JP7435445B2 - Photosensitive colored resin compositions, cured products, image display devices and lighting - Google Patents

Description

The present invention relates to a photosensitive colored resin composition, and further relates to a cured product obtained by curing the photosensitive colored resin composition, and an image display device and illumination containing the cured product.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2018-136491 filed with the Japan Patent Office on July 20, 2018, as well as the documents cited in this specification, etc. A part or all of the content disclosed in the above is cited here and incorporated as the disclosure content of this specification.

Conventionally, organic electroluminescent devices included in organic field displays and organic field lighting have been manufactured by forming barrier ribs (banks) on a substrate and then laminating various functional layers within the area surrounded by the barrier ribs. Manufactured. As a method of easily forming such partition walls, a method of forming them by a photolithography method using a photosensitive resin composition is known.

In addition, as a method for laminating various functional layers in an area surrounded by partition walls, first, ink containing the material constituting the functional layer is prepared, and then the prepared ink is applied to the area surrounded by partition walls (pixel area). ) is known. Among these methods, the inkjet method is often adopted because it is easy to accurately inject a predetermined amount of ink into a predetermined location.

Furthermore, when forming a functional layer using ink, ink repellency is added to the partition walls in order to prevent ink from adhering to the partition walls and to prevent inks injected between adjacent regions from mixing with each other. may be required to be granted.
Furthermore, in recent years, various properties other than ink repellency have been required for partition walls, and various photosensitive resin compositions have been developed. For example, colored partition walls are required from the viewpoint of improving contrast and preventing reflection. Patent Document 1 describes a partition wall having both a fine line pattern and a minute contact hole by using a negative photosensitive resin composition containing two specific types of alkali-soluble resins and having a solid content acid value in a specific range. It is described that the black organic pigment contained therein has good dispersibility in the alkaline developer used for development, and also has good storage stability. Patent Document 2 discloses that by using a negative photosensitive resin composition containing a specific ink repellent agent and a specific photopolymerization initiator, good ink repellency can be achieved even in a mirror projection (MPA) method, and lines on a mask can be improved. It is stated that width reproduction is improved.

International Publication No. 2013/069789 International Publication No. 2012/147626

In recent years, the development of colored partition walls has been actively conducted, and for example, in order to form a functional layer with a predetermined thickness using an ink containing components with low solvent solubility, it is necessary to It is necessary to inject a large amount of dilute ink into the tank, which naturally requires thick colored partition walls.
Even such thick colored partition walls are required to exhibit higher ink repellency in order to prevent inks from mixing with each other between adjacent regions. Furthermore, in order to spread the ink uniformly over the pixel region and form a uniform functional layer without coating defects or unevenness at the edge portions, it is desirable that the side surfaces of the partition walls have a vertically tapered shape. The thicker the film is, the more likely it is that the side surfaces of the partition wall will be partially developed and unevenness will occur.Therefore, the thicker the film, the less unevenness there is and the need for a vertically tapered shape.

The present inventors investigated and found that it is difficult to achieve both high ink repellency and a good tapered shape in thick-film partition walls with the photosensitive colored resin composition described in Patent Document 1. It was done.
On the other hand, it has been found that in the photosensitive colored resin composition described in Patent Document 2, the surface of the coating film is too hardened compared to the lower part of the coating film, and a vertically tapered shape cannot be obtained.

The present invention has been made in view of the above circumstances, that is, it provides a photosensitive colored resin composition that has high ink repellency and is capable of forming partition walls with a good tapered shape. The purpose is to
Another object of the present invention is to provide a cured product obtained by curing the photosensitive colored resin composition, and an image display device and illumination containing the cured product.

As a result of intensive studies, the present inventors discovered that the above problems can be solved by combining a specific oxime ester photopolymerization initiator in a photosensitive colored resin composition containing a colorant and a liquid repellent, and have developed the present invention. It was completed.
That is, the gist of the present invention is as follows.

[1] A photosensitive colored resin composition containing (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent. ,
The photopolymerization initiator (A) is an oxime ester photopolymerization initiator (A1) whose absorbance at a wavelength of 400 nm is 20% or more of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. , contains an oxime ester photopolymerization initiator (A2) whose absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm;
A photosensitive colored resin composition, wherein the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.

[2] The photosensitive colored resin composition according to [1], wherein the oxime ester photopolymerization initiator (A1) contains an oxime ester photopolymerization initiator having a nitro group and a carbazole skeleton.
[3] The photosensitive colored resin composition according to [1] or [2], wherein the oxime ester photopolymerization initiator (A2) contains a compound represented by the following general formula (A2-1).

(In formula (A2-1), R ^13A represents an alkyl group that may have a substituent or an aromatic ring group that may have a substituent.
R ^14A represents an alkyl group or an aromatic ring group.
R ^15A represents a monovalent substituent.
n represents 0 or 1.
h represents an integer from 0 to 2. )

[4] The photosensitive colored resin composition according to [3], wherein in the formula (A2-1), R ^14A is an aromatic ring group.

[5] A photosensitive colored resin composition containing (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent, ,
The photopolymerization initiator (A) is an oxime ester photopolymerization initiator (A3) in which the absorbance at a wavelength of 400 nm is 8 to 30% of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. Contains
A photosensitive colored resin composition, wherein the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.

[6] The photosensitive colored resin according to any one of [1] to [5], wherein the fluorine atom-containing resin having a crosslinking group has one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Composition.
[7] The colorant (D) contains at least one selected from the group consisting of red pigments and orange pigments, and at least one selected from the group consisting of blue pigments and violet pigments, [1] - The photosensitive colored resin composition according to any one of [6].

[8] The colorant (D) is selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. The photosensitive colored resin composition according to any one of [1] to [7], which contains at least one organic black pigment.

(In formula (1), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ^- , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N = _CH2 , N= ^CHR21 , N= ^CR21R22 , SH, ^SR21 , ^{SOR21 ,} _SO2R21 ^{, SO3R21} , _{SO3H , SO3-} ^, _{SO2NH2 , SO2NHR} ²¹ or SO ₂ NR ²¹ R ²² ;
At least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ is may be bonded or may be bonded to each other by oxygen atoms, sulfur atoms, NH or ^NR bridges;
R ²¹ and R ²² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms; Represents 2 to 12 alkynyl groups. )

[9] The photosensitive colored resin composition according to any one of [1] to [8], which is used for forming partition walls.

[10] A cured product obtained by curing the photosensitive colored resin composition according to any one of [1] to [9].
[11] An image display device comprising the cured product according to [10].
[12] Illumination comprising the cured product according to [10].

According to the present invention, it is possible to provide a photosensitive colored resin composition that has high ink repellency and is capable of forming partition walls with a good tapered shape.

FIG. 1 is an explanatory diagram for evaluating the perpendicularity of the taper of a line pattern.

The present invention will be explained in detail below. Note that the following description is an example of the embodiment of the present invention, and the present invention is not limited to these unless it exceeds the gist thereof.
In the present invention, "(meth)acrylic" means "one or both of acrylic and methacrylic", and "total solid content" refers to the solvent in the photosensitive colored resin composition. shall mean all components other than Furthermore, in the present invention, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as lower and upper limits.
In addition, in the present invention, the term "(co)polymer" includes both a single polymer (homopolymer) and a copolymer (copolymer), and also includes "(acid)anhydride", "(Anhydrous)...acid" means to include both acids and their anhydrides.
In the present invention, a partition wall material refers to a bank material, a wall material, and a wall material, and similarly, a partition wall refers to a bank, a wall, and a wall.
In the present invention, the weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene measured by GPC (gel permeation chromatography).
In the present invention, the acid value refers to the acid value in terms of effective solid content, unless otherwise specified, and is calculated by neutralization titration.

In the present invention, the partition wall is, for example, a material for partitioning a functional layer (organic layer) in an active drive type organic electroluminescent device, and a material for configuring the functional layer in the partitioned area (pixel area). It is used to form pixels and the like consisting of functional layers and partition walls by ejecting and drying a certain ink.

[1] Photosensitive colored resin composition The photosensitive colored resin composition of the present invention comprises (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) Contains a liquid repellent as an essential component, and may further contain other components as necessary, such as a solvent.

The photosensitive colored resin composition according to the first aspect of the present invention includes (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) A photosensitive colored resin composition containing a liquid repellent, wherein the photopolymerization initiator (A) has an absorbance at a wavelength of 400 nm that is 20% higher than the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. % or more, and an oxime ester photopolymerization initiator (A1) whose absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. It contains an initiator (A2), and the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.

The photosensitive colored resin composition according to the second aspect of the present invention includes (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) A photosensitive colored resin composition containing a liquid repellent, wherein the photopolymerization initiator (A) has an absorbance at a wavelength of 400 nm that is 8% relative to an absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. The liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.

Hereinafter, unless otherwise specified, "the photosensitive colored resin composition of the present invention" refers to both the photosensitive colored resin composition according to the first aspect and the photosensitive colored resin composition according to the second aspect. refers to

[1-1] Components and composition of photosensitive colored resin composition The components constituting the photosensitive colored resin composition of the present invention and their composition will be explained in order.

[1-1-1] Component (A); Photopolymerization initiator The photosensitive colored resin composition of the present invention contains (A) a photopolymerization initiator. (A) The photopolymerization initiator is not particularly limited as long as it is a compound that polymerizes the (C) photopolymerizable compound with actinic rays, for example, polymerizes the ethylenically unsaturated bond possessed by the (C) photopolymerizable compound.

The photopolymerization initiator (A) in the photosensitive colored resin composition according to the first aspect of the present invention has an absorbance at a wavelength of 400 nm that is 20% higher than the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. % or more (hereinafter may be abbreviated as "oxime ester photoinitiator (A1)"), and the absorbance at a wavelength of 400 nm is between 300 and 400 nm. The oxime ester photopolymerization initiator (A2) is 10% or less of the absorbance at the maximum absorption wavelength (λ _max ) of (hereinafter sometimes abbreviated as "oxime ester photopolymerization initiator (A2)"). ).

In order to impart ink repellency to the partition walls, it is necessary to fix a liquid repellent to the surface of the partition walls. However, if the degree of hardening of the coating film after exposure to ultraviolet rays is insufficient, part of the film surface will dissolve during development processing, and the liquid repellent will flow out into the developer. When an oxime ester photopolymerization initiator (A2) that mainly utilizes i-line is used alone as a photopolymerization initiator, ink repellency is impaired due to insufficient curing after exposure to ultraviolet light.

In order to increase the degree of curing by ultraviolet light exposure, among oxime ester photopolymerization initiators that have an absorption band in the i-line, one that can also be used in the h-line, that is, an oxime ester-based photopolymerization initiator that has a sufficiently high absorbance at a wavelength of 400 nm. A method using a polymerization initiator (A1) can be mentioned.

On the other hand, when forming a thick film pattern, for example, the ultraviolet light that penetrates through the surface of the paint film during exposure to UV light is absorbed by the photopolymerization initiator, colorant, etc. contained in the paint film, making it difficult for it to penetrate into the inside of the paint film. , the degree of curing of the lower part of the coating tends to be lower than that of the upper part of the coating. Therefore, during the development process, the lower part of the coating film with a low degree of hardening may be excessively developed, resulting in a narrow pattern width.

When the oxime ester photopolymerization initiator (A1) is used alone, the ink repellency improves due to the improved curability in the upper part of the coating film, but most of the H-rays are caused by the initiation of oxime ester photopolymerization in the upper part of the coating film. The number of h-lines reaching the lower part of the coating film decreases, and the pattern width at the lower part of the coating film becomes narrower than that at the upper part of the coating film, further impairing the verticality of the taper on the side surface of the partition wall.

Therefore, by combining the oxime ester photopolymerization initiator (A1) and the oxime ester photopolymerization initiator (A2), the h The radiation absorption rate can be relatively low, that is, the H-ray can be transmitted to the bottom of the coating film, and the oxime ester photopolymerization initiator (A1) promotes curing using the H-ray near the glass substrate. This is thought to improve the perpendicularity of the taper on the side surface of the partition wall. In addition, by using the oxime ester photopolymerization initiator (A1) and the oxime ester photopolymerization initiator (A2) together, curing using i-line and h-line is performed near the film surface, resulting in ink repellency. is considered to be sufficient.

[1-1-1-1] Oxime ester photopolymerization initiator (A1)
The oxime ester photopolymerization initiator (A1) has an absorption maximum between wavelengths of 300 and 400 nm, and the absorbance at a wavelength of 400 nm is greater than the absorbance at the maximum absorption wavelength (λ _max ) between 300 and 400 nm. It is 20% or more. In this way, the oxime ester photopolymerization initiator (A1) has sufficient absorbance at a wavelength of 400 nm, and can be cured by fully utilizing not only the i-line but also the h-line of the ultraviolet rays emitted by the high-pressure mercury lamp. It is thought that the reaction can be accelerated.

The absorbance of the oxime ester photopolymerization initiator (A1) at a wavelength of 400 nm is not particularly limited as long as it is 20% or more of the absorbance at the maximum absorption wavelength (λ _max ) between 300 and 400 nm; Preferably, 30% or more, more preferably 32% or more, even more preferably 35% or more, particularly preferably 40% or more, and preferably 80% or less, more preferably 70% or less, and 60% or less. It is more preferably 50% or less, even more preferably 40% or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be high, and when it is equal to or less than the upper limit, the tapered shape of the side surface of the partition wall tends to be good. For example, the absorbance of the oxime ester photopolymerization initiator (A1) at a wavelength of 400 nm is preferably 20 to 80%, more preferably 25 to 70%, of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. It is preferably 30 to 60%, even more preferably 30 to 50%, and particularly preferably 32 to 40%.

Further, the maximum absorption wavelength (λ _max ) between 300 and 400 nm of the oxime ester photoinitiator (A1) is not particularly limited, but is preferably 320 nm or more, more preferably 340 nm or more, even more preferably 360 nm or more, and , preferably 390 nm or less, more preferably 380 nm or less, particularly preferably 370 nm or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be high, and when it is equal to or less than the upper limit, the tapered shape of the side surface of the partition wall tends to be good. For example, the maximum absorption wavelength (λ _max ) in the wavelength range of 300 to 400 nm of the oxime ester photopolymerization initiator (A1) is preferably 320 to 390 nm, more preferably 340 to 380 nm, and even more preferably 360 to 370 nm.

To measure the absorbance and maximum absorption wavelength of the oxime ester photopolymerization initiator (A1), first create a 0.01% by mass PGMEA (propylene glycol monomethyl ether acetate) solution of the oxime ester photopolymerization initiator (A1). It can be obtained by irradiating it with light with a wavelength of 300 to 400 nm using a spectrophotometer and measuring every 1 nm. Examples of spectrophotometers include, but are not limited to, UV-3000 series (manufactured by Shimadzu Corporation) and V-700 series (manufactured by JASCO Corporation). A 1 cm square quartz cell can be used as the measurement cell.

The oxime ester photopolymerization initiator (A1) has an absorbance at a wavelength of 400 nm that is 20% or more of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm, but has a high absorbance at a wavelength of 400 nm. Examples of such initiators include those having a fluorene skeleton or carbazole skeleton bound to an electron-withdrawing group such as a nitro group, and oxime ester photopolymerization initiators having a nitro group and a carbazole skeleton are preferred.

The chemical structure of the oxime ester photopolymerization initiator (A1) is not particularly limited, but from the viewpoint of ink repellency and tapered shape, it is preferred to be a compound having a chemical structure represented by the following general formula (A1-1). preferable.

(In formula (A1-1), R ^1A , R ^3A , R ^4A , R ^5A , R ^6A and R ^8A each independently represent a hydrogen atom, a nitro group, an alkyl group, or an aromatic ring group.
R ^2A and R ^7A each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic ring group which may have a substituent, a nitro group, or the following general formula (A1-2 ) represents a monovalent group represented by However, either one or both of R ^2A and R ^7A is a monovalent group represented by the following general formula (A1-2).
At least one of R ^1A to R ^8A is a nitro group.
R ^9A represents a hydrogen atom or an alkyl group.
m and n each independently represent 0 or 1. )

(In formula (A1-2), R ^11A represents an alkyl group or an aromatic ring group.
R ^12A represents an alkyl group which may have a substituent or an aromatic ring group which may have a substituent. )

(R ^1A , R ^3A , R ^4A , R ^5A , R ^6A and R ^8A )
The alkyl groups in R ^1A , R ^3A , R ^4A , R ^5A , R ^6A and R ^8A in the above formula (A1-1) may be linear, branched, or cyclic, or may be a combination thereof. There may be. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 8 or less, and more preferably 6 or less. When the amount is equal to or more than the lower limit, the solubility in a solvent tends to increase, and when the amount is equal to or less than the upper limit, the ink repellency tends to increase. For example, the number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 6.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Among these, from the viewpoint of ink repellency, methyl group, An ethyl group or a propyl group is preferable, and a methyl group is more preferable.

Examples of the aromatic ring group in R ^1A , R ^3A , R ^4A , R ^5A , R ^6A and R ^8A of the above formula (A1-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is not particularly limited, but is usually 4 or more, preferably 6 or more, preferably 20 or less, and more preferably 12 or less. When the amount is equal to or more than the lower limit, the solubility in a solvent tends to increase, and when the amount is equal to or less than the upper limit, the ink repellency tends to increase. For example, the number of carbon atoms in the aromatic ring group is preferably 4 to 20, more preferably 4 to 12.
Specific examples of the aromatic ring group include phenyl group, naphthyl group, anthracenyl group, thienyl group, furyl group, benzothienyl group, benzofuryl group, etc. Among these, phenyl group is preferred from the viewpoint of ink repellency. It is more preferable.

Among these, from the viewpoint of ink repellency, R ^1A , R ^3A , R ^4A , R ^5A , R ^6A and R ^8A are preferably each independently a hydrogen atom or a nitro group, and more preferably a hydrogen atom. preferable.

( ^R2A and ^R7A )
The alkyl groups in R ^2A and R ^7A of the above formula (A1-1) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 8 or less, and more preferably 6 or less. When the amount is equal to or more than the lower limit, the solubility in a solvent tends to increase, and when the amount is equal to or less than the upper limit, the ink repellency tends to increase. For example, the number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 1 to 6.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Among these, from the viewpoint of ink repellency, methyl group, An ethyl group or a propyl group is preferable, and a methyl group is more preferable.
Examples of the substituent that the alkyl group may have include a hydroxyl group and a carboxyl group, and a hydroxyl group is preferred from the viewpoint of developability.

Examples of the aromatic ring group in R ^2A and R ^7A of the above formula (A1-1) include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms is not particularly limited, but is usually 4 or more, preferably 6 or more, more preferably 10 or more, and preferably 20 or less, more preferably 12 or less. When the amount is equal to or more than the lower limit, the solubility in a solvent tends to increase, and when the amount is equal to or less than the upper limit, the ink repellency tends to increase. For example, the number of carbon atoms in the aromatic ring group is preferably 4 to 20, more preferably 4 to 12.

Specific examples of the aromatic ring group include phenyl group, naphthyl group, anthracenyl group, thienyl group, furyl group, benzothienyl group, and benzofuryl group. Among these, phenyl groups and naphthyl groups are more preferred from the viewpoint of ink repellency.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group and an alkyl group, with an alkyl group being preferred from the viewpoint of developability.

In the above formula (A1-1), either or both of R ^2A and R ^7A is a monovalent group represented by the above general formula (A1-2).

The alkyl group in R ^11A of the above formula (A1-2) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 5 or less, and more preferably 3 or less. Sensitivity tends to improve when the value is below the upper limit. For example, the number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, pentyl group, etc. Among these, methyl group is preferred from the viewpoint of ink repellency.

Examples of the aromatic ring group for R ^11A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. When the value is equal to or more than the lower limit, the solubility in the solvent tends to be improved, and when the value is equal to or less than the upper limit, the taper shape tends to be improved. For example, the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, and even more preferably 5 to 12 carbon atoms.

Specific examples of the aromatic ring group include phenyl group, naphthyl group, thienyl group, furyl group, etc. Among these, from the viewpoint of tapered shape, phenyl group or naphthyl group is preferable, and phenyl group is more preferable.

Among these, R ^11A is preferably an alkyl group, more preferably a methyl group, from the viewpoint of ink repellency.

The alkyl group in R ^12A may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 3 or more, more preferably 5 or more, even more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and 10 or less. It is more preferably 8 or less, even more preferably 7 or less, and particularly preferably 7 or less. When the amount is equal to or more than the lower limit, the solubility in the solvent tends to be improved, and when it is equal to or less than the upper limit, the developability tends to be improved. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, even more preferably 5 to 10 carbon atoms, even more preferably 5 to 8 carbon atoms, and particularly preferably 5 to 7 carbon atoms.
Specific examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, cyclopentyl group, cyclohexyl group, etc. Among these, from the viewpoint of developability, , isopentyl group, hexyl group, and heptyl group are preferable, and heptyl group is more preferable.
Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, etc. From the viewpoint of ease of synthesis, it is preferable that the alkyl group is unsubstituted.

Examples of the aromatic ring group for R ^12A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more. Further, it is preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. When the amount is equal to or more than the lower limit, the solubility in the solvent tends to be improved, and when the amount is equal to or less than the upper limit, the developability tends to be improved. The aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, even more preferably 4 to 12 carbon atoms, and even more preferably 5 to 12 carbon atoms.

Specific examples of the aromatic ring group include phenyl group, naphthyl group, thienyl group, furyl group, etc. Among these, from the viewpoint of developability, phenyl group or naphthyl group is preferable, and phenyl group is more preferable.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group, an alkyl group, an alkoxy group, an alkoxy group substituted with an alkoxy group, an alkoxy group substituted with a hydroxyl group, and the like. Among these, from the viewpoint of developability, an alkyl group, an alkoxy group substituted with an alkoxy group, or an alkoxy group substituted with a hydroxyl group are preferable. Examples of the alkyl group in the substituent which the aromatic ring group may have include alkyl having 1 to 6 carbon atoms, preferably alkyl having 1 to 4 carbon atoms, and more preferably alkyl having 1 to 3 carbon atoms. , methyl is particularly preferred. The alkoxy group in the substituent that the aromatic ring group may have, and the alkoxy group substituted on the alkoxy group in the substituent that the aromatic ring group may have, include alkoxy groups having 1 to 8 carbon atoms. Alkoxy having 1 to 6 carbon atoms is preferred, and alkoxy having 1 to 4 carbon atoms is more preferred.

Further, in the above formula (A1-1), m and n each independently represent 0 or 1, and 0 is preferable from the viewpoint of the contact angle, while 1 is preferable from the viewpoint of the tapered shape.

Among these, from the viewpoint of ink repellency, it is preferable that R ^2A and R ^7A are each independently a nitro group or a monovalent group represented by the above general formula (A1-2), and R ^2A is a nitro group. And it is more preferable that R ^7A is a monovalent group represented by the above general formula (A1-2).

(Nitro group)
At least one of R ^1A to R ^8A is a nitro group.
Among R ^1A to R ^8A , the number of nitro groups is not particularly limited, but is usually 1 or more, preferably 4 or less, more preferably 3 or less, and even more preferably 2 or less. When the amount is below the upper limit, developability tends to be improved. The number of nitro groups is preferably 1 to 4, more preferably 1 to 3, even more preferably 1 to 2.

Among these, from the viewpoint of ink repellency, it is preferable that R ^2A or R ^7A is a nitro group.
On the other hand, from the viewpoint of sensitivity, it is preferable that one or both of R ^4A and R ^5A is a nitro group, and it is more preferable that R ^4A and R ^5A are nitro groups.

( ^R9A )
The alkyl group for R ^9A in the above formula (A1-1) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. When the amount is equal to or more than the lower limit, the solubility in a solvent tends to improve, and when the amount is equal to or less than the upper limit, the ink repellency tends to be improved. For example, the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, even more preferably 1 to 6 carbon atoms, and particularly preferably 2 to 6 carbon atoms.
Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, etc. Among these, from the viewpoint of ink repellency, methyl group, It is preferably an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and even more preferably an ethyl group.

Specific examples of known compounds of the oxime ester photopolymerization initiator (A1) include the following.

Among these oxime ester photopolymerization initiators (A1), from the viewpoint of tapered shape, a compound having a chemical structure represented by the above formula (A1-11) is preferable.

[1-1-1-2] Oxime ester photopolymerization initiator (A2)
The oxime ester photopolymerization initiator (A2) has an absorption maximum between wavelengths of 300 and 400 nm, and the absorbance at a wavelength of 400 nm is greater than the absorbance at the maximum absorption wavelength (λ _max ) between 300 and 400 nm. It is 10% or less. In this way, the oxime ester photopolymerization initiator (A2) has a sufficiently low absorbance at a wavelength of 400 nm, and can be cured mainly using the i-line without making much use of the h-line among the ultraviolet rays emitted by the high-pressure mercury lamp. In order to accelerate the reaction, the absorption rate of H-rays in the upper part of the coating film can be lowered, and the H-rays can be transmitted to the vicinity of the glass substrate at the lower part of the coating film. It is thought that curing in the lower part of the film can be promoted and the verticality of the resulting pattern will be improved.

The absorbance of the oxime ester photopolymerization initiator (A2) at a wavelength of 400 nm is not particularly limited as long as it is 10% or less of the absorbance at the maximum absorption wavelength (λ _max ) between 300 and 400 nm; It is preferably 3% or less, more preferably 1% or less, preferably 0.01% or more, more preferably 0.05% or more, even more preferably 0.1% or more, and 0.3% or more. It is even more preferable, and 0.5% or more is particularly preferable. When the value is less than the upper limit, the tapered shape of the side surface of the partition wall tends to be better, and when it is more than the lower limit, the i-line curability tends to be sufficiently developed. For example, the absorbance of the oxime ester photopolymerization initiator (A2) at a wavelength of 400 nm is preferably 0.01 to 10%, and preferably 0.05 to 10%, of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. It is more preferably 5%, even more preferably 0.1 to 3%, even more preferably 0.3 to 3%, and particularly preferably 0.5 to 1%.

Further, the maximum absorption wavelength (λ _max ) between 300 and 400 nm of the oxime ester photoinitiator (A2) is not particularly limited, but is preferably 310 nm or more, more preferably 320 nm or more, even more preferably 325 nm or more, and , 350 nm or less is preferable, 340 nm or less is more preferable, and even more preferably 330 nm or less. When the value is equal to or more than the lower limit, the i-line curability tends to be good, and when the value is equal to or less than the upper limit, the tapered shape of the side surface of the partition wall tends to be good. For example, the maximum absorption wavelength (λ _max ) in the wavelength range of 300 to 400 nm of the oxime ester photopolymerization initiator (A2) is preferably 310 to 350 nm, more preferably 320 to 340 nm, even more preferably 325 to 340 nm.

To measure the absorbance and maximum absorption wavelength of the oxime ester photopolymerization initiator (A2), first create a 0.01% by mass PGMEA (propylene glycol monomethyl ether acetate) solution of the oxime ester photopolymerization initiator (A2). , it can be measured using a spectrophotometer in the same manner as the oxime ester photopolymerization initiator (A1).

The oxime ester photopolymerization initiator (A2) has an absorbance at a wavelength of 400 nm that is 10% or less of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm, but the absorbance at a wavelength of 400 nm is low. Examples include oxime ester photopolymerization initiators that do not have an electron-withdrawing group such as a nitro group in their skeletons, such as diphenyl sulfide, carbazole, and fluorene; for example, oxime ester photopolymerization initiators that do not have substituents in their skeletons; Examples include photopolymerization initiators and oxime ester photopolymerization initiators having substituents such as arylcarbonyl groups and alkoxy groups on their skeletons.

The chemical structure of the oxime ester photopolymerization initiator (A2) is not particularly limited, but from the viewpoint of a tapered shape, it preferably contains a compound represented by the following general formula (A2-1).

(In formula (A2-1), R ^13A represents an alkyl group that may have a substituent or an aromatic ring group that may have a substituent.
R ^14A represents an alkyl group or an aromatic ring group.
R ^15A represents a monovalent substituent.
n represents 0 or 1.
h represents an integer from 0 to 2. )

( ^R13A )
The alkyl group for R ^13A in the above formula (A2-1) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 4 or more, more preferably 6 or more, and preferably 20 or less, more preferably 10 or less, even more preferably 8 or less, and 7 or less. Even more preferred. When the content is below the upper limit, the solubility in the solvent tends to be improved. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, even more preferably 1 to 8 carbon atoms, even more preferably 1 to 7 carbon atoms, and particularly preferably 4 to 7 carbon atoms.

Specific examples of alkyl groups include methyl group, ethyl group, propyl group, butyl group, pentyl group, isopentyl group, hexyl group, cyclopentyl group, cyclohexyl group, cyclopentylmethyl group, cyclopentylethyl group, cyclohexylmethyl group, cyclohexylethyl group. Among these, from the viewpoint of developability, methyl group, hexyl group, isopentyl group, hexyl group, cyclopentylmethyl group, and cyclohexylmethyl group are preferable, and hexyl group and cyclopentylmethyl group are more preferable.

Examples of substituents that the alkyl group may have include aromatic ring groups, hydroxyl groups, carboxyl groups, etc. From the viewpoint of ease of synthesis, it is preferable that the alkyl group is unsubstituted.

The aromatic ring group for R ^13A in the above formula (A2-1) includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. When the amount is equal to or more than the lower limit, the solubility in the solvent tends to be improved, and when the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, even more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.

Specific examples of the aromatic ring group include phenyl group, naphthyl group, pyridyl group, furyl group, etc. Among these, from the viewpoint of developability, phenyl group or naphthyl group is preferable, and phenyl group is more preferable.
Examples of the substituent that the aromatic ring group may have include a hydroxyl group and an alkyl group, with an alkyl group being preferred from the viewpoint of developability.
Among these, from the viewpoint of the tapered shape, R ^13A is preferably an alkyl group which may have a substituent.

( ^R14A )
The alkyl group for R ^14A in the above formula (A2-1) may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 5 or less, and more preferably 3 or less. Sensitivity tends to improve when the value is below the upper limit. For example, the number of carbon atoms in the alkyl group is preferably 1 to 5, more preferably 1 to 3.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, pentyl group, etc. Among these, methyl group is preferable from the viewpoint of tapered shape.

The aromatic ring group for R ^14A in the above formula (A2-1) includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. When the amount is equal to or more than the lower limit, the solubility in a solvent tends to be improved, and when the amount is equal to or less than the upper limit, the sensitivity tends to be improved. For example, the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, even more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.

Specific examples of the aromatic ring group include phenyl group, naphthyl group, pyridyl group, furyl group, etc. Among these, from the viewpoint of tapered shape, phenyl group or naphthyl group is preferable, and phenyl group is more preferable.

Among these, R ^14A in the above formula (A2-1) is preferably an aromatic ring group, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group, from the viewpoint of contact angle. On the other hand, from the viewpoint of tapered shape, methyl group is preferable.

( ^R15A )
The monovalent substituent for R ^15A in the above formula (A2-1) is not particularly limited, but from the viewpoint of developability, R ^16A -O- or R ^16A -(C=O)- is preferable.

Examples of R ^16A include an alkyl group that may have a substituent and an aromatic ring group that may have a substituent.
The alkyl group in R ^16A may be linear, branched, cyclic, or a combination thereof. The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and preferably 8 or less, more preferably 5 or less. When the amount is equal to or more than the lower limit, the developability tends to be good, and when it is less than the upper limit, the tapered shape tends to be good. For example, the number of carbon atoms in the alkyl group is preferably 1 to 8, more preferably 2 to 5.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, pentyl group, etc. Among these, from the viewpoint of solubility, methyl group and ethyl group are preferable, and ethyl group is more preferable.
Examples of the substituent that the alkyl group may have include a hydroxyl group and a carboxyl group, and a hydroxyl group is preferred from the viewpoint of developability.

Examples of the aromatic ring group for R ^16A include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, preferably 30 or less, more preferably 20 or less, and even more preferably 12 or less. When the amount is equal to or more than the lower limit, the developability tends to be good, and when it is less than the upper limit, the tapered shape tends to be good. For example, the aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 4 to 20 carbon atoms, even more preferably 4 to 12 carbon atoms, and particularly preferably 5 to 12 carbon atoms.
Specific examples of the aromatic ring group include phenyl group, naphthyl group, thienyl group, furyl group, benzothienyl group, and benzofuryl group. Among these, from the viewpoint of tapered shape, benzothienyl group or benzofuryl group is preferable, and benzofuryl group is more preferable.
Examples of the substituent that the aromatic ring group may have include an alkyl group, a hydroxyl group, and a carboxyl group, and unsubstituted is preferable from the viewpoint of synthesis.

From the viewpoint of the tapered shape, the monovalent substituents for R ^15A in the above formula (A2-1) include R ^16A -O-, where R ^16A is a hydroxyl-substituted ethyl group, and R where R ^16A is a benzofuryl group. ^16A -(C=O)- is preferred, and R ^16A -O-, where R ^16A is a hydroxyl-substituted ethyl group, is more preferred.

(n)
In the above formula (A2-1), n represents 0 or 1. From the viewpoint of the tapered shape, n is preferably 1, while from the viewpoint of sensitivity, n is preferably 0.

(h)
In the above formula (A2-1), h represents an integer of 0 to 2. From the viewpoint of the tapered shape, h is preferably 0 or 1, and more preferably 0.
When h is an integer of 1 or more, the substitution position of R ^15A is not particularly limited, but from a synthetic viewpoint, the o-position or the p-position is preferable, and the p-position is more preferable.

Specific examples of known compounds of the oxime ester photopolymerization initiator (A2) include the following.

Among these, from the viewpoint of tapered shape, a compound having a chemical structure represented by the above formula (A2-19) is preferable. On the other hand, from the viewpoint of contact angle, a compound having a chemical structure represented by the above formula (A2-17) or (A2-18) is preferable.

The photopolymerization initiator (A) in the photosensitive colored resin composition according to the first aspect of the present invention is a photopolymerization initiator other than the oxime ester photoinitiator (A1) and the oxime ester photoinitiator (A2). It may contain an initiator (hereinafter sometimes referred to as "other photopolymerization initiator"). Other photopolymerization initiators may be oxime ester compounds or may be other than oxime ester compounds.

As other photopolymerization initiators, those commonly used in this field can be used. For example, metallocene compounds containing titanocene compounds described in Japanese Unexamined Patent Publication No. 59-152396 and Japanese Unexamined Patent Application No. 61-151197; hexaarylbiimidazole derivatives described in Japanese Unexamined Patent Publication No. 2000-56118. Class: Halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α- Examples include radical activators such as amino acid salts, N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives, and the like.

Specifically, for example, metallocene compounds include dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis(2,3,4,5,6-pentafluorophenyl ), dicyclopentadienyl titanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyl titanium bis(2,4,6-trifluorophenyl), dicyclopentadienyl titanium di( 2,6-difluorophenyl), dicyclopentadienyl titanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5,6-pentafluorophenyl), Di(methylcyclopentadienyl) titanium bis(2,6-difluorophenyl), dicyclopentadienyl titanium [2,6-di-fluoro-3-(pyrrol-1-yl)phenyl], and the like.

In addition, as biimidazole derivatives, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, (4'-methoxyphenyl) )-4,5-diphenylimidazole dimer and the like.

Further, as halomethylated oxadiazole derivatives, 2-trichloromethyl-5-(2'-benzofuryl)-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'- benzofuryl)vinyl]-1,3,4-oxadiazole, 2-trichloromethyl-5-[β-(2'-(6''-benzofuryl)vinyl)]-1,3,4-oxadiazole, Examples include 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

Further, as halomethyl-s-triazine derivatives, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis( trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl) -s-triazine and the like.

Further, as α-aminoalkylphenone derivatives, 2-methyl-1[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4- Morpholinophenyl)butan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzo ate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal)cyclohexanone, 7-diethylamino-3-( Examples include 4-diethylaminobenzoyl)coumarin and 4-(diethylamino)chalcone.

Other photopolymerization initiators may be used alone or in combination of two or more.

[1-1-1-3] Oxime ester photopolymerization initiator (A3)
As mentioned above, the photopolymerization initiator (A) in the photosensitive colored resin composition according to the second aspect of the present invention has an absorbance at a wavelength of 400 nm and an absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm. 8 to 30% of the oxime ester photopolymerization initiator (A3) (hereinafter sometimes abbreviated as "oxime ester photopolymerization initiator (A3)"). By containing the oxime ester photopolymerization initiator (A3) in this way, the liquid repellent can be fixed by curing using H-rays in the upper part of the coating film, and a certain amount of H-rays can be transmitted to the lower part of the coating film. It is thought that by doing so, curing using H-rays near the glass substrate is promoted and the verticality of the taper on the side surface of the partition wall becomes better.

The oxime ester photopolymerization initiator (A3) may be used alone or in a mixture of two or more types.
When it is a mixture of two or more types, for example, when it is a mixture of an oxime ester photopolymerization initiator (A3-1) and an oxime ester photopolymerization initiator (A3-2), the oxime ester photopolymerization initiator To determine the absorbance of the agent (A3) at a wavelength of 400 nm, first measure the absorbance of the oxime ester photopolymerization initiator (A3-1) at a wavelength of 400 nm and the absorbance of the oxime ester photopolymerization initiator (A3-2) at a wavelength of 400 nm. Then, by weighted average of the content ratio (based on mass) of the oxime ester photopolymerization initiator (A3-1) and the oxime ester photopolymerization initiator (A3-2) in the photosensitive colored resin composition. It can be calculated. The same applies to the case of three or more types.

The absorbance of the oxime ester photopolymerization initiator (A3) at a wavelength of 400 nm is not particularly limited as long as it is 8 to 30% of the absorbance at the maximum absorption wavelength (λ _max ) between 300 and 400 nm, but it is 10% or more. It is preferably 15% or more, more preferably 20% or more, even more preferably 23% or more, and preferably 28% or less, more preferably 27% or less, and even more preferably 26% or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be high, and when it is equal to or less than the upper limit, the tapered shape of the side surface of the partition wall tends to be good. For example, the absorbance of the oxime ester photopolymerization initiator (A3) at a wavelength of 400 nm is preferably 8 to 28% of the absorbance at a maximum absorption wavelength (λ _max ) between 300 and 400 nm, more preferably 10 to 28%. It is preferably 15 to 28%, even more preferably 20 to 27%, and particularly preferably 23 to 26%.

The photopolymerization initiator (A) in the photosensitive colored resin composition according to the second aspect of the present invention may contain a photopolymerization initiator other than the oxime ester photopolymerization initiator. Examples of the photopolymerization initiator other than the oxime ester photopolymerization initiator include those mentioned above as other photopolymerization initiators.

Furthermore, the photopolymerization initiator in the photosensitive colored resin composition of the present invention may contain a sensitizing dye and a polymerization accelerator depending on the wavelength of the image exposure light source, if necessary, for the purpose of increasing sensitivity. Can be done. As the sensitizing dye, xanthene dyes described in Japanese Patent Application Laid-Open No. 4-221958, Japanese Patent Application Publication No. 4-219756, Japanese Patent Application Publication No. 3-239703, and Japanese Patent Application Publication No. 5-289335 are used. Coumarin dyes having a heterocycle as described in JP-A-3-239703, 3-ketocoumarin compounds as described in JP-A-5-289335, pyrromethene as described in JP-A-6-19240 Pigments, others, Japanese Patent Publication No. 47-2528, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 1984-37377, Japanese Patent Application Publication No. 48-84183, Japanese Patent Application Publication No. 1984-84183, Japanese Unexamined Patent Publication No. 52-112681, Japanese Unexamined Patent Application No. 58-15503, Unexamined Japanese Patent Application No. 60-88005, Unexamined Japanese Patent Application No. 59-56403, Unexamined Japanese Patent Application No. 2-69 Hei 2-69 , having a dialkylaminobenzene skeleton as described in Japanese Patent Application Publication No. 57-168088, Japanese Publication No. 5-107761, Japanese Patent Application Publication No. 5-210240, and Japanese Patent Application Publication No. 4-288818. Examples include dyes and the like.

Among these sensitizing dyes, preferred are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Particularly preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzophenone, and 3,3'-diaminobenzophenone. , 3,4-diaminobenzophenone and other benzophenone compounds; 2-(p-dimethylaminophenyl)benzoxazole, 2-(p-diethylaminophenyl)benzoxazole, 2-(p-dimethylaminophenyl)benzo[4,5 ] Benzoxazole, 2-(p-dimethylaminophenyl)benzo[6,7]benzoxazole, 2,5-bis(p-diethylaminophenyl)-1,3,4-oxazole, 2-(p-dimethylaminophenyl) ) Benzothiazole, 2-(p-diethylaminophenyl)benzothiazole, 2-(p-dimethylaminophenyl)benzimidazole, 2-(p-diethylaminophenyl)benzimidazole, 2,5-bis(p-diethylaminophenyl)- 1,3,4-thiadiazole, (p-dimethylaminophenyl)pyridine, (p-diethylaminophenyl)pyridine, (p-dimethylaminophenyl)quinoline, (p-diethylaminophenyl)quinoline, (p-dimethylaminophenyl)pyrimidine , (p-diethylaminophenyl)pyrimidine and other p-dialkylaminophenyl group-containing compounds. The most preferred among these is 4,4'-dialkylaminobenzophenone.
The sensitizing dyes may also be used alone or in combination of two or more.

Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, and aliphatic amines such as n-butylamine and N-methyldiethanolamine.
One type of polymerization accelerator may be used alone, or two or more types may be used in combination.
Further, it is preferable to use a chain transfer agent in combination with the photopolymerization initiator. Examples of the chain transfer agent include mercapto group-containing compounds and carbon tetrachloride, and it is more preferable to use mercapto group-containing compounds because they tend to have a high chain transfer effect. This is thought to be because bond cleavage is likely to occur due to the small S--H bond energy, and hydrogen abstraction reactions and chain transfer reactions are likely to occur. Suitable for increasing sensitivity.

The mercapto group-containing compound is preferably a mercapto group-containing compound having an aromatic ring or an aliphatic mercapto group-containing compound, and more preferably an aliphatic mercapto group-containing compound.
Examples of mercapto group-containing compounds having an aromatic ring include 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 3-mercapto-1,2,4-triazole, and 2-mercapto-4 (3H). -quinazoline, β-mercaptonaphthalene, 1,4-dimethylmercaptobenzene, etc., and from the viewpoint of high sensitivity, 2-mercaptobenzothiazole and 2-mercaptobenzimidazole are preferred.
Examples of aliphatic mercapto group-containing compounds include hexanedithiol, decanedithiol, butanediol bis(3-mercaptopropionate), butanediol bisthioglycolate, ethylene glycol bis(3-mercaptopropionate), and ethylene. Glycol bisthioglycolate, trimethylolpropane tris(3-mercaptopropionate), trimethylolpropane tristhioglycolate, trishydroxyethyltristhiopropionate, 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) mercaptobutyrate), pentaerythritol tris(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H, 5H)-trione and the like.

Among them, from the viewpoint of ink repellency, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis ( 3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione are more preferred; Erythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferred.

One type of chain transfer agent may be used alone, or two or more types may be used in combination.

The content ratio of the photopolymerization initiator (A) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 0.1% by mass or more, preferably 1% by mass or more in the total solid content of the photosensitive colored resin composition. It is at least 15% by mass, preferably at most 10% by mass, more preferably at most 8% by mass, and even more preferably at most 5% by mass. It is. When the amount is equal to or more than the lower limit, sufficient ink repellency tends to occur, and when it is equal to or less than the upper limit, developability tends to be improved. For example, the content of the photopolymerization initiator (A) in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and 2 to 8% by mass. More preferably, 3 to 5% by mass is particularly preferred.

In the photosensitive colored resin composition according to the first aspect of the present invention, the content of the oxime ester photopolymerization initiator (A1) in the photopolymerization initiator (A) is also not particularly limited, but is usually 20% by mass or more. is preferably 30% by mass or more, more preferably 40% by mass or more, even more preferably 45% by mass or more, even more preferably 50% by mass or more, particularly preferably 60% by mass or more, and most preferably 70% by mass or more. . Further, it is usually 90% by mass or less, preferably 85% by mass or less, and more preferably 80% by mass or less. When the amount is equal to or more than the lower limit, sufficient ink repellency tends to occur, and when it is equal to or less than the upper limit, the tapered shape tends to be good. For example, the content of the oxime ester photoinitiator (A1) in the photoinitiator (A) is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, and even more preferably 60 to 85% by mass. , 70 to 80% by mass is particularly preferred.

The content ratio of the oxime ester photopolymerization initiator (A2) in the photopolymerization initiator (A) is also not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 15% by mass or more. , more preferably 20% by mass or more. Further, it is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the value is equal to or more than the lower limit, the tapered shape tends to be good, and when the value is equal to or less than the upper limit, sufficient ink repellency tends to occur. For example, the content of the oxime ester photopolymerization initiator (A2) in the photopolymerization initiator (A) is preferably 5 to 70% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 50% by mass. , 15 to 40% by mass is even more preferred, and 20 to 30% by mass is particularly preferred.

The content ratio of the oxime ester photopolymerization initiator (A2) is usually 10 parts by mass or more, preferably 20 parts by mass or more, and 25 parts by mass, based on 100 parts by mass of the oxime ester photoinitiator (A1). The above is more preferable, and 30 parts by mass or more is even more preferable. Further, the amount is usually 70 parts by mass or less, preferably 60 parts by mass or less, more preferably 55 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 45 parts by mass or less, and particularly preferably 40 parts by mass or less. When the value is equal to or more than the lower limit, the tapered shape tends to be good, and when the value is equal to or less than the upper limit, sufficient ink repellency tends to occur. For example, the content ratio of the oxime ester photopolymerization initiator (A2) to 100 parts by weight of the oxime ester photopolymerization initiator (A1) is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, and 20 to 70% by mass. It is more preferably 55% by weight, even more preferably 20-50% by weight, particularly preferably 25-45% by weight, particularly preferably 30-40% by weight.

Furthermore, in the photosensitive colored resin composition according to the second aspect of the present invention, the content of the oxime ester photopolymerization initiator (A3) in the total solid content is not particularly limited, but is usually 0.1% by mass or more. The content is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. Further, it is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less. When the amount is equal to or more than the lower limit, sufficient ink repellency tends to occur, and when it is equal to or less than the upper limit, the tapered shape tends to be good. For example, the content of the oxime ester photopolymerization initiator (A3) in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, and 2 to 8% by mass. % by weight is more preferable, and 3 to 5% by weight is particularly preferable.

Furthermore, the blending ratio of (A) photopolymerization initiator to (C) photopolymerizable compound in the photosensitive colored resin composition of the present invention is not particularly limited, but may be based on 100 parts by mass of (C) photopolymerizable compound. , preferably 1 part by mass or more, more preferably 5 parts by mass or more, even more preferably 10 parts by mass or more, even more preferably 12 parts by mass or more, particularly preferably 15 parts by mass or more, and preferably 200 parts by mass or less, The amount is more preferably 100 parts by mass or less, even more preferably 50 parts by mass or less, even more preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less. Setting the sensitivity at or above the lower limit value tends to provide appropriate sensitivity, and setting it at or below the upper limit value tends to make it easier to form a desired pattern shape. For example, the blending ratio of (A) photopolymerization initiator to 100 parts by mass of (C) photopolymerizable compound is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, even more preferably 10 to 50 parts by mass, It is even more preferably 12 to 30 parts by weight, particularly preferably 15 to 20 parts by weight.

When the photosensitive colored resin composition of the present invention contains a chain transfer agent, its content is not particularly limited, but is usually 0.01% by mass or more, preferably 0.01% by mass or more in the total solid content of the photosensitive colored resin composition. .1% by mass or more, more preferably 0.5% by mass or more, even more preferably 0.8% by mass or more, and usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, and Preferably it is 2% by mass or less. Setting the value above the lower limit value tends to increase the sensitivity, and setting the value below the upper limit value tends to make it easier to form a desired pattern. When a chain transfer agent is included, for example, the content of the chain transfer agent in the total solid content of the photosensitive colored resin composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass. , more preferably 0.5 to 3% by weight, particularly preferably 0.8 to 2% by weight.

Furthermore, the content ratio of the chain transfer agent to (A) the photopolymerization initiator in the photosensitive colored resin composition is not particularly limited, but is preferably 5 parts by mass or more with respect to 100 parts by mass of the (A) photopolymerization initiator. , more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, and preferably 500 parts by mass or less, more preferably 300 parts by mass or less, even more preferably 100 parts by mass or less, Particularly preferably 50 parts by mass or less. Setting the value above the lower limit value tends to result in high sensitivity, and setting the value below the upper limit value tends to make it easier to form a desired pattern. When a chain transfer agent is included, for example, the content ratio of the chain transfer agent to 100 parts by mass of (A) photopolymerization initiator is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, and 15 to 100 parts by mass. parts by weight is more preferable, and 20 to 50 parts by weight is particularly preferable.

[1-1-2] Component (B); Alkali-soluble resin The photosensitive colored resin composition of the present invention contains (B) an alkali-soluble resin. In the present invention, the alkali-soluble resin (B) is not particularly limited as long as it can be developed with an alkaline developer.
Examples of the alkali-soluble resin include various resins having a carboxyl group or a hydroxyl group, and those having a carboxyl group are preferred from the viewpoint of excellent developability.
In addition, an alkali-soluble resin having an ethylenically unsaturated group is preferable because it improves the verticality of the side surface of the partition wall, suppresses the outflow of the liquid repellent agent due to thermal melting of the partition wall, and makes it easier to maintain ink repellency. .

From the viewpoint of ink repellency, the alkali-soluble resin (B) of the photosensitive colored resin composition of the present invention is an acrylic copolymer resin (B11) having an ethylenically unsaturated group in the side chain (hereinafter referred to as "acrylic copolymer resin"). (B11)" may be abbreviated as "(B11)"). On the other hand, from the viewpoint of pattern linearity, it is preferable to include epoxy (meth)acrylate resin (B12).

Furthermore, from the viewpoint of achieving both ink repellency and linearity, it is preferable that the alkali-soluble resin (B) contains both an acrylic copolymer resin (B11) and an epoxy (meth)acrylate resin (B12).

First, the acrylic copolymer resin (B11) will be explained in detail.

[Acrylic copolymer resin (B11)]
The acrylic copolymer resin (B11) has an ethylenically unsaturated group in the side chain. It is thought that by having an ethylenically unsaturated group, photocuring occurs upon exposure to light, resulting in a stronger film, and the liquid repellent is less likely to flow out during development.

(Partial structure represented by general formula (I))
The partial structure of the acrylic copolymer resin (B11) containing a side chain having an ethylenically unsaturated group is not particularly limited, but from the viewpoint of ease of radical dispersion due to the flexibility of the membrane, for example, the following general formula It is preferable to have a partial structure represented by (I).

(In formula (I), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. * represents a bond.)

Further, among the partial structures represented by the formula (I), from the viewpoint of sensitivity and alkali developability, the partial structure represented by the following general formula (I') is preferable.

(In formula (I'), R ¹ and R ² each independently represent a hydrogen atom or a methyl group. R ^X represents a hydrogen atom or a polybasic acid residue.)

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of 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. Examples include one or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred. are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (I), its content is not particularly limited, but it is based on the total number of moles of the constituent units of the acrylic copolymer resin (B11). It is preferably at least 10 mol%, more preferably at least 20 mol%, even more preferably at least 30 mol%, even more preferably at least 40 mol%, particularly preferably at least 50 mol%, and preferably at most 90 mol%. It is more preferably at most mol%, even more preferably at most 80 mol%, even more preferably at most 75 mol%, particularly preferably at most 70 mol%. When the content is equal to or more than the lower limit, the ink repellency tends to improve, and when the content is equal to or less than the upper limit, the amount of residue tends to be reduced. When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (I), for example, the content of the partial structure represented by the general formula (I) is preferably 10 to 90 mol%, It is more preferably 20 to 85 mol%, even more preferably 30 to 80 mol%, even more preferably 40 to 75 mol%, and particularly preferably 50 to 70 mol%.

When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (I'), the content ratio is not particularly limited, but is based on the total number of moles of the constituent units of the acrylic copolymer resin (B11). is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 25 mol% or more, even more preferably 30 mol% or more, particularly preferably 35 mol% or more, and preferably 80 mol% or less, It is more preferably 75 mol% or less, even more preferably 70 mol% or less, and particularly preferably 65 mol% or less. When the amount is equal to or more than the lower limit, alkaline developability tends to be good, and when it is equal to or less than the upper limit, development adhesion tends to be easily ensured. When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (I'), for example, the content of the partial structure represented by the general formula (I') is 10 to 80 mol%. It is preferably 20 to 80 mol%, even more preferably 25 to 75 mol%, even more preferably 30 to 70 mol%, and particularly preferably 35 to 65 mol%.

(Substructure represented by general formula (II))
When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (I), other partial structures included are not particularly limited, but from the viewpoint of development adhesion, for example, the following general formula (II) ) is also preferable.

In the above formula (II), R ³ represents a hydrogen atom or a methyl group, and R ⁴ represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or a substituent Represents an alkenyl group that may have.

( ^R4 )
In the formula (II), ^R represents an alkyl group that may have a substituent, an aromatic ring group that may have a substituent, or an alkenyl group that may have a substituent. .
Examples of the alkyl group for R ⁴ include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, particularly preferably 8 or more, and preferably 20 or less, It is more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and particularly preferably 12 or less. When the amount is equal to or more than the lower limit, the film strength tends to increase and development adhesion improves, and when it is equal to or less than the upper limit, the amount of residue tends to be reduced. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 3 to 18 carbon atoms, even more preferably 5 to 16 carbon atoms, even more preferably 8 to 14 carbon atoms, and particularly preferably 8 to 12 carbon atoms.

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

Examples of the aromatic ring group for R ⁴ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, more preferably 24 or less, more preferably 22 or less, even more preferably 20 or less, and particularly preferably 18 or less. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. For example, the aromatic ring group preferably has 6 to 24 carbon atoms, more preferably 6 to 22 carbon atoms, even more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 18 carbon atoms.
The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and a pyrene ring. ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.
Further, the aromatic heterocyclic group in the aromatic heterocyclic group may be a single ring or a condensed ring, such as a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, and a pyrazole ring. , imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrole ring, furofuran ring, thienofuran ring, benzisoxazole 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, etc. Among these, from the viewpoint of developability, a benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.
In addition, the substituents that the aromatic ring group may have include methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, and epoxy group. , oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferable.

Examples of the alkenyl group for R ⁴ include linear, branched or cyclic alkenyl groups. The carbon number is 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and even more preferably 14 or less. It is particularly preferable that Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.

In addition, as substituents that the alkenyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

In this way, R ⁴ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkenyl group which may have a substituent. From the viewpoint of developability and film strength, an alkyl group or an alkenyl group is preferable, and an alkyl group is more preferable.

When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (II), its content is not particularly limited, but it is based on the total number of moles of the constituent units of the acrylic copolymer resin (B11). It is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, particularly preferably 20 mol% or more, and preferably 70 mol% or less, more preferably 60 mol% or less, and 50 mol% or more. % or less is more preferable, and 40 mol% or less is particularly preferable. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (II), for example, the content of the partial structure represented by the general formula (II) is preferably 1 to 70 mol%, It is more preferably 5 to 60 mol%, even more preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%.

(Substructure represented by general formula (III))
When the acrylic copolymer resin (B11) contains a partial structure represented by the above general formula (I), the other contained partial structure is represented by the following general formula (III) from the viewpoint of heat resistance and film strength. Preferably, a partial structure is included.

In the above formula (III), R ⁵ represents a hydrogen atom or a methyl group, and R ⁶ represents an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an alkenyl group that may have a substituent. represents an optionally substituted alkynyl group, hydroxyl group, carboxyl group, halogen atom, optionally substituted alkoxy group, thiol group, or optionally substituted alkyl sulfide group. t represents an integer from 0 to 5.

( ^R6 )
In the formula (III), R ⁶ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxyl group, or a carboxyl group. , represents a halogen atom, an alkoxy group which may have a substituent, a thiol group, or an alkyl sulfide group which may have a substituent.
Examples of the alkyl group for R ⁶ include linear, branched, or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, even more preferably 5 or more, and 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. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. For example, the alkyl group preferably has 1 to 20 carbon atoms, more preferably 3 to 18 carbon atoms, even more preferably 5 to 16 carbon atoms, even more preferably 5 to 14 carbon atoms, and particularly preferably 5 to 12 carbon atoms.

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

Examples of the alkenyl group for R ⁶ include linear, branched, or cyclic alkenyl groups. The carbon number is 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and even more preferably 14 or less. It is particularly preferable that Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. For example, the alkenyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.

In addition, as substituents that the alkenyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

Examples of the alkynyl group for R ⁶ include linear, branched or cyclic alkynyl groups. The carbon number is 2 or more, preferably 22 or less, more preferably 20 or less, even more preferably 18 or less, even more preferably 16 or less, and even more preferably 14 or less. It is particularly preferable that Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. For example, the alkynyl group preferably has 2 to 22 carbon atoms, more preferably 2 to 20 carbon atoms, even more preferably 2 to 18 carbon atoms, even more preferably 2 to 16 carbon atoms, and particularly preferably 2 to 14 carbon atoms.

In addition, as substituents that the alkynyl group may have, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group From the viewpoint of developability, hydroxy groups and oligoethylene glycol groups are preferred.

Examples of the halogen atom in R ⁶ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among these, a fluorine atom is preferred from the viewpoint of ink repellency.

Examples of the alkoxy group for R ⁶ include linear, branched, or cyclic alkoxy groups. The number of carbon atoms is 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less, and even more preferably 12 or less. It is particularly preferable that Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. For example, the alkoxy group preferably has 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, even more preferably 1 to 16 carbon atoms, even more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms.

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

Examples of the alkyl sulfide group for R ⁶ include linear, branched or cyclic alkyl sulfide groups. The number of carbon atoms is preferably 1 or more, preferably 20 or less, more preferably 18 or less, even more preferably 16 or less, even more preferably 14 or less. , 12 or less is particularly preferable. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. For example, the number of carbon atoms in the alkyl sulfide group is preferably 1 to 20, more preferably 1 to 18, even more preferably 1 to 16, even more preferably 1 to 14, and particularly preferably 1 to 12.

In addition, substituents that the alkyl group in the alkyl sulfide 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 preferable.

In this way, R ⁶ is an alkyl group that may have a substituent, an alkenyl group that may have a substituent, an alkynyl group that may have a substituent, a hydroxyl group, a carboxyl group, or a halogen group. represents an atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an alkyl sulfide group which may have a substituent, and among these, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable. preferable.

In the formula (III), t represents an integer of 0 to 5, but from the viewpoint of ease of manufacture, t is preferably 0.

When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (III), its content is not particularly limited, but it is based on the total number of moles of the constituent units of the acrylic copolymer resin (B11). The content is preferably 0.5 mol% or more, more preferably 1 mol% or more, and even more preferably 2 mol% or more. Moreover, it is preferably 50 mol% or less, more preferably 30 mol% or less, even more preferably 20 mol% or less, even more preferably 10 mol% or less, and particularly preferably 5 mol% or less. Setting the amount above the lower limit value tends to improve the development adhesion, and setting it below the upper limit value tends to reduce the amount of residue. When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (III), for example, the content of the partial structure represented by the general formula (III) is 0.5 to 50 mol%. It is preferably 0.5 to 30 mol%, even more preferably 1 to 20 mol%, even more preferably 1 to 10 mol%, and particularly preferably 2 to 5 mol%.

(Substructure represented by general formula (IV))
When the acrylic copolymer resin (B11) has a partial structure represented by the above general formula (I), from the viewpoint of developability, a partial structure represented by the following general formula (IV) may be included as another partial structure. It is also preferable to have

In the above formula (IV), R ⁷ represents a hydrogen atom or a methyl group.

When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (IV), its content is not particularly limited, but it is based on the total number of moles of the constituent units of the acrylic copolymer resin (B11). It is preferably 5 mol% or more, more preferably 10 mol% or more, even more preferably 20 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less. When the amount is equal to or more than the lower limit, the developability tends to improve, and when it is equal to or less than the upper limit, the developer adhesion tends to improve. When the acrylic copolymer resin (B11) contains a partial structure represented by the general formula (IV), for example, the content of the partial structure represented by the general formula (IV) is preferably 5 to 80 mol%, It is more preferably 10 to 70 mol%, and even more preferably 20 to 60 mol%.

On the other hand, the acid value of the acrylic copolymer resin (B11) is not particularly limited, but is preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, even more preferably 50 mgKOH/g or more, even more preferably 60 mgKOH/g or more. Also, it is preferably 150 mgKOH/g or less, more preferably 140 mgKOH/g or less, even more preferably 130 mgKOH/g or less, even more preferably 120 mgKOH/g or less. When the amount is equal to or more than the lower limit, the developability tends to improve, and when it is equal to or less than the upper limit, the developer adhesion tends to improve. For example, the acid value of the acrylic copolymer resin (B11) is preferably 30 to 150 mgKOH/g, more preferably 40 to 140 mgKOH/g, even more preferably 50 to 130 mgKOH/g, and particularly preferably 60 to 120 mgKOH/g.

The weight average molecular weight (Mw) of the acrylic copolymer resin (B11) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, still more preferably 6000 or more, even more preferably 7000 or more, and particularly preferably is 8,000 or more, and is usually 30,000 or less, preferably 20,000 or less, more preferably 15,000 or less, even more preferably 10,000 or less. When the amount is equal to or more than the lower limit, the development adhesion tends to improve, and when the amount is less than the upper limit, the amount of residue tends to be reduced. For example, the weight average molecular weight (Mw) of the acrylic copolymer resin (B11) is preferably 1,000 to 30,000, more preferably 2,000 to 20,000, even more preferably 4,000 to 15,000, even more preferably 6,000 to 15,000, especially 7,000 to 10,000. Preferably, 8,000 to 10,000 is particularly preferable.

(B) The content ratio of the acrylic copolymer resin (B11) contained in the alkali-soluble resin is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and 70% by mass. % or more, preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less. When the content is equal to or more than the lower limit, the ink repellency tends to improve, and when the content is equal to or less than the upper limit, the amount of residue tends to be reduced. For example, the content of the acrylic copolymer resin (B11) in the alkali-soluble resin (B) is preferably 10 to 95% by mass, more preferably 30 to 95% by mass, even more preferably 50 to 90% by mass, and even more preferably 70 to 95% by mass. 85% by weight is particularly preferred.

In addition, when the alkali-soluble resin (B) contains both the acrylic copolymer resin (B11) and the epoxy (meth)acrylate resin (B12), the content ratio of the acrylic copolymer resin (B11) is ) and the epoxy (meth)acrylate resin (B12), preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, particularly 70% by mass or more. It is preferably 95% by mass or less, more preferably 90% by mass or less, even more preferably 85% by mass or less. When the content is equal to or more than the lower limit, the ink repellency tends to improve, and when the content is equal to or less than the upper limit, the amount of residue tends to be reduced. (B) When the alkali-soluble resin contains both the acrylic copolymer resin (B11) and the epoxy (meth)acrylate resin (B12), the content of the acrylic copolymer resin (B11) and the epoxy (meth)acrylate resin (B12) The content of the acrylic copolymer resin (B11) relative to the total ratio is preferably 10 to 95% by mass, more preferably 30 to 95% by mass, even more preferably 50 to 90% by mass, and particularly preferably 70 to 85% by mass. .

Specific examples of the acrylic copolymer resin (B11) include, for example, resins described in Japanese Patent Application Publication No. 8-297366 and Japanese Patent Application Publication No. 2001-89533.

Next, the epoxy (meth)acrylate resin (B12) will be explained in detail.

[Epoxy (meth)acrylate resin (B12)]
Epoxy (meth)acrylate resin (B12) is produced by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin, optionally reacting with an isocyanate group-containing compound, and then reacting with a polybasic acid or its anhydride. It is a resin made by For example, by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, an ethylenically unsaturated bond is added to the epoxy compound via an ester bond (-COO-), and Examples include those in which one carboxy group of a polybasic acid anhydride is added to the hydroxyl group generated at that time. Also included are those added by simultaneously adding a polyhydric alcohol when adding a polybasic acid anhydride.

Also included in the epoxy (meth)acrylate resin (B12) is a resin obtained by reacting a compound having a functional group that can further react with the carboxyl group of the resin obtained in the above reaction.
In this way, epoxy (meth)acrylate resin has virtually no epoxy groups due to its chemical structure, and is not limited to "(meth)acrylate", but it is made from an epoxy compound (epoxy resin) as a raw material. And since "(meth)acrylate" is a typical example, it is named this way according to common usage.

Here, the epoxy resin includes a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins. Further, 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 than divalent phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane. Epoxy resin, dihydroxylfluorene type epoxy resin, dihydroxylalkyleneoxylfluorene type epoxy resin, diglycidyl etherified product of 9,9-bis(4'-hydroxyphenyl)fluorene, 1,1-bis(4'-hydroxy Examples include diglycidyl etherified products of (phenyl)adamantane, and those having an aromatic ring in the main chain can be preferably used.

Among them, from the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, polymerized epoxy resin of phenol and dicyclopentadiene, and 9,9-bis(4'-hydroxyphenyl)fluorene are used. Diglycidyl etherified products, etc. are preferred, and bisphenol A epoxy resin is particularly preferred.
Specific examples of epoxy resins include bisphenol A type epoxy resins (for example, "jER (registered trademark, hereinafter the same applies)", "jER1001", "jER1002", "jER1004" manufactured by Mitsubishi Chemical Corporation, Nippon Chemical Co., Ltd.), "NER-1302" manufactured by Yakusha (epoxy equivalent: 323, softening point 76°C), etc.), bisphenol F type resin (for example, "jER807", "jER4004P", "jER4005P", "jER4007P", manufactured by Mitsubishi Chemical Corporation), Nippon Kayaku Co., Ltd.'s "NER-7406" (epoxy equivalent: 350, softening point: 66°C), etc.), bisphenol S-type epoxy resin, biphenyl glycidyl ether (for example, Mitsubishi Chemical's "jERYX-4000"), phenol novolac Type epoxy resin (for example, "EPPN (registered trademark, hereinafter the same)-201" manufactured by Nippon Kayaku Co., Ltd., "jER152", "jER154" manufactured by Mitsubishi Chemical Corporation, "DEN-438" manufactured by Dow Chemical Company) , (o, m, p-)cresol novolac type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same)-102S", "EOCN-1020", "EOCN-104S" manufactured by Nippon Kayaku Co., Ltd.), Triglycidyl isocyanurate (for example, "TEPIC (registered trademark)" manufactured by Nissan Chemical Co., Ltd.), trisphenolmethane type epoxy resin (for example, "EPPN-501", "EPPN-502", "EPPN" manufactured by Nippon Kayaku Co., Ltd.), -503''), alicyclic epoxy resins (Daicel's ``Celoxide (registered trademark, hereinafter the same applies) 2021P'', ``Celoxide EHPE''), epoxy resins that are glycidylated phenolic resins produced by the reaction of dicyclopentadiene and phenol. (For example, "EXA-7200" manufactured by DIC, "NC-7300" manufactured by Nippon Kayaku Co., Ltd.), epoxy resins represented by the following general formulas (i-11) to (i-14), etc. It can be used for. Specifically, the epoxy resin represented by the following general formula (i-11) is "XD-1000" manufactured by Nippon Kayaku Co., Ltd., and the epoxy resin represented by the following general formula (i-12) is "XD-1000" manufactured by Nippon Kayaku Co., Ltd. Examples include "NC-3000" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "ESF-300" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (i-14).

In the above general formula (i-11), n is an average value and represents a number from 0 to 10. Each R ¹¹¹ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Note that a plurality of R ^111s present in one molecule may be the same or different.

In the above general formula (i-12), n is an average value and represents a number from 0 to 10. Each R ¹²¹ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, a phenyl group, a naphthyl group, or a biphenyl group. Note that the plurality of R ^121s present in one molecule may be the same or different.

In the above general formula (i-13), X represents a linking group represented by the following general formula (i-13-1) or (i-13-2). However, the molecular structure contains one or more adamantane structures. c represents 2 or 3.

In the above general formulas (i-13-1) and (i-13-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ each independently represent an adamantyl group which may have a substituent, hydrogen Represents an atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or a phenyl group which may have a substituent. * represents a bond.

In the general formula (i-14), p and q each independently represent an integer of 0 to 4, and R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom. R ¹⁴³ and R ¹⁴⁴ each independently represent an alkylene group having 1 to 4 carbon atoms. x and y each independently represent an integer of 0 or more.

Among these, it is preferable to use an epoxy resin represented by any of the general formulas (i-11) to (i-14).

Examples of ethylenically unsaturated monocarboxylic acids include (meth)acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri(meth)acrylate succinic anhydride adduct, and pentaerythritol tri(meth)acrylate succinic anhydride adduct. Erythritol tri(meth)acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta(meth)acrylate succinic anhydride adduct, dipentaerythritol penta(meth)acrylate phthalic anhydride adduct, dipentaerythritol penta(meth)acrylate tetrahydro Examples include phthalic anhydride adducts and reaction products of (meth)acrylic acid and ε-caprolactone. Among these, (meth)acrylic acid is preferred 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, -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 anhydrides thereof. Among these, from the viewpoint of outgas, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable, and succinic anhydride or tetrahydrophthalic anhydride is more preferable.

By using a polyhydric alcohol, the molecular weight of the epoxy (meth)acrylate resin (B12) can be increased and branching can be introduced into the molecule, which tends to balance the molecular weight and viscosity. Furthermore, the rate of introduction of acid groups into the molecule can be increased, and sensitivity, adhesion, etc. tend to be more balanced.
Examples of the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferable that there be.

Examples of the epoxy (meth)acrylate resin include those described in Korean Patent Publication No. 10-2013-0022955 in addition to those mentioned above.

The acid value of the epoxy (meth)acrylate resin (B12) is not particularly limited, but is preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, It is particularly preferably at least 80 mgKOH/g, preferably at most 200 mgKOH/g, more preferably at most 180 mgKOH/g, even more preferably at most 150 mgKOH/g, even more preferably at most 120 mgKOH/g, and particularly preferably at most 110 mgKOH/g. When the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved. The acid value of the epoxy (meth)acrylate resin (B12) is preferably 10 to 200 mgKOH/g, more preferably 30 to 180 mgKOH/g, even more preferably 50 to 150 mgKOH/g, even more preferably 70 to 120 mgKOH/g, and even more preferably 80 to 120 mgKOH/g. ~110 mgKOH/g is particularly preferred.

The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (B12) is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, even more preferably 3500 or more, and usually 30000 or less. , preferably 15,000 or less, more preferably 10,000 or less, further preferably 8,000 or less, particularly preferably 5,000 or less. When the content is equal to or more than the lower limit, the film strength tends to improve, and when the content is equal to or less than the upper limit, the amount of residue tends to be reduced. The weight average molecular weight (Mw) of the epoxy (meth)acrylate resin (B12) is preferably 1,000 to 30,000, more preferably 2,000 to 15,000, even more preferably 3,000 to 10,000, even more preferably 3,500 to 8,000, particularly 3,500 to 5,000. preferable.

(B) When the alkali-soluble resin contains epoxy (meth)acrylate resin (B12), its content is not particularly limited, but it is preferably 10% by mass or more in the alkali-soluble resin (B), and more preferably 20% by mass or more. It is preferably 30% by mass or more, more preferably 35% by mass or more, further preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less. When the content is equal to or more than the lower limit, the amount of residue tends to be reduced, and when the content is equal to or less than the upper limit, the ink repellency tends to be improved. When the alkali-soluble resin (B) contains epoxy (meth)acrylate resin (B12), the content in the alkali-soluble resin (B) is preferably 10 to 90% by mass, more preferably 20 to 70% by mass, and 30 to 50% by weight is more preferable, and 35 to 50% by weight is particularly preferable.

The epoxy (meth)acrylate resin (B12) can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, the acid or ester compound having an ethylenically unsaturated bond is added thereto in the coexistence of a catalyst and a thermal polymerization inhibitor, and then the polybasic acid or its A method can be used in which the reaction is continued by adding an anhydride. Examples include methods described in Japanese Patent No. 3938375 and Japanese Patent No. 5169422.

Here, examples of the organic solvent used in the reaction include one or more organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, and propylene glycol monomethyl ether acetate. In addition, the above-mentioned catalysts include tertiary amines such as triethylamine, benzyldimethylamine, and tribenzylamine, tertiary amines such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride. Examples include one or more of quaternary amminium salts, phosphorus compounds such as triphenylphosphine, and stibines such as triphenylstibine. Furthermore, examples of the thermal polymerization inhibitor include one or more of hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, and the like.

Furthermore, 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 per chemical equivalent of the epoxy group of the epoxy resin. The amount can be set to . Further, the temperature during the addition reaction can be generally 60 to 150°C, preferably 80 to 120°C. Furthermore, the amount of polybasic acid (anhydride) to be used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, per 1 chemical equivalent of the hydroxyl group produced in the addition reaction. The amount can be set to a chemical equivalent.

Among epoxy (meth)acrylate resins (B12), from the viewpoint of film strength and linearity, epoxy (meth)acrylate resins having a partial structure represented by the following general formula (i), and those having a partial structure represented by the following general formula (ii). The resin preferably contains at least one selected from the group consisting of an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii), and an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (iii).

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.

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

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

Among these, first, we will explain in detail about the epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (B12-1)") having a partial structure represented by the following general formula (i). Describe.

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.

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

Examples of divalent aliphatic groups include linear, branched, and cyclic groups. Among these, linear ones are preferable from the viewpoint of development solubility, while annular 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 more than the lower limit, the film strength tends to improve, and when the content is equal to or less than the upper limit, the ink repellency tends to improve. For example, the divalent aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.

Specific examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, and the like. Among these, methylene groups are preferred from the viewpoint of ink repellency and manufacturing cost.
Specific examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group as a side chain to the above-mentioned divalent linear aliphatic group. Examples include structures having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.
The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings in the divalent cyclic aliphatic group is preferably 1 to 10, more preferably 1 to 5.
Specific examples of divalent cyclic aliphatic groups include rings in which two hydrogen atoms are removed such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. The following groups are mentioned. Among these, from the viewpoint of film strength and developability, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.

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

Further, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the divalent aromatic ring group preferably has 4 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring. Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

Further, the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a shinoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of production cost, 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 a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of curability, non-substitution is preferred.

Furthermore, as a group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group may be used. Examples include groups in which one or more ring groups are connected.
The number of divalent aliphatic 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 amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved. For example, the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3.
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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3.

Specific examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the following formulas (i-A) to (i-F), etc. can be mentioned. Among these, a group represented by the following formula (i-A) is preferred from the viewpoint of skeletal rigidity and membrane hydrophobization.

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

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

In formula (i-1), R ^a and R ^b have the same meanings as in formula (i) above. R ^Y 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.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of 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. Examples include one or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred. are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

The repeating unit structure represented by the above formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (B12-1) may be one type or two or more types.

Further, the number of partial structures represented by the formula (i) contained in one molecule of the epoxy (meth)acrylate resin (B12-1) is not particularly limited, but is preferably 1 or more, more preferably 2 or more, It is more preferably 3 or more, more preferably 10 or less, and even more preferably 8 or less. When the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved. For example, the number of partial structures represented by the formula (i) contained in one molecule of epoxy (meth)acrylate resin (B12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 to 8. is even more preferable.

Further, the number of partial structures represented by the formula (i-1) contained in one molecule of the epoxy (meth)acrylate resin (B12-1) is not particularly limited, but is preferably 1 or more, and 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 amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved. For example, the number of partial structures represented by the formula (i-1) contained in one molecule of epoxy (meth)acrylate resin (B12-1) is preferably 1 to 10, more preferably 2 to 8, and 3 -8 is more preferred.

Specific examples of the epoxy (meth)acrylate resin (B12-1) are listed below.

Next, the epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (B12-2)") having a partial structure represented by the following general formula (ii) will be described in detail. .

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

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

The number of rings an aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings an aliphatic cyclic group has is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially 15 or less. preferable. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, even more preferably 6 to 20 carbon atoms, and particularly preferably 8 to 15 carbon atoms.

Specific examples of the aliphatic ring in the aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, adamantane rings are preferred from the viewpoint of film strength and developability.

On the other hand, the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, 4 or less. is more preferable. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings an aromatic ring group has is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 4, and particularly preferably 2 to 4.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, 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, even more preferably 15 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the aromatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, even more preferably 8 to 20 carbon atoms, even more preferably 10 to 15 carbon atoms, and particularly preferably 12 to 15 carbon atoms.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, Examples include a fluorene ring. Among these, fluorene rings are preferred from the viewpoint of patterning properties.

Furthermore, in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain, the divalent hydrocarbon group is not particularly limited, but includes, for example, a divalent aliphatic group, a divalent aromatic ring group, and one or more divalent hydrocarbon groups. Examples include a group in which a divalent aliphatic group and one or more divalent aromatic ring groups are connected.

Examples of divalent aliphatic groups include linear, branched, and cyclic groups. Among these, linear ones are preferred from the viewpoint of improving developability, while cyclic ones are preferred from the viewpoint of film strength. 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the divalent aliphatic group preferably has 1 to 25 carbon atoms, more preferably 3 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms.

Specific examples of the divalent linear aliphatic group include methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, and the like. Among these, methylene groups are preferred from the viewpoint of ink repellency.
Specific examples of the divalent branched aliphatic group include a methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group as a side chain to the above-mentioned divalent linear aliphatic group. Examples include structures having a group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and the like.

The number of rings that the divalent cyclic aliphatic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings in the divalent cyclic aliphatic group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, and particularly preferably 2 to 5.

Specific examples of divalent cyclic aliphatic groups include rings in which two hydrogen atoms are removed such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, and cyclododecane ring. The following groups are mentioned. Among these, from the viewpoint of film strength, a group obtained by removing two hydrogen atoms from an adamantane ring is preferable.

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

Further, examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. The divalent aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a single ring or a fused ring. Examples of the divalent aromatic hydrocarbon ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, which have two free valences, Examples include groups such as a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

Further, the aromatic heterocycle in the aromatic heterocyclic group may be a single ring or a condensed ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, and indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Examples include groups such as a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a shinoline ring, a quinoxaline ring, a phenanthridine ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Among these, from the viewpoint of production cost, 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 a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group. Among these, from the viewpoint of curability, non-substitution is preferred.

Furthermore, as a group linking one or more divalent aliphatic groups and one or more divalent aromatic ring groups, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic ring group may be used. Examples include groups in which one or more ring groups are connected.
The number of divalent aliphatic 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 amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved. For example, the number of divalent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3.
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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of divalent aromatic ring groups is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3.

Specific examples of groups that connect one or more divalent aliphatic groups and one or more divalent aromatic ring groups include groups represented by the above formulas (i-A) to (i-F), etc. can be mentioned. Among these, from the viewpoint of achieving both film strength and ink repellency, the group represented by the formula (ic) is preferred.

The bonding mode of the cyclic hydrocarbon group as a side chain 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 replaced with the side chain. Examples include an embodiment in which a cyclic hydrocarbon group, which is a side chain, includes one carbon atom of an aliphatic group.

Furthermore, from the viewpoint of ink repellency, the partial structure represented by the formula (ii) is preferably a partial structure represented by the following formula (ii-1).

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.

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

The number of rings an aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings an aliphatic cyclic group has is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 2 to 3.
The number of carbon atoms in the aliphatic cyclic group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, even more preferably 20 or less, and especially 15 or less. preferable. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, even more preferably 6 to 20 carbon atoms, and particularly preferably 8 to 15 carbon atoms.

Specific examples of the aliphatic ring in the aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, adamantane rings are preferred from the viewpoint of achieving both film strength and developability.

On the other hand, the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings in the aromatic ring group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Further, 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. The aromatic ring group preferably has 4 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, and even more preferably 6 to 15 carbon atoms.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, fluorene rings are preferred from the viewpoint of achieving both film strength and developability.

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

n represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. When the amount is equal to or more than the lower limit, the developability tends to be improved, and when it is less than the upper limit, the film strength tends to be improved. For example, n is preferably an integer of 1 or more and 3 or less, more preferably an integer of 2 or more and 3 or less.

Among these, from the viewpoint of achieving both film strength and developability, R ^α is preferably a monovalent aliphatic cyclic group, and more preferably an adamantyl group.

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

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

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

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

The number of rings that the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings an aliphatic cyclic group has is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.
Further, the number of carbon atoms in the aliphatic cyclic group is usually 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and still more preferably 8 to 30 carbon atoms.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, adamantane rings are preferred from the viewpoint of achieving both film strength and developability.

On the other hand, the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings that the aromatic ring group has is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or more. It is preferably 15 or less, particularly preferably 15 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the aromatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, even more preferably 8 to 20 carbon atoms, and particularly preferably 10 to 15 carbon atoms.

Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, fluorene rings are preferred from the viewpoints of film strength and developability.

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

Among these, from the viewpoint of achieving both film strength and developability, R ^β is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.
On the other hand, from the viewpoint of achieving both film strength and developability, R ^β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

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

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

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

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

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of 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. Examples include one or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred. are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

The partial structure represented by the above formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (B12-2) may be one type or two or more types.

Further, the number of partial structures represented by the formula (ii) contained in one molecule of the epoxy (meth)acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Further, it is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved. For example, the number of partial structures represented by the formula (ii) contained in one molecule of epoxy (meth)acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 to 10. is even more preferable.

Furthermore, the number of partial structures represented by the formula (ii-1) contained in one molecule of the epoxy (meth)acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved. For example, the number of partial structures represented by the formula (ii-1) contained in one molecule of epoxy (meth)acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.

Further, the number of partial structures represented by the above formula (ii-2) contained in one molecule of the epoxy (meth)acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved. For example, the number of partial structures represented by the formula (ii-2) contained in one molecule of epoxy (meth)acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.

Further, the number of partial structures represented by the above formula (ii-3) contained in one molecule of the epoxy (meth)acrylate resin (B12-2) is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved. For example, the number of partial structures represented by the formula (ii-3) contained in one molecule of epoxy (meth)acrylate resin (B12-2) is preferably 1 to 20, more preferably 1 to 15, and 3 -10 is more preferred.

Next, the epoxy (meth)acrylate resin (hereinafter sometimes referred to as "epoxy (meth)acrylate resin (B12-3)") having a partial structure represented by the following general formula (iii) will be described in detail. .

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

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

The alkylene group may be a straight chain or a branched chain, but from the viewpoint of development solubility it is preferably a straight chain, and from the viewpoint of development adhesion it is preferably a branched chain. The number of carbon atoms is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 2 to 4 carbon atoms.

Specific examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, hexylene group, and heptylene group. From the viewpoint of achieving both film strength and developability, ethylene group or propylene group is preferable, and propylene group group is more preferred.

Examples of substituents that 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; carboxyl group. Among these, unsubstituted compounds are preferred from the viewpoint of ease of synthesis.

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

The number of rings that the aliphatic cyclic group has is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings an aliphatic cyclic group has is preferably 1 to 10, more preferably 1 to 5, and even more preferably 2 to 5.
Further, the number of carbon atoms in the aliphatic cyclic group is usually 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 amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the aliphatic cyclic group preferably has 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and still more preferably 8 to 30 carbon atoms.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. Among these, adamantane rings are preferred from the viewpoint of achieving both film strength and developability.

On the other hand, the number of rings that the aromatic ring group has is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved. For example, the number of rings that the aromatic ring group has is preferably 1 to 10, more preferably 1 to 5, even more preferably 2 to 5, and particularly preferably 3 to 5.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and still more preferably 20 or more. It is preferably 15 or less, particularly preferably 15 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved, and when it is less than the upper limit, the developability tends to be improved.
Specific examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring. Among these, fluorene rings are preferred from the viewpoint of achieving both film strength and developability. For example, the aromatic ring group preferably has 4 to 40 carbon atoms, more preferably 6 to 30 carbon atoms, even more preferably 8 to 20 carbon atoms, and particularly preferably 10 to 15 carbon atoms.

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

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

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

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

In formula (iii-1), R ^e and γ have the same meanings as in formula (iii) above. R ^W 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.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of 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. Examples include one or more selected from acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferred. are tetrahydrophthalic acid and biphenyltetracarboxylic acid.

Further, the number of repeating unit structures represented by the formula (iii) contained in one molecule of the epoxy (meth)acrylate resin (B12-3) is not particularly limited, but is preferably 1 or more, more preferably 5 or more. , more preferably 10 or more, preferably 18 or less, and even more preferably 15 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved. For example, the number of repeating unit structures represented by the formula (iii) contained in one molecule of epoxy (meth)acrylate resin (B12-3) is preferably 1 to 18, more preferably 5 to 15, and 10 to 15 is more preferred.

Further, the number of repeating unit structures represented by the formula (iii-1) contained in one molecule of epoxy (meth)acrylate resin (B12-3) is not particularly limited, but is preferably 1 or more, and 3 or more is preferably It is more preferably 5 or more, further preferably 18 or less, and even more preferably 15 or less. When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved. For example, the number of repeating unit structures represented by the formula (iii-1) contained in one molecule of epoxy (meth)acrylate resin (B12-3) is preferably 1 to 18, more preferably 3 to 15, 5 to 15 is more preferable.

Specific examples of the epoxy (meth)acrylate resin (B12-3) are listed below.

As described above, the alkali-soluble resin (B) in the present invention may contain other alkali-soluble resins in addition to the acrylic copolymer resin (B11) and the epoxy (meth)acrylate resin (B12).

The acid value of the alkali-soluble resin of component (B) is not particularly limited, but is preferably 30 mgKOH/g or more, more preferably 50 mgKOH/g or more, even more preferably 70 mgKOH/g or more, and preferably 200 mgKOH/g or less. , more preferably 150 mgKOH/g or less, and even more preferably 100 mgKOH/g or less. When the amount is equal to or more than the lower limit, the developability tends to improve, and when it is equal to or less than the upper limit, the developer adhesion tends to improve. In addition, in the case of a mixture of two or more types of alkali-soluble resins (B), the acid value means a weighted average value according to their content ratios. For example, the acid value of the alkali-soluble resin as component (B) is preferably 30 to 200 mgKOH/g, more preferably 50 to 150 mgKOH/g, and even more preferably 70 to 100 mgKOH/g.

The content ratio of the alkali-soluble resin (B) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more based on the total solid content. Mass % or more, more preferably 30 mass % or more, even more preferably 40 mass % or more, particularly preferably 50 mass % or more, and usually 90 mass % or less, preferably 80 mass % or less, more preferably 70 mass % It is as follows. When the content is equal to or more than the lower limit, the shape of the partition wall tends to be improved, and when the content is equal to or less than the upper limit, the ink repellency tends to be improved. For example, the content of the alkali-soluble resin (B) in the total solid content of the photosensitive colored resin composition is preferably 5 to 90% by mass, more preferably 10 to 90% by mass, even more preferably 20 to 80% by mass, Even more preferably 30 to 80% by weight, particularly preferably 40 to 70% by weight, particularly preferably 50 to 70% by weight.

Further, the total content of (C) the photopolymerizable compound and the content of (B) the alkali-soluble resin in the total solid content is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more. , more preferably 60% by mass or more, particularly preferably 80% by mass or more, further preferably 95% by mass or less, more preferably 92% by mass or less, even more preferably 90% by mass or less. When the content is equal to or more than the lower limit, the ink repellency tends to improve, and when the content is equal to or less than the upper limit, the shape of the partition walls tends to improve. For example, the total content of (C) the photopolymerizable compound and (B) the alkali-soluble resin in the total solid content of the photosensitive colored resin composition is preferably 10 to 95% by mass, and 30 to 92% by mass. is more preferable, 60 to 90% by weight is even more preferable, and particularly preferably 80 to 90% by weight.

[1-1-3] Component (C); Photopolymerizable compound The photosensitive colored resin composition of the present invention contains (C) a photopolymerizable compound. (C) It is thought that by including the photopolymerizable compound, the curability of the coating film increases and the ink repellency improves.
The photopolymerizable compound used here refers to a compound having one or more ethylenically unsaturated bonds in its molecule, but it has polymerizability, crosslinkability, and associated dissolution of the exposed and non-exposed areas in the developing solution. It is preferable that the compound has two or more ethylenically unsaturated bonds in the molecule, from the viewpoint of being able to expand the difference in sex, and the unsaturated bonds are those derived from a (meth)acryloyloxy group, that is, , (meth)acrylate compounds are more preferred.

In the present invention, it is particularly desirable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated bonds in one molecule. The number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is not particularly limited, but is preferably 2 or more, more preferably 3 or more, even more preferably 5 or more, and preferably 15. The number is more preferably 10 or less, further preferably 8 or less, particularly preferably 7 or less. When the amount is equal to or more than the lower limit, polymerizability tends to improve and ink repellency increases, and when the amount is equal to or less than the upper limit, developability tends to improve. For example, the number of ethylenically unsaturated groups that the polyfunctional ethylenic monomer has is preferably 2 to 15, more preferably 2 to 10, even more preferably 2 to 8, even more preferably 3 to 7. , 5 to 7 are particularly preferred.
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, etc. Examples include esters obtained by an esterification reaction between a polyhydric hydroxy compound and an unsaturated carboxylic acid and a polybasic carboxylic acid.

Examples of the ester of the aliphatic polyhydroxy compound and unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, Acrylic acid esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, and methacrylic acid esters in which the acrylate of these exemplary compounds is replaced with methacrylate. , itaconate ester instead of itaconate, crotonate ester instead of cronate, maleate ester instead of maleate, and the like.

Examples of esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids include acrylic esters and methacrylic 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 polyhydric hydroxy compounds such as aliphatic polyhydroxy compounds and aromatic polyhydroxy compounds with unsaturated carboxylic acids and polybasic carboxylic acids are not necessarily single products, but are typical examples. 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.

In addition, examples of the polyfunctional ethylenic monomer used in the present invention include a polyisocyanate compound and a hydroxyl group-containing (meth)acrylic ester, or a polyisocyanate compound, a polyol, and a hydroxyl group-containing (meth)acrylic ester. Urethane (meth)acrylates such as those obtained; Epoxy acrylates such as addition reaction products of polyvalent epoxy compounds and hydroxy (meth)acrylate or (meth)acrylic acid; Acrylamides such as ethylene bisacrylamide; Diallyl phthalate Allyl esters such as esters, and vinyl group-containing compounds such as divinyl phthalate are useful.
Examples of the urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical 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 Gosei Kagaku Kogyo Co., Ltd.).

Among these, it is preferable to use urethane (meth)acrylates as the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid as the photopolymerizable compound (C) from the viewpoint of the verticality of the side surface of the partition wall and ink repellency. , dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, 2-tris(meth)acryloyloxymethylethylphthalate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, di It is more preferable to use a dibasic acid anhydride adduct of pentaerythritol penta(meth)acrylate, a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate, and the like.
These may be used alone or in combination of two or more.

In the present invention, the molecular weight of the photopolymerizable compound (C) is not particularly limited, but from the viewpoint of ink repellency and verticality of the side surface of the partition, it is preferably 100 or more, more preferably 150 or more, still more preferably 200 or more, Even more preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, more preferably 700 or less. For example, the molecular weight of the photopolymerizable compound (C) is preferably from 100 to 1,000, more preferably from 150 to 1,000, even more preferably from 200 to 1,000, even more preferably from 300 to 700, even more preferably from 400 to 700, and even more preferably from 500 to 700. is particularly preferred.
The number of carbon atoms in the photopolymerizable compound (C) is not particularly limited, but from the viewpoint of ink repellency and verticality of the side surface of the partition, it is preferably 7 or more, more preferably 10 or more, even more preferably 15 or more, and even more It is preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, particularly preferably 30 or less. For example, the number of carbon atoms in the photopolymerizable compound (C) is preferably 7 to 50, more preferably 10 to 40, even more preferably 15 to 35, even more preferably 20 to 30, particularly preferably 25 to 30.
In addition, from the viewpoint of ink repellency and verticality of the side surface of the partition wall, ester (meth)acrylates, epoxy (meth)acrylates, and urethane (meth)acrylates are preferable, and among them, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, Erythritol tri(meth)acrylate dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate and other trifunctional or higher functional ester (meth)acrylates, 2,2,2-tris(meth)acryloyloxymethylethyl Additions of acid anhydrides to trifunctional or higher functional ester (meth)acrylates, such as dibasic acid anhydride adducts of phthalic acid and dipentaerythritol penta(meth)acrylate, improve ink repellency and verticality of partition walls. It is more preferable in terms of.

The content of the photopolymerizable compound (C) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more in the total solid content. The content is at least 15% by mass, more preferably at least 15% by mass, usually at most 80% by mass, preferably at most 60% by mass, more preferably at most 40% by mass, even more preferably at most 30% by mass. When the amount is at least the lower limit, the perpendicularity of the side surfaces of the partition walls during exposure tends to be good, and when it is at most the upper limit, the developability tends to be good. For example, the content of the photopolymerizable compound (C) in the total solid content of the photosensitive colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, and even more preferably 10 to 40% by mass. , 15 to 30% by mass is particularly preferred.

Further, the content ratio of (C) photopolymerizable compound to 100 parts by mass of (B) alkali-soluble resin is not particularly limited, but is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and Preferably 15 parts by mass or more, particularly preferably 20 parts by mass or more, usually 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 70 parts by mass or less, still more preferably 50 parts by mass or less, particularly preferably 40 parts by mass or less. It is preferably less than parts by mass. When the content is equal to or more than the lower limit, ink repellency tends to be good and the perpendicularity of the side surface of the partition wall tends to be good, and when the content is equal to or less than the upper limit, the developability tends to be good. For example, the content ratio of the photopolymerizable compound (C) to 100 parts by mass of the alkali-soluble resin (B) is preferably 1 to 150 parts by mass, more preferably 5 to 100 parts by mass, even more preferably 10 to 70 parts by mass, and 15 to 150 parts by mass. It is even more preferably 50 parts by weight, and particularly preferably 20 to 40 parts by weight.

[1-1-4] (D) Colorant The photosensitive colored resin composition of the present invention contains (D) a colorant. By containing the coloring agent (D), it is possible to obtain appropriate light absorbing properties, particularly appropriate light blocking properties when used for forming light blocking members such as colored partition walls.

The type of colorant (D) used in the present invention is not particularly limited, and pigments or dyes may be used. Among these, from the viewpoint of durability, it is preferable to use pigments.

(D) The coloring agent may contain one type of pigment, or two or more types of pigments. In particular, from the viewpoint of uniformly blocking light in the visible region, it is preferable to use two or more types.
(D) The type of pigment that can be used as the colorant is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, it is preferable to use organic pigments from the viewpoint of controlling the transmission wavelength of the photosensitive colored resin composition and curing it efficiently.
Examples of organic pigments include organic colored pigments and organic black pigments. Here, the organic colored pigment refers to an organic pigment exhibiting a color other than black, and includes red pigments, orange pigments, blue pigments, violet pigments, green pigments, yellow pigments, and the like.

Among organic pigments, it is preferable to use organic coloring pigments from the viewpoint of light-shielding properties and ultraviolet absorption properties.
One type of organic coloring pigment may be used alone, or two or more types may be used in combination. In particular, when used for light-shielding applications, it is more preferable to use a combination of organic coloring pigments of different colors, and it is even more preferable to use a combination of organic coloring pigments that exhibit a color close to black.

The chemical structure of these organic pigments is not particularly limited, but examples include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, perylene-based, and the like. Specific examples of pigments that can be used are shown below using pigment numbers. Terms such as "C.I. Pigment Red 2" listed below mean color index (C.I.).

As a red pigment, C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276. Among these, C.I. I. Pigment Red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. I. Pigment Red 177, 209, 224, and 254. In addition, in terms of dispersibility and light blocking properties, C. I. It is preferable to use Pigment Red 177, 254, and 272, and when curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use a red pigment with low ultraviolet absorbance.From this point of view, C ．． I. It is more preferable to use Pigment Red 254 and 272.

As the orange pigment, C. I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, C. I. Pigment Orange 13, 43, 64, and 72 are preferably used, and when curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use orange pigments with low ultraviolet absorbance; from this point of view, is C. I. It is more preferable to use Pigment Orange 64 and 72.

As a blue pigment, C. I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among these, from the viewpoint of light-shielding properties, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. I. Pigment Blue 15:6 may be mentioned.
In addition, in terms of dispersibility and light blocking properties, C. I. Pigment Blue 15:6, 16, and 60 are preferably used. When curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use blue pigments with low ultraviolet absorbance; from this point of view, is C. I. It is more preferable to use Pigment Blue 60.

As a purple pigment, C. I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, from the viewpoint of light-shielding properties, C.I. I. Pigment Violet 19, 23, more preferably C.I. I. Pigment Violet 23 may be mentioned.
In addition, in terms of dispersibility and light blocking properties, C. I. It is preferable to use Pigment Violet 23 and 29. When curing the photosensitive colored resin composition with ultraviolet rays, it is preferable to use a purple pigment with a low ultraviolet absorption rate, and from this point of view, C. I. It is more preferable to use Pigment Violet 29.

Examples of organic coloring pigments that can be used in addition to red pigments, orange pigments, blue pigments, and purple pigments include green pigments and yellow pigments.
As a green pigment, C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55. Among these, C. I. Pigment Green 7 and 36 can be mentioned.
As a yellow pigment, C. I. Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136, 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, and 208 can be mentioned. Among these, C. I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, more preferably C.I. I. Pigment Yellow 83, 138, 139, 150, and 180.

Among these, from the viewpoint of light blocking properties and shape control, it is preferable to use at least one selected from the group consisting of red pigments, orange pigments, blue pigments, and violet pigments.

Among these, from the viewpoint of light-shielding properties and shape control, it is preferable to contain at least one or more of the following pigments.
Red pigment: C. I. Pigment Red 177, 254, 272
Orange pigment: C. I. Pigment orange 43, 64, 72
Blue pigment: C. I. Pigment Blue 15:6,60
Purple pigment: C. I. pigment violet 23, 29

In addition, when using two or more types of organic coloring pigments in combination, the combination of organic coloring pigments is not particularly limited, but from the viewpoint of light shielding, at least one type selected from the group consisting of red pigments and orange pigments, and blue pigments. and at least one selected from the group consisting of purple pigments.
The combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, examples include a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment, an orange pigment, and a violet pigment. .

Furthermore, a black pigment may be used in addition to these organic coloring pigments. Further, in addition to the organic coloring pigment, a black pigment may also be used.
Examples of the black pigment include inorganic black pigments and organic black pigments, but from the viewpoint of light-shielding properties, it is preferable to contain one or both of carbon black and organic black pigments.

Among black pigments, it is preferable to use organic black pigments from the viewpoint of suppressing absorption of ultraviolet rays and making it easier to control the shape, and in particular from the viewpoint of light-shielding properties, organic black pigments represented by the following general formula (1) are preferred. At least one compound selected from the group consisting of a compound (hereinafter also referred to as "compound (1)"), a geometric isomer of compound (1), a salt of compound (1), and a salt of a geometric isomer of compound (1) It is preferable to use an organic black pigment containing seeds (hereinafter sometimes referred to as "organic black pigment represented by general formula (1)").

In formula (1), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ^- , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N = _CH2 , N= ^CHR21 , N= ^CR21R22 , SH, ^SR21 , ^SOR21 _, ^{SO2R21 , SO3R21} , _{SO3H , SO3-} ^, _{SO2NH2 , SO2NHR} ²¹ or SO ₂ NR ²¹ R ²² ;
At least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ is may be bonded or may be bonded to each other by oxygen atoms, sulfur atoms, NH or ^NR bridges;
R ²¹ and R ²² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms; Represents 2 to 12 alkynyl groups.

Compound (1) and geometric isomers of compound (1) have the following core structures (however, substituents in the structural formulas are omitted), and the trans-trans isomer is probably the most stable.

When compound (1) is anionic, its charge can be transferred to any known suitable cation, such as a metal, organic, inorganic or metal-organic cation, in particular an alkali metal, alkaline earth metal, transition metal, primary ammonium , secondary ammonium, tertiary ammonium such as trialkylammonium, quaternary ammonium such as tetraalkylammonium, or a salt compensated with an organometallic complex. Moreover, when the geometric isomer of compound (1) is anionic, a similar salt is preferable.

Regarding the substituents in general formula (1) and their definitions, the following are preferable because the shielding rate tends to be high. This is because the following substituents have no absorption and are considered not to affect the hue of the pigment.
R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.
R ¹³ and R ¹⁸ each independently preferably represent a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , bromine atom, chlorine atom, CH ₃ , C ₂ H ₅ , N(CH ₃ ) ₂ , N(CH ₃ ) (C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^- , more preferably a hydrogen atom or SO ₃ H, particularly preferably is a hydrogen atom.

R ¹¹ and R ¹⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, and more preferably R ¹¹ is the same as R ¹⁶ , R ¹² is the same as R ¹⁷ , R ¹³ is the same as R ¹⁸ , R ¹⁴ is the same as R ¹⁹ , and R ¹⁵ is the same as R ²⁰ . are the same.

Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2 - Ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a trimethylcyclohexyl group, a tuzyl group, a norbornyl group, a bornyl group, and a norcalyl group. , calyl group, menthyl group, norpinyl group, pinyl group, adamantan-1-yl group or adamantan-2-yl group.

Examples of alkenyl groups having 2 to 12 carbon atoms include vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, and 1,3-butadiene group. -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2-buten-1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group or dodecenyl group.

Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, , 4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thujen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadien-1 -yl group, 7,7-dimethyl-2,4-norcaladien-3-yl group, or camphenyl group.

Examples of the alkynyl group having 2 to 12 carbon atoms include 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, and 2-methyl-3-butyn-2-yl group. group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octyn-8-yl group, 1-nonyn-9-yl group, It is a 1-decyn-10-yl group or a 1-dodecyn-12-yl group.

The halogen atom is, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

The organic black pigment represented by the general formula (1) is preferably a compound represented by the following general formula (2) (hereinafter also referred to as "compound (2)"), and a geometric isomer of the compound (2). It is an organic black pigment containing at least one member selected from the group consisting of:

A specific example of such an organic black pigment is the trade name Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF).
This organic black pigment is preferably used after being dispersed using a dispersant, solvent, and method described below. Furthermore, the presence of the sulfonic acid derivative of compound (1), especially the sulfonic acid derivative of compound (2), during dispersion may improve dispersibility and storage stability. It is preferable to include.

Examples of organic black pigments other than the organic black pigment represented by the general formula (1) include aniline black and perylene black.

On the other hand, examples of inorganic black pigments include carbon black, acetylene black, lamp black, bone black, graphite, iron black, cyanine black, titanium black, and the like. Among these, carbon black can be preferably used from the viewpoint of light-shielding properties and image characteristics. Examples of carbon black include the following carbon blacks.

Made by Mitsubishi Chemical: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, #5, #10, #20, #25, #30, #32, #33, #40 , #44, #45, #47, #50, #52, #55, #650, #750, #850, #900, #950, #960, #970, #980, #990, #1000, # 2200, #2300, #2350, #2400, #2600, #2650, #3030, #3050, #3150, #3250, #3400, #3600, #3750, #3950, #4000, #4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B
Manufactured by Degussa: Printex (registered trademark, same hereinafter) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex8 5, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, PrintexG, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBla ck4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW18, Color Black FW200, Color Black S160, Col or Black S170
Manufactured by Cabot: Monarch (registered trademark, same hereinafter) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1 400, Monarch4630, REGAL (registered trademark, same hereinafter) 99, REGAL99R, REGAL415, REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, the same applies hereinafter) XC72R, ELFTEX (registered trademark) Trademark)-8
Made by Birler: RAVEN (registered trademark, same hereinafter) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RA VEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U , RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black coated with resin may be used. Use of resin-coated carbon black has the effect of improving adhesion to glass substrates and volume resistivity. As the resin-coated carbon black, for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be suitably used. Resin-coated carbon black is preferably used in terms of volume resistivity and dielectric constant.

The carbon black to be subjected to the resin coating treatment preferably has a total content of Na and Ca of 100 ppm or less. Carbon black usually contains Na, Ca, K, Mg, Al, Fe, etc. mixed in from raw material oil, combustion oil (or gas), reaction stop water, granulation water, and reactor materials during manufacturing. Contains ash with a composition of Among these, Na and Ca are generally contained in amounts of several hundred ppm or more each, but by reducing their content, it is possible to suppress penetration into transparent electrodes (ITO) and other electrodes, and to This tends to prevent short circuits.

A method for reducing the content of ash containing Na and Ca is to carefully select materials with as low a content as possible as raw material oil, fuel oil (or gas), and reaction termination water when manufacturing carbon black. This can be achieved by minimizing the amount of alkaline substances added to adjust the structure. Another method includes a method in which carbon black produced from a furnace is washed with water, hydrochloric acid, etc. to dissolve and remove Na and Ca.

Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide, and a poorly soluble solvent is added to the water, the carbon black migrates to the solvent side and completely separates from the water. At the same time, most of the Na and Ca present in the carbon black are dissolved and removed by water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, it may be possible to use only the carbon black manufacturing process with carefully selected raw materials or the water or acid dissolution method alone, but it is possible to reduce the total amount of Na and Ca to 100 ppm or less, but by using both methods together The total amount of Na and Ca can be easily reduced to 100 ppm or less.

Further, the resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, it is possible to coat even minute units, which is preferable. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 mL/100 g or less. By setting it within the above range, a coating film with good light-shielding properties tends to be obtained. The average particle diameter refers to the number average particle diameter, and particle image analysis involves taking several fields of view of photographs taken at tens of thousands of magnifications using an electron microscope, and measuring approximately 2000 to 3000 particles in these photographs using an image processing device. means the equivalent circle diameter determined by

There are no particular limitations on the method for preparing resin-coated carbon black, but for example, after suitably adjusting the blending amounts of carbon black and resin, 1. After mixing and stirring a resin solution in which a resin and a solvent such as cyclohexanone, toluene, or xylene are mixed and dissolved by heating, and a suspension in which carbon black and water are mixed to separate the carbon black and water, 2. A method of removing water and heating and kneading the resulting composition into a sheet, pulverizing it, and then drying it; 2. A method of mixing and stirring a resin solution and a suspension prepared in the same manner as described above to granulate carbon black and resin, and then separating and heating the resulting granules to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in the above-mentioned solvent, carbon black is added, mixed and dried, the solvent is removed to obtain carboxylic acid-impregnated carbon black, and a resin is added to this. method of dry blending; 4. A suspension is prepared by stirring the reactive group-containing monomer component constituting the resin to be coated with water at high speed, and after polymerization, the reactive group-containing resin is obtained from the polymer suspension by cooling. A method may be adopted in which carbon black is added and kneaded, the carbon black and a reactive group are reacted (grafted with carbon black), and the mixture is cooled and pulverized.

The type of resin to be coated is not particularly limited, but synthetic resins are common, and resins that have a benzene ring in their structure have a stronger action as an amphoteric surfactant. Preferred from the viewpoint of dispersibility and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, and alkylbenzene resin, as well as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, and modified polyphenylene. Thermoplastic resins such as oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyamino bismaleimide, polyethersulfopolyphenylenesulfone, polyarylate, and polyetheretherketone can be used. The amount of coating resin is preferably 1 to 30% by mass based on the total amount of carbon black and resin. There is a tendency that sufficient coverage can be obtained by setting the amount to be equal to or more than the lower limit value. On the other hand, by setting the amount to be less than or equal to the above upper limit, there is a tendency that adhesion between resins can be prevented and dispersibility can be improved.

Carbon black coated with a resin in this manner can be used as a coloring agent for colored partition walls according to a conventional method. When such carbon black is used, a colored partition wall with a high light shielding rate and a low surface reflectance tends to be formed at low cost. It is also assumed that by coating the carbon black surface with a resin, there is a function to confine ash containing Na and Ca into the carbon black.

These pigments are preferably used in a dispersed manner so that the average particle diameter is usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Here, the standard for the average particle diameter is the number of pigment particles.
Further, the average particle diameter of the pigment is a value determined from the pigment particle diameter measured by dynamic light scattering (DLS). Particle size measurement is performed using a sufficiently diluted photosensitive colored resin composition (usually diluted to give a pigment concentration of about 0.005 to 0.2% by mass. However, if the concentration recommended by the measuring device is (according to its concentration) and measured at 25°C.

Furthermore, in addition to the above-mentioned organic colored pigments and black pigments, dyes may be used. Examples of dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinone imine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.
Examples of azo dyes include C.I. I. Acid Yellow 11, C. I. Acid Orange 7, C. I. Acid Red 37, C. I. Acid Red 180, C. I. Acid Blue 29, C. I. Direct Red 28, C. I. Direct Red 83, C. I. Direct Yellow 12, C. I. Direct Orange 26, C. I. Direct Green 28, C. I. Direct Green 59, C. I. Reactive Yellow 2, C. I. Reactive Red 17, C. I. Reactive Red 120, C. I. Reactive Black 5, C. I. Disperse Orange 5, C. I. Dispersed Red 58, C. I. Disperse Blue 165, C. I. Basic Blue 41, C. I. Basic Red 18, C. I. Mordant Red 7, C. I. Mordant Yellow 5, C. I. Examples include Mordant Black 7.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C. I. Acid Blue 40, C. I. Acid Green 25, C. I. Reactive Blue 19, C. I. Reactive Blue 49, C. I. Dispersed Red 60, C. I. Disperse Blue 56, C. I. Examples include Disperse Blue 60.
In addition, examples of phthalocyanine dyes include C.I. I. Pad Blue 5 etc. are quinone imine dyes such as C.I. I. Basic Blue 3, C. I. Basic Blue 9 etc. are used as quinoline dyes such as C.I. I. Solvent Yellow 33, C. I. Acid Yellow 3, C. I. Disperse Yellow 64 and the like are used as nitro dyes such as C.I. I. Acid Yellow 1, C. I. Acid Orange 3, C. I. Examples include Disperse Yellow 42.

The content of the colorant (D) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more in the total solid content. It is preferably 4% by mass or more, and more preferably 4% by mass or more. Also, it is usually 50% by mass or less, preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, even more preferably 15% by mass or less, particularly preferably 10% by mass or less, and 6 The most preferable amount is % by mass or less. When the amount is equal to or more than the lower limit, light-shielding properties tend to be ensured, and when the amount is equal to or less than the upper limit, ink repellency tends to be improved. For example, the content of the colorant (D) in the total solid content of the photosensitive colored resin composition is preferably 1 to 50% by mass, more preferably 1 to 30% by mass, even more preferably 2 to 25% by mass, and 2% by mass. It is even more preferably 20% by weight, even more preferably 3% to 15% by weight, and particularly preferably 4% to 10% by weight.

[1-1-5] Component (E); Liquid repellent The photosensitive colored resin composition of the present invention contains a fluorine atom-containing resin having a crosslinking group as the liquid repellent (E). Since ink repellency can be imparted to the surface of the partition wall obtained by containing a fluorine atom-containing resin having a crosslinking group, it is thought that the obtained partition wall can be used to prevent color mixing in each light emitting part (pixel) of the organic layer. It will be done.

Examples of the crosslinking group include an epoxy group or an ethylenically unsaturated group, and an ethylenically unsaturated group is preferable from the viewpoint of suppressing outflow of the liquid-repellent component of the developer.
By using a liquid repellent having a crosslinking group, it is possible to accelerate the crosslinking reaction on the surface of the formed coating film when it is exposed to light, making it difficult for the liquid repellent to flow out during the development process, and as a result, the resulting partition wall It is thought that this can be made to exhibit high ink repellency.

Further, since the resin is a fluorine atom-containing resin, the fluorine atom-containing resin tends to be oriented on the surface of the partition wall, thereby preventing ink bleeding and color mixing. More specifically, the group having a fluorine atom tends to repel ink and prevent ink from bleeding or color mixing due to ink entering an adjacent region beyond a partition wall.

Further, the fluorine atom-containing resin having a crosslinking group preferably has one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. By having one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain, the fluorine atom-containing resin becomes more easily oriented on the surface of the partition wall, exhibiting higher ink repellency, and preventing ink bleeding and color mixing. There is a tendency to prevent further.

Examples of the perfluoroalkyl group include a perfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, and the like. Perfluoroalkylene ether chains include -CF ₂ -O-, -(CF ₂ ) ₂ -O-, -(CF ₂ ) ₃ -O-, -CF ₂ -C(CF ₃ )O-, -C( Examples include CF ₃ )-CF ₂ -O- and divalent groups having repeating units thereof.

Specific examples of fluorine atom-containing resins having crosslinking groups include acrylic copolymer resins having epoxy groups and perfluoroalkyl groups, acrylic copolymer resins having epoxy groups and perfluoroalkylene ether chains, ethylenically unsaturated groups and Acrylic copolymer resin with perfluoroalkyl group, acrylic copolymer resin with ethylenically unsaturated group and perfluoroalkylene ether chain, epoxy(meth)acrylate resin with epoxy group and perfluoroalkyl group, epoxy group and perfluoro Epoxy(meth)acrylate resin with alkylene ether chain, epoxy(meth)acrylate resin with ethylenically unsaturated group and perfluoroalkyl group, epoxy(meth)acrylate resin with ethylenically unsaturated group and perfluoroalkylene ether chain , etc. Among these, from the viewpoint of ink repellency, acrylic copolymer resins having an ethylenically unsaturated group and perfluoroalkyl group, and acrylic copolymer resins having an ethylenically unsaturated group and perfluoroalkylene ether chain are preferred; More preferred is an acrylic copolymer resin having a saturated group and a perfluoroalkylene ether chain.

Commercial products of fluorine atom-containing resins having these crosslinking groups include "Megafac (registered trademark, hereinafter the same) F116", "Megafac F120", "Megafac F142D", and "Megafac F144D" manufactured by DIC Corporation. , "Megafuck F150", "Megafuck F160", "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", " ``Megafac RS402'', ``Megafac RS501'', ``Megafac RS502'', ``Megafac RS-72-K'', ``Megafac RS-78'', ``DEFENSA (registered trademark, hereinafter the same) MCF300'', ``DEFENSA''MCF310'', ``DEFENSA MCF312'', ``DEFENSA MCF323'', 3M Japan's ``Florado FC430'', ``Florado FC431'', ``FC-4430'', ``FC4432'', AGC's ``Asahi Guard (registered trademark) AG710''. , "Surflon (registered trademark, hereinafter the same) S-382", "Surflon SC-101", "Surflon SC-102", "Surflon SC-103", "Surflon SC-104", "Surflon SC-105" A fluorine-containing organic compound commercially available under a trade name such as "Surflon SC-106" can be used.
Among these, "Megafac RS-72-K", "Megafac RS-78", etc. can be preferably used as the acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene group.

The fluorine atom content in the fluorine atom-containing resin having a crosslinking group is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. Preferably, 25% by mass or more is even more preferable. Further, it is preferably 50% by mass or less, more preferably 35% by mass or less. By setting the amount above the lower limit value, there is a tendency to suppress the outflow to the pixel area, and by setting it below the above upper limit value, there is a tendency to exhibit a high contact angle. For example, the fluorine atom content in the fluorine atom-containing resin having a crosslinking group is preferably 5 to 50% by mass, more preferably 10 to 35% by mass, and 20 to 35% by mass. More preferably, 25 to 35% by mass is particularly preferred.

The molecular weight of the fluorine atom-containing resin having a crosslinking group is not particularly limited, and may be a low molecular weight compound or a high molecular weight compound. A high molecular weight substance is preferable because it suppresses fluidity during post-baking and can suppress outflow from partition walls.From this point of view, the number average molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 or more. , more preferably 500 or more, preferably 100,000 or less, and more preferably 10,000 or less. For example, the molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 to 100,000, more preferably 500 to 10,000.

The content of the liquid repellent (E) in the photosensitive colored resin composition of the present invention is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.1% by mass or more in the total solid content. It is 0.5% by mass or more, and usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less. When the value is equal to or higher than the lower limit value, there is a tendency to exhibit high ink repellency, and when the value is equal to or less than the upper limit value, there is a tendency that outflow to the pixel area can be suppressed. For example, the content of the liquid repellent (E) is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and more preferably 0.5 to 2% by mass based on the total solid content of the photosensitive colored resin composition. % is more preferred.

Further, the content ratio of the fluorine atom-containing resin having a crosslinking group is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, and more preferably 0.5% by mass or more in the total solid content. The content is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less. When the value is equal to or higher than the lower limit value, there is a tendency to exhibit high ink repellency, and when the value is equal to or less than the upper limit value, there is a tendency that outflow to the pixel area can be suppressed. For example, the content of the fluorine atom-containing resin having a crosslinking group is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass, and 0.5% by mass based on the total solid content of the photosensitive colored resin composition. ˜2% by mass is more preferred.

On the other hand, in the photosensitive colored resin composition of the present invention, a surfactant may be used together with (E) a liquid repellent. The surfactant can be used for the purpose of improving the coating properties of the photosensitive colored resin composition as a coating solution and the developability of the coating film, among others, silicone-based surfactants and those that do not have a crosslinking group. Fluorine-based surfactants are preferred.
In particular, silicone-based surfactants are preferable because they have the effect of removing the residue of the photosensitive colored resin composition from unexposed areas during development and also have the function of developing wettability, and polyether-modified silicone More preferred are surfactants.

As the fluorine-based surfactant without a crosslinking group, a compound having a fluoroalkyl or fluoroalkylene group at at least one of the terminal, main chain, and side chain is suitable.
These commercially available products include, for example, "BM-1000" and "BM-1100" manufactured by BM Chemie, "Megafac F142D", "Megafac F172", "Megafac F173", and "Megafac F183" manufactured by DIC Corporation. ", "Megafac F470,""MegafacF475,""MegafacF554,""MegafacF559,""FC430" manufactured by 3M Japan, and "DFX-18" manufactured by Neos.

In addition, examples of silicone surfactants include "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032Additive", "SH8400", manufactured by Dow Corning Toray Industries, Inc. Commercially available products such as BYK (registered trademark, hereinafter the same) 323 and BYK330 manufactured by BYK Chemie Co., Ltd. can be mentioned.
The surfactant may include things other than fluorine-based surfactants and silicone-based surfactants, and other surfactants include nonionic, anionic, cationic, and amphoteric surfactants. It will 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, pentaerythritol fatty acid esters, polyoxyethylene pentaerythritol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, sorbitol fatty acid esters, polyoxy Examples include ethylene sorbitol fatty acid esters. Examples of these commercially available products include polyoxyethylene surfactants such as "Emulgen (registered trademark, the same hereinafter) 104P" and "Emulgen A60" manufactured by Kao Corporation.

Examples of the anionic surfactants include alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, polyoxyethylene alkyl ether sulfonates, alkyl sulfates, alkyl sulfate ester salts, and higher alcohol sulfates. Ester salts, aliphatic 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 these, special polymer surfactants are preferred, and special polycarboxylic acid type polymer surfactants are more preferred. Commercially available products can be used as such anionic surfactants.For example, alkyl sulfate ester salts are available from Kao Corporation, such as "Emar (registered trademark, hereinafter the same applies) 10", and alkylnaphthalene sulfonate salts are available from Kao Corporation. Examples of special polymer surfactants include "Homogenol (registered trademark) L-18" and "Homogenol L-100" made by Kao Corporation, such as "Perex (registered trademark) NB-L" manufactured by Kao Corporation. .

Further, examples of the cationic surfactants include quaternary ammonium salts, imidazoline derivatives, alkylamine salts, etc., and examples of the amphoteric surfactants include betaine type compounds, imidazolium salts, imidazolines, and amino acids. Examples include. Among these, quaternary ammonium salts are preferred, and stearyltrimethylammonium salts are more preferred. Commercially available products include, for example, alkylamine salts such as "Acetamin (registered trademark) 24" manufactured by Kao Corporation, and quaternary ammonium salts such as "Cortamine (registered trademark) 24P" and "Cortamine (registered trademark) 24P" manufactured by Kao Corporation. 86W".

Further, surfactants may be used in combination of two or more types, for example, silicone surfactant/fluorine surfactant, silicone surfactant/special polymer surfactant, fluorine surfactant. /Special polymeric surfactant combinations, etc. Among these, a combination of silicone surfactant/fluorosurfactant is preferred. Examples of the silicone surfactant/fluorosurfactant combination include "DFX-18" manufactured by NEOS, "BYK-300" or "BYK-330" manufactured by BYK Chemie, and "S-" manufactured by AGC Seimi Chemical. 393", "KP340" manufactured by Shin-Etsu Silicone / "F-554" or "F-559" manufactured by DIC, "SH7PA" manufactured by Dow Corning Toray / "DS-401" manufactured by Daikin, "L" manufactured by NUC -77''/FC4430 manufactured by 3M Japan.

[1-1-6] (F) Dispersant The photosensitive colored resin composition of the present invention contains (F) a dispersant in order to finely disperse the (D) colorant and stabilize the dispersion state. It is preferable to include.
(F) As the dispersant, a polymeric dispersant having a functional group is preferable, and from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or a base thereof; a primary, secondary or tertiary Polymer dispersants having functional groups such as an amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine, and pyrazine are preferred. In particular, polymeric dispersants having basic functional groups such as primary, secondary or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine and pyrazine disperse pigments. It is particularly preferred from the viewpoint that it can be dispersed with a small amount of dispersant.

Examples of polymeric dispersants include urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants consisting of monomers and macromonomers having amino groups, and polyoxyethylene alkyl ethers. Examples include a polyoxyethylene diester dispersant, a polyether phosphate dispersant, a polyester phosphate dispersant, a sorbitan aliphatic ester dispersant, an aliphatic modified polyester dispersant, and the like.

Specific examples of such dispersants include trade names such as EFKA (registered trademark, manufactured by BASF Corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie Corporation), DISPARON (registered trademark, manufactured by Kusumoto Kasei Co., Ltd.), and SOLSPERSE. (registered trademark, manufactured by Lubrizol Co., Ltd.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Ajisper (registered trademark, manufactured by Ajinomoto Co., Ltd.), and the like.
These polymer dispersants may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the polymeric dispersant is usually 700 or more, preferably 1,000 or more, and usually 100,000 or less, preferably 50,000 or less. For example, the weight average molecular weight (Mw) of the polymer dispersant is preferably 700 to 100,000, more preferably 1,000 to 50,000.
Among these, from the viewpoint of pigment dispersibility, (F) the dispersant preferably contains either or both of a urethane polymer dispersant and an acrylic polymer dispersant having a functional group; It is particularly preferred to include a molecular dispersant.
Further, from the viewpoint of dispersibility and storage stability, a polymer dispersant having a basic functional group and either or both of a polyester bond and a polyether bond is preferable.

Urethane-based and acrylic-based polymer dispersants include, for example, DISPERBYK-160 to 167, 182 series (all urethane-based), DISPERBYK-2000, 2001, BYK-LPN21116 (all acrylic-based), etc. (all of the above are manufactured by BYK Chemie) ).
To specifically illustrate a preferable chemical structure as a urethane-based polymer dispersant, for example, a polyisocyanate compound, a compound with a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the molecule, and a polyisocyanate compound in the same molecule. Examples include dispersion resins having a weight average molecular weight of 1,000 to 200,000, which are obtained by reacting active hydrogen with a compound having a tertiary amino group. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino groups can be converted into quaternary ammonium bases.

Examples of the above polyisocyanate compounds include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolydine diisocyanate, etc. Aromatic diisocyanates, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, aliphatic diisocyanates such as dimer acid diisocyanate, isophorone diisocyanate, 4,4'-methylene bis(cyclohexyl isocyanate), ω, ω '-diisocyanate Alicyclic diisocyanates such as dimethylcyclohexane, xylylene diisocyanate, aliphatic diisocyanates with aromatic rings such as α, α, α', α'-tetramethylxylylene diisocyanate, lysine ester triisocyanate, 1,6, 11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanate methyloctane, 1,3,6-hexamethylene triisocyanate, bicycloheptane triisocyanate, tris (isocyanate phenylmethane), tris (isocyanate phenyl) thiophosphate, etc. Examples include triisocyanates, trimers thereof, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, and most preferred are trimers of tolylene diisocyanate and isophorone diisocyanate.
These may be used alone or in combination of two or more.

As a method for producing isocyanate trimers, the polyisocyanates are treated with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, etc. to form isocyanate groups. After the trimerization is stopped by adding a catalyst poison, unreacted polyisocyanate is removed by solvent extraction and thin film distillation to obtain the desired isocyanurate group-containing polyisocyanate.

Compounds having a number average molecular weight of 300 to 10,000 and having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, etc., and compounds in which one terminal hydroxyl group of these compounds has 1 to 1 carbon atoms. Examples include those alkoxylated with 25 alkyl groups and mixtures of two or more of these.
Examples of polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. Examples of polyether diols include those obtained by copolymerizing alkylene oxides alone or by copolymerizing them, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and the like. Examples include mixtures of two or more of these.

Polyether ester diols include those obtained by reacting ether group-containing diols or mixtures with other glycols with dicarboxylic acids or their anhydrides, or by reacting polyester glycols with alkylene oxides, such as poly(polyester diols). Oxytetramethylene) adipate and the like. The most preferred polyether glycols are polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or compounds in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

Polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 ,6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2 , 5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, aliphatic glycols such as 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, xylene Aromatic glycols such as lene glycol and bishydroxyethoxybenzene, N-alkyl dialkanolamines such as N-methyldiethanolamine, etc.), such as polyethylene adipate, polybutylene adipate, and polyhexamethylene adipate. , polyethylene/propylene adipate, etc., or polylactone diols or polylactone monools obtained using the above diols or monohydric alcohols having 1 to 25 carbon atoms as an initiator, such as polycaprolactone glycol, polymethylvalerolactone, and these. A mixture of two or more types may be mentioned. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

Examples of polycarbonate glycol include poly(1,6-hexylene) carbonate, poly(3-methyl-1,5-pentylene) carbonate, etc.; examples of polyolefin glycol include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. can be mentioned.
These may be used alone or in combination of two or more.

The number average molecular weight of the compound having one or two hydroxyl groups in the same molecule is usually 300 to 10,000, preferably 500 to 6,000, more preferably 1,000 to 4,000.

A compound having an active hydrogen and a tertiary amino group in the same molecule will be explained.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, nitrogen atom, or sulfur atom, includes hydrogen atoms in functional groups such as hydroxyl groups, amino groups, and thiol groups, and among them, amino groups, especially primary The hydrogen atom of the amino group is preferred.

The tertiary amino group is not particularly limited, but includes, for example, an amino group having an alkyl group having 1 to 4 carbon atoms, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.

Examples of such compounds having active hydrogen and a tertiary amino group in the same molecule include N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, and N,N-dimethyl-1,3-propanediamine. , N-dipropyl-1,3-propanediamine, N,N-dibutyl-1,3-propanediamine, N,N-dimethylethylenediamine, N,N-diethylethylenediamine, N,N-dipropylethylenediamine, N,N -dibutylethylenediamine, N,N-dimethyl-1,4-butanediamine, N,N-diethyl-1,4-butanediamine, N,N-dipropyl-1,4-butanediamine, N,N-dibutyl-1 , 4-butanediamine and the like.

Further, when the tertiary amino group has a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocycle include a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, a benzimidazole ring, and a benzo ring. 5-membered nitrogen-containing hetero rings such as triazole ring, benzoxazole ring, benzothiazole ring, and benzothiadiazole ring; 6-membered nitrogen-containing hetero rings such as pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, isoquinoline ring, etc. Examples include rings. Among these nitrogen-containing heterocycles, an imidazole ring or a triazole ring is preferred.

Specific examples of these compounds having an imidazole ring and an amino group include 1-(3-aminopropyl)imidazole, histidine, 2-aminoimidazole, and 1-(2-aminoethyl)imidazole. Further, specific examples of compounds having a triazole ring and an amino group include 3-amino-1,2,4-triazole, 5-(2-amino-5-chlorophenyl)-3-phenyl-1H-1 , 2,4-triazole, 4-amino-4H-1,2,4-triazole-3,5-diol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1 , 4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, and the like. Among them, N,N-dimethyl-1,3-propanediamine, N,N-diethyl-1,3-propanediamine, 1-(3-aminopropyl)imidazole, and 3-amino-1,2,4-triazole. preferable.
These may be used alone or in combination of two or more.

The preferred blending ratio of raw materials when producing a urethane polymer dispersant is 10 to 200 parts of a compound with a number average molecular weight of 300 to 10,000 having one or two hydroxyl groups in the same molecule to 100 parts by mass of the polyisocyanate compound. parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, and 0.2 to 25 parts by weight, preferably 0.3 to 24 parts by weight of a compound having active hydrogen and a tertiary amino group in the same molecule. Part by mass.

The urethane polymer dispersant is produced according to a known method for producing polyurethane resins. Solvents used during production usually include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate, benzene, toluene, xylene, and hexane. Hydrocarbons such as diacetone alcohol, isopropanol, sec-butanol, tertiary-butanol, and other alcohols; chlorides such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; dimethylformamide and N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. These may be used alone or in combination of two or more.

In the above production, a urethanization reaction catalyst is usually used. Examples of this catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannath octoate, iron-based catalysts such as iron acetylacetonate and ferric chloride, triethylamine, triethylenediamine, etc. Examples include grade amine type. These may be used alone or in combination of two or more.

The amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled within the range of 1 to 100 mgKOH/g based on the amine value after reaction. More preferably, it is in the range of 5 to 95 mgKOH/g. The amine value is a value obtained by neutralizing and titrating a basic amino group with an acid and expressed in mg of KOH in correspondence with the acid value. When the amount is equal to or more than the lower limit, the dispersion ability tends to be improved, and when the amount is less than the upper limit, the developability tends to be improved.

In addition, when isocyanate groups remain in the polymeric dispersant in the above reaction, it is preferable to further inactivate the isocyanate groups with an alcohol or an amino compound because the stability of the product over time increases.
The weight average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When the amount is equal to or more than the lower limit, the dispersibility and dispersion stability tend to improve, and when the amount is less than the upper limit, the solubility tends to improve and the dispersibility improves.

The acrylic polymer dispersant includes an unsaturated group-containing monomer having a functional group (the functional group referred to herein is the functional group described above as a functional group contained in the polymer dispersant); It is preferable to use a random copolymer, a graft copolymer, or a block copolymer with an unsaturated group-containing monomer having no functional group. These copolymers can be produced by known methods.

Examples of unsaturated group-containing monomers having functional groups include (meth)acrylic acid, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyl phthalic acid, and 2-(meth)acrylic acid. unsaturated monomers having a carboxyl group such as loyloxyethyl hexahydrophthalic acid and acrylic acid dimer; tertiary amino groups such as dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate and quaternized products thereof; A specific example is an unsaturated monomer having a quaternary ammonium base. These may be used alone or in combination of two or more.

Examples of unsaturated group-containing monomers that do not have functional groups include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl ( meth)acrylate, t-butyl(meth)acrylate, benzyl(meth)acrylate, phenyl(meth)acrylate, cyclohexyl(meth)acrylate, phenoxyethyl(meth)acrylate, phenoxymethyl(meth)acrylate, 2-ethylhexyl(meth)acrylate Acrylate, isobornyl (meth)acrylate, tricyclodecane (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, N-vinylpyrrolidone, styrene and its derivatives, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, N - N-substituted maleimides such as benzylmaleimide, acrylonitrile, vinyl acetate and polymethyl (meth)acrylate macromonomers, polystyrene macromonomers, poly2-hydroxyethyl (meth)acrylate macromonomers, polyethylene glycol macromonomers, polypropylene glycol macromonomers, poly Examples include macromonomers such as caprolactone macromonomer. These may be used alone or in combination of two or more.

The acrylic polymer dispersant is particularly preferably an AB or BAB block copolymer consisting of an A block having a functional group and a B block not having a functional group. In addition to partial structures derived from unsaturated group-containing monomers containing the above-mentioned functional groups, the block may also contain partial structures derived from unsaturated group-containing monomers that do not contain the above-mentioned functional groups. may be contained in the A block in either random copolymerization or block copolymerization. Further, the content of the partial structure not containing a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, and more preferably 30% by mass or less.

The B block consists of a partial structure derived from an unsaturated group-containing monomer that does not contain the above functional group, but one B block contains partial structures derived from two or more types of monomers. These may be contained in the B block in either random copolymerization or block copolymerization.
The AB or BAB block copolymer is prepared, for example, by the living polymerization method shown below.
Living polymerization methods include anionic living polymerization methods, cationic living polymerization methods, and radical living polymerization methods.

When synthesizing this acrylic polymer dispersant, the methods described in Japanese Patent Application Laid-Open No. 9-62002 and P. Lutz, P. Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Miji, Koichi Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Collection of Polymer Papers, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takuzo Aida, Shohei Inoue, Organic Synthetic Chemistry, 43, 300 (1985), D. Y. Sogoh, W. R. Known methods such as those described in Hertler et al, Macromolecules, 20, 1473 (1987) can be employed.

The acrylic polymer dispersant that can be used in the present invention may be an AB block copolymer or a BAB block copolymer, and the A block constituting the copolymer may be an AB block copolymer or a BAB block copolymer. /B block ratio is preferably 1/99 to 80/20, especially 5/95 to 60/40 (mass ratio), and by keeping it within this range, a balance between dispersibility and storage stability can be ensured. Tend.
Further, the amount of quaternary ammonium base in 1 g of AB block copolymer or BAB block copolymer that can be used in the present invention is usually preferably 0.1 to 10 mmol; By keeping it within this range, there is a tendency to ensure good dispersibility.

Note that such block copolymers may normally contain amino groups generated during the manufacturing process, but the amine value is about 1 to 100 mgKOH/g, and from the viewpoint of dispersibility, Preferably 10 mgKOH/g or more, more preferably 30 mgKOH/g or more, even more preferably 50 mgKOH/g or more, and preferably 90 mgKOH/g or less, more preferably 80 mgKOH/g or less, still more preferably 75 mgKOH/g or less. For example, the amine value of the block copolymer is preferably 10 to 90 mgKOH/g, more preferably 30 to 80 mgKOH/g, even more preferably 50 to 75 mgKOH/g.
Here, the amine value of the dispersant such as these block copolymers is expressed by the mass of KOH equivalent to the amount of base per gram of solid content excluding the solvent in the dispersant sample, and is measured by the following method.
Accurately weigh 0.5 to 1.5 g of the dispersant sample into a 100 mL beaker and dissolve it in 50 mL of acetic acid. This solution is neutralized and titrated with a 0.1 mol/L HClO ₄ acetic acid solution using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following formula.

Amine value [mgKOH/g] = (561 × V) / (W × S) [However, W: Dispersant sample weighed amount [g], V: Titration amount at the titration end point [mL], S: Dispersant Represents the solid content concentration [mass%] of the sample. ]
In addition, the acid value of this block copolymer depends on the presence or absence and type of acidic groups that are the source of the acid value, but in general, the lower the better, it is usually 10 mgKOH/g or less, and its weight average molecular weight (Mw ) is preferably in the range of 1000 to 100000. By keeping it within the above range, there is a tendency that good dispersibility can be ensured.

When the polymer dispersant has a quaternary ammonium base as a functional group, the specific structure of the polymer dispersant is not particularly limited. It is preferable to have the unit (i).

In the above formula (i), R ³¹ to R ³³ are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or a substituent-containing aryl group. represents an optionally aralkyl group;
Two or more of R ³¹ to R ³³ may be bonded to each other to form a cyclic structure;
R ³⁴ is a hydrogen atom or a methyl group;
X is a divalent linking group;
Y ^- is a counter-anion.

The number of carbon atoms in the alkyl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but it is preferably 1 or more and 10 or less, and 6 It is more preferable that it is below. For example, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 6. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, butyl , a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms in the aryl group which may have a substituent in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 6 or more, and preferably 16 or less, and 12 It is more preferable that it is below. For example, the number of carbon atoms in the aryl group is preferably 6 to 16, more preferably 6 to 12. Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, etc. Among these, phenyl group, methylphenyl group, ethylphenyl group , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group.

The number of carbon atoms in the optionally substituted aralkyl group in R ³¹ to R ³³ of the above formula (i) is not particularly limited, but is usually 7 or more, and preferably 16 or less, and 12 It is more preferable that it is below. For example, the number of carbon atoms in the aralkyl group is preferably 7 to 16, more preferably 7 to 12. Specific examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group, etc. Among these, phenylmethyl group, phenylethyl group A phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

Among these, from the viewpoint of dispersibility, it is preferable that R ³¹ to R ³³ are each independently an alkyl group or an aralkyl group. Specifically, R ³¹ and R ³³ are each independently a methyl group, or an ethyl group, and R ³² is preferably a phenylmethyl group or a phenylethyl group, and it is more preferable that R ³¹ and R ³³ are a methyl group, and R ³² is a phenylmethyl group. .

In addition, when the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, a repeating unit represented by the following formula (ii) (hereinafter sometimes referred to as "repeat unit (ii)") ) is preferable.

In the above formula (ii), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. is an optionally aralkyl group;
R ³⁵ and R ³⁶ may be combined with each other to form a cyclic structure;
R ³⁷ is a hydrogen atom or a methyl group;
Z is a divalent linking group.

As the alkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably employed.
As the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably employed.
As the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (ii), those exemplified as R ³¹ to R ³³ of the above formula (i) can be preferably employed.

Among these, it is preferable that R ³⁵ and R ³⁶ are each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

Examples of substituents that the alkyl group, aralkyl group, or aryl group in R ³¹ to R ³³ of the above formula (i) and R ³⁵ and R ³⁶ of the above formula (ii) may have include a halogen atom, an alkoxy group, Examples include benzoyl group and hydroxyl group.

In the above formulas (i) and (ii), the divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ⁴³ - group, -COOR ⁴⁴ - group [wherein R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms], etc., and are preferred. is a -COO-R ⁴⁴ - group.
In the above formula (i), examples of the counter anion Y ^- include Cl ^- , Br ^- , I ^- , ClO ₄ ^- , BF ₄ ^- , CH ₃ COO ^- , PF ₆ ^- and the like.

The content ratio of the repeating unit represented by the formula (i) is not particularly limited, but from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii) are Based on the total content of repeating units, it is preferably 60 mol% or less, more preferably 50 mol% or less, even more preferably 40 mol% or less, particularly preferably 35 mol% or less, Moreover, it is preferably 5 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more. For example, the content ratio of the repeating unit represented by the formula (i) is 5 relative to the sum of the content ratio of the repeating unit represented by the formula (i) and the content ratio of the repeating unit represented by the formula (ii). It is preferably 60 to 60 mol%, more preferably 10 to 50 mol%, even more preferably 20 to 40 mol%, and particularly preferably 30 to 35 mol%.

Further, the content ratio of the repeating unit represented by the formula (i) to all repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol % or more, and 5 mol %. % or more, more preferably 10 mol% or more, further preferably 50 mol% or less, more preferably 30 mol% or less, and 20 mol% or less. is more preferable, and particularly preferably 15 mol% or less. For example, the content of the repeating unit represented by formula (i) in all repeating units of the polymer dispersant is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, and 10 to 20 mol%. More preferably, 10 to 15 mol% is particularly preferred.

Further, the content ratio of the repeating unit represented by the formula (ii) to all repeating units of the polymer dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol % or more, and 10 mol %. % or more, more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, and 40 mol% or less. is more preferable, more preferably 30 mol% or less, and particularly preferably 25 mol% or less. For example, the content of the repeating unit represented by formula (ii) in all repeating units of the polymer dispersant is preferably 5 to 60 mol%, more preferably 10 to 40 mol%, and 15 to 30 mol%. More preferably, 20 to 25 mol% is particularly preferred.

In addition, from the viewpoint of increasing the compatibility with binder components such as solvents and improving dispersion stability, the polymer dispersant is used as a repeating unit represented by the following formula (iii) (hereinafter referred to as "repeating unit (iii)"). ) is preferable.

In the above formula (iii), R ⁴⁰ is an ethylene group or a propylene group;
R ⁴¹ is an alkyl group that may have a substituent;
R ⁴² is a hydrogen atom or a methyl group;
n is an integer from 1 to 20.

The number of carbon atoms in the optionally substituted alkyl group in R ⁴¹ of the above formula (iii) is not particularly limited, but is 1 or more, preferably 2 or more, and 10 or less. It is preferably 6 or less, and more preferably 6 or less. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, butyl , a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group. For example, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 2 to 6.

Further, n in the above formula (iii) is 1 or more, preferably 2 or more, and preferably 10 or less, and 5 or less, from the viewpoint of compatibility and dispersibility with binder components such as solvents. It is more preferable that For example, n is preferably 1 to 10, more preferably 2 to 5.

Further, the content ratio of the repeating unit represented by the formula (iii) to all repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, and preferably 2 mol% or more. It is more preferably 4 mol% or more, further preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When it is within the above range, it tends to be possible to achieve both compatibility with binder components such as solvents and dispersion stability. For example, the content of the repeating unit represented by formula (iii) in all repeating units of the polymer dispersant is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and 4 to 10 mol%. More preferred.

In addition, from the viewpoint of increasing the compatibility of the dispersant with a binder component such as a solvent and improving dispersion stability, a polymer dispersant is used in a repeating unit represented by the following formula (iv) (hereinafter referred to as a "repeat unit (iv)"). )”) is preferable.

In the above formula (iv), R is ^an alkyl group that may have a substituent, an aryl group that may have a substituent, or an aralkyl group that may have a substituent;
R ³⁹ is a hydrogen atom or a methyl group.

The number of carbon atoms in the optionally substituted alkyl group in R ³⁸ of the above formula (iv) is not particularly limited, but is 1 or more, preferably 2 or more, and preferably 4 or more. More preferably, it is 10 or less, and more preferably 8 or less. Specific examples of alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, etc. Among these, methyl, ethyl, propyl, butyl , a pentyl group, or a hexyl group, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group. Further, it may be either linear or branched. It may also contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group. For example, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 2 to 8, even more preferably 4 to 8.

The number of carbon atoms in the optionally substituted aryl group in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 6 or more, preferably 16 or less, and 12 or less. More preferably, it is 8 or less. Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, etc. Among these, phenyl group, methylphenyl group, ethylphenyl group , dimethylphenyl group, or diethylphenyl group, and more preferably phenyl group, methylphenyl group, or ethylphenyl group. For example, the aryl group preferably has 6 to 16 carbon atoms, more preferably 6 to 12 carbon atoms, and even more preferably 8 to 12 carbon atoms.

The number of carbon atoms in the optionally substituted aralkyl group in R ³⁸ of the above formula (iv) is not particularly limited, but is usually 7 or more, preferably 16 or less, and 12 or less. More preferably, it is 10 or less. Specific examples of aralkyl groups include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group, etc. Among these, phenylmethyl group, phenylethyl group A phenylpropyl group, or a phenylbutyl group is preferable, and a phenylmethyl group or a phenylethyl group is more preferable. For example, the number of carbon atoms in the aralkyl group is preferably 7 to 16, more preferably 7 to 12, even more preferably 7 to 10.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, and more preferably a methyl group, an ethyl group, or a phenylmethyl group.
Examples of the substituent that the alkyl group in R ³⁸ may have include a halogen atom and an alkoxy group. Furthermore, examples of the substituent that the aryl group or aralkyl group may have include a chain alkyl group, a halogen atom, an alkoxy group, and the like. Furthermore, the chain alkyl group represented by R ³⁸ includes both straight chain and branched chain alkyl groups.

Further, from the viewpoint of dispersibility, the content ratio of the repeating unit represented by the formula (iv) to all repeating units of the polymer dispersant is preferably 30 mol% or more, and 40 mol% or more. The content is more preferably 50 mol% or more, further preferably 80 mol% or less, and more preferably 70 mol% or less. For example, the content of the repeating unit represented by the formula (iv) in all repeating units of the polymer dispersant is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and 50 to 70 mol%. More preferred.

The polymer dispersant may have repeating units other than repeating unit (i), repeating unit (ii), repeating unit (iii), and repeating unit (iv). Examples of such repeating units include styrenic monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as (meth)acrylic acid chloride; (meth)acrylamide, N- Examples include repeating units derived from monomers such as (meth)acrylamide monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; and N-methacryloylmorpholine.

From the viewpoint of further improving dispersibility, the polymer dispersant includes an A block having repeating units (i) and repeating units (ii), and a B block having no repeating units (i) and repeating units (ii). It is preferable that it is a block copolymer having the following. The block copolymer is preferably an AB block copolymer or a BAB block copolymer. Surprisingly, by introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant tends to be significantly improved. Further, it is preferable that the B block has a repeating unit (iii), and more preferably a repeating unit (iv).

In the A block, the repeating unit (i) and the repeating unit (ii) may be contained in either random copolymerization or block copolymerization. In addition, two or more types of repeating units (i) and repeating units (ii) may be contained in one A block, and in that case, each repeating unit can be randomly copolymerized, It may be contained in any form of block copolymerization.

Further, repeating units other than repeating unit (i) and repeating unit (ii) may be contained in the A block, and examples of such repeating units include the above-mentioned (meth)acrylic acid ester monomer. Examples include repeating units derived from polymers. The content of repeating units other than repeating units (i) and repeating units (ii) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%; Most preferably, it is not contained in the block.

Repeating units other than repeating units (iii) and (iv) may be contained in the B block, and examples of such repeating units include styrene monomers such as styrene and α-methylstyrene; (meth)acrylate monomers such as meth)acrylic acid chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Ether; examples include repeating units derived from monomers such as N-methacryloylmorpholine. The content of repeating units other than repeating units (iii) and repeating units (iv) in block B is preferably 0 to 50 mol%, more preferably 0 to 20 mol%; Most preferably, it is not contained in the block.

When the photosensitive colored resin composition of the present invention contains (F) a dispersant, its content is not particularly limited, but it is preferably 0.1% by mass or more in the total solid content of the photosensitive colored resin composition. , more preferably 0.5% by mass or more, preferably 8% by mass or less, more preferably 5% by mass or less, even more preferably 3% by mass or less, particularly preferably 2% by mass or less. When the amount is at least the lower limit, it tends to suppress the generation of residue due to aggregates, and when it is at most the upper limit, the ink repellency and developability tend to improve. For example, when the photosensitive colored resin composition contains the dispersant (F), the content of the dispersant (F) in the total solid content of the photosensitive colored resin composition is preferably 0.1 to 8% by mass, More preferably 0.1 to 5% by weight, even more preferably 0.5 to 3% by weight, particularly preferably 0.5 to 2% by weight.

[1-1-7] Ultraviolet absorber The photosensitive colored 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 causing the ultraviolet absorber to absorb a specific wavelength of the light source used for exposure. By adding an ultraviolet absorber, effects such as improving the perpendicularity of the side surfaces of the partition walls after development and eliminating residues remaining in unexposed areas after development can be obtained. As the ultraviolet absorber, from the viewpoint of inhibiting light absorption of the photopolymerization initiator (A), for example, a compound having an absorption maximum between wavelengths of 250 nm and 400 nm can be used.
The ultraviolet absorber preferably contains one or both of a benzotriazole compound and a triazine compound. By containing one or both of a benzotriazole compound and a triazine compound, the light absorption rate of the initiator at the bottom of the film decreases, and the line width at the bottom of the coating decreases, thereby reducing the verticality effect on the side surface of the partition wall. It is thought that it can be obtained.

Examples of benzotriazole compounds include 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 3-[3-tert-butyl- Octyl 5-(5-chloro-2H-benzotriazol-2-yl)-4-hydroxyphenyl]propionate, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl) )-4-hydroxyphenyl]ethylhexyl 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, 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, 3-[3-tert-butyl-5-(5-chloro-2H-benzotriazol-2-yl) )-4-hydroxyphenyl]propionic acid and C7-9 linear and branched alkyl alcohols.

Commercially available benzotriazole compounds include, for example, Sumisorb (registered trademark, hereinafter the same) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical), JF77, JF78, JF79, JF80, JF83 ( (manufactured by Johoku Chemical Industry), TINUVIN (registered trademark, same hereinafter) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, "TINUVIN 928", TINUVIN928, TINUVIN1130 (B ASF), EVERSORB70, EVERSORB71, EVERSORB72 , EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Eiguang Chemical Industry Co., Ltd., Taiwan), Tomisorb (registered trademark, the same applies hereinafter) 10 0, TomiSorb 600 (manufactured by API Corporation), SEESORB (registered trademark) ) 701, SEESORB702, SEESORB703, SEESORB704, SEESORB706, SEESORB707, SEESORB709 (manufactured by Cipro Kasei), and RUVA-93 (manufactured by Otsuka Chemical Co., Ltd.).

Examples of triazine compounds include 2-[4,6-di(2,4-xylyl)-1,3,5-triazin-2-yl]-5-octyloxyphenol, 2-[4,6-bis( 2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl)-4 , 6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-ethylhexyl glycidyl ether reaction product, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-( Examples include 2,4-dibutoxyphenyl)-1,3-5-triazine. Among these, hydroxyphenyltriazine compounds are preferred from the viewpoint of the perpendicularity of the side surfaces of the partition walls and ink repellency.
Examples of commercially available triazine compounds include TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, and TINUVIN479 (manufactured by BASF).

Other ultraviolet absorbers include benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, dinaphthalene compounds, phenanthroline compounds, dyes, and the like.
More specifically, for example, Sumisorb 130 (manufactured by Sumitomo Chemical), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Eikoh Chemical Industries, Taiwan), Tomisorb 800 (manufactured by API Corporation), SEESORB100, SEESORB101, SEESORB101S, SEESORB102, S EESORB103, SEESORB105, Benzophenone compounds such as SEESORB106, SEESORB107, and SEESORB151 (manufactured by Cipro Kasei); Benzoate compounds such as Sumisorb 400 (manufactured by Sumitomo Chemical) and phenyl salicylate; 2-ethylhexyl cinnamate, 2-ethylhexyl paramethoxycinnamate, isopropyl methoxycinnamate, methoxy Cinnamic acid derivatives such as isoamyl cinnamate; α-naphthol, β-naphthol, α-naphthol methyl ether, α-naphthol ethyl ether, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene , 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, etc. naphthalene derivatives; anthracene and its derivatives such as anthracene and 9,10-dihydroxyanthracene; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p -dyes such as aminobenzoic acid dyes; and the like. Among these, from the viewpoint of ink repellency, it is preferable to use cinnamic acid derivatives and naphthalene derivatives, and it is particularly preferable to use cinnamic acid derivatives. These light absorbers can be used alone or in combination of two or more.

Among these, from the viewpoint of the tapered shape, either or both of benzotriazole compounds and hydroxyphenyltriazine compounds are preferred, and benzotriazole compounds are particularly preferred.

As the ultraviolet absorber, one type of compound may be used alone, or two or more types of compounds may be used in combination.

When the photosensitive colored resin composition of the present invention contains an ultraviolet absorber, its content is not particularly limited, but is usually 0.01% by mass or more, preferably 0.01% by mass or more in the total solid content of the photosensitive colored resin composition. 0.05% by mass or more, more preferably 0.1% by mass or more, even more preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and usually 15% by mass or less, preferably 10% by mass. The content is more preferably 5% by mass or less, still more preferably 3% by mass or less. When the content is equal to or more than the lower limit, the perpendicularity of the side surface of the partition wall tends to be improved, and when the content is equal to or less than the upper limit, the ink repellency tends to be improved. For example, when the photosensitive colored resin composition contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the photosensitive colored resin composition is preferably 0.01 to 15% by mass, and 0.05 to 15% by mass. It is more preferably 10% by weight, even more preferably 0.1 to 5% by weight, even more preferably 0.5 to 3% by weight, and particularly preferably 1 to 3% by weight.

Further, when the photosensitive colored resin composition of the present invention contains an ultraviolet absorber, the blending ratio to (A) photopolymerization initiator is as follows: (A) The amount of ultraviolet absorber to 100 parts by mass of photopolymerization initiator. is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, even 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 more. It is not more than 200 parts by mass, more preferably not more than 100 parts by mass. When the content is equal to or more than the lower limit, the perpendicularity of the side surface of the partition wall tends to be improved, and when the content is equal to or less than the upper limit, the ink repellency tends to be improved. When the photosensitive colored resin composition of the present invention contains an ultraviolet absorber, the amount of the ultraviolet absorber blended is preferably 1 to 500 parts by mass, and 10 to 300 parts by mass relative to 100 parts by mass of (A) photopolymerization initiator. It is more preferably 30 to 200 parts by weight, even more preferably 50 to 100 parts by weight, and particularly preferably 80 to 100 parts by weight.

[1-1-8] Polymerization inhibitor The photosensitive colored resin composition of the present invention preferably contains a polymerization inhibitor. Since the inclusion of a polymerization inhibitor inhibits radical polymerization, it tends to be possible to increase the taper angle of the obtained partition walls.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, from the viewpoint of polymerization inhibition ability, hydroquinone or methoxyphenol is preferred, and methylhydroquinone is more preferred.

It is preferable to contain one or more kinds of polymerization inhibitors. Usually, when producing the alkali-soluble resin (B), a polymerization inhibitor may be included in the resin, and it may be used as is, or in addition to the polymerization inhibitor contained in the resin, the same, Alternatively, a different polymerization inhibitor may be added at the time of producing the photosensitive colored resin composition.

When the photosensitive colored resin composition contains a polymerization inhibitor, its content is not particularly limited, but it is usually 0.0005% by mass or more, preferably 0.001% by mass in the total solid content of the photosensitive colored resin composition. It is at least 0.01% by mass, more preferably at least 0.01% by mass, and usually at most 0.1% by mass, preferably at most 0.08% by mass, and more preferably at most 0.05% by mass. There is a tendency that the taper angle can be increased by making the above lower limit value or more, and the ink repellency tends to be higher by making the above upper limit value or less. For example, when the photosensitive colored resin composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the total solid content of the photosensitive colored resin composition is preferably 0.0005 to 0.1% by mass, and 0.0005 to 0.1% by mass. 001 to 0.08% by mass is more preferred, and 0.01 to 0.05% by mass is even more preferred.

[1-1-9] Thermal polymerization initiator Furthermore, the photosensitive colored resin composition of the present invention may contain a thermal polymerization initiator. Containing a thermal polymerization initiator tends to increase the degree of crosslinking of the membrane. Specific examples of such thermal polymerization initiators include azo compounds, organic peroxides, hydrogen peroxide, and the like. These may be used alone or in combination of two or more.

In addition, when a thermal polymerization initiator is used together with the photopolymerization initiator in hopes of improving ink repellency or increasing the crosslinking density of the film, the total content ratio of these initiators will increase the photopolymerization rate in the photosensitive colored resin composition. It is preferable to set the content ratio of the initiator so that the content ratio of the photopolymerization initiator and the thermal polymerization initiator is the same, and from the viewpoint of ink repellency, the content ratio of the photopolymerization initiator and the thermal polymerization initiator is set such that the content ratio of the photopolymerization initiator and the thermal polymerization initiator The amount of polymerization initiator is preferably 5 to 300 parts by mass.

[1-1-10] Amino Compound The photosensitive colored resin composition of the present invention may contain an amino compound to promote thermosetting. In this case, the content of the amino compound is usually 40% by mass or less, preferably 30% by mass or less in the total solid content of the photosensitive colored resin composition. Further, it is usually 0.5% by mass or more, preferably 1% by mass or more. By setting it below the above-mentioned upper limit, there is a tendency to be able to maintain storage stability, and by setting it above the above-mentioned lower limit, there is a tendency that sufficient thermosetting properties can be ensured. For example, when the photosensitive colored resin composition contains an amino compound, the content in the total solid content of the photosensitive colored resin composition is preferably 0.5 to 40% by mass, more preferably 1 to 30% by mass. .

Examples of the amino compound include amino compounds having a methylol group as a functional group and at least two alkoxymethyl groups obtained by condensing and modifying the same with an alcohol having 1 to 8 carbon atoms. Specifically, for example, melamine resin obtained by polycondensing melamine and formaldehyde; benzoguanamine resin obtained by polycondensing benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensing glycoluril and formaldehyde; Examples include polycondensed urea resins; resins in which formaldehyde is copolycondensed with two or more of melamine, benzoguanamine, glycoluril, or urea; and modified resins in which the methylol groups of the above resins are modified by alcohol condensation. These may be used alone or in combination of two or more. Among the amino compounds, melamine resins and modified resins thereof are preferred, modified resins in which the modification ratio of methylol groups is 70% or more are more preferred, and modified resins in which the modification ratio of methylol groups is 80% or more are particularly preferred.

As specific examples of the above amino compounds, melamine resins and modified resins thereof include "Cymel" (registered trademark, hereinafter the same) 300, 301, 303, 350, 736, 738, 370, 771 manufactured by Cytec Corporation, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158, and "Nikalac" (registered trademark, same hereinafter) manufactured by Sanwa Chemical Co., Ltd. ) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302, etc. Examples of the benzoguanamine resin and its modified resin include Cymel 1123, 1125, and 1128 manufactured by Cytec. Examples of the glycoluril resin and its modified resin include "Cymel" 1170, 1171, 1174, and 1172 manufactured by Cytec Corporation, and "Nicalac" MX-270 manufactured by Sanwa Chemical Company. Further, examples of the above-mentioned urea resin and its modified resin include "UFR" (registered trademark) 65, 300 manufactured by Cytec Co., Ltd. and "Nikalac" MX-290 manufactured by Sanwa Chemical Company.

[1-1-11] Silane coupling agent It is also preferable to add a silane coupling agent to the photosensitive colored resin composition of the present invention in order to improve the adhesion with the substrate. Various types of silane coupling agents can be used, such as epoxy, methacrylic, amino, and imidazole, but epoxy and imidazole silane coupling agents are particularly preferred from the viewpoint of improving adhesion. 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 colored resin composition.

[1-1-12] Inorganic filler In addition, the photosensitive colored resin composition of the present invention not only has improved strength as a cured product, but also has a suitable interaction with an alkali-soluble resin (formation of a matrix structure). An inorganic filler may be contained for the purpose of improving the verticality and taper angle of the coating film. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, and those surface-treated with various silane coupling agents.

The average particle diameter of these inorganic fillers is usually 0.005 to 2 μm, preferably 0.01 to 1 μm. The average particle diameter referred to in this embodiment is a value measured using a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter. Among these inorganic fillers, silica sol and silica sol modified products tend to have excellent dispersion stability and taper angle improvement effects, and are therefore preferably blended. When the photosensitive colored resin composition of the present invention contains these inorganic fillers, the content thereof is usually 5% by mass or more, preferably 10% by mass or more in the total solid content from the viewpoint of ink repellency. It is usually 80% by mass or less, preferably 70% by mass or less. For example, when the photosensitive colored resin composition contains an inorganic filler, the content in the total solid content of the photosensitive colored resin composition is preferably 5 to 80% by mass, more preferably 10 to 70% by mass.

[1-1-13] Adhesion Improver The photosensitive colored resin composition of the present invention may contain a phosphoric acid-based ethylenic monomer for the purpose of imparting adhesion to the substrate. As the phosphoric acid-based ethylenic monomer, (meth)acryloyloxy group-containing phosphates are preferred, and those represented by the following general formulas (g1), (g2), and (g3) are preferred.

[In the above general formulas (g1), (g2), and (g3), R ⁵¹ represents a hydrogen atom or a methyl group, l and l' are integers of 1 to 10, and m is 1, 2, or 3. ]

These phosphoric acid-based ethylenic monomers may be used alone or in combination of two or more. When these phosphoric acid-based ethylenic monomers are used, their content is usually preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and 0.02% by mass or more, more preferably 0.05% by mass or more, in the total solid content of the photosensitive colored resin composition. It is more preferably 1% by mass or more, particularly preferably 0.2% by mass or more. Further, it is preferably 4% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the amount is equal to or more than the lower limit, the effect of improving the adhesion with the substrate tends to be sufficient, whereas when it is less than the upper limit, it tends to easily suppress deterioration of the adhesion with the substrate. For example, when the photosensitive colored resin composition contains a phosphoric acid-based ethylenic monomer, the content in the total solid content of the photosensitive colored resin composition is preferably 0.02 to 4% by mass, and 0.05 to 4% by mass. It is more preferably 3% by weight, even more preferably 0.1-2% by weight, particularly preferably 0.2-1% by weight.

[1-1-14] Solvent The photosensitive colored resin composition of the present invention usually contains a solvent, and the above-mentioned components are used in a state in which they are dissolved or dispersed in the solvent. 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, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methyl-3-methoxybutanol, 3-methoxy-1-butanol, triethylene glycol monomethyl ether, Glycol monoalkyl ethers such as triethylene glycol monoethyl ether and tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, 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, 3- Methoxy-1-butyl 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, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,4-butanediol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;
Such as acetone, methyl ethyl ketone, methyl isopropyl ketone, methyl amyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxy methyl pentanone Ketones;
Monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol Class;
Aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane;
Alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl;
Aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;
Amyl formate, ethyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, benzoic Ethyl acid, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, γ-butyrolactone, etc. linear or cyclic esters;
Alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride and amyl chloride;
Etherketones such as methoxymethylpentanone;
Nitriles such as acetonitrile and benzonitrile;
These include tetrahydrofurans such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

Commercially available solvents applicable 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).

The above-mentioned solvent is capable of dissolving or dispersing each component in the photosensitive colored resin composition, and is selected depending on the method of using the photosensitive colored resin composition of the present invention, but from the viewpoint of coating properties. It is preferable to select one having a boiling point in the range of 60 to 280° C. under atmospheric pressure. More preferably, it has a boiling point of 70°C or higher and 260°C or lower, 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 alone or in combination of two or more. In addition, these solvents have a total solid content in the photosensitive colored resin composition of usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more. , usually 90% by mass or less, preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 35% by mass or less. By setting it to the lower limit value or more, there is a tendency to suppress the occurrence of coating unevenness, and by setting it to the above upper limit value or less, there is a tendency that the occurrence of foreign matter, repellency, etc. can be suppressed. For example, the solvent has a total solid content in the photosensitive colored resin composition of preferably 10 to 90% by mass, more preferably 15 to 50% by mass, even more preferably 20 to 40% by mass, particularly preferably 25% by mass. It is preferable to use it in an amount of 35% by mass.

[1-2] Method for preparing photosensitive colored resin composition The photosensitive colored resin composition of the present invention is prepared by mixing the above-mentioned components using a stirrer.
For example, when the colorant (D) contains a solvent-insoluble component such as a pigment, it is preferable to perform a dispersion treatment in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, etc. Since the colorant (D) is made into fine particles by the dispersion treatment, the coating properties of the photosensitive colored resin composition are improved.

Dispersion treatment is usually preferably carried out in a system that uses part or all of (D) a colorant, a solvent, and (F) a dispersant, and (B) an alkali-soluble resin (hereinafter referred to as "subject to dispersion treatment"). The mixture and the composition obtained by this treatment are sometimes referred to as "ink" or "pigment dispersion"). In particular, it is preferable to use a polymer dispersant as the dispersant (F) because it suppresses thickening of the obtained ink and photosensitive colored resin composition over time (excellent dispersion stability).
As described above, in the process of producing a photosensitive colored resin composition, it is preferable to produce a pigment dispersion containing at least (D) a colorant, a solvent, and (F) a dispersant.
As the (D) colorant, organic solvent, and (F) dispersant that can be used in the pigment dispersion, those described as those that can be used in the photosensitive colored resin composition can be preferably employed. . Furthermore, as the content ratio of each colorant in the colorant (D) in the pigment dispersion, those described as the content ratio in the photosensitive colored resin composition can be preferably adopted.

When dispersing the colorant (D) with a sand grinder, glass beads or zirconia beads having a particle size of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually from 0°C to 100°C, preferably from room temperature to 80°C. The appropriate dispersion time varies depending on the composition of the liquid, the size of the dispersion processing apparatus, etc., and is therefore adjusted as appropriate. A guideline for dispersion is to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the photosensitive colored resin composition is in the range of 50 to 300.

Further, the dispersed particle size of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like.
Next, the ink obtained by the above dispersion treatment and the other components mentioned above contained in the photosensitive colored resin composition are mixed to form a uniform solution. In the manufacturing process of the photosensitive colored resin composition, fine dust may be mixed into the liquid, so it is desirable to filter the obtained photosensitive colored resin composition using a filter or the like.

[2] Partition wall and method for forming the same The cured product of the present invention can be obtained by curing the photosensitive colored resin composition of the present invention. The photosensitive colored resin composition of the present invention can be used to form partition walls, and can be particularly suitably used to form partition walls for partitioning organic layers of an organic electroluminescent device.
The method for forming partition walls using the photosensitive colored resin composition described above is not particularly limited, and conventionally known methods can be employed. The method for forming the partition walls includes, for example, a coating step in which a photosensitive colored resin composition is applied onto a substrate to form a photosensitive colored resin composition layer, and an exposure step in which the photosensitive colored resin composition layer is exposed. Examples include methods including: Specific examples of methods for forming such banks include an inkjet method and a photolithography method.

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

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

In the coating process of applying a photosensitive colored resin composition onto a substrate in the photolithography method, a contact transfer type coating device such as a roll coater, reverse coater, or bar coater or a spinner (rotating Coat the photosensitive colored resin composition using a non-contact type coating device such as a curtain flow coater (type coating device) or curtain flow coater, and if necessary, remove the solvent by drying to form a photosensitive colored resin composition layer. do.

Next, in the exposure step, the photosensitive colored resin composition is irradiated with active energy rays such as ultraviolet rays and excimer laser light using a negative mask to form the photosensitive colored resin composition layer in accordance with the bank pattern. Partially exposed. For exposure, a light source that emits ultraviolet rays, such as a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a xenon lamp, or a carbon arc lamp, can be used. The exposure amount varies depending on the composition of the photosensitive colored resin composition, but is preferably about 10 to 400 mJ/cm ² , for example.

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

Thereafter, the developed partition walls are post-baked and cured by heating. Post-baking is preferably performed at 150-250°C for 15-60 minutes.

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

[3] Organic electroluminescent device The organic electroluminescent device of the present invention includes partition walls made of the above-described photosensitive colored resin composition.
Various organic electroluminescent devices are manufactured using a substrate provided with a barrier rib pattern manufactured by the method described above. The method for forming an organic electroluminescent device is not particularly limited, but preferably, after forming a barrier rib pattern on a substrate by the method described above, ink is injected into an area surrounded by the barrier ribs on the substrate to form pixels, etc. An organic electroluminescent device is manufactured by forming an organic layer.

When the partition wall has a skirted shape, the ink for forming the organic layer is repelled by the skirt portion of the partition wall, so that the area surrounded by the partition wall may not be sufficiently covered with the ink for forming the organic layer. On the other hand, by creating a good shape with no hemline, the area surrounded by the partition wall can be sufficiently covered with the ink for forming the organic layer. Thereby, for example, the problem of halation in organic EL display elements can be solved.

As the solvent used when forming the ink for forming the organic layer, water, organic solvents, and mixed solvents thereof can be used. The organic solvent is not particularly limited as long as it can be removed from the film formed after the ink is injected. Specific examples of 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. Further, surfactants, antioxidants, viscosity modifiers, ultraviolet absorbers, etc. can be added to the ink.

As a method for injecting ink into the area surrounded by the partition wall, an inkjet method is preferable because a small amount of ink can be easily injected into a predetermined location. The ink used to form the organic layer is appropriately selected depending on the type of organic electroluminescent device to be manufactured. When injecting ink by an inkjet method, the viscosity of the ink is not particularly limited as long as the ink can be well ejected from an 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.

Types of organic electroluminescent 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 stacked in the opening surrounded by the partition walls. Ru. On the other hand, in the top emission type, for example, partition walls 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 the opening surrounded by the partition walls. Created by
Note that examples of the light-emitting layer include organic electroluminescent layers as described in Japanese Patent Application Publication No. 2009-146691 and Japanese Patent No. 5734681. Alternatively, quantum dots such as those described in Japanese Patent No. 5653387 and Japanese Patent No. 5653101 may be used.

[4] Image display device The image display device of the present invention includes the cured product of the present invention, and particularly includes one containing the organic electroluminescent device of the present invention. As for an image display device including an organic electroluminescent device, there are no particular restrictions on the type or structure of the image display device, and for example, it can be assembled according to a conventional method using an active drive type organic electroluminescent device. For example, the image display device of the present invention can be formed by the method described in "Organic EL Display" (Ohmsha, published August 20, 2004, written by Shizushi Tokito, Chihaya Adachi, and Hideyuki Murata). can do. For example, an image may be displayed by combining an organic electroluminescent device that emits white light and a color filter, or an image may be displayed by combining organic electroluminescent devices that emit light of different colors, such as RGB.

[5] Illumination The illumination of the present invention includes the cured product of the present invention, and particularly includes the illumination containing the organic electroluminescent element of the present invention. There are no particular restrictions on the type or structure, and the organic electroluminescent device of the present invention can be assembled using conventional methods. The organic electroluminescent device may be driven by a simple matrix drive method or an active matrix drive method.
In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. Furthermore, organic electroluminescent elements emitting different colors of light may be combined to form a white color by mixing the respective colors, or the color mixing ratio may be adjusted to provide a color toning function.

Hereinafter, the photosensitive colored 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 unless the gist thereof is exceeded.

<Alkali-soluble resin-I>
A copolymer resin whose constituent monomers are dicyclopentanyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6) is subjected to an addition reaction of an equal amount of acrylic acid with glycidyl methacrylate, and then anhydrous An alkali-soluble acrylic copolymer resin to which tetrahydrophthalic acid is added at a molar ratio of 0.39 to 1 mole of the above copolymer resin. The weight average molecular weight (Mw) measured by GPC in terms of polystyrene was 9000, and the acid value was 80 mgKOH/g. PGMEA (propylene glycol monomethyl ether acetate) was added to this to make the solid content concentration 42.7% by mass.

<Alkali-soluble resin-II>
"ZCR-1642H" manufactured by Nippon Kayaku Co., Ltd. (weight average molecular weight (Mw) = 6500, acid value = 98 mgKOH/g). PGMEA was added to this to make the solid content concentration 40.0% by mass.

<Dispersant-I>
"BYK-LPN21116" manufactured by BYK Chemie (acrylic A-B consisting of an A block with a quaternary ammonium base and a tertiary amino group in the side chain, and a B block without a quaternary ammonium base and a tertiary amino group) Block copolymer.Amine value is 70mgKOH/g.Acid value is 1mgKOH/g or less.)
The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a). The content ratios of repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of dispersant-I are 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. It is.

<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <Solvent-II>
MB: 3-methoxy-1-butanol <Photopolymerizable compound-I>
DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Kayaku Co., Ltd. <Photopolymerizable compound-II>
TMP-A: Trimethylolpropane triacrylate manufactured by Kyoeisha Chemical Co., Ltd.

<Photopolymerization initiator-1>
A compound having the following chemical structure was used. When this compound is dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm is 34% higher than the absorbance at 368 nm, which is the maximum absorption wavelength (λ _max ) between 300 and 400 nm. %Met. This corresponds to the oxime ester photopolymerization initiator (A1).

<Photopolymerization initiator-2>
IRGACURE (registered trademark, hereinafter the same) OXE-01 manufactured by BASF was used. When this compound is dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm is 0 compared to the absorbance at 329 nm, which is the maximum absorption wavelength (λ _max ) between 300 and 400 nm. It was .7%. This corresponds to the oxime ester photopolymerization initiator (A2).

<Photopolymerization initiator-3>
TRONLY (registered trademark) TR-PBG-305 manufactured by Changzhou Strong Electronics New Materials Co., Ltd. was used. When this compound is dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm is 0 compared to the absorbance at 329 nm, which is the maximum absorption wavelength (λ _max ) between 300 and 400 nm. It was .6%. This corresponds to the oxime ester photopolymerization initiator (A2).

<Photopolymerization initiator-4>
A compound having the following chemical structure obtained by the method described in Synthesis Example 2 of Japanese Patent Application Publication No. 2018-002962 was used. The absorbance at a wavelength of 400 nm was 33% of the absorbance at 368 nm, which is the maximum absorption wavelength (λ _max ) between 300 and 400 nm. This corresponds to the oxime ester photopolymerization initiator (A1).

<Photopolymerization initiator-5>
A compound having the following chemical structure was used. When this compound is dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm is 1% compared to the absorbance at 328 nm, which is the maximum absorption wavelength (λ _max ) between wavelengths 300 and 400 nm. It was .1%. This corresponds to the oxime ester photopolymerization initiator (A2).

<Photopolymerization initiator-6>
IRGACURE OXE-02 manufactured by BASF was used. When this compound is dissolved in PGMEA to a concentration of 0.01% by mass, the absorbance at a wavelength of 400 nm is 0 compared to the absorbance at 336 nm, which is the maximum absorption wavelength (λ _max ) between wavelengths 300 and 400 nm. It was .1%. This corresponds to the oxime ester photopolymerization initiator (A2).

<Liquid repellent-I>
Megafac RS-72-k manufactured by DIC Corporation (fluorine atom-containing oligomer having an ethylenic double bond as a crosslinking group)
<Additive-I>
KAYAMER (registered trademark) PM-21 manufactured by Nippon Kayaku Co., Ltd.

<Preparation of pigment dispersion 1>
The pigment, dispersant, alkali-soluble resin, and solvent listed in Table 1 were mixed at the mass ratio listed in Table 1. Note that the amounts of the dispersant and the alkali-soluble resin in Table 1 are the solid content, and the amount of the solvent also includes the amount of the dispersant and the solvent derived from the alkali-soluble resin.
This solution was subjected to a dispersion treatment using a paint shaker at a temperature of 25 to 45°C for 3 hours. Zirconia beads with a diameter of 0.5 mm were used as beads, and 2.5 times the mass of the dispersion was added. After the dispersion treatment was completed, the beads and the dispersion liquid were separated using a filter to prepare a pigment dispersion liquid 1.

<Preparation of photosensitive colored resin composition>
Using the pigment dispersion 1 prepared above, each component was added so that the solid content of each component in the total solid content was as shown in Table 2, and further, the total solid content was 31% by mass. %, and each solvent was added and diluted so that Solvent-I/Solvent-II=80/20 (mass ratio) in all solvents, stirred and dissolved, and Examples 1 to 4 and Comparative Photosensitive colored resin compositions of Examples 1 to 3 were prepared. Using the obtained photosensitive colored resin composition, evaluation was performed by the method described below.
In the table, the weighted average value (%) of absorbance at 400 nm indicates the value (%) of absorbance at a wavelength of 400 nm of the oxime ester photopolymerization initiator (A3) in the second embodiment of the present invention.

22.34 parts by mass of photopolymerizable compound-I in Example 1 was changed to 11.17 parts by mass of photopolymerizable compound-I and 11.17 parts by mass of photopolymerizable compound-II, and the rest was the same as in Example 1. A photosensitive colored resin composition having the same formulation as Example 5 was prepared.

The method of performance evaluation will be explained below.

<Creation of substrate for contact angle measurement>
A photosensitive colored resin composition was coated onto a glass substrate using a spinner so that it had a thickness of 6.0 μm after being heated and cured. Thereafter, it was dried by heating on a hot plate at 100° C. for 90 seconds to obtain a coated film substrate. Next, the obtained coated substrate was developed with an aqueous solution containing 0.04% by mass of KOH and 0.07% by mass of Emulgen A-60 (surfactant manufactured by Kao Corporation). The film was developed by spraying at 24° C., and the time required for the paint film to be completely removed by development was determined as the break time.
Next, a coated substrate prepared separately under the same conditions as above was exposed to ultraviolet light using a high-pressure mercury lamp at an exposure dose of 50 mJ/cm ² without using a mask. At this time, the intensity at a wavelength of 365 nm was 45 mW/cm ² . This was developed using the same developing solution and developing conditions as described above for a developing time 1.6 times the break time, and then washed with pure water for 10 seconds. This substrate was heated and cured in an oven at 230° C. for 30 minutes to obtain a substrate for contact angle measurement.

<Measurement of PGMEA contact angle>
Using a contact angle measuring device Drop Master 500 manufactured by Kyowa Interface Science Co., Ltd., under the conditions of 23 ° C. and 50% humidity, the contact angle was measured 1 second after dropping 0.7 μL of PGMEA onto the contact angle measurement substrate, and the results are shown below. are shown in Table 2. The larger the contact angle, the higher the ink repellency.

<Creation of line pattern board>
The photosensitive colored resin composition was applied onto a glass substrate using a spinner so as to have a thickness of 6.0 μm after being heated and cured. Thereafter, it was dried by heating on a hot plate at 100° C. for 90 seconds to obtain a coated film substrate. Next, the obtained coated film substrate was exposed to ultraviolet light using a high-pressure mercury lamp using a photomask. The exposure amount was 50 mJ/cm ² and the exposure gap was 130 μm. At this time, the intensity at a wavelength of 365 nm was 45 mW/cm ² . The photomask used was an exposure mask having linear openings with various widths of 5 to 50 μm (5 to 20 μm: every 1 μm, 25 to 50 μm: every 5 μm). Next, in the same manner as in <Preparation of substrate for contact angle measurement>, development was performed for a development time 1.6 times the break time, washed with pure water for 10 seconds, and heated in an oven at 230° C. for 30 minutes. It was cured to create a line-shaped patterned substrate assuming partition walls.

<Evaluation of verticality of taper>
Among the linear pattern substrates, a cross section of a pattern corresponding to a linear opening having an opening width of 20 μm was observed using a SEM at a magnification of 5000 times. As shown in the conceptual diagram of FIG. 1, among the pattern widths parallel to the substrate surface, the minimum width 4 was defined as the minimum width, and the maximum width 3 existing above the minimum width was defined as the maximum width. The verticality of the taper of the linear pattern was evaluated based on the difference between the maximum width and the minimum width, and the results are shown in Table 2. The smaller the difference between the maximum width and the minimum width, the more vertical the partition wall is formed.

As is clear from the comparison of Examples 1 to 4 and Comparative Examples 1 to 2 in Table 2, by combining the oxime ester photoinitiator (A1) with the oxime ester photoinitiator (A2), each Compared to the case of using either alone, it is possible to achieve both ink repellency and perpendicularity of the taper of the partition walls.

In order to ensure ink repellency, it is necessary to fix a liquid repellent agent to the surface of the partition wall. However, if the degree of hardening of the coating film after exposure to ultraviolet rays is insufficient, part of the film surface will dissolve during the next development process, and the liquid repellent will flow out into the developer. When one type of oxime ester photopolymerization initiator (A2), which mainly uses i-rays, is used alone as a photopolymerization initiator, for example, as in Comparative Example 2, curing after exposure to ultraviolet rays is insufficient. Therefore, ink repellency is impaired.

On the other hand, when forming a thick film pattern with a film thickness of 5 μm or more, the ultraviolet light that penetrates from the surface of the paint film during exposure to UV light is absorbed by the photopolymerization initiator, colorant, etc. contained in the paint film, and penetrates into the inside of the paint film. It is difficult to penetrate, and the degree of curing at the bottom of the coating tends to be lower than at the top. Therefore, there is a problem that the lower part of the coating film, which has a low degree of hardening, is excessively developed during the development process, resulting in a narrow pattern width.

When a highly sensitive oxime ester photopolymerization initiator (A2) was further used in comparison with Comparative Example 2, as in Comparative Example 3, the ink repellency improved, but the pattern at the bottom of the coating film The width became narrower and the verticality of the taper became worse. This is because the use of a highly sensitive oxime ester photopolymerization initiator (A2) increased the curing properties of the upper part of the coating film, and although it was possible to fix the liquid repellent on the surface of the partition wall, This is thought to be because the curing properties of the lower part of the coating film could not be increased due to the use of i-line, and the pattern width at the upper part of the coating film was wider than that at the lower part of the coating film.

On the other hand, as another method to increase the degree of curing by UV exposure, among oxime ester photopolymerization initiators that have an absorption band in the i-line, those that can also be used in the h-line, that is, have a sufficiently high absorbance at a wavelength of 400 nm. A method using an oxime ester photopolymerization initiator (A1) can be mentioned.

When an oxime ester photopolymerization initiator (A1) is used to ensure ink repellency, the degree of curing of the upper part of the coating film increases due to its high sensitivity, and the pattern width of the upper part becomes wider. However, when focusing on the h-line, which contributes to the high sensitivity of the oxime ester photoinitiator (A1), when the oxime ester-based photoinitiator (A1) is used alone, most of the h-line The upper part of the coating film is absorbed by the oxime ester photopolymerization initiator (A1), and fewer H lines reach the lower part of the coating film, and the pattern width at the lower part of the coating film becomes narrower, making the taper more vertical. tends to be damaged. This tendency is clear from the results of Comparative Example 1.

On the other hand, as in Examples 1 to 4, by combining the oxime ester photopolymerization initiator (A1) and the oxime ester photopolymerization initiator (A2), the oxime ester photopolymerization initiator (A1) alone Compared to the case of It is thought that curing using the H-rays in the lower part is promoted, and the perpendicularity of the taper of the partition wall becomes better. In addition, by using the oxime ester photopolymerization initiator (A1) and the oxime ester photopolymerization initiator (A2) together, curing using i-line and h-line is performed near the film surface, resulting in ink repellency. It is thought that this will be sufficient.

1 Pattern 2 Glass substrate 3 Maximum value of pattern width (maximum width)
4 Minimum value of pattern width (minimum width)

Claims (11)

A photosensitive colored resin composition containing (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent,
An oxime ester photopolymerization initiator (A1) in which the photopolymerization initiator (A) has an absorbance at a wavelength of 400 nm that is 20% or more of the absorbance at a maximum absorption wavelength (λmax) between 300 and 400 nm; Contains an oxime ester photopolymerization initiator (A2) whose absorbance at a wavelength of 400 nm is 10% or less of the absorbance at a maximum absorption wavelength (λmax) between 300 and 400 nm,
The liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group,
The alkali-soluble resin (B) has an ethylenically unsaturated group,
In the total solid content of the photosensitive colored resin composition,
The content ratio of the photopolymerization initiator (A) is 0.1 to 15% by mass,
The content of the alkali-soluble resin (B) is 5 to 90% by mass,
The content of the photopolymerizable compound (C) is 1 to 80% by mass,
The content of the colorant (D) is 1 to 15 % by mass,
The content ratio of the liquid repellent (E) is 0.01 to 5% by mass,
The content of the oxime ester photopolymerization initiator (A1) in the photopolymerization initiator (A) is 90% by mass or less, and the content of the oxime ester photopolymerization initiator (A2) is 5% by mass. % or more. The photosensitive colored resin composition according to claim 1, wherein the oxime ester photopolymerization initiator (A1) contains an oxime ester photopolymerization initiator having a nitro group and a carbazole skeleton. The photosensitive colored resin composition according to claim 1 or 2, wherein the oxime ester photopolymerization initiator (A2) contains a compound represented by the following general formula (A2-1).

(In formula (A2-1), R ^13A represents an alkyl group that may have a substituent or an aromatic ring group that may have a substituent.
R ^14A represents an alkyl group or an aromatic ring group.
R ^15A represents a monovalent substituent.
n represents 0 or 1.
h represents an integer from 0 to 2. ) The photosensitive colored resin composition according to claim 3, wherein in the formula (A2-1), R ^14A is an aromatic ring group. The photosensitive colored resin composition according to any one of claims 1 to 4, wherein the fluorine atom-containing resin having a crosslinking group has one or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. Any one of claims 1 to 5, wherein the colorant (D) contains at least one selected from the group consisting of red pigments and orange pigments, and at least one selected from the group consisting of blue pigments and violet pigments. The photosensitive colored resin composition according to item 1. The coloring agent (D) is at least one member selected from the group consisting of a compound represented by the following general formula (1), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound. The photosensitive colored resin composition according to any one of claims 1 to 6, comprising an organic black pigment comprising:

(In formula (1), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ each independently represent a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ^- , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N = _CH2 , N= ^CHR21 , N= ^CR21R22 , SH, ^SR21 , ^SOR21 _, ^{SO2R21 , SO3R21} , _{SO3H , SO3-} ^, _{SO2NH2 , SO2NHR} ²¹ or SO ₂ NR ²¹ R ²² ;
At least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ is may be bonded or may be bonded to each other by oxygen atoms, sulfur atoms, NH or ^NR bridges;
R ²¹ and R ²² each independently represent an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms; Represents 2 to 12 alkynyl groups. ) The photosensitive colored resin composition according to any one of claims 1 to 7, which is used for forming partition walls. A cured product obtained by curing the photosensitive colored resin composition according to any one of claims 1 to 8. An image display device comprising the cured product according to claim 9. Illumination comprising the cured product according to claim 9.

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