensitivity.
Commercially available triazine compounds include, for example, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).

Other UV absorbers include, for example, Sumisorb 130 (manufactured by Sumitomo Chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Eikoh Chemical Co., Ltd.), Tomisorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102. , SEESORB103, SEESORB105, SEESORB106, SEESORB107, SEESORB151 (manufactured by Shipro Kasei) and other benzophenone compounds; Sumisorb 400 (manufactured by Sumitomo Chemical Co., Ltd.), benzoate compounds such as phenyl salicylate; 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, Cinnamic acid derivatives such as isopropyl methoxycinnamate and isoamyl methoxycinnamate; , 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, Naphthalene derivatives such as 2,7-dihydroxynaphthalene; anthracene and its derivatives such as anthracene and 9,10-dihydroxyanthracene; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate Dyes such as dyes, triazine dyes and p-aminobenzoic acid dyes; Among these, from the viewpoint of exposure sensitivity, cinnamic acid derivatives and naphthalene derivatives are preferred, and cinnamic acid derivatives are particularly preferred.

When the photosensitive resin composition of the present invention contains an ultraviolet absorber, the content is not particularly limited, but usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.05% by mass or more in the total solid content is 0.1% by mass or more, more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less , more preferably 3% by mass or less. The taper angle tends to increase when the lower limit value or more is used, and the sensitivity tends to be high when the upper limit value or less is used.

In addition, the blending ratio of (C) to the photopolymerization initiator is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 10 parts by mass or more, as the blending amount of the ultraviolet absorber with respect to 100 parts by mass of the photopolymerization initiator (C). 30 parts by mass or more, more preferably 50 parts by mass or more, particularly preferably 80 parts by mass or more, usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, further preferably 150 parts by mass It is below. The taper angle tends to increase when the lower limit value or more is used, and the sensitivity tends to be high when the upper limit value or less is used.

[1-1-7] Polymerization Inhibitor The photosensitive resin composition of the present invention may contain a polymerization inhibitor. It is thought that the inclusion of a polymerization inhibitor inhibits radical polymerization, and thus the taper angle of the obtained partition walls can be increased.
Polymerization inhibitors include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, methylhydroquinone or methoxyphenol is preferred, and methylhydroquinone is more preferred, from the viewpoint of the ability to inhibit polymerization.

It is preferable to contain one or more polymerization inhibitors. Normally, when producing the (B) alkali-soluble resin, the resin may contain a polymerization inhibitor, which may be used as the polymerization inhibitor of the present invention. In addition, the same or different polymerization inhibitor may be added during the production of the photosensitive resin composition.

When the photosensitive resin composition contains a polymerization inhibitor, the content ratio is not particularly limited, but usually 0.0005% by mass or more, preferably 0.001% by mass or more in the total solid content of the photosensitive resin composition , more preferably 0.01% by mass or more, and usually 0.3% by mass or less, preferably 0.2% by mass or less, and more preferably 0.1% by mass or less. The taper angle tends to be increased by making it equal to or greater than the lower limit, and the high sensitivity tends to be maintained by making it equal to or less than the upper limit.

[1-1-8] Amino Compound The photosensitive resin composition of the present invention may contain an amino compound in order to accelerate thermosetting. When the photosensitive resin composition contains an amino compound, its content is not particularly limited, but is usually 40% by mass or less, preferably 30% by mass or less, based on the total solid content of the photosensitive resin composition. Moreover, it is usually 0.5% by mass or more, preferably 1% by mass or more. When the content is equal to or less than the upper limit, storage stability tends to be maintained, and when the content is equal to or greater than the lower limit, sufficient thermosetting property tends to be ensured.

Examples of amino compounds include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups obtained by subjecting the methylol group to condensation-denaturation with an alcohol having 1 to 8 carbon atoms. Specifically, for example, melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by polycondensation of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril and formaldehyde; Examples include polycondensed urea resins; resins obtained by co-polycondensing two or more of melamine, benzoguanamine, glycoluril, or urea with formaldehyde; and modified resins obtained by modifying the methylol groups of the above resins by alcohol condensation. These may be used individually by 1 type, and may use 2 or more types together. Of these amino compounds, melamine resins and modified resins thereof are preferred, modified resins having a modified ratio of methylol groups of 70% or more are more preferred, and modified resins having a modified ratio of methylol groups of 80% or more are particularly preferred.

Specific examples of the amino compounds include melamine resins and modified resins thereof; 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nikalac" (registered trademark) MW-390, MW-100LM manufactured by Sanwa Chemical Co., Ltd. , MX-750LM, MW-30M, MX-45, MX-302 and the like. Examples of the benzoguanamine resin and its modified resin include Cymel (registered trademark) 1123, 1125 and 1128 manufactured by Cytech. Examples of the glycoluril resin and modified resin thereof include "Cymel" (registered trademark) 1170, 1171, 1174, and 1172 manufactured by Cytec Co., Ltd., and "Nikalac" (registered trademark) MX manufactured by Sanwa Chemical Co., Ltd. -270 and the like. Examples of the urea resin and its modified resin include "UFR" (registered trademark) 65, 300 manufactured by Cytec Co., Ltd., and "Nikalac" (registered trademark) MX-290 manufactured by Sanwa Chemical Co., Ltd. be done.

[1-1-9] Colorant The photosensitive resin composition of the invention may contain a colorant for the purpose of coloring the partition walls. As the coloring agent, known coloring agents such as pigments and dyes can be used. Further, when using a pigment, for example, a known dispersant or dispersing aid may be used in combination so that the pigment can stably exist in the photosensitive resin composition without aggregating.
In particular, it is preferable to use a black colorant because it is effective to obtain a clear pixel display by coloring the ink-repellent partition walls black. Examples of black colorants include black dyes, black pigments, carbon black, titanium black, and organic black pigments. In addition, from the viewpoint of low conductivity, it is also preferable to use a black colorant obtained by mixing a plurality of kinds of organic color pigments.

When the photosensitive resin composition of the present invention contains a coloring agent, the content is not particularly limited, but from the viewpoint of plate-making properties and color characteristics, the total solid content of the photosensitive resin composition is usually 60% by mass. Below, preferably 40% by mass or less.
On the other hand, when the purpose is to reduce the outgassing from the partition walls, it is desirable to reduce the colorant component in the partition walls from the viewpoint of suppressing the outgassing derived from the colorant or the dispersant. The content is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 0% by mass, based on the total solid content of the photosensitive resin composition.

[1-1-10] Coatability improver, development improver The photosensitive resin composition of the present invention contains a coatability improver and a development improver to improve the coatability and development solubility. good too. Known cationic, anionic, nonionic, fluorine-based and silicone-based surfactants can be used as coatability improvers or development improvers. Surfactants can be used for the purpose of improving the applicability of the photosensitive resin composition as a coating liquid and the developability of the coating film. Among them, fluorine-based or silicone-based surfactants are preferred.
In particular, during development, there is an action to remove the residue of the photosensitive resin composition from the unexposed area, also, since it has a function to express the wettability, silicone-based surfactants are preferable, polyether-modified silicone-based Surfactants are more preferred.

Compounds having a fluoroalkyl or fluoroalkylene group on at least one of the terminal, main chain and side chain are suitable as the fluorosurfactant. Specifically, 1,1,2,2-tetrafluorooctyl (1,1,2,2-tetrafluoropropyl) ether, 1,1,2,2-tetrafluorooctylhexyl ether, octaethylene glycol di( 1,1,2,2-tetrafluorobutyl) ether, hexaethylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, octapropylene glycol di(1,1,2,2- tetrafluorobutyl) ether, hexapropylene glycol di(1,1,2,2,3,3-hexafluoropentyl) ether, sodium perfluorododecylsulfonate, 1,1,2,2,8,8,9, Examples include 9,10,10-decafluorododecane, 1,1,2,2,3,3-hexafluorodecane, and the like. These commercial products include, for example, "BM-1000" and "BM-1100" manufactured by BM Chemie, "Megafac F470" and "Megafac F475" manufactured by DIC, "FC430" manufactured by 3M Japan, and Neos. "DFX-18" manufactured by K.K.

Examples of silicone surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive" and "SH8400" manufactured by Dow Corning Toray Co., Ltd. Commercial products such as "BYK323" and "BYK330" manufactured by BYK-Chemie can be mentioned.
Surfactants other than fluorine-based surfactants and silicone-based surfactants may be included, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants. be done.

Examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene fatty acid esters, Glycerin fatty acid esters, polyoxyethylene glycerin fatty acid esters, pentaerythrityl fatty acid esters, polyoxyethylene pentaerythritic fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbit fatty acid esters, polyoxy Ethylene sorbite fatty acid esters and the like can be mentioned. Examples of these commercially available products include polyoxyethylene-based surfactants such as "Emulgen 104P" and "Emulgen A60" manufactured by Kao Corporation.

Examples of the anionic surfactant include alkylsulfonates, alkylbenzenesulfonates, alkylnaphthalenesulfonates, polyoxyethylene alkylethersulfonates, alkylsulfates, alkylsulfates, and higher alcohol sulfuric acid. Ester salts, fatty alcohol sulfate ester salts, polyoxyethylene alkyl ether sulfates, polyoxyethylene alkyl phenyl ether sulfates, alkyl phosphate ester salts, polyoxyethylene alkyl ether phosphates, polyoxyethylene alkyl phenyl ether phosphates, special Examples include polymeric surfactants. Among them, a special polymeric surfactant is preferable, and a special polycarboxylic acid type polymeric surfactant is more preferable. As such anionic surfactants, commercially available products can be used. For example, for alkyl sulfate ester salts, "Emal 10" manufactured by Kao Corporation, etc., and for alkylnaphthalene sulfonates, "Pelex NB-L" manufactured by Kao Corporation. As special polymeric surfactants, Kao Corporation's "Homogenol L-18" and "Homogenol L-100" can be mentioned.

Furthermore, examples of cationic surfactants include quaternary ammonium salts, imidazoline derivatives, and alkylamine salts, and examples of amphoteric surfactants include betaine compounds, imidazolium salts, imidazolines, and amino acids. etc. Among these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Commercially available alkylamine salts include, for example, "Acetamine 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "Cortamine 24P" and "Cortamine 86W" manufactured by Kao Corporation.
In addition, two or more surfactants may be used in combination. For example, silicone surfactant/fluorosurfactant, silicone surfactant/special polymer surfactant, fluorine surfactant / A combination of special polymeric surfactants. Among them, a combination of silicone surfactant/fluorosurfactant is preferable. In this combination of silicone surfactant / fluorosurfactant, for example, "DFX-18" manufactured by Neos, "BYK-300" or "BYK-330" manufactured by BYK Chemie / "S -393”, “KP340” manufactured by Shin-Etsu Silicone Co., Ltd. / “Megafac F-478” or “Megafac F-475” manufactured by DIC, “SH7PA” manufactured by Dow Corning Toray / “DS-401” manufactured by Daikin, "L-77" manufactured by NUC and "FC4430" manufactured by 3M Japan.

Further, when a surfactant is used, its content is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, more preferably 0.005 to 1% by mass, based on the total solid content in the photosensitive resin composition. 01 to 0.5% by weight, most preferably 0.03 to 0.3% by weight. When the surfactant content is equal to or higher than the lower limit, the coating film tends to exhibit smoothness and uniformity, and when the content is equal to or lower than the upper limit, the coating film exhibits smoothness and uniformity. It tends to be easy and suppress the deterioration of other properties.

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

[1-1-12] Phosphoric Acid-Based Adhesion Improver It is also preferable to add a phosphoric acid-based adhesion improver to the photosensitive resin composition of the present invention in order to improve the adhesion to the substrate. (Meth)acryloyloxy group-containing phosphates are preferable as the phosphoric acid-based adhesion improver, and among them, those represented by the following general formulas (Va), (Vb), and (Vc) are preferable.

In general formulas (Va), (Vb) and (Vc) above, R ⁸ represents a hydrogen atom or a methyl group, r and r' are integers of 1 to 10, and s is 1, 2 or 3.

When the photosensitive resin composition of the present invention contains a phosphoric acid-based adhesion improver, the content is not particularly limited. It is more preferably 0.5% by mass or more, more preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less. Adhesion to the substrate tends to improve when the content is equal to or higher than the lower limit, and surface curability tends to improve when the content is equal to or lower than the upper limit.

[1-1-13] Inorganic filler In addition, the photosensitive resin composition of the present invention has improved strength as a cured product, and has an appropriate interaction (formation of a matrix structure) with an alkali-soluble resin to form a coating film. An inorganic filler may be contained for the purpose of improving flatness and taper angle. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, and those surface-treated with various silane coupling agents.

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

[1-1-14] Solvent The photosensitive resin composition of the present invention usually contains a solvent, and is used in a state in which each of the above components is dissolved or dispersed in the solvent (hereinafter referred to as a photosensitive resin composition containing a solvent A photosensitive resin composition may be referred to as a “photosensitive resin composition solution”). The solvent is not particularly limited, but includes, for example, the organic solvents described below.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, tri Glycol monoalkyl ethers such as ethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol methyl ether; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether , glycol dialkyl ethers such as dipropylene glycol dimethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate , triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, 3-methyl-3-methoxybutyl acetate, 3-methoxy-1-butyl acetate; ethylene glycol diacetate, 1 ,3-butylene glycol diacetate, 1,6-hexanol diacetate and other glycol diacetates; cyclohexanol acetate and other alkyl acetates; amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether , ethyl isobutyl ether, dihexyl ether; Ketones such as hexyl ketone, methyl nonyl ketone, methoxymethylpentanone; methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxy monohydric or polyhydric alcohols such as methylpentanol, glycerin, benzyl alcohol; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene and bicyclohexyl; aromatic hydrocarbons such as benzene, toluene, xylene and cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate, Propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethoxypropion Linear or cyclic esters such as methyl acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid; halogenated hydrocarbons such as butyl chloride and amyl chloride; ether ketones such as methoxymethylpentanone; Nitriles such as tetrahydrofuran such as tetrahydrofuran, dimethyltetrahydrofuran, dimethoxytetrahydrofuran, and the like.

Commercially available solvents corresponding to the above include Mineral Spirit, Valsol #2, Apco #18 Solvent, Apco Thinner, 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, diglyme (all trade names), and the like.

The solvent is capable of dissolving or dispersing each component in the photosensitive resin composition, and is selected according to the method of using the photosensitive resin composition of the present invention. It is preferable to select one having a boiling point in the range of 60 to 280° C. under atmospheric pressure (1013.25 hPa). More preferably, it has a boiling point of 70° C. or higher and 260° C. or lower, such as propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate and 3-methoxy-1-butyl acetate.

These solvents can be used singly or in combination of two or more. Further, these solvents have a total solid content in the photosensitive resin composition solution of usually 10% by mass or more, preferably 15% by mass or more, more preferably 18% by mass or more, and usually 90% by mass or less. It is preferably used in an amount of 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less. When it is at least the above lower limit, a coating film tends to be obtained even with a large film thickness, and when it is at most the above upper limit, there is a tendency that moderate coating uniformity can be obtained.

[1-2] Physical Properties of Photosensitive Resin Composition Physical properties of the photosensitive resin composition of the present invention include, for example, acid value. The acid value relative to the total solid content of the photosensitive resin composition is not particularly limited, but is preferably 20 mg-KOH/g or more, more preferably 22 mg-KOH/g or more, further preferably 24 mg-KOH/g or more, and 26 mg-KOH. / g or more is more preferable, 28 mg-KOH / g or more is particularly preferable, and usually 60 mg-KOH / g or less, preferably 55 mg-KOH / g or less, more preferably 50 mg-KOH / g or less, 40 mg-KOH /g or less is more preferable, and 35 mg-KOH/g or less is particularly preferable. When it is at least the above lower limit, the solubility in the developer is high, and the taper angle tends to increase because the unexposed portion can be sufficiently dissolved and removed. tend to be better.

[1-3] Method for Preparing Photosensitive Resin Composition The photosensitive resin composition of the present invention is prepared by mixing the above components with a stirrer. In addition, you may filter using a membrane filter etc. so that the prepared photosensitive resin composition may be uniform.

[2] Partitions and Method for Forming Partitions The photosensitive resin composition of the present invention can be suitably used for forming partitions, particularly partitions for partitioning the organic layers (light-emitting portions) of organic electroluminescence elements. The partition wall of the present invention is composed of the photosensitive resin composition of the present invention.
The method for forming the partition walls (banks) using the photosensitive resin composition described above is not particularly limited, and conventionally known methods can be employed. A method for forming the partition walls includes, for example, a coating step of applying a photosensitive resin composition onto a substrate to form a photosensitive resin composition layer, and an exposure step of exposing the photosensitive resin composition layer. method. A specific example of a method for forming such partition walls is a photolithographic method.

In the photolithography method, a photosensitive resin composition is applied to the entire area of the substrate where the partition walls are to be formed to form a photosensitive resin composition layer. After the formed photosensitive resin composition layer is exposed according to a predetermined pattern of barrier ribs, the exposed photosensitive resin composition layer is developed to form barrier ribs on the substrate.

In the coating step of applying a photosensitive resin composition onto a substrate in the photolithography method, a contact transfer type coating device such as a roll coater, reverse coater, bar coater, etc. or a spinner (rotary A photosensitive resin composition is applied using a non-contact type coating device such as a coating device) or a curtain flow coater, and if necessary, the solvent is removed by drying to form a photosensitive resin composition layer.

Next, in the exposure step, a negative mask is used to irradiate the photosensitive resin composition with active energy rays such as ultraviolet light and excimer laser light, and the photosensitive resin composition layer is partially exposed according to the partition wall pattern. exposed to For exposure, a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an extra-high pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used. Although the amount of exposure varies depending on the composition of the photosensitive resin composition, it is preferably about 10 to 400 mJ/cm ² , for example.

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

After that, the barrier ribs are obtained by subjecting the developed barrier rib pattern to post-baking and heat curing. Post-baking is preferably carried out at 150-250° C. for 15-60 minutes.

A cleaning treatment may be performed for the purpose of cleaning the unexposed portions after the formation of the barrier ribs. The cleaning method is not particularly limited, and includes plasma irradiation, excimer light irradiation, and UV irradiation. In excimer light irradiation or UV irradiation, active oxygen can decompose and remove organic matter adhering to the pixel portion due to the light irradiation.

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

[3] Organic electroluminescence device The organic electroluminescence device of the present invention comprises partition walls made of the photosensitive resin composition described above.
Various optical elements are manufactured using the substrate provided with the partition pattern manufactured by the method described above. The method for forming the organic electroluminescence device is not particularly limited, but preferably, after forming the partition pattern on the substrate by the above method, ink is injected into the region surrounded by the partition on the substrate to form pixels and the like. An organic electroluminescence device is manufactured by forming an organic layer.
Types of organic electroluminescence devices include bottom emission type and top emission type.
In the bottom emission type, for example, partition walls are 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 electrode layer are laminated in an opening surrounded by the partition walls. be. On the other hand, in the top emission type, for example, barrier ribs are formed on a glass substrate laminated with a metal electrode layer, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are stacked in an opening surrounded by the barrier ribs. created by
Examples of the light-emitting layer include organic electroluminescent layers as described in JP-A-2009-146691 and Japanese Patent No. 5734681. Quantum dots as described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may also be used.

Water, an organic solvent, and a mixed solvent thereof can be used as the solvent used when forming the ink for forming the organic layer. The organic solvent is not particularly limited as long as it can be removed from the film formed after injecting the ink. Specific examples of organic solvents include toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropyl alcohol, ethyl acetate and butyl acetate, 3-phenoxytoluene, etc. In addition, surfactants, antioxidants, viscosity modifiers, ultraviolet absorbers, and the like can be added to the ink.

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

[4] Image Display Device The image display device of the present invention includes the organic electroluminescence device described above. There are no particular restrictions on the type or structure of the image display device as long as it contains an organic electroluminescence element, and for example, it can be assembled according to a conventional method using an active drive type organic electroluminescence element. For example, the image display device of the present invention is formed by the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata). can do. For example, an image may be displayed by combining an organic electroluminescent element that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent elements emitting different colors such as RGB.

[5] Lighting Lighting of the present invention includes the organic electroluminescence device described above. There are no particular restrictions on the type and structure, and the organic electroluminescence device of the present invention can be assembled according to a conventional method. The organic electroluminescence element may be of a simple matrix drive system or an active matrix drive system.
In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. Alternatively, organic electroluminescence elements emitting different colors may be combined to form a white color by mixing the colors, or a color mixing ratio may be adjusted to provide a toning function.

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

[1] Preparation and evaluation of photosensitive resin composition Propylene glycol monomethyl ether acetate was used so that each component was used at the blending ratio (parts by mass) shown in Table 1, and the total solid content was 19% by mass. was used to stir each component until uniform to prepare photosensitive resin compositions of Examples and Comparative Examples. In addition, the mixing ratio (mass part) of each component in Table 1 means the value of solid content.
The symbols in the table represent the following.

a-1: A fluorine atom-containing acrylic resin (liquid repellent agent) having an adamantane skeleton and an ethylenic double bond, obtained by synthesis according to the following procedure
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 55 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 105° C. while stirring under a nitrogen stream. Then, 20 parts by mass of a compound (aa-1) containing a poly(perfluoroalkylene ether) chain having the chemical structure shown below and 50.1 parts by mass of 3-hydroxy-1-adamantyl methacrylate were added to propylene glycol monomethyl ether acetate 84. .6 parts by mass of a monomer solution, and a polymerization initiator solution of 10.6 parts by mass of t-butylperoxy-2-ethylhexanoate as a polymerization initiator dissolved in 10.6 parts by mass of propylene glycol monomethyl ether acetate. The three types of dripping liquids were set in separate dripping devices, respectively, and were simultaneously dripped over 2 hours while the inside of the glass flask was kept at 105°C. After completion of dropping, the mixture was stirred at 105° C. for 5 hours, and 103.5 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (aa-2) solution.

(In the formula (aa-1), X is a perfluoromethylene group or a perfluoroethylene group, and an average of 7 perfluoromethylene groups and an average of 8 perfluoroethylene groups are present per molecule, The average number of fluorine atoms is 46.)

Next, 0.1 parts by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 parts by mass of tin octylate as a urethanization catalyst were added to the polymer (aa-2) solution obtained above, and the mixture was stirred under an air stream. Stirring was started, and 29.9 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining the temperature at 60°C. After the completion of dropwise addition, the mixture was stirred at 60°C for 2 hours, then heated to 80°C and stirred for 10 hours. Disappearance of the isocyanate group was confirmed by IR spectrum measurement. , a propylene glycol monomethyl ether acetate solution containing 50% by mass of an acrylic resin (a-1) having an adamantane skeleton and an ethylenic double bond was obtained. The obtained acrylic resin (a-1) had a polystyrene-equivalent weight average molecular weight (Mw) of 10,000 measured by GPC. Also, the double bond equivalent was 480.

a-2: A fluorine atom-containing acrylic resin having an ethylenic double bond (liquid repellent agent), synthesized by the following procedure
A glass flask equipped with a stirrer, a thermometer, a condenser, and a dropping device was charged with 35 parts by mass of propylene glycol monomethyl ether acetate as a solvent, and the temperature was raised to 105° C. while stirring under a nitrogen stream. Then, 20 parts by mass of the compound (aa-1), a monomer solution obtained by dissolving 46.1 parts by mass of 2-hydroxyethyl methacrylate in 84.6 parts by mass of propylene glycol monomethyl ether acetate, and t-butylperoxy as a polymerization initiator. Three types of dropping liquids, including a polymerization initiator solution in which 10.6 parts by mass of 2-ethylhexanoate is dissolved in 10.6 parts by mass of propylene glycol monomethyl ether acetate, are set in separate dropping devices, and the glass flask is While maintaining the inside at 105° C., the mixture was added dropwise over 2 hours. After completion of dropping, the mixture was stirred at 105° C. for 5 hours, and 83.5 parts by mass of the solvent was distilled off under reduced pressure to obtain a polymer (ab-2) solution.

Next, 0.1 part by mass of p-methoxyphenol as a polymerization inhibitor and 0.03 part by mass of tin octylate as a urethanization catalyst were added to the polymer (ab-2) solution obtained above, and the mixture was stirred under an air stream. Stirring was started, and 33.3 parts by mass of 2-acryloyloxyethyl isocyanate was added dropwise over 1 hour while maintaining the temperature at 60°C. After the dropwise addition was completed, the mixture was stirred at 60°C for 2 hours, then heated to 80°C and stirred for 10 hours. After confirming disappearance of the isocyanate group by IR spectrum measurement, 50.0 parts by mass of propylene glycol monomethyl ether acetate was added. , to obtain a propylene glycol monomethyl ether acetate solution containing 50% by mass of an acrylic resin (a-2) having an ethylenic double bond. The obtained acrylic resin (a-2) had a polystyrene equivalent weight average molecular weight (Mw) measured by GPC of 12,000. Also, the double bond equivalent was 340.

b-1: Alkali-soluble resin having an ethylenic double bond (corresponding to epoxy (meth)acrylate resin (b1-3)) synthesized by the following procedure
Bisphenol A type epoxy compound represented by the following formula (epoxy equivalent: 186 g/eq, mixture of m and n in the formula from 1 to 20) 100 parts by mass, acrylic acid 40 parts by mass, p-methoxyphenol 0.06 mass 2.4 parts by mass of triphenylphosphine and 126 parts by mass of propylene glycol monomethyl ether acetate were charged into a reaction vessel and stirred at 95° C. until the acid value became 5 mg-KOH/g or less. Next, 12 parts by mass of propylene glycol monomethyl ether acetate was added to 80 parts by mass of the reaction solution obtained by the above reaction, succinic anhydride was added, and the mixture was reacted at 95° C. for 3 hours to obtain a solid content acid value of 60 mg-KOH/g. An alkali-soluble resin (b-1) solution having a polystyrene equivalent weight average molecular weight (Mw) of 8,000 as measured by GPC was obtained.

c-1: Dipentaerythritol hexaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd.)
d-1: 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole (manufactured by Hodogaya Chemical Co., Ltd.)
d-2: Irgacure 369 (manufactured by BASF, compound with the following chemical structure)

d-3: A compound having the following chemical structure (oxime ester compound, satisfying the general formula (D-1))

e-1: 2-mercaptobenzimidazole (manufactured by Tokyo Kasei Co., Ltd.)
e-2: Pentaerythritol tetrakis (3-mercaptopropionate) (manufactured by Yodo Chemical Co., Ltd.)
f-1: TINUVIN384-2 (manufactured by BASF, UV absorber)
g-1: KAYAMER PM-21 (manufactured by Nippon Kayaku Co., Ltd.)

The physical properties of the photosensitive resin composition were evaluated by the methods described below.
(Measurement of contact angle)
Each photosensitive resin composition was applied onto a glass substrate using a spinner so as to have a thickness of 1.7 μm after heat curing. After that, it was dried by heating on a hot plate at 115° C. for 2 minutes, and the entire surface of the resulting coating film was exposed to light of 150 mJ/cm ² using an exposure machine MA-1100 manufactured by Dainippon Kaken Co., Ltd. without using a mask. exposed. At this time, the intensity at a wavelength of 365 nm was 40 mW/cm ² . Next, after spray development with a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 24° C. for 80 seconds, 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 substrate for contact angle measurement with a cured product.

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

Next, the substrate for contact angle measurement was irradiated with ultraviolet rays (UV) for 3 minutes using a dry processor VUM-3073 manufactured by ORC. At this time, the intensity at a wavelength of 254 nm was 9 mW/cm ² . The contact angle of the UV-irradiated substrate was measured in the same manner as described above. Table 1 shows the results.

(Evaluation of rate of decrease in contact angle due to UV irradiation)
The rate of decrease in contact angle due to UV irradiation was derived from the following formula and evaluated according to the following criteria. However, when the contact angle was less than 30° before the UV irradiation, NA (Not Available) was used without calculating the rate of decrease in the contact angle.
Reduction rate of contact angle (%)
= 100-{(contact angle after UV irradiation)/(contact angle before UV irradiation)} × 100
A: The contact angle before UV irradiation was 30° or more, and the rate of decrease in contact angle after UV irradiation was less than 35%.
B: The contact angle before UV irradiation was 30° or more, and the rate of decrease in contact angle after UV irradiation was 35% or more.
C: The contact angle before UV irradiation did not show 30° or more.
A is the preferred performance.

[2] Formation and evaluation of partition walls Formation of partition walls and performance evaluation were performed by the methods described below.
(Formation of partition wall)
Using a spinner, each photosensitive resin composition was applied onto the ITO film of a glass substrate having an ITO film formed thereon so as to have a thickness of 1.7 μm after heat curing. After that, it was dried by heating on a hot plate at 115 ° C. for 2 minutes, and a photomask (a mask having a plurality of 80 μm × 280 μm covering parts at 40 μm intervals) was used on the obtained coating film, and the exposure gap was 16 μm. Exposure was performed using an exposure machine MA-1100 manufactured by Kaken Co., Ltd. At this time, the intensity at a wavelength of 365 nm was 40 mW/cm ² , the exposure amount was 150 mJ/cm ² , and the exposure was performed in air. Next, after spray development with a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution at 24° C. for 80 seconds, it was washed with pure water for 1 minute. By these operations, the substrate on which unnecessary portions were removed and the pattern was formed was cured by heating in an oven at 230° C. for 30 minutes to obtain a substrate having grid-like partition walls without residue.

(UV resistance evaluation (inkjet coating suitability of partition walls))
The substrate having the grid-like partition walls was irradiated with ultraviolet (UV) rays for 3 minutes using a dry processor VUM-3073 manufactured by ORC. At this time, the intensity at a wavelength of 254 nm was 9 mW/cm ² .
Ink jet coating was performed using DMP-2831 manufactured by Fuji Film Co., Ltd. on the pixel portion surrounded by the grid-like partition walls of the substrate after the UV irradiation. A solvent (isoamyl benzoate) was used alone as the ink, and 480 pL of ink was applied per pixel, and the presence or absence of breakage (a phenomenon in which the ink crosses over the partition and mixes into the adjacent pixel portion) was evaluated. Breakage tends to be suppressed as the ink repellency of the partition wall increases. In Examples 1 to 5, the wetting and spreading property inside the partition walls after the inkjet coating was good, and there was no overflow to the outside of the partition walls.

It was confirmed that the coated substrates using the photosensitive resin compositions of Examples 1 to 5 had a low rate of decrease in contact angle after UV irradiation and had good IJ coating suitability after UV irradiation.
On the other hand, the coated substrate using the photosensitive resin composition of Comparative Example 1 showed a significant decrease in the contact angle after UV irradiation. Further, the coated substrate using the photosensitive resin composition of Comparative Example 2 had a low contact angle even before UV irradiation.

Although the detailed mechanism of the effect of the present invention has not been clarified, it is considered as follows.
The photosensitive resin compositions of Examples 1 to 5 contain a fluorine atom-containing acrylic resin (a-1) having an adamantane skeleton and an ethylenic double bond as a liquid-repellent agent. By having it, the decomposition of the liquid repellent agent in UV irradiation is suppressed, the abundance of fluorine atoms on the barrier rib surface after UV irradiation can be maintained, the contact angle decrease rate after UV irradiation is low, and the IJ coating suitability is improved. Conceivable. In addition, since the content of (B) the alkali-soluble resin relative to 100 parts by mass of the (C) photopolymerizable compound is 500 parts by mass or less, the photocurability can be increased, and a sufficient amount of repellency can be obtained during exposure processing. It is believed that the liquid agent can be fixed on the pattern surface, thereby increasing the contact angle even before the UV irradiation.

On the other hand, the photosensitive resin composition of Comparative Example 1 contains a fluorine atom-containing acrylic resin (a-2) as a liquid repellent agent, but does not have an adamantane skeleton, so it is decomposed by UV irradiation. It is thought that the amount of fluorine atoms present on the barrier rib surface after UV irradiation decreased, and the rate of decrease in the contact angle after UV irradiation decreased.

In addition, although the photosensitive resin composition of Comparative Example 2 contains a fluorine atom-containing acrylic resin (a-1) having an adamantane skeleton and an ethylenic double bond as a liquid repellent agent, (C) the photopolymerizable compound 100 When the content ratio of the alkali-soluble resin (B) exceeds 500 parts by mass, the photocurability is low, and a sufficient amount of the liquid-repellent agent cannot be fixed to the pattern surface during the exposure process, resulting in subsequent development. It is thought that the liquid-repellent agent flowed out during the treatment, and the contact angle became lower than before the UV irradiation.

Claims (8)

A photosensitive resin composition containing (A) a liquid repellent agent, (B) an alkali-soluble resin, (C) a photopolymerizable compound, and (D) a photopolymerization initiator,
The (A) liquid repellent agent contains a fluorine atom-containing acrylic resin (a) having an adamantane skeleton and an ethylenic double bond,
The content ratio of the (B) alkali-soluble resin to 100 parts by mass of the (C) photopolymerizable compound is 300 parts by mass or less,
The fluorine atom - containing acrylic resin (a) has a partial structure represented by the following general formula (1-1) and a partial structure represented by the following general formula (2),
The (C) photopolymerizable compound contains an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid ,
The (C) photopolymerizable compound is an ethylenically unsaturated compound derived from a (meth)acryloyloxy group.
A photosensitive resin composition characterized by having 5 or more saturated bonds .

(In formula (1-1), R ¹ and R ³ each independently represent a hydrogen atom or a methyl group.
X ¹ represents an adamantylene group optionally having a substituent.
X2 ^represents a urethane bond or an ester bond.
X3 ^represents a divalent hydrocarbon group.
* represents a bond. )

(In Formula (2), R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group.
^X4 represents a perfluoroalkylene group. A plurality of X ⁴ contained in formula (2) may be the same or different, and in the case of different ones, they may exist randomly or in blocks.
Each X ⁵ independently represents a direct bond or any divalent linking group.
n is an integer of 1 or more.
* represents a bond. ) 2. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin (B) contains an epoxy (meth)acrylate resin (b1). The photosensitive resin composition according to claim 1 or 2 , wherein the content of (A) the liquid repellent agent is 2% by mass or less in the total solid content. 4. The photosensitive resin composition according to any one of claims 1 to 3 , which is used for forming partition walls. A partition made of the photosensitive resin composition according to any one of claims 1 to 4 . An organic electroluminescence device comprising the partition according to claim 5 . An image display device comprising the organic electroluminescence device according to claim 6 . A lighting comprising the organic electroluminescent device according to claim 6 .