CN112313579A

CN112313579A - Photosensitive colored resin composition, cured product, image display device, and illumination

Info

Publication number: CN112313579A
Application number: CN201980042006.6A
Authority: CN
Inventors: 利光惠理子; 平冈紫阳; 泽井良尚; 中谷和裕; 斋藤惠子
Original assignee: Mitsubishi Chemical Corp
Current assignee: Mitsubishi Chemical Corp
Priority date: 2018-07-20
Filing date: 2019-07-18
Publication date: 2021-02-02
Also published as: KR20210032320A; JPWO2020017576A1; TW202008078A; JP7435445B2; WO2020017576A1

Abstract

The invention provides a photosensitive coloring material capable of forming a partition wall with high ink repellency and good taper shapeA resin composition. The photosensitive colored resin composition comprises (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent, wherein the photopolymerization initiator (A) comprises an oxime ester photopolymerization initiator (A1) and an oxime ester photopolymerization initiator (A2), and the absorbance of the oxime ester photopolymerization initiator (A1) at a wavelength of 400nm is relative to the maximum absorption wavelength (lambda) between 300 and 400nm_max) The absorbance of the oxime ester photopolymerization initiator (A2) at a wavelength of 400nm is 20% or more, and the absorbance is relative to the maximum absorption wavelength (lambda) between 300 and 400nm_max) The absorbance of the liquid repellent (E) containing a fluorine atom-containing resin having a crosslinking group is 10% or less.

Description

Photosensitive colored resin composition, cured product, image display device, and illumination

Technical Field

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 an illumination device each including the cured product.

The entire contents of the specification, claims, drawings and abstract of Japanese patent application 2018-136491, which is published by the patent office in 2018, 7/20/h, and the whole or part of the contents of documents cited in the specification and the like are incorporated herein as the disclosure of the present specification.

Background

Organic electroluminescent elements included in organic field displays, organic field illuminations, and the like have been conventionally manufactured by forming partition walls (banks) on a substrate and then laminating various functional layers in regions surrounded by the partition walls. As a method for easily forming such partition walls, a method of forming the partition walls by photolithography using a photosensitive resin composition is known.

In addition, as a method of laminating various functional layers in the region surrounded by the partition walls, there is known a method of preparing ink including a material constituting the functional layers first, and then injecting the prepared ink into the region (pixel region) surrounded by the partition walls. In this method, an ink jet method is often employed for the reason that a given amount of ink can be easily injected into a given site accurately.

Further, when the functional layer is formed using ink, it is sometimes required to impart ink repellency to the partition walls for the purpose of preventing adhesion of ink to the partition walls, preventing mixing of ink injected between adjacent regions, and the like.

In recent years, partition walls have been required to have various properties in addition to ink repellency, and various photosensitive resin compositions have been developed. For example, a colored partition wall has been proposed from the viewpoint of improving contrast and preventing reflection. Patent document 1 describes the following: by using a negative photosensitive resin composition containing two specific alkali-soluble resins and having a solid acid value in a specific range, partition walls having both fine line patterns and fine contact holes can be formed, and the black organic pigment contained therein has good dispersibility in an alkali developing solution used for development and also has good storage stability. Patent document 2 describes the following: by using a negative photosensitive resin composition containing a specific ink-repellent agent and a specific photopolymerization initiator, the ink-repellency in the Mirror Projection (MPA) system is also good, and the reproduction of the line width of the mask becomes good.

Documents of the prior art

Patent document

Patent document 1: international publication No. 2013/069789

Patent document 2: international publication No. 2012/147626

Disclosure of Invention

Problems to be solved by the invention

In recent years, much effort has been put on the development of colored partition walls, and for example, in order to form a functional layer having a predetermined film thickness using an ink containing a component having low solubility in a solvent, it is necessary to inject a large amount of a thin ink into a region surrounded by the colored partition walls, which inevitably requires thick colored partition walls.

Such thick colored partition walls are also required to exhibit higher ink repellency in order to prevent mixing of inks between adjacent regions and the like. In addition, in order to uniformly spread the ink in the pixel region and form a uniform functional layer without coating defects or unevenness at the edge portion, it is desirable that the side surfaces of the partition walls have a vertical tapered shape. On the other hand, since the thicker the film, the more easily the side faces of the partition walls are developed locally by development to generate irregularities, the thicker the film, the more required the film is to be formed into a vertical tapered shape with less irregularities.

The present inventors have found through studies that it is difficult to achieve both high ink repellency and good tapered shape in the partition walls of thick films when the photosensitive colored resin composition described in patent document 1 is used.

On the other hand, it has been found that when the photosensitive colored resin composition described in patent document 2 is used, the surface of the coating film is more likely to be over-cured than the lower portion of the coating film, and cannot be formed into a vertical tapered shape.

The present invention has been made in view of the above-mentioned background, and an object of the present invention is to provide a photosensitive colored resin composition capable of forming partition walls having high ink repellency and a good tapered shape.

Another object of the present invention is to provide a cured product obtained by curing the photosensitive colored resin composition, an image display device and an illumination device including the cured product.

Means for solving the problems

As a result of intensive studies, the present inventors have found that the above problems can be solved by combining a specific oxime ester type photopolymerization initiator with a photosensitive colored resin composition containing a colorant and a liquid repellent, and have completed the present invention.

That is, the gist of the present invention is as follows.

[1] A photosensitive colored resin composition comprising (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent,

wherein the photopolymerization initiator (A) is usedThe agent contains an oxime ester photopolymerization initiator (A1) and an oxime ester photopolymerization initiator (A2), wherein the absorbance of the oxime ester photopolymerization initiator (A1) at a wavelength of 400nm is relative to the maximum absorption wavelength (. lamda.) of 300 to 400nm_max) The absorbance of the oxime ester photopolymerization initiator (A2) at a wavelength of 400nm is 20% or more, and the absorbance is relative to the maximum absorption wavelength (lambda) between 300 and 400nm_max) The absorbance of the light beam is 10% or less,

The liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.

[2] The photosensitive colored resin composition according to the above [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) comprises a compound represented by the following general formula (A2-1).

[ chemical formula 1]

(in the formula (A2-1), R^13ARepresents an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent.

R^14ARepresents an alkyl group or an aromatic ring group.

R^15ARepresents a substituent having a valence of 1.

n represents 0 or 1.

h represents an integer of 0 to 2. )

[4]Above-mentioned [3]The photosensitive colored resin composition, wherein, in the formula (A2-1), R^14AIs an aromatic ring group.

[5] A photosensitive colored resin composition comprising (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent,

wherein the photopolymerization initiator (A) contains an oxime ester photopolymerization initiator (A3) which is an ester photopolymerization initiator(A3) Absorbance at a wavelength of 400nm relative to the maximum absorption wavelength (lambda) between 300 and 400nm _max) The absorbance of the solution is 8-30%,

[6] The photosensitive colored resin composition according to any one of the above [1] to [5], wherein the fluorine-containing resin having a crosslinking group has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain.

[7] The photosensitive colored resin composition according to any one of the above [1] to [6], wherein the colorant (D) contains at least one selected from a red pigment and an orange pigment, and at least one selected from a blue pigment and a violet pigment.

[8] The photosensitive colored resin composition according to any one of the above [1] to [7], wherein the colorant (D) contains an organic black pigment containing at least one 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.

[ chemical formula 2]

(in the formula (1), R¹¹And R¹⁶Each independently represents a hydrogen atom, CH₃、CF₃Fluorine atom or chlorine atom;

R¹²、R¹³、R¹⁴、R¹⁵、R¹⁷、R¹⁸、R¹⁹and R²⁰Each independently represents a hydrogen atom, a halogen atom, R²¹、COOH、COOR²¹、COO^-、CONH₂、CONHR²¹、CONR²¹R²²、CN、OH、OR²¹、COCR²¹、OOCNH₂、OOCNHR²¹、OOCNR²¹R²²、NO₂、NH₂、NHR²¹、NR²¹R²²、NHCOR²²、NR²¹COR²²、N＝CH₂、N＝CHR²¹、N＝CR²¹R²²、SH、SR²¹、SOR²¹、SO₂R²¹、SO₃R²¹、SO₃H、SO₃ ^-、SO₂NH₂、SO₂NHR²¹Or SO₂NR²¹R²²；

Is selected from R¹²And R¹³、R¹³And R¹⁴、R¹⁴And R¹⁵、R¹⁷And R¹⁸、R¹⁸And R¹⁹And R ¹⁹And R²⁰Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR²¹Bridging to bond to each other;

R²¹and R²²Each independently represents 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 an alkynyl group having 2 to 12 carbon atoms. )

[9] The photosensitive colored resin composition according to any one of the above [1] to [8], which is a photosensitive colored resin composition 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 of [10 ].

[12] An illumination device comprising the cured product according to [10 ].

ADVANTAGEOUS EFFECTS OF INVENTION

According to the present invention, a photosensitive colored resin composition capable of forming partition walls having high ink repellency and a good tapered shape can be provided.

Drawings

FIG. 1 is an explanatory view of the evaluation of verticality of the taper of a linear pattern.

Description of the symbols

1 pattern

2 glass substrate

Maximum pattern width (maximum width)

4 minimum value of Pattern Width (minimum Width)

Detailed Description

The present invention will be specifically described below. The following description is an example of the embodiment of the present invention, and the present invention is not limited to these descriptions within the scope not exceeding the gist thereof.

In the present invention, "a (meth) acryloyl group" means "either one or both of an acryloyl group and a methacryloyl group", and "the entire solid content" means the entire components of the photosensitive colored resin composition excluding the solvent. In the present invention, the numerical range expressed by using "to" means a range including numerical values described before and after "to" as the lower limit value and the upper limit value thereof.

In the present invention, the term "(co) polymer" includes both homopolymer (homopolymer) and copolymer (copolymer), and the terms "acid (anhydride)", "… acid (anhydride)" include both acid and anhydride thereof.

In the present invention, the partition wall material refers to a dam material, a wall material, and similarly, the partition wall refers to a dam, a wall, and a wall.

In the present invention, the weight average molecular weight refers to a weight average molecular weight (Mw) based on GPC (gel permeation chromatography) in terms of polystyrene.

In the present invention, the acid value is not particularly limited, and is calculated by neutralization titration, assuming that the acid value is in terms of the effective solid content.

In the present invention, the partition walls are, for example, portions for partitioning the functional layer (organic layer) in the active-drive-type organic electroluminescent element, and are used for forming pixels including the functional layer and the partition walls by discharging ink, which is a material for constituting the functional layer, to the partitioned regions (pixel regions) and drying the ink.

[1] Photosensitive colored resin composition

The photosensitive colored resin composition of the present invention contains (a) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent as essential components, and may further contain other components as necessary, and may further contain, for example, a solvent.

The photosensitive colored resin composition according to embodiment 1 of the present invention comprises (a) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent, wherein the photopolymerization initiator (a) comprises an oxime ester photopolymerization initiator (a1) and an oxime ester photopolymerization initiator (a2), and the absorbance of the oxime ester photopolymerization initiator (a1) at a wavelength of 400nm is relative to the maximum absorption wavelength (λ) between 300 and 400nm _max) The absorbance of the oxime ester photopolymerization initiator (A2) at a wavelength of 400nm is 20% or more, and the absorbance is relative to the maximum absorption wavelength (lambda) between 300 and 400nm_max) The absorbance of the liquid repellent (E) is 10% or less, and the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.

The photosensitive colored resin composition according to embodiment 2 of the present invention comprises (a) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent, wherein the photopolymerization initiator (a) comprises an oxime ester photopolymerization initiator (A3) having an absorbance at a wavelength of 400nm relative to a maximum absorption wavelength (λ) between 300 and 400nm, and the oxime ester photopolymerization initiator (A3)_max) The absorbance is 8 to 30%, and the liquid repellent (E) contains a fluorine atom-containing resin having a crosslinking group.

Hereinafter, unless otherwise specified, "photosensitive colored resin composition of the present invention" refers to both the photosensitive colored resin composition of embodiment 1 and the photosensitive colored resin composition of embodiment 2.

[1-1] Components and compositions of photosensitive colored resin compositions

The components constituting the photosensitive colored resin composition of the present invention and the composition thereof will be explained in order.

[1-1-1] (A) component: 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 capable of polymerizing the photopolymerizable compound (C) by actinic rays, for example, a compound capable of polymerizing an ethylenically unsaturated bond of the photopolymerizable compound (C).

The photosensitive colored resin composition according to embodiment 1 of the present invention contains (a) a photopolymerization initiator: an oxime ester photopolymerization initiator (A1) (hereinafter, also simply referred to as "oxime ester photopolymerization initiator (A1)") having an absorbance at a wavelength of 400nm of 20% or more with respect to an absorbance at a maximum absorption wavelength (. lamda.max) of 300 to 400nm, and an oxime ester photopolymerization initiator (A2) (hereinafter, also simply referred to as "oxime ester photopolymerization initiator (A2)") having an absorbance at a wavelength of 400nm of 10% or less with respect to an absorbance at a maximum absorption wavelength (. lamda.max) of 300 to 400 nm.

In order to impart ink repellency to the partition walls, it is necessary to fix a liquid repellent to the surfaces of the partition walls. However, if the degree of curing of the coating film after ultraviolet exposure is insufficient, a part of the film surface is dissolved during the development treatment, and the liquid repellent flows out into the developer. When an oxime ester type photopolymerization initiator (a2) mainly using i-rays is used alone as a photopolymerization initiator, curing after ultraviolet exposure is insufficient, and thus ink repellency is impaired.

In order to increase the degree of curing by ultraviolet light exposure, a method of using an oxime ester photopolymerization initiator (a1) which has an absorption band for i-rays and can also utilize h-rays, that is, which has sufficiently high absorbance at a wavelength of 400nm, is exemplified.

On the other hand, in the case of forming a thick film pattern, for example, ultraviolet rays entering from the surface of the coating film during ultraviolet ray exposure are absorbed by a photopolymerization initiator, a colorant, and the like contained in the coating film, and are less likely to penetrate into the coating film, which tends to lower the degree of curing in the lower portion of the coating film than in the upper portion of the coating film. Therefore, the lower portion of the coating film having a low degree of curing may be excessively developed during the development process, resulting in a narrow pattern width.

When the oxime ester photopolymerization initiator (a1) is used alone, the ink repellency is increased due to the improved curability of the upper portion of the coating film, but most of the h-rays are absorbed by the oxime ester photopolymerization initiator (a1) at the upper portion of the coating film, and the h-rays reaching the lower portion of the coating film become smaller, so that the pattern width of the lower portion of the coating film becomes narrower than that of the upper portion of the coating film, and the perpendicularity of the taper of the side surfaces of the partition walls is further impaired.

Therefore, it is considered that the combination of the oxime ester photopolymerization initiator (a1) and the oxime ester photopolymerization initiator (a2) can reduce the absorption rate of h-rays at the upper part of the coating film relatively compared to the case of using the oxime ester photopolymerization initiator (a1) alone, that is, can transmit h-rays to the lower part of the coating film, thereby promoting the curing by h-rays in the vicinity of the glass substrate by the oxime ester photopolymerization initiator (a1) and improving the perpendicularity of the taper shape of the side faces of the partition walls. Further, it is considered that when an oxime ester photopolymerization initiator (a1) and an oxime ester photopolymerization initiator (a2) are used in combination, curing using i-rays and h-rays occurs in the vicinity of the film surface, and the ink repellency is sufficient.

[1-1-1-1] Oxime ester photopolymerization initiator (A1)

The oxime ester photopolymerization initiator (A1) has a maximum absorption at a wavelength of 300 to 400nm, and the absorbance at a wavelength of 400nm is relative to the maximum absorption wavelength (. lamda.) at a wavelength of 300 to 400nm_max) The absorbance of (A) is 20% or more. Since the oxime ester photopolymerization initiator (a1) has sufficient absorbance at a wavelength of 400nm, it is considered that ultraviolet rays emitted from a high-pressure mercury lamp can be sufficiently utilized not only for i-rays and h-rays, and the curing reaction can be accelerated.

Provided that the oxime ester photopolymerization initiator (A1) has an absorbance at a wavelength of 400nm relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) The absorbance at (b) is not particularly limited, but is preferably 25% or more, more preferably 30% or more, further preferably 32% or more, further preferably 35% or more, particularly preferably 40% or more, and is preferably 80% or less, more preferably 70% or less, further preferably 60% or less, and the likeThe one-step ratio is preferably 50% or less, and particularly preferably 40% or less. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, 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 400nm is relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm _max) The absorbance is preferably 20 to 80%, more preferably 25 to 70%, further preferably 30 to 60%, further preferably 30 to 50%, and particularly preferably 32 to 40%.

Further, the oxime ester photopolymerization initiator (A1) has a maximum absorption wavelength (. lamda.) of 300 to 400nm_max) Not specifically defined, it is preferably 320nm or more, more preferably 340nm or more, further preferably 360nm or more, and further preferably 390nm or less, more preferably 380nm or less, particularly preferably 370nm or less. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, the tapered shape of the side surface of the partition wall tends to be good. For example, the oxime ester photopolymerization initiator (A1) has a maximum absorption wavelength (. lamda.) of 300 to 400nm_max) Preferably 320 to 390nm, more preferably 340 to 380nm, and further preferably 360 to 370 nm.

The absorbance and the maximum absorption wavelength of the oxime ester photopolymerization initiator (a1) were measured by first preparing a 0.01 mass% PGMEA (propylene glycol monomethyl ether acetate) solution of the oxime ester photopolymerization initiator (a1), irradiating the solution with light having a wavelength of 300 to 400nm using a spectrophotometer, and measuring the solution at 1nm intervals. Examples of the spectrophotometer include, but are not limited to, UV-3000 series (manufactured by Shimadzu corporation) and V-700 series (manufactured by Nippon corporation). As the measuring cell, a 1cm square quartz cell can be used.

The oxime ester photopolymerization initiator (A1) has an absorbance at a wavelength of 400nm relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) A photopolymerization initiator having an absorbance of 20% or more, and examples of the material having a high absorbance at a wavelength of 400nm include a material having a fluorene skeleton and a carbazole skeleton bonded theretoThose having electron-withdrawing groups such as nitro groups are preferably oxime ester photopolymerization initiators having nitro groups and carbazole skeletons.

The chemical structure of the oxime ester photopolymerization initiator (a1) is not particularly limited, but a compound having a chemical structure represented by the following general formula (a1-1) is preferable from the viewpoint of ink repellency and tapered shape.

[ chemical formula 3]

(in the formula (A1-1), R^1A、R^3A、R^4A、R^5A、R^6AAnd R^8AEach independently represents a hydrogen atom, a nitro group, an alkyl group, or an aromatic ring group,

R^2Aand R^7AEach independently represents a hydrogen atom, an alkyl group optionally having a substituent, an aromatic ring group optionally having a substituent, a nitro group, or a 1-valent group represented by the following general formula (A1-2). And, R^2AAnd R^7AEither or both of them are a 1-valent group represented by the following general formula (A1-2),

R^1A～R^8Aat least one or more of them is a nitro group,

R^9Arepresents a hydrogen atom or an alkyl group,

m and n each independently represent 0 or 1. )

[ chemical formula 4]

(in the formula (A1-2), R^11ARepresents an alkyl group or an aromatic ring group,

R^12Arepresents an alkyl group optionally having a substituent, or an aromatic ring group optionally having a substituent. )

(R^1A、R^3A、R^4A、R^5A、R^6AAnd R^8A)

R in the above formula (A1-1)^1A、R^3A、R^4A、R^5A、R^6AAnd R^8AThe alkyl group in (3) may be linear, branched, cyclic, or a group bonded to them. The number of carbon atoms of 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 be improved, and when the amount is equal to or less than the upper limit, the ink repellency tends to be improved. For example, the number of carbon atoms of 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, and the like, and among these, from the viewpoint of ink repellency, methyl group, ethyl group, and propyl group are preferable, and methyl group is more preferable.

R as the above formula (A1-1)^1A、R^3A、R^4A、R^5A、R^6AAnd R^8AAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms is not particularly limited, but is usually 4 or more, preferably 6 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 be improved, and when the amount is equal to or less than the upper limit, the ink repellency tends to be improved. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 20, more preferably 4 to 12.

Specific examples of the aromatic ring group include: phenyl, naphthyl, anthracenyl, thienyl, furyl, benzothienyl, benzofuryl and the like, and among these aromatic ring groups, phenyl is more preferable from the viewpoint of ink repellency.

Of these groups, R is from the viewpoint of ink repellency^1A、R^3A、R^4A、R^5A、R^6AAnd R^8AEach independently is preferably a hydrogen atom or a nitro group, more preferably a hydrogen atom.

(R^2AAnd R^7A)

R of the above formula (A1-1)^2AAnd R^7AThe alkyl group in (1) may be linear, branched, cyclic, or a combination thereofA group of (1). The number of carbon atoms of 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 be improved, and when the amount is equal to or less than the upper limit, the ink repellency tends to be improved. For example, the number of carbon atoms of the alkyl group is preferably 1 to 8, more preferably 1 to 6.

Examples of the substituent optionally contained in the alkyl group include a hydroxyl group and a carboxyl group, and a hydroxyl group is preferable from the viewpoint of developability.

R as the above formula (A1-1)^2AAnd R^7AAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. 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 be improved, and when the amount is equal to or less than the upper limit, the ink repellency tends to be improved. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 20, more preferably 4 to 12.

Specific examples of the aromatic ring group include: phenyl, naphthyl, anthracenyl, thienyl, furyl, benzothienyl, benzofuryl and the like. Among these aromatic ring groups, phenyl and naphthyl are more preferable from the viewpoint of ink repellency.

Examples of the substituent optionally contained in the aromatic ring group include a hydroxyl group and an alkyl group, and an alkyl group is preferable from the viewpoint of developability.

In the above formula (A1-1), R^2AAnd R^7AEither or both of them are 1-valent groups represented by the above general formula (A1-2).

R of the above formula (A1-2)^11AThe alkyl group in (3) may be linear, branched, cyclic, or a group bonded to them. The number of carbon atoms in the alkyl group is not particularly limited It is usually 1 or more, preferably 5 or less, and more preferably 3 or less. When the value is equal to or less than the upper limit, the sensitivity tends to be good. For example, the number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3.

Specific examples of the alkyl group include: methyl, ethyl, propyl, pentyl, and the like, and among these, methyl is preferred from the viewpoint of ink repellency.

As R^11AAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms of the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. When the amount is not less than the lower limit, the solubility in a solvent tends to be good, and when the amount is not more than the upper limit, the tapered shape tends to be good. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, and further preferably 5 to 12.

Specific examples of the aromatic ring group include: phenyl, naphthyl, thienyl, furyl, and the like, and among these, from the viewpoint of the tapered shape, phenyl or naphthyl is preferred, and phenyl is more preferred.

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

R^12AThe alkyl group in (3) may be linear, branched, cyclic, or a group bonded to them. The number of carbon atoms of the alkyl group is not particularly limited, and is usually 1 or more, preferably 3 or more, more preferably 5 or more, and further preferably 6 or more, and is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, further preferably 8 or less, and particularly preferably 7 or less. When the content is not less than the lower limit, solubility in a solvent tends to be good, and when the content is not more than the upper limit, developability tends to be good. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 3 to 15, further preferably 5 to 10, further preferably 5 to 8, and particularly preferably 5 to 7.

Specific examples of the alkyl group include: methyl group, ethyl group, propyl group, butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, cyclopentyl group, cyclohexyl group, and the like, and of these, isopentyl group, hexyl group, and heptyl group are preferable, and heptyl group is more preferable, from the viewpoint of developability.

Examples of the substituent optionally contained in the alkyl group include: the aromatic ring group, hydroxyl group, carboxyl group and the like are preferably unsubstituted from the viewpoint of ease of synthesis.

As R^12AAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms of 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 further preferably 12 or less. When the content is not less than the lower limit, solubility in a solvent tends to be good, and when the content is not more than the upper limit, developability tends to be good. The number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, further preferably 4 to 12, and further preferably 5 to 12.

Specific examples of the aromatic ring group include: phenyl, naphthyl, thienyl, furyl, and the like, and among these, from the viewpoint of developability, phenyl or naphthyl is preferred, and phenyl is more preferred.

Examples of the substituent optionally contained in the aromatic ring group include: hydroxyl, alkyl, alkoxy substituted with alkoxy, alkoxy substituted with hydroxyl, 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 is preferable. Examples of the alkyl group in the substituent optionally contained in the aromatic ring group include an alkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group. Examples of the alkoxy group substituted on the alkoxy group in the substituent optionally contained in the aromatic ring group and the alkoxy group in the substituent optionally contained in the aromatic ring group include an alkoxy group having 1 to 8 carbon atoms, preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms.

In the formula (a1-1), m and n each independently represent 0 or 1, and are preferably 0 from the viewpoint of the contact angle, and 1 from the viewpoint of the tapered shape.

Of these, R is R from the viewpoint of ink repellency^2AAnd R^7AEach independently is preferably a nitro group or a 1-valent group represented by the above general formula (A1-2), more preferably R^2AIs nitro, and R^7AIs a 1-valent group represented by the general formula (A1-2).

(Nitro)

R^1A～R^8AAt least one of them is a nitro group.

R^1A～R^8AThe number of nitro groups in (b) is not particularly limited, but is usually 1 or more, preferably 4 or less, more preferably 3 or less, and further preferably 2 or less. When the amount is equal to or less than the above upper limit, the developability tends to be good. The number of nitro groups is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 to 2.

Of these, R is preferable from the viewpoint of ink repellency^2AOr R^7AIs nitro.

On the other hand, from the viewpoint of sensitivity, R is preferred^4AAnd R^5AEither or both of which are nitro groups, more preferably R^4AAnd R^5AIs nitro.

(R^9A)

R in the above formula (A1-1)^9AThe alkyl group in (3) may be linear, branched, cyclic, or a group bonded to them. The number of carbon atoms of the alkyl group is not particularly limited, and is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 8 or less, and further preferably 6 or less. When the amount is equal to or more than the lower limit, the solubility in the solvent tends to be good, and when the amount is equal to or less than the upper limit, the ink repellency tends to be good. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 8, further preferably 1 to 6, and particularly preferably 2 to 6.

Specific examples of the alkyl group include: among these groups, from the viewpoint of ink repellency, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, a heptyl group, an octyl group, and the like are preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, or a hexyl group is more preferable, and an ethyl group is even more preferable.

Specific examples of the known compounds of the oxime ester photopolymerization initiator (a1) include the following.

[ chemical formula 5]

Among these oxime ester photopolymerization initiators (a1), compounds having a chemical structure represented by the above formula (a1-11) are preferable from the viewpoint of tapered shape.

[1-1-1-2] Oxime ester photopolymerization initiator (A2)

The oxime ester photopolymerization initiator (A2) has a maximum absorption at a wavelength of 300 to 400nm, and the absorbance at a wavelength of 400nm is relative to the maximum absorption wavelength (. lamda.) at a wavelength of 300 to 400nm_max) The absorbance of (A) is 10% or less. As described above, the absorbance of the oxime ester photopolymerization initiator (a2) at a wavelength of 400nm is sufficiently low, and it is considered that h-rays are hardly utilized among ultraviolet rays emitted from a high-pressure mercury lamp, but the curing reaction is promoted mainly by i-rays, so that the absorption rate of h-rays at the upper part of the coating film can be reduced, h-rays can be transmitted to the vicinity of the glass substrate at the lower part of the coating film, the curing at the lower part of the coating film by the oxime ester photopolymerization initiator (a1) can be promoted, and the perpendicularity of the obtained pattern can be improved.

Provided that the oxime ester photopolymerization initiator (A2) has an absorbance at a wavelength of 400nm relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) The absorbance at (b) is not particularly limited, but is preferably 5% or less, more preferably 3% or less, further preferably 1% or less, and is preferably 0.01% or more, more preferably 0.05% or more, further preferably 0.1% or more, further preferably 0.3% or more, and particularly preferably 0.5% or more. When the upper limit value or less is less, there is a taper of the side surface of the partition wallThe shape tends to be good, and the curability by i-ray tends to be sufficiently exhibited by the value of the lower limit or more. For example, the absorbance of the oxime ester photopolymerization initiator (A2) at a wavelength of 400nm is relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) The absorbance is preferably 0.01 to 10%, more preferably 0.05 to 5%, further preferably 0.1 to 3%, further preferably 0.3 to 3%, particularly preferably 0.5 to 1%.

Further, the oxime ester photopolymerization initiator (A2) has a maximum absorption wavelength (. lamda.) of 300 to 400nm_max) Without particular limitation, it is preferably 310nm or more, more preferably 320nm or more, and still more preferably 325nm or more, and further preferably 350nm or less, more preferably 340nm or less, and still more preferably 330nm or less. When the lower limit value is not less than the above lower limit value, curability by i-ray tends to be good, and when the upper limit value is not more than the above upper limit value, tapered shape of the side surface of the partition wall tends to be good. For example, the oxime ester photopolymerization initiator (A2) has a maximum absorption wavelength (. lamda.) of 300 to 400nm _max) Preferably 310 to 350nm, more preferably 320 to 340nm, and further preferably 325 to 340 nm.

The absorbance and the maximum absorption wavelength of the oxime ester photopolymerization initiator (a2) were measured by the same method as that of the oxime ester photopolymerization initiator (a1) using a spectrophotometer, except that a 0.01 mass% PGMEA (propylene glycol monomethyl ether acetate) solution of the oxime ester photopolymerization initiator (a2) was prepared.

The oxime ester photopolymerization initiator (A2) has an absorbance at a wavelength of 400nm relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) The photopolymerization initiator having an absorbance of 10% or less, and examples of the material having a low absorbance at a wavelength of 400nm include oxime ester photopolymerization initiators having no electron-withdrawing group such as a nitro group on a skeleton such as diphenyl sulfide, carbazole, fluorene, etc., oxime ester photopolymerization initiators having no substituent on the skeleton, and oxime ester photopolymerization initiators having a substituent such as an aryl carbonyl group, alkoxy group, etc. on the skeleton.

The chemical structure of the oxime ester photopolymerization initiator (a2) is not particularly limited, but preferably contains a compound represented by the following general formula (a2-1) from the viewpoint of tapered shape.

[ chemical formula 6]

(in the formula (A2-1), R^13ARepresents an optionally substituted alkyl group or an optionally substituted aromatic ring group,

R^14Arepresents an alkyl group or an aromatic ring group,

R^15Arepresents a substituent having a valence of 1,

n represents a number of 0 or 1,

h represents an integer of 0 to 2. )

(R^13A)

R in the above formula (A2-1)^13AThe alkyl group in (3) may be linear, branched, cyclic, or a group bonded to them. The number of carbon atoms of the alkyl group is not particularly limited, and is usually 1 or more, preferably 4 or more, more preferably 6 or more, and preferably 20 or less, more preferably 10 or less, further preferably 8 or less, and further preferably 7 or less. When the content is not more than the above upper limit, the solubility in the solvent tends to be good. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 8, further preferably 1 to 7, and particularly preferably 4 to 7.

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

As R in the above formula (A2-1)^13AAs the aromatic ring group in (1), there may be mentioned: aromatic hydrocarbon ring groups and aromatic heterocyclic groups. The number of carbon atoms of the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. When the content is not less than the lower limit, solubility in a solvent tends to be good, and when the content is not more than the upper limit, developability tends to be good. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, further preferably 4 to 12, and particularly preferably 5 to 12.

Specific examples of the aromatic ring group include: phenyl, naphthyl, pyridyl, furyl, and the like, and among these, from the viewpoint of developability, phenyl or naphthyl is preferred, and phenyl is more preferred.

Among these, R is R from the viewpoint of the tapered shape ^13APreferred is an alkyl group optionally having a substituent.

(R^14A)

R in the above formula (A2-1)^14AThe alkyl group in (3) may be linear, branched, cyclic, or a group bonded to them. The number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 or more, preferably 5 or less, and more preferably 3 or less. When the value is equal to or less than the upper limit, the sensitivity tends to be good. For example, the number of carbon atoms of 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., and among these, methyl group is preferable from the viewpoint of tapered shape.

As R in the above formula (A2-1)^14AAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms of the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, and preferably 30 or less, more preferably 20 or less, and further preferablyPreferably 12 or less. When the lower limit value is not less than the above-mentioned lower limit value, the solubility in a solvent tends to be good, and when the upper limit value is not more than the above-mentioned upper limit value, the sensitivity tends to be good. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, further preferably 4 to 12, and particularly preferably 5 to 12.

Specific examples of the aromatic ring group include: phenyl, naphthyl, pyridyl, furyl and the like, and among these, from the viewpoint of the tapered shape, phenyl or naphthyl is preferred, and phenyl is more preferred.

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

(R^15A)

R in the above formula (A2-1)^15AThe substituent having a valence of 1 in (A) is not particularly limited, but R is preferably R from the viewpoint of developability^16A-O-, or R^16A-(C＝O)-。

As R^16AExamples thereof include an alkyl group optionally having a substituent, and an aromatic ring group optionally having a substituent.

R^16AThe alkyl group in (3) may be linear, branched, cyclic, or a group bonded to them. The number of carbon atoms of the alkyl group is not particularly limited, and 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 upper limit value is not less than the lower limit value, the developability tends to be good, and when the lower limit value is not more than the upper limit value, the tapered shape tends to be good. For example, the number of carbon atoms of 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., of these, from the viewpoint of solubility, methyl group and ethyl group are preferred, and ethyl group is more preferred.

As R^16AAs the aromatic ring group in (3), an aromatic ring group and an aromatic heterocyclic group are exemplified. The number of carbon atoms of the aromatic ring group is not particularly limited, but is usually 4 or more, preferably 5 or more, and preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. When the upper limit value is not less than the lower limit value, the developability tends to be good, and when the lower limit value is not more than the upper limit value, the tapered shape tends to be good. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 4 to 20, further preferably 4 to 12, and particularly preferably 5 to 12.

Specific examples of the aromatic ring group include: phenyl, naphthyl, thienyl, furyl, benzothienyl, benzofuryl, and the like. Among these aromatic ring groups, a benzothienyl group or a benzofuranyl group is preferable, and a benzofuranyl group is more preferable, from the viewpoint of a tapered shape.

Examples of the substituent optionally contained in the aromatic ring group include an alkyl group, a hydroxyl group, and a carboxyl group, and from the viewpoint of synthesis, the substituent is preferably unsubstituted.

As R in the above formula (A2-1)^15AThe substituent having a valence of 1 in (1) is preferably R from the viewpoint of tapered shape^16AR being hydroxy-substituted ethyl^16A-O-、R^16AR being a benzofuranyl radical^16A- (C ═ O) -, more preferably R^16AR being hydroxy-substituted ethyl^16A-O-。

(n)

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

(h)

In the 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, R^15AThe substitution position(s) is not particularly limited, but from the viewpoint of synthesis, the ortho-position or the para-position is preferred, and the para-position is more preferred.

Specific examples of the known compounds of the oxime ester photopolymerization initiator (a2) include the following.

[ chemical formula 7]

[ chemical formula 8]

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

The photopolymerization initiator (a) in the photosensitive colored resin composition according to embodiment 1 of the present invention may contain a photopolymerization initiator (hereinafter, also referred to as "other photopolymerization initiator") other than the oxime ester type photopolymerization initiator (a1) and the oxime ester type photopolymerization initiator (a 2). The other photopolymerization initiator may be an oxime ester compound or a compound other than an oxime ester compound.

As other photopolymerization initiators, those generally used in the art can be used. Examples thereof include: metallocene compounds containing a titanocene compound as described in Japanese patent laid-open Nos. 59-152396 and 61-151197; hexaarylbiimidazole derivatives as described in Japanese patent laid-open No. 2000-56118; halomethylation described in Japanese patent application laid-open No. 10-39503

Oxadiazole derivatives, halomethyl s-triazine derivatives, N-aryl- α -amino acids such as N-phenylglycine, N-aryl- α -amino acid salts, radical activators such as N-aryl- α -amino acid esters, and α -aminoalkylphenone derivatives.

Specifically, examples of the metallocene compound include: dicyclopentadienyl titanium dichloride, dicyclopentadienyl diphenyltitanium, dicyclopentadienyl bis (2,3,4,5, 6-pentafluorophenyl) titanium, dicyclopentadienyl bis (2,3,5, 6-tetrafluorophenyl) titanium, dicyclopentadienyl bis (2,4, 6-trifluorophenyl) titanium, dicyclopentadienyl bis (2, 6-difluorophenyl) titanium, dicyclopentadienyl bis (2, 4-difluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2,3,4,5, 6-pentafluorophenyl) titanium, bis (methylcyclopentadienyl) bis (2, 6-difluorophenyl) titanium, dicyclopentadienyl [2, 6-difluoro-3- (prop-1-yl) phenyl ] titanium, and the like.

Further, examples of the diimidazole derivatives include: 2- (2 '-chlorophenyl) -4, 5-diphenylimidazole 2-mer, 2- (2' -chlorophenyl) -4, 5-bis (3 '-methoxyphenyl) imidazole 2-mer, 2- (2' -fluorophenyl) -4, 5-diphenylimidazole 2-mer, 2- (2 '-methoxyphenyl) -4, 5-diphenylimidazole 2-mer, (4' -methoxyphenyl) -4, 5-diphenylimidazole dimer, and the like.

In addition, as halomethylation

Oxadiazole derivatives, there may be mentioned: 2-trichloromethyl-5- (2' -benzofuranyl) -1,3,4-

Diazole, 2-trichloromethyl-5- [ beta- (2' -benzofuranyl) ethenyl]-1,3,4-

Diazole, 2-trichloromethyl-5- [ beta- (2' - (6 "-benzofuranyl) vinyl)]-1,3,4-

Diazole, 2-trichloromethyl-5-furyl-1, 3,4-

Oxadiazoles, and the like.

Further, examples of the halomethyl-s-triazine derivatives include: 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, there can be mentioned: 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisopentylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1, 4-dimethylaminobenzoate, 2, 5-bis (4-diethylaminobenzylidene) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, and mixtures thereof, 4- (diethylamino) chalcone, and the like.

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

[1-1-1-3] Oxime ester photopolymerization initiator (A3)

As described above, the photopolymerization initiator (A) in the photosensitive colored resin composition according to embodiment 2 of the invention contains the absorbance at a wavelength of 400nm relative to the maximum absorption wavelength (. lamda.) between wavelengths 300 and 400nm_max) An oxime ester photopolymerization initiator (A3) (hereinafter, also referred to simply as "oxime ester photopolymerization initiator (A3)") having an absorbance of 8 to 30%. As described above, it is considered that the inclusion of the oxime ester photopolymerization initiator (a3) makes it possible to fix the liquid repellent by curing with h-rays on the upper portion of the coating film, and also makes it possible to promote the curing with h-rays near the glass substrate by allowing a certain amount of h-rays to pass through the lower portion of the coating film, thereby improving the verticality of the taper of the side surfaces of the partition walls.

The oxime ester photopolymerization initiator (a3) may be a single one or a mixture of two or more kinds.

In the case of a mixture of two or more kinds, for example, in the case of a mixture of an oxime ester photopolymerization initiator (A3-1) and an oxime ester photopolymerization initiator (A3-2), the absorbance of the oxime ester photopolymerization initiator (A3) at a wavelength of 400nm can be calculated by first measuring the absorbance of the oxime ester photopolymerization initiator (A3-1) at a wavelength of 400nm and the absorbance of the oxime ester photopolymerization initiator (A3-2) at a wavelength of 400nm, respectively, and weighting and averaging the results thereof by the content ratios (mass basis) of the oxime ester photopolymerization initiator (A3-1) and the oxime ester photopolymerization initiator (A3-2) in the photosensitive colored resin composition. The same applies to three or more cases.

Provided that the oxime ester photopolymerization initiator (A3) has an absorbance at a wavelength of 400nm relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) The absorbance at (b) is not particularly limited as long as it is 8 to 30%, but is preferably 10% or more, more preferably 15% or more, further preferably 20% or more, further preferably 23% or more, and is preferably 28% or less, more preferably 27% or less, further preferably 26% or less. When the lower limit value is not less than the lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the upper limit value, 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 400nm is relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) The absorbance is preferably 8 to 28%, more preferably 10 to 28%, further preferably 15 to 28%, further preferably 20 to 27%, and particularly preferably 23 to 26%.

The photopolymerization initiator (a) in the photosensitive colored resin composition according to embodiment 2 of the present invention may contain a photopolymerization initiator other than an oxime ester photopolymerization initiator. As the photopolymerization initiator other than the oxime ester type photopolymerization initiator, those explained as other photopolymerization initiators in the foregoing can be cited.

In addition, a sensitizing dye or a polymerization accelerator corresponding to the wavelength of the image exposure light source may be blended in the photopolymerization initiator in the photosensitive colored resin composition of the present invention as needed for the purpose of improving the sensitivity. Examples of the sensitizing dye include: JP-A-4-221958, JP-A-4-219756, xanthene dye, JP-A-3-239703, coumarin dye having a heterocyclic ring, JP-A-3-239703, 3-oxocoumarin compound, JP-A-5-289335, tolylpyrrole dye, JP-A-6-19240, JP-A-47-2528, JP-A-54-155292, JP-A-45-37377, JP-A-48-84183, JP-A-52-112681, JP-A-58-15503, JP-A-60-05, JP-A-59-56403, And pigments having a dialkylaminobenzene skeleton as described in Japanese patent laid-open Nos. H2-69, 57-168088, 5-107761, 5-210240 and 4-288818.

Among these sensitizing dyes, preferred is an amino group-containing sensitizing dye, and more preferred is a compound having an amino group and a phenyl group in the same molecule. Particularly preferred are benzophenone-based compounds such as 4,4 '-dimethylaminobenzophenone, 4' -diethylaminobenzophenone, 2-aminobenzophenone, 4 '-diaminobenzophenone, 3' -diaminobenzophenone and 3, 4-diaminobenzophenone; 2- (p-dimethylaminophenyl) benzo

Azole, 2- (p-diethylaminophenyl) benzo

Azole, 2- (p-dimethylaminophenyl) benzo [4,5 ]]Benzo (b) is

Azole, 2- (p-dimethylaminophenyl) benzo [6,7 ]]Benzo (b) is

Oxazole, 2, 5-bis (p-diethylaminophenyl) -1,3,4-

Azole, 2- (p-dimethylaminophenyl)) And p-dialkylaminophenyl group-containing compounds such as benzothiazole, 2- (p-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2, 5-bis (p-diethylaminophenyl) -1,3, 4-thiadiazole, p-dimethylaminophenyl (p-diethylaminophenyl) pyridine, p-dimethylaminophenyl (p-dimethylaminophenyl) quinoline, p-diethylaminophenyl) quinoline, p-dimethylaminophenyl (p-diethylaminophenyl) pyrimidine, and p-diethylaminophenyl (p-diethylaminophenyl) pyrimidine. Among them, the most preferable is 4, 4' -dialkylaminobenzophenone.

One of the sensitizing dyes may be used alone, or two or more of them may be used in combination.

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.

The polymerization accelerator may be used alone or in combination of two or more.

Further, it is preferable to use the photopolymerization initiator in combination with a chain transfer agent. The chain transfer agent includes a mercapto group-containing compound, carbon tetrachloride and the like, and the mercapto group-containing compound is more preferably used because it tends to have a high chain transfer effect. This is presumably because the bond cleavage is likely to occur due to the small S — H bond energy, and further, the hydrogen abstraction reaction and the chain transfer reaction are likely to occur. This is preferable because high sensitivity is obtained.

The thiol-group-containing compound is preferably a thiol-group-containing compound having an aromatic ring or an aliphatic thiol-group-containing compound, and more preferably an aliphatic thiol-group-containing compound.

Examples of the mercapto group-containing compound having an aromatic ring include: 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzo

Oxazole, 3-mercapto-1, 2, 4-triazole, 2-mercapto-4 (3H) -quinazoline, β -mercaptonaphthalene, 1, 4-dimethylmercaptobenzene, etc., and from the viewpoint of high sensitivity, 2-mercapto is preferableBenzothiazole, 2-mercaptobenzimidazole.

Examples of the aliphatic mercapto group-containing compound include: hexanedithiol, decanedithiol, butanediol bis (3-mercaptopropionate), butanediol bis (mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), ethylene glycol bis (mercaptoacetate), trimethylolpropane tris (3-mercaptopropionate), trimethylolpropane tris (mercaptoacetate), trihydroxyethyl trimercaptopropionate, pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tris (3-mercaptopropionate), butanediol bis (3-mercaptobutyrate), ethylene glycol bis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, and the like.

Among these, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3-mercaptobutyrate), 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6(1H,3H,5H) -trione, and pentaerythritol tetrakis (3-mercaptopropionate) and pentaerythritol tetrakis (3-mercaptobutyrate) are more preferable from the viewpoint of ink repellency.

The chain transfer agent may be used alone or in combination of two or more.

The content of the photopolymerization initiator (a) in the photosensitive colored resin composition of the present invention is not particularly limited, and is usually 0.1% by mass or more, preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 3% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and further preferably 5% by mass or less, of the total solid content of the photosensitive colored resin composition. When the amount is equal to or more than the lower limit, sufficient ink repellency tends to be generated, and when the amount is equal to or less than the upper limit, developability tends to be good. For example, the content of the photopolymerization initiator (a) in the entire solid content of the photosensitive colored resin composition is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, still more preferably 2 to 8% by mass, and particularly preferably 3 to 5% by mass.

In the photosensitive colored resin composition according to embodiment 1 of the present invention, the content of the oxime ester type photopolymerization initiator (a1) in the photopolymerization initiator (a) is not particularly limited, but is usually 20 mass% or more, preferably 30 mass% or more, more preferably 40 mass% or more, further preferably 45 mass% or more, further preferably 50 mass% or more, particularly preferably 60 mass% or more, and most preferably 70 mass% or more. The content 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 be generated, and when the amount is equal to or less than the upper limit, the tapered shape tends to be favorable. For example, the content of the oxime ester photopolymerization initiator (a1) in the photopolymerization initiator (a) is preferably 30 to 90% by mass, more preferably 50 to 90% by mass, still more preferably 60 to 85% by mass, and particularly preferably 70 to 80% by mass.

(A) The content of the oxime ester photopolymerization initiator (a2) in the photopolymerization initiator is not particularly limited, and is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. The content is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, still more preferably 40% by mass or less, and particularly preferably 30% by mass or less. When the amount is equal to or more than the lower limit, the tapered shape tends to be satisfactory, and when the amount is equal to or less than the upper limit, sufficient ink repellency tends to be generated. 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, still more preferably 10 to 50% by mass, still more preferably 15 to 40% by mass, and particularly preferably 20 to 30% by mass.

The content of the oxime ester photopolymerization initiator (a2) is usually 10 parts by mass or more, preferably 20 parts by mass or more, more preferably 25 parts by mass or more, and further preferably 30 parts by mass or more, relative to 100 parts by mass of the oxime ester photopolymerization initiator (a 1). 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, further preferably 50 parts by mass or less, further preferably 45 parts by mass or less, and particularly preferably 40 parts by mass or less. When the amount is equal to or more than the lower limit, the tapered shape tends to be satisfactory, and when the amount is equal to or less than the upper limit, sufficient ink repellency tends to be generated. For example, the content of the oxime ester photopolymerization initiator (a2) is preferably 10 to 70% by mass, more preferably 10 to 60% by mass, even more preferably 20 to 55% by mass, even more preferably 20 to 50% by mass, particularly preferably 25 to 45% by mass, and particularly preferably 30 to 40% by mass, based on 100 parts by mass of the oxime ester photopolymerization initiator (a 1).

In the photosensitive colored resin composition according to embodiment 2 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 mass% or more, preferably 1 mass% or more, more preferably 2 mass% or more, and still more preferably 3 mass% or more. The content is usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, and still more preferably 5% by mass or less. When the amount is equal to or more than the lower limit, sufficient ink repellency tends to be generated, and when the amount is equal to or less than the upper limit, the tapered shape tends to be favorable. For example, the content of the oxime ester photopolymerization initiator (a3) in the entire solid content of the photosensitive colored resin composition is preferably 0.1 to 15% by mass, more preferably 1 to 10% by mass, even more preferably 2 to 8% by mass, and particularly preferably 3 to 5% by mass.

The blending ratio of the photopolymerization initiator (a) to the photopolymerizable compound (C) in the photosensitive colored resin composition of the present invention is not particularly limited, but is preferably 1 part by mass or more, more preferably 5 parts by mass or more, further preferably 10 parts by mass or more, further preferably 12 parts by mass or more, and particularly preferably 15 parts by mass or more, and is preferably 200 parts by mass or less, more preferably 100 parts by mass or less, further preferably 50 parts by mass or less, further preferably 30 parts by mass or less, and particularly preferably 20 parts by mass or less, with respect to 100 parts by mass of the photopolymerizable compound (C). When the lower limit value is not less than the lower limit value, appropriate sensitivity tends to be obtained, and when the upper limit value is not more than the upper limit value, formation into a desired pattern shape tends to be facilitated. For example, the blending ratio of the photopolymerization initiator (a) to 100 parts by mass of the photopolymerizable compound (C) is preferably 1 to 200 parts by mass, more preferably 5 to 100 parts by mass, still more preferably 10 to 50 parts by mass, still more preferably 12 to 30 parts by mass, and particularly preferably 15 to 20 parts by mass.

When the photosensitive colored resin composition of the present invention contains a chain transfer agent, the content thereof is not particularly limited, but is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and still more preferably 0.8% by mass or more, and is usually 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less, and still more preferably 2% by mass or less, of the total solid content of the photosensitive colored resin composition. When the lower limit value is not less than the lower limit value, the sensitivity tends to be improved, and when the upper limit value is not more than the upper limit value, a desired pattern tends to be easily formed. When the chain transfer agent is contained, for example, the content of the chain transfer agent in the entire solid content of the photosensitive colored resin composition is preferably 0.01 to 5% by mass, more preferably 0.1 to 4% by mass, even more preferably 0.5 to 3% by mass, and particularly preferably 0.8 to 2% by mass.

The content of the chain transfer agent in the photosensitive colored resin composition with respect to the photopolymerization initiator (a) is not particularly limited, but is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, and is preferably 500 parts by mass or less, more preferably 300 parts by mass or less, further preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less, with respect to 100 parts by mass of the photopolymerization initiator (a). When the lower limit value is not less than the above-described lower limit value, high sensitivity tends to be obtained, and when the upper limit value is not more than the above-described upper limit value, a desired pattern tends to be easily formed. When the chain transfer agent is contained, the content of the chain transfer agent is preferably 5 to 500 parts by mass, more preferably 10 to 300 parts by mass, still more preferably 15 to 100 parts by mass, and particularly preferably 20 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator (a).

[1-1-2] (B) component: 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 alkali developing solution.

The alkali-soluble resin includes various resins having a carboxyl group or a hydroxyl group, but is preferably an alkali-soluble resin having a carboxyl group from the viewpoint of excellent developability.

In addition, the alkali-soluble resin having an ethylenically unsaturated group is preferable because the verticality of the side surfaces of the partition walls is improved, the outflow of the liquid repellent due to the thermal fusion of the partition walls can be suppressed, and the ink repellency can be easily maintained.

The alkali-soluble resin (B) of the photosensitive colored resin composition of the present invention preferably contains an acrylic copolymer resin (B11) having an ethylenically unsaturated group in the side chain (hereinafter, also simply referred to as "acrylic copolymer resin (B11)") from the viewpoint of ink repellency. On the other hand, from the viewpoint of the linearity of the pattern, the epoxy (meth) acrylate resin (B12) is preferably contained.

Further, from the viewpoint of satisfying 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 described in detail.

[ acrylic copolymer resin (B11) ]

The acrylic copolymer resin (B11) has an ethylenically unsaturated group in a side chain. It is considered that, when the composition has an ethylenically unsaturated group, photocuring by exposure occurs to form a stronger film, and the composition is less likely to cause the bleeding of the liquid repellent during development.

(partial structure represented by the general formula (I))

The partial structure of the acrylic copolymer resin (B11) having a side chain having an ethylenically unsaturated group is not particularly limited, but preferably has a partial structure represented by the following general formula (I), for example, from the viewpoint of easy emission of radicals generated along with flexibility of the film.

[ chemical formula 9]

(in the formula (I), R¹And R²Each independently represents a hydrogen atom or a methyl group, and represents a bonding position. )

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

[ chemical formula 10]

(in the formula (I'), R¹And R²Each independently represents a hydrogen atom or a methyl group, R^XRepresents a hydrogen atom or a polybasic acid residue. )

The polybasic acid residue refers to a 1-valent group obtained by removing 1 OH group from a polybasic acid or an anhydride thereof. Examples of the polybasic acid include one or more selected from the group consisting of maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, endomethenyltetrahydrophthalic acid, hexachloronorbornene diacid, methyltetrahydrophthalic acid, and biphenyl tetracarboxylic acid.

Among these, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferable, and tetrahydrophthalic acid and biphenyltetracarboxylic acid are more preferable, from the viewpoint of patterning characteristics.

When the acrylic copolymer resin (B11) includes a partial structure represented by the above general formula (I), the content ratio thereof is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 30 mol% or more, further preferably 40 mol% or more, and particularly preferably 50 mol% or more, and further preferably 90 mol% or less, more preferably 85 mol% or less, further preferably 80 mol% or less, and further preferably 75 mol% or less, and particularly preferably 70 mol% or less, relative to the total number of moles of the structural units of the acrylic copolymer resin (B11). When the amount is equal to or more than the lower limit, the ink repellency tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (I), the content ratio of the partial structure represented by the general formula (I) is, for example, preferably 10 to 90 mol%, more preferably 20 to 85 mol%, still more preferably 30 to 80 mol%, still 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 above general formula (I'), the content ratio thereof is not particularly limited, but is preferably 10 mol% or more, more preferably 20 mol% or more, further preferably 25 mol% or more, further preferably 30 mol% or more, and particularly preferably 35 mol% or more, and further preferably 80 mol% or less, more preferably 75 mol% or less, further preferably 70 mol% or less, and particularly preferably 65 mol% or less, relative to the total number of moles of the structural units of the acrylic copolymer resin (B11). When the amount is equal to or more than the lower limit, the alkali developability tends to be good, and when the amount is equal to or less than the upper limit, the development adhesion tends to be ensured. When the acrylic copolymer resin (B11) includes the partial structure represented by the general formula (I '), the content ratio of the partial structure represented by the general formula (I') is, for example, preferably 10 to 80 mol%, more preferably 20 to 80 mol%, still more preferably 25 to 75 mol%, still more preferably 30 to 70 mol%, and particularly preferably 35 to 65 mol%.

(partial Structure represented by the general formula (II))

When the acrylic copolymer resin (B11) contains a partial structure represented by the above general formula (I), the other partial structures that may be contained are not particularly limited, but from the viewpoint of development adhesion, for example, it preferably has a partial structure represented by the following general formula (II).

[ chemical formula 11]

In the above formula (II), R³Represents a hydrogen atom or a methyl group, R⁴Represents an alkyl group optionally having a substituent, an aromatic ring group optionally having a substituent, or an alkenyl group optionally having a substituent.

(R⁴)

In the above formula (II), R⁴Represents an alkyl group optionally having a substituent, an aromatic ring group optionally having a substituent, or an alkenyl group optionally having a substituent.

As R⁴Examples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, particularly preferably 8 or more, and further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, particularly preferably 12 or less. When the amount is equal to or more than the lower limit, the film strength tends to be improved and the development adhesion tends to be improved, and when the amount is equal to or less than the upper limit, the amount of residue tends to be reduced. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 3 to 18, further preferably 5 to 16, further preferably 8 to 14, and particularly preferably 8 to 12.

Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl and the like. Of these, from the viewpoint of developability, dicyclopentyl group or dodecyl group is preferable, and dicyclopentyl group is more preferable.

Further, as the substituent optionally contained in the alkyl group, there may be mentioned: 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.

As R⁴As the aromatic ring group in (1), there may be mentioned: a 1-valent aromatic hydrocarbon ring group and a 1-valent aromatic heterocyclic group. The number of carbon atoms is preferably 6 or more, and also preferably 24 or less, more preferably 22 or less, further preferably 20 or less, and particularly preferably 18 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. For example, the number of carbon atoms of the aromatic ring group is preferably 6 to 24, more preferably 6 to 22, still more preferably 6 to 20, and particularly preferably 6 to 18.

The aromatic hydrocarbon ring in the aromatic hydrocarbon ring group may be a single ring or a condensed ring, and examples thereof include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,

A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc.

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring, and examples thereof include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, or the like,

A diazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furopyrrole ring, a furofuran ring, a thienofuran ring, a benzisoxazole ring

An azole ring, a benzisothiazole ring, a benzimidazole ring, a heterocyclic ring, a,A pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a triazine ring, a quinoline ring,

pyridine ring, quinazoline ring, azulene ring, etc. Of these, benzene rings or naphthalene rings are preferable, and benzene rings are more preferable, from the viewpoint of developability.

Further, as the substituent optionally having an aromatic ring group, there may be mentioned: methyl group, ethyl group, propyl group, methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxyl group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxyl group and oligoethylene glycol group are preferable.

As R⁴Examples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. For example, the number of carbon atoms of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

In addition, as the substituent optionally having an alkenyl group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.

Like this, R⁴Represents an alkyl group optionally having a substituent, an aryl group optionally having a substituent, or an alkenyl group optionally having a substituent, but among these groups, 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 above general formula (II), the content ratio thereof is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, further preferably 10 mol% or more, and particularly preferably 20 mol% or more, and further preferably 70 mol% or less, more preferably 60 mol% or less, further preferably 50 mol% or less, and particularly preferably 40 mol% or less, relative to the total number of moles of the structural units of the acrylic copolymer resin (B11). When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (II), the content ratio of the partial structure represented by the general formula (II) is preferably 1 to 70 mol%, more preferably 5 to 60 mol%, still more preferably 10 to 50 mol%, and particularly preferably 20 to 40 mol%, for example.

(partial structure represented by the general formula (III))

When the acrylic copolymer resin (B11) contains a partial structure represented by the above general formula (I), it is preferable that the acrylic copolymer resin (B11) contains a partial structure represented by the following general formula (III) as another partial structure that can be contained, from the viewpoint of heat resistance and film strength.

[ chemical formula 12]

In the above formula (III), R⁵Represents a hydrogen atom or a methyl group, R⁶Represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group, or an alkylthio group optionally having a substituent. t represents an integer of 0 to 5.

(R⁶)

In the above formula (III), R⁶Represents an alkyl group optionally having a substituent, an alkenyl group optionally having a substituent, an alkynyl group optionally having a substituent, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group optionally having a substituent, a thiol group, or an alkylthio group optionally having a substituent.

As R⁶Examples of the alkyl group in (1) include linear, branched or cyclic alkyl groups. The number of carbon atoms is preferably 1 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. For example, the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 3 to 18, further preferably 5 to 16, further preferably 5 to 14, and particularly preferably 5 to 12.

Specific examples of the alkyl group include: methyl, ethyl, cyclohexyl, dicyclopentyl, dodecyl and the like. Among these alkyl groups, from the viewpoint of developability and film strength, dicyclopentyl group or dodecyl group is preferable, and dicyclopentyl group is more preferable.

As R⁶Examples of the alkenyl group in (1) include straight-chain, branched or cyclic alkenyl groups. The number of carbon atoms is 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. For example, the number of carbon atoms of the alkenyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

As R⁶Examples of the alkynyl group in (3) include a linear, branched or cyclic alkynyl group. The number of carbon atoms is 2 or more, and is preferably 22 or less, more preferably 20 or less, further preferably 18 or less, further preferably 16 or less, and particularly preferably 14 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. For example, the number of carbon atoms of the alkynyl group is preferably 2 to 22, more preferably 2 to 20, further preferably 2 to 18, further preferably 2 to 16, and particularly preferably 2 to 14.

Further, as the substituent optionally having the alkynyl group, there may be mentioned: methoxy group, ethoxy group, chloro group, bromo group, fluoro group, hydroxy group, amino group, epoxy group, oligoethylene glycol group, phenyl group, carboxyl group, etc., and from the viewpoint of developability, hydroxy group and oligoethylene glycol group are preferable.

As R⁶The halogen atom in (b) may be a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and among these, a fluorine atom is preferable from the viewpoint of ink repellency.

As R⁶Examples of the alkoxy group in (1) include linear, branched or cyclic alkoxy groups. The number of carbon atoms is 1 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. For example, the alkoxy group has preferably 1 to 20 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 16 carbon atoms, yet more preferably 1 to 14 carbon atoms, and particularly preferably 1 to 12 carbon atoms.

Further, as the substituent optionally having an alkoxy group, there may be mentioned: 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.

As R⁶The alkylthio group in (1) may be a straight-chain, branched or cyclic alkylthio group. The number of carbon atoms is preferably 1 or more, and is preferably 20 or less, more preferably 18 or less, further preferably 16 or less, further preferably 14 or less, and particularly preferably 12 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. For example, the number of carbon atoms of the alkylthio group is preferably 1 to 20, more preferably 1 to 18, further preferably 1 to 16, further preferably 1 to 14, and particularly preferably 1 to 12.

In addition, as the substituent optionally having an alkyl group in the alkylthio group, there can be mentioned: 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.

Like this, R⁶Represents an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted alkynyl group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a hydroxyalkyl group, a thiol group, or an optionally substituted alkylthio group, and among these groups, from the viewpoint of developability, a hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.

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

When the acrylic copolymer resin (B11) contains a partial structure represented by the above general formula (III), the content ratio thereof is not particularly limited, but is preferably 0.5 mol% or more, more preferably 1 mol% or more, and still more preferably 2 mol% or more, relative to the total number of moles of the structural units of the acrylic copolymer resin (B11). Further, it is preferably 50 mol% or less, more preferably 30 mol% or less, further preferably 20 mol% or less, further preferably 10 mol% or less, and particularly preferably 5 mol% or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more than the upper limit, the amount of residue tends to be reduced. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (III), for example, the content ratio of the partial structure represented by the general formula (III) is preferably 0.5 to 50 mol%, more preferably 0.5 to 30 mol%, still more preferably 1 to 20 mol%, still more preferably 1 to 10 mol%, and particularly preferably 2 to 5 mol%.

(partial structure represented by the general formula (IV))

When the acrylic copolymer resin (B11) has a partial structure represented by the above general formula (I), it is preferable that the acrylic copolymer resin (B11) has a partial structure represented by the following general formula (IV) as another partial structure that may be contained, from the viewpoint of developability.

[ chemical formula 13]

In the above formula (IV), R⁷Represents a hydrogen atom or a methyl group.

When the acrylic copolymer resin (B11) contains a partial structure represented by the above general formula (IV), the content ratio thereof is not particularly limited, but is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and further preferably 80 mol% or less, more preferably 70 mol% or less, further preferably 60 mol% or less, relative to the total number of moles of the structural units of the acrylic copolymer resin (B11). When the amount is not less than the lower limit, the developability tends to be improved, and when the amount is not more than the upper limit, the development adhesion tends to be improved. When the acrylic copolymer resin (B11) contains the partial structure represented by the general formula (IV), the content ratio of the partial structure represented by the general formula (IV) is, for example, preferably 5 to 80 mol%, more preferably 10 to 70 mol%, and still 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 30mgKOH/g or more, more preferably 40mgKOH/g or more, still more preferably 50mgKOH/g or more, and yet more preferably 60mgKOH/g or more, and is preferably 150mgKOH/g or less, more preferably 140mgKOH/g or less, yet more preferably 130mgKOH/g or less, and yet more preferably 120mgKOH/g or less. When the amount is not less than the lower limit, the developability tends to be improved, and when the amount is not more than the upper limit, the development adhesion tends to be improved. For example, the acid value of the acrylic copolymer resin (B11) is preferably 30 to 150mgKOH/g, more preferably 40 to 140mgKOH/g, still more preferably 50 to 130mgKOH/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, and is usually 1000 or more, preferably 2000 or more, more preferably 4000 or more, further preferably 6000 or more, further preferably 7000 or more, particularly preferably 8000 or more, and is usually 30000 or less, preferably 20000 or less, more preferably 15000 or less, further preferably 10000 or less. When the amount is not less than the lower limit, the development adhesion tends to be improved, and when the amount is not more 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 1000 to 30000, more preferably 2000 to 20000, further preferably 4000 to 15000, further preferably 6000 to 15000, particularly preferably 7000 to 10000, and particularly preferably 8000 to 10000.

(B) The content 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, further preferably 50% by mass or more, particularly preferably 70% by mass or more, and is preferably 95% by mass or less, more preferably 90% by mass or less, further preferably 85% by mass 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 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) contained in the alkali-soluble resin (B) is preferably 10 to 95% by mass, more preferably 30 to 95% by mass, still more preferably 50 to 90% by mass, and particularly preferably 70 to 85% by mass.

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

Specific examples of the acrylic copolymer resin (B11) include: the resins described in Japanese patent laid-open Nos. 8-297366 and 2001-89533.

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

[ epoxy (meth) acrylate resin (B12) ]

The epoxy (meth) acrylate resin (B12) is obtained by adding an ethylenically unsaturated monocarboxylic acid or ester compound to an epoxy resin, optionally reacting an isocyanate group-containing compound, and then further reacting a polybasic acid or an anhydride thereof. Examples thereof include: the resin is obtained by ring-opening addition of a carboxyl group of an unsaturated monocarboxylic acid to an epoxy group of an epoxy resin, thereby adding an ethylenically unsaturated bond to the epoxy compound via an ester bond (-COO-), and simultaneously adding one carboxyl group of a polybasic acid anhydride to a hydroxyl group generated thereby. Further, a resin obtained by adding a polyhydric alcohol simultaneously with the addition of a polybasic acid anhydride may be mentioned.

Further, a resin obtained by further reacting a compound having a reactive functional group with a carboxyl group of the resin obtained by the above reaction is also included in the above epoxy (meth) acrylate resin (B12).

As described above, the epoxy (meth) acrylate resin is not limited to the "(meth) acrylate" resin having substantially no epoxy group in the chemical structure, but is named as usual because an epoxy compound (epoxy resin) is used as a raw material and the "(meth) acrylate" is a typical example.

Here, the epoxy resin is a material including a raw material compound before forming a resin by thermosetting, and the epoxy resin can be appropriately selected from known epoxy resins and used. In addition, as the epoxy resin, a compound obtained by reacting a phenol compound with epichlorohydrin may be used. The phenolic compound is preferably a compound having a phenolic hydroxyl group at a valence of 2 or more, and may be a monomer or a polymer.

Specific examples thereof include: bisphenol a epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, biphenol novolac epoxy resins, triphenol epoxy resins, epoxy resins polymerized from phenol and dicyclopentane, dihydroxyfluorene epoxy resins, dihydroxyalkyleneoxyfluorene epoxy resins, diglycidyl etherate of 9, 9-bis (4 '-hydroxyphenyl) fluorene, diglycidyl etherate of 1, 1-bis (4' -hydroxyphenyl) adamantane, and the like, and those having an aromatic ring in the main chain as described above can be preferably used.

Among these, bisphenol a epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins, epoxy resins polymerized with phenol and dicyclopentane, diglycidyl etherate of 9, 9-bis (4' -hydroxyphenyl) fluorene, and the like are preferable from the viewpoint of high cured film strength, and bisphenol a epoxy resins are particularly preferable.

Specific examples of the epoxy resin include, for example: bisphenol A-type epoxy resins (for example, "jER (registered trademark, same below)" 828 ", jER 1001", jER1002 ", jER 1004", produced by Mitsubishi Chemical corporation, "NER-1302" (epoxy equivalent 323, softening point 76 ℃) produced by Nippon Chemical corporation), bisphenol F-type resins (for example, "jER 807", "jER 4004P", jER4005P ", and" jER4007P ", produced by Nippon Chemical corporation," NER-7406 "(epoxy equivalent 350, softening point 66 ℃)), bisphenol S-type epoxy resins, biphenyl glycidyl ethers" (for example, "jERYX-4000", produced by Mitsubishi Chemical corporation), phenol novolac-type epoxy resins (for example, "EPPN (registered trademark, same below) -201", produced by Nippon Chemical corporation, "jER 152", and "jER 154", produced by Dow Chemical corporation, produced by Nippon Chemical corporation), (o-, m-, and P-) cresol novolak type epoxy resins (for example, "EOCN (registered trademark), the same below)" 102S "," EOCN-1020 "," EOCN-104S ", manufactured by Nippon Kagaku K.K.), triglycidyl isocyanurate (for example," TEPIC (registered trademark) ", manufactured by Nissan chemical Co., Ltd.), triphenol methane type epoxy resins (for example," EPPN-501 "," EPPN-502 "," EPPN-503 ", manufactured by Nippon Kagaku K.K.)," Celloxide (registered trademark, the same below) 2021P "," Celloxide EHPE ", manufactured by Daluosiwaukee Co., Ltd.), epoxy resins obtained by glycidating a phenol resin produced by reacting dicyclopentadiene with phenol (for example," EXA-7200 ", manufactured by DIC Kagaku K.K.", "EXA-7300", manufactured by Nippon Kagaku K.K.), Epoxy resins represented by the following general formulae (i-11) to (i-14). Specific examples thereof include: "XD-1000" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (i-11), "NC-3000" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (i-12), "ESF-300" manufactured by Nippon Kabushiki Kaisha as an epoxy resin represented by the following general formula (i-14), and the like.

[ chemical formula 14]

In the above general formula (i-11), n is an average value and represents 0A number of 10. R¹¹¹Each 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. In addition, a plurality of R present in 1 molecule¹¹¹Each may be the same or different.

[ chemical formula 15]

In the general formula (i-12), n is an average value and represents a number of 0 to 10. R¹²¹Each 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. In addition, a plurality of R present in 1 molecule¹²¹Each may be the same or different.

[ chemical formula 16]

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). Wherein the molecular structure contains more than 1 adamantane structure, and c represents 2 or 3.

[ chemical formula 17]

In the above general formulae (i-13-1) and (i-13-2), R¹³¹～R¹³⁴And R¹³⁵～R¹³⁷Each independently represents an adamantyl group optionally having a substituent, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms optionally having a substituent, or a phenyl group optionally having a substituent, and represents a bonding position.

[ chemical formula 18]

In the general formula (i-14), p and q each independently represent an integer of 0 to 4, R¹⁴¹And R¹⁴²Each independently represents an alkyl group having 1 to 4 carbon atoms or a halogen atom, R¹⁴³And R¹⁴⁴Each independently represents an alkylene group having 1 to 4 carbon atoms, and x and y each independently represents an integer of 0 or more.

Among these, the epoxy resins represented by any of the general formulae (i-11) to (i-14) are preferably used.

Examples of ethylenically unsaturated monocarboxylic acids include: (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, and the like, and pentaerythritol tri (meth) acrylate succinic anhydride adducts, pentaerythritol tri (meth) acrylate tetrahydrophthalic anhydride adducts, dipentaerythritol penta (meth) acrylate succinic anhydride adducts, dipentaerythritol penta (meth) acrylate phthalic anhydride adducts, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride adducts, reaction products of (meth) acrylic acid and epsilon-caprolactone, and the like. Among them, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

Examples of the polybasic acid (acid anhydride) include: succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetrahydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, and acid anhydrides thereof. Among them, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferable from the viewpoint of outgassing, and succinic anhydride or tetrahydrophthalic anhydride is more preferable.

By using a polyol, the molecular weight of the epoxy (meth) acrylate resin (B12) tends to be increased, and a molecular weight and viscosity tend to be balanced by introducing a branch into the molecule. Further, the introduction rate of an acid group into a molecule tends to be increased, and a balance between sensitivity, adhesion, and the like tends to be easily obtained.

The polyol is preferably one or two or more polyols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2, 3-propanetriol, for example.

As the epoxy (meth) acrylate resin, in addition to those described above, epoxy (meth) acrylate resins described in Korean laid-open patent No. 10-2013-0022955 and the like can be cited.

The acid value of the epoxy (meth) acrylate resin (B12) is not particularly limited, but is preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, further preferably 50mgKOH/g or more, further preferably 70mgKOH/g or more, particularly preferably 80mgKOH/g or more, and further preferably 200mgKOH/g or less, more preferably 180mgKOH/g or less, further preferably 150mgKOH/g or less, further preferably 120mgKOH/g or less, and particularly preferably 110mgKOH/g or less. When the amount is not less than the lower limit, the developability tends to be improved, and when the amount is not more 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 200mgKOH/g, more preferably 30 to 180mgKOH/g, still more preferably 50 to 150mgKOH/g, yet more preferably 70 to 120mgKOH/g, and particularly preferably 80 to 110 mgKOH/g.

The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (B12) is not particularly limited, and is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, and still more preferably 3500 or more, and is usually 30000 or less, preferably 15000 or less, more preferably 10000 or less, still more preferably 8000 or less, and particularly preferably 5000 or less. When the content is not less than the lower limit, the film strength tends to be improved, and when the content is not more than the upper limit, the content of the residue tends to be reduced. The weight average molecular weight (Mw) of the epoxy (meth) acrylate resin (B12) is preferably 1000 to 30000, more preferably 2000 to 15000, still more preferably 3000 to 10000, still more preferably 3500 to 8000, and particularly preferably 3500 to 5000.

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

The epoxy (meth) acrylate resin (B12) can be synthesized by a conventionally known method. Specifically, the following method may be used: dissolving the epoxy resin in an organic solvent, adding the acid or ester compound having an ethylenically unsaturated bond to the mixture in the presence of a catalyst and a thermal polymerization inhibitor to carry out an addition reaction, and adding a polybasic acid or an anhydride thereof to the mixture to continue the reaction. For example, methods described in japanese patent No. 3938375 and japanese patent No. 5169422 are cited.

Among these, as the organic solvent used for the reaction, one or two or more kinds of organic solvents such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate and the like can be mentioned. Examples of the catalyst include tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, quaternary ammonium salts such as tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride and trimethylbenzylammonium chloride, phosphorus compounds such as triphenylphosphine, and triphenylphosphonium

Etc. of

Class, etc. or two or more. The thermal polymerization inhibitor may be one or more selected from hydroquinone, hydroquinone monomethyl ether, and methyl hydroquinone.

The acid or ester compound having an ethylenically unsaturated bond may be used in an amount of usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, based on 1 chemical equivalent of the epoxy group in the epoxy resin. The temperature during the addition reaction is usually 60 to 150 ℃, preferably 80 to 120 ℃. The amount of the polybasic acid (acid anhydride) used is usually 0.1 to 1.2 stoichiometric equivalents, preferably 0.2 to 1.1 stoichiometric equivalents, based on the stoichiometric equivalent of the hydroxyl group 1 generated by the addition reaction.

From the viewpoint of film strength and linearity, the epoxy (meth) acrylate resin (B12) 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 (i), an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (ii), and an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (iii).

[ chemical formula 19]

In the formula (i), R^aRepresents a hydrogen atom or a methyl group, R^bRepresents a 2-valent hydrocarbon group optionally having a substituent. The benzene ring in formula (i) may be further substituted with an optional substituent, and represents a bonding position.

[ chemical formula 20]

In the formula (ii), R^cEach independently represents a hydrogen atom or a methyl group, R^dRepresents a 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain, and represents a bonding position.

[ chemical formula 21]

In the formula (iii), R^eRepresents a hydrogen atom or a methyl group, and gamma represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent. The benzene ring in formula (iii) may be further substituted with an optional substituent, which represents a bonding position.

Among these, first, an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (i) (hereinafter, also simply referred to as "epoxy (meth) acrylate resin (B12-1)") will be described in detail.

[ chemical formula 22]

(R^b)

In the above formula (i), R^bRepresents a 2-valent hydrocarbon group optionally having a substituent.

As the 2-valent hydrocarbon group, there may be mentioned: a group in which a 2-valent aliphatic group, a 2-valent aromatic group, and 1 or more 2-valent aliphatic groups are linked to 1 or more 2-valent aromatic groups.

Examples of the 2-valent aliphatic group include linear, branched, and cyclic 2-valent aliphatic groups. Among these, a linear 2-valent aliphatic group is preferable from the viewpoint of developing solubility, and a cyclic 2-valent aliphatic group is preferable from the viewpoint of reducing permeation of the developing solution into the exposed portion. 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 further preferably 10 or less. When the lower limit value is not less than the above-described lower limit value, the film strength tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the ink repellency tends to be improved. For example, the number of carbon atoms of the 2-valent aliphatic group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 10.

Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene is preferable from the viewpoint of ink repellency and production cost.

Specific examples of the branched aliphatic group having a valence of 2 include: the aforementioned 2-valent linear aliphatic group has a structure having a side chain such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, or the like.

The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of rings in the 2-valent cyclic aliphatic group is preferably 1 to 10, and more preferably 1 to 5.

Specific examples of the cyclic aliphatic group having a valence of 2 include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring or a cyclododecane ring. Among these, from the viewpoint of film strength and developability, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.

As the substituent optionally having the 2-valent aliphatic group, there can be mentioned: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

Further, as the aromatic ring group having a valence of 2, there may be mentioned: a 2-valent aromatic hydrocarbon ring group and a 2-valent 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 further 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of carbon atoms of the aromatic ring group having a valence of 2 is preferably 4 to 20, more preferably 5 to 15, and further preferably 6 to 10.

The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group having a valence of 2, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring, perylene,

A ring, a benzophenanthrene ring, an acenaphthene ring, an anthryl ring, a fluorene ring, etc.

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group having a valence of 2 include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole ring having 2 free valences,

An azole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a pyridine ring,

a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. Of these, from the viewpoint of production cost, it is excellentIs selected from a benzene ring or a naphthalene ring having 2 free valences, and more preferably a benzene ring having 2 free valences.

As the substituent optionally having a 2-valent aromatic ring group, there can be mentioned: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

Examples of the group in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic groups are linked include groups in which 1 or more of the 2-valent aliphatic groups and 1 or more of the 2-valent aromatic groups are linked.

The number of the 2-valent aliphatic group is not particularly limited, and 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 not less than the lower limit, the developability tends to be improved, and when the amount is not more than the upper limit, the film strength tends to be improved. For example, the number of the 2-valent aliphatic groups is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3.

The number of the aromatic ring groups having a valence of 2 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of the aromatic ring groups having a valence of 2 is preferably 1 to 10, more preferably 1 to 5, and further preferably 1 to 3.

Specific examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the following formulae (i-A) to (i-F). Among these, from the viewpoint of rigidity of the skeleton and hydrophobization of the film, a group represented by the following formula (i-a) is preferable.

[ chemical formula 23]

As described above, the benzene ring in the formula (i) may be further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1 or 2 or more.

Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

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

[ chemical formula 24]

In the formula (i-1), R^aAnd R^bThe same as in the above formula (i). R^YRepresents a hydrogen atom or a polybasic acid residue. Denotes the bonding site. The benzene ring in the formula (i-1) may be further substituted with an optional substituent.

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

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

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

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

[ chemical formula 25]

[ chemical formula 26]

[ chemical formula 27]

[ chemical formula 28]

[ chemical formula 29]

[ chemical formula 30]

[ chemical formula 31]

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

[ chemical formula 32]

(R^d)

In the above formula (ii), R^dRepresents a 2-valent 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 of the aliphatic ring group is not particularly limited, and 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of rings in the aliphatic ring group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3.

The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and particularly preferably 15 or less carbon atoms. When the amount is equal to or more than the lower limit, the film strength 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 aliphatic ring group has preferably 4 to 40 carbon atoms, more preferably 4 to 30 carbon atoms, still more preferably 6 to 20 carbon atoms, and particularly preferably 8 to 15 carbon atoms.

Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of film strength and developability.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, and more preferably 3 or more, and is usually 10 or less, preferably 5 or less, and more 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 the amount is equal to or 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, further preferably 1 to 4, and particularly preferably 2 to 4.

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

Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzopyrene ring,

A ring, a benzophenanthrene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of patterning characteristics.

In addition, the 2-valent hydrocarbon group in the 2-valent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and examples thereof include: a 2-valent aliphatic group, a 2-valent aromatic group, and a group in which 1 or more 2-valent aliphatic groups and 1 or more 2-valent aromatic groups are linked.

Examples of the 2-valent aliphatic group include linear, branched, and cyclic 2-valent aliphatic groups. Among these, a linear 2-valent aliphatic group is preferable from the viewpoint of improving developability, and a cyclic 2-valent aliphatic group is preferable 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 further 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of carbon atoms of the 2-valent aliphatic group is preferably 1 to 25, more preferably 3 to 20, and further preferably 6 to 15.

Specific examples of the 2-valent linear aliphatic group include: methylene, ethylene, n-propylene, n-butylene, n-hexylene, n-heptylene, and the like. Among these, methylene group is used from the viewpoint of ink repellency.

The number of rings of the 2-valent cyclic aliphatic group is not particularly limited, and 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of rings in the 2-valent cycloaliphatic group is preferably 1 to 10, more preferably 1 to 5, still more preferably 1 to 3, and particularly preferably 2 to 5.

Specific examples of the cyclic aliphatic group having a valence of 2 include: a group obtained by removing 2 hydrogen atoms from a ring such as a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isoborneol ring, an adamantane ring or a cyclododecane ring. Among these, from the viewpoint of film strength, a group obtained by removing 2 hydrogen atoms from the adamantane ring is preferable.

Examples of the substituent optionally having the 2-valent aliphatic group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

Further, as the aromatic ring group having a valence of 2, there may be mentioned: a 2-valent aromatic hydrocarbon ring group and a 2-valent 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 further 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 the amount is equal to or less than the upper limit, the developability tends to be improved. The number of carbon atoms of the aromatic ring group having a valence of 2 is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15.

The aromatic hydrocarbon ring in the 2-valent aromatic hydrocarbon ring group may be a single ring or a condensed ring. As the aromatic hydrocarbon ring group having a valence of 2, for example: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene with 2 free valencesCyclo, tetracyclic ring, pyrene ring, benzopyrene ring,

The aromatic heterocyclic group in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group having a valence of 2 include: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, imidazole, or imidazole rings having 2 free valences,

a pyridine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, etc. Among these, from the viewpoint of production cost, a benzene ring or a naphthalene ring having 2 free valences is preferable, and a benzene ring having 2 free valences is more preferable.

Specific examples of the group in which 1 or more aliphatic groups having a valence of 2 are linked to 1 or more aromatic groups having a valence of 2 include groups represented by the above formulas (i-A) to (i-F). Among these, the group represented by the above formula (i-C) is preferable from the viewpoint of satisfying both the film strength and the ink repellency.

The bonding mode of the cyclic hydrocarbon group as the side chain of these 2-valent hydrocarbon groups is not particularly limited, and examples thereof include: the side chain is substituted for 1 hydrogen atom of an aliphatic group or an aromatic ring group, or a cyclic hydrocarbon group having 1 carbon atom of an aliphatic group as a side chain.

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

[ chemical formula 33]

In the formula (ii-1), R^cR has the same meaning as the above formula (ii)^αRepresents an optionally substituted 1-valent cyclic hydrocarbon group, and n is an integer of 1 or more. The benzene ring in the formula (ii-1) may be furtherOne step is substituted with an optional substituent.

(R^α)

In the above formula (ii-1), R^αRepresents an optionally substituted 1-valent cyclic hydrocarbon group.

The number of rings of the aliphatic ring group is not particularly limited, and 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of rings in the aliphatic ring group is preferably 1 to 6, more preferably 1 to 4, still more preferably 1 to 3, and particularly preferably 2 to 3.

Specific examples of the alicyclic ring in the alicyclic ring group include: cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornyl ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of compatibility between film strength and developability.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is 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 the amount is equal to or 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 further preferably 2 to 5.

Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of 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 further 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 the amount is equal to or less than the upper limit, the developability tends to be improved. The number of carbon atoms of the aromatic ring group is preferably 4 to 30, more preferably 5 to 20, and further preferably 6 to 15.

Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of compatibility between film strength and developability.

Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

n represents an integer of 1 or more, but is preferably 2 or more, and is preferably 3 or less. When the amount is not less than the lower limit, the developability tends to be improved, and when the amount is not more 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.

Of these, R is from the viewpoint of compatibility between film strength and developability^αPreferably a 1-valent aliphatic ring group, more preferably an adamantyl group.

As described above, the benzene ring in the formula (ii-1) may be further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

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

[ chemical formula 34]

[ chemical formula 35]

[ chemical formula 36]

[ chemical formula 37]

[ chemical formula 38]

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

[ chemical formula 39]

In the formula (ii-2), R^cR has the same meaning as in the above formula (ii)^βRepresents an optionally substituted 2-valent cyclic hydrocarbon group. The benzene ring in the formula (ii-2) may be further substituted with an optional substituent.

(R^β)

In the above formula (ii-2), R^βRepresents an optionally substituted 2-valent cyclic hydrocarbon group.

The number of rings of the aliphatic ring group is not particularly limited, and 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of rings in the aliphatic ring group is preferably 1 to 10, more preferably 1 to 5, and further preferably 2 to 5.

The aliphatic ring group has usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, and still more preferably 30 or less carbon atoms. When the amount is equal to or more than the lower limit, the film strength 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 aliphatic ring group has preferably 4 to 40 carbon atoms, more preferably 6 to 35 carbon atoms, and still more preferably 8 to 30 carbon atoms.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 3 or more, and is 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 the amount is equal to or 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, further preferably 2 to 5, and particularly preferably 3 to 5.

Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.

Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of film strength and developability.

Of these, R is from the viewpoint of compatibility between film strength and developability^βPreferably a 2-valent aliphatic ring group, more preferably a 2-valent adamantyl ring group.

On the other hand, from the viewpoint of compatibility between film strength and developability, R^βPreferably a 2-valent aromatic ring group, more preferably a 2-valent fluorene ring group.

As described above, the benzene ring in the formula (ii-2) may be further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

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

[ chemical formula 40]

[ chemical formula 41]

[ chemical formula 42]

[ chemical formula 43]

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

[ chemical formula 44]

In the formula (ii-3), R^cAnd R^dThe same as in the above formula (ii). R^ZRepresents a hydrogen atom or a polybasic acid residue.

The partial structure represented by the above formula (ii-3) contained in 1 molecule of the epoxy (meth) acrylate resin (B12-2) may be one kind or two or more kinds.

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

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

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

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

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

[ chemical formula 45]

In the formula (iii), R^eRepresents a hydrogen atom or a methyl group, and gamma represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent. The benzene ring in formula (iii) may be further substituted with an optional substituent. Denotes the bonding site.

(γ)

In the above formula (iii), γ represents a single bond, -CO-, an alkylene group optionally having a substituent, or a 2-valent cyclic hydrocarbon group optionally having a substituent.

The alkylene group may be linear or branched, and is preferably linear from the viewpoint of developing solubility, and is preferably branched from the viewpoint of developing adhesion. The number of carbon atoms is not particularly limited, and 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 the amount is equal to or less than the upper limit, the developability tends to be improved. For example, the number of carbon atoms of the alkylene group is preferably 1 to 6, more preferably 1 to 4, and further preferably 2 to 4.

Specific examples of the alkylene group include: methylene, ethylene, propylene, butylene, hexylene, and heptylene are preferably ethylene or propylene, and more preferably propylene, from the viewpoint of satisfying both film strength and developability.

Examples of the substituent optionally contained in the alkylene group include: alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

The cyclic hydrocarbon group having a valence of 2 includes a 2-valent aliphatic ring group and a 2-valent aromatic ring group.

Examples of the aromatic ring group include an aromatic ring group and an aromatic heterocyclic group. The number of carbon atoms of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, further preferably 10 or more, and preferably 40 or less, more preferably 30 or less, further preferably 20 or less, and 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 the amount is equal to or less than the upper limit, the developability tends to be improved.

Specific examples of the aromatic ring in the aromatic ring group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, etc. Among these, the fluorene ring is preferable from the viewpoint of compatibility between film strength and developability. For example, the number of carbon atoms of the aromatic ring group is preferably 4 to 40, more preferably 6 to 30, further preferably 8 to 20, and particularly preferably 10 to 15.

Examples of the substituent optionally contained in the cyclic hydrocarbon group include: an alkyl group having 1 to 5 carbon atoms such as a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, etc.; alkoxy groups having 1 to 5 carbon atoms such as methoxy and ethoxy; a hydroxyl group; a nitro group; a cyano group; carboxyl groups, and the like. Among these, from the viewpoint of ease of synthesis, the compound is preferably unsubstituted.

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

As mentioned above, the benzene ring in formula (iii) may be further substituted with an optional substituent. Examples of the substituent include: hydroxyl, methyl, methoxy, ethyl, ethoxy, propyl, propoxy, and the like. The number of the substituents is not particularly limited, and may be 1 or 2 or more. Among these, from the viewpoint of curability, the resin is preferably unsubstituted.

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

[ chemical formula 46]

In the formula (iii-1), R^eAnd gamma is as defined above for formula (iii), R^WRepresents a hydrogen atom or a polybasic acid residue, and represents a bonding position. The benzene ring in the formula (iii-1) may be further substituted with an optional substituent.

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

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

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

[ chemical formula 47]

[ chemical formula 48]

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 30mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more, and is preferably 200mgKOH/g or less, more preferably 150mgKOH/g or less, and still more preferably 100mgKOH/g or less. When the amount is not less than the lower limit, the developability tends to be improved, and when the amount is not more than the upper limit, the development adhesion tends to be improved. When the alkali-soluble resin (B) is a mixture of two or more types, the acid value represents a weighted average value corresponding to the content ratio. For example, the acid value of the alkali-soluble resin of component (B) is preferably 30 to 200mgKOH/g, more preferably 50 to 150mgKOH/g, and still more preferably 70 to 100 mgKOH/g.

The content of the alkali-soluble resin (B) in the photosensitive colored resin composition of the present invention is not particularly limited, and is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, further preferably 40% by mass or more, particularly preferably 50% by mass or more, and further usually 90% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass or less, relative to the total solid content. When the lower limit value is not less than the above-described lower limit value, the shape of the partition wall tends to be good, and when the upper limit value is not more than the above-described upper limit value, the ink repellency tends to be improved. For example, the content ratio 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 mass, particularly preferably 40 to 70% by mass, and particularly preferably 50 to 70% by mass.

The total of the content of the photopolymerizable compound (C) and the content of the alkali-soluble resin (B) in the total solid content is not particularly limited, but is preferably 10% by mass or more, more preferably 30% by mass or more, further preferably 60% by mass or more, and particularly preferably 80% by mass or more, and is preferably 95% by mass or less, more preferably 92% by mass or less, and further preferably 90% by mass or less. When the lower limit value is not less than the above-described lower limit value, the ink repellency tends to be improved, and when the upper limit value is not more than the above-described upper limit value, the shape of the partition wall tends to be good. For example, the total of the content of the photopolymerizable compound (C) and the alkali-soluble resin (B) in the entire solid content of the photosensitive colored resin composition is preferably 10 to 95% by mass, more preferably 30 to 92% by mass, even more preferably 60 to 90% by mass, and particularly preferably 80 to 90% by mass.

[1-1-3] (C) component: photopolymerizable compound

The photosensitive colored resin composition of the present invention contains (C) a photopolymerizable compound. It is considered that the inclusion of the photopolymerizable compound (C) improves the curability of the coating film and improves the ink repellency.

The photopolymerizable compound used herein is a compound having 1 or more ethylenically unsaturated bonds in the molecule, but is preferably a compound having 2 or more ethylenically unsaturated bonds in the molecule from the viewpoints of polymerizability, crosslinkability, and the ability to amplify the difference in developer solubility between an exposed portion and a non-exposed portion associated therewith, and is more preferably a compound in which the unsaturated bond is derived from a (meth) acryloyloxy group, that is, a (meth) acrylate compound.

In the present invention, a polyfunctional ethylenic monomer having 2 or more ethylenically unsaturated bonds in 1 molecule is particularly preferably used. The number of the ethylenically unsaturated groups of the polyfunctional ethylenic monomer is not particularly limited, but is preferably 2 or more, more preferably 3 or more, further preferably 5 or more, and further preferably 15 or less, more preferably 10 or less, further preferably 8 or less, and particularly preferably 7 or less. When the amount is not less than the lower limit, the polymerizability and the ink repellency tend to be improved, and when the amount is not more than the upper limit, the developability tends to be more favorable. For example, the number of ethylenically unsaturated groups in the polyfunctional ethylenic monomer is preferably 2 to 15, more preferably 2 to 10, further preferably 2 to 8, further preferably 3 to 7, and particularly preferably 5 to 7.

Specific examples of the photopolymerizable compound include: esters of aliphatic polyols with unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds with unsaturated carboxylic acids; esters obtained by esterification of a polyol such as an aliphatic polyol or an aromatic polyol with an unsaturated carboxylic acid or a polycarboxylic acid, and the like.

Examples of the ester of the aliphatic polyhydric compound and the unsaturated carboxylic acid include acrylic acid esters of aliphatic polyhydric compounds such as ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate, methacrylic acid esters obtained by replacing acrylic acid esters of these exemplified compounds with methacrylic acid esters, itaconic acid esters similarly obtained by replacing acrylic acid esters, crotonic acid esters obtained by replacing crotonic acid esters, and maleic acid esters obtained by replacing maleic acid esters.

Examples of the ester of an aromatic polyol and an unsaturated carboxylic acid include acrylic acid esters and methacrylic acid esters of an aromatic polyol such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinol diacrylate, resorcinol dimethacrylate and 1,2, 3-benzenetriol triacrylate.

The ester obtained by esterification of a polyvalent hydroxyl compound such as an aliphatic polyhydroxy compound or an aromatic polyhydroxy compound with an unsaturated carboxylic acid or a polyvalent carboxylic acid is not necessarily a single one, and representative specific examples thereof include a condensate of acrylic acid, phthalic acid and ethylene glycol; condensates of acrylic acid, maleic acid, and diethylene glycol; a condensate of methacrylic acid, terephthalic acid and pentaerythritol; condensates of acrylic acid, adipic acid, butanediol, and glycerol, and the like.

Further, as examples of the polyfunctional ethylenic monomer used in the present invention, urethane (meth) acrylates obtained by reacting a polyisocyanate compound with a hydroxyl group-containing (meth) acrylate or a polyol and a hydroxyl group-containing (meth) acrylate; epoxy acrylates such as addition reaction products of a polyhydric epoxy compound with hydroxy (meth) acrylate or (meth) acrylic acid; acrylamides such as ethylene bisacrylamide; allyl esters such as diallyl phthalate; vinyl group-containing compounds such as divinyl phthalate and the like are useful.

Examples of the urethane (meth) acrylates include: DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Kagaku Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Ningmura Kagaku K.K.), UA-306H, UA-510H, UF-8001G (manufactured by Kaitai Kagaku K.K.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Kagaku K.K.), and the like.

Among these, from the viewpoint of the verticality of the side surfaces of the partition walls and the ink repellency, as the photopolymerizable compound (C), urethane (meth) acrylates are preferably used as esters of an aliphatic polyhydric compound and an unsaturated carboxylic acid, and more preferably dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, 2-tri (meth) acryloyloxymethylethyl phthalate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, a dibasic anhydride adduct of dipentaerythritol penta (meth) acrylate, a dibasic anhydride adduct of pentaerythritol tri (meth) acrylate, and the like are used.

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 is preferably 100 or more, more preferably 150 or more, further preferably 200 or more, further preferably 300 or more, particularly preferably 400 or more, most preferably 500 or more, preferably 1000 or less, and more preferably 700 or less, from the viewpoint of ink repellency and perpendicularity of the side surfaces of the partition walls. For example, the molecular weight of the photopolymerizable compound (C) is preferably 100 to 1000, more preferably 150 to 1000, further preferably 200 to 1000, further preferably 300 to 700, further preferably 400 to 700, and particularly preferably 500 to 700.

The number of carbon atoms of the photopolymerizable compound (C) is not particularly limited, but is preferably 7 or more, more preferably 10 or more, further preferably 15 or more, further preferably 20 or more, particularly preferably 25 or more, preferably 50 or less, more preferably 40 or less, further preferably 35 or less, and particularly preferably 30 or less, from the viewpoint of ink repellency and perpendicularity of the side surfaces of the partition walls. For example, the number of carbon atoms of the photopolymerizable compound (C) is preferably 7 to 50, more preferably 10 to 40, still more preferably 15 to 35, still more preferably 20 to 30, and particularly preferably 25 to 30.

In addition, from the viewpoint of ink repellency and perpendicularity of the side surfaces of the partition walls, ester (meth) acrylates, epoxy (meth) acrylates, and urethane (meth) acrylates are preferable, and among them, from the viewpoint of ink repellency and perpendicularity of the side surfaces of the partition walls, trifunctional or higher ester (meth) acrylates such as pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, and adducts of anhydrides of trifunctional or higher ester (meth) acrylates such as 2,2, 2-tris (meth) acryloyloxymethylethyl phthalate, and dibasic anhydride adducts of dipentaerythritol penta (meth) acrylate are more preferable.

The content of the photopolymerizable compound (C) in the photosensitive colored resin composition of the invention is not particularly limited, but is usually 1 mass% or more, preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, and usually 80 mass% or less, preferably 60 mass% or less, more preferably 40 mass% or less, further preferably 30 mass% or less in the total solid content. When the lower limit value is not less than the lower limit value, the verticality of the side surfaces of the barrier ribs during exposure tends to be good, and when the upper limit value is not more than the upper limit value, the developability tends to be good. For example, the content of the photopolymerizable compound (C) in the entire solid content of the photosensitive colored resin composition is preferably 1 to 80% by mass, more preferably 5 to 60% by mass, still more preferably 10 to 40% by mass, and particularly preferably 15 to 30% by mass.

The content of the photopolymerizable compound (C) is not particularly limited, and is usually 1 part by mass or more, preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 15 parts by mass or more, and particularly preferably 20 parts by mass or more, and is usually 150 parts by mass or less, preferably 100 parts by mass or less, more preferably 70 parts by mass or less, further preferably 50 parts by mass or less, and particularly preferably 40 parts by mass or less, relative to 100 parts by mass of the alkali-soluble resin (B). When the amount is equal to or more than the lower limit, the ink repellency tends to be good and the perpendicularity of the side surfaces of the partition walls tends to be good, and when the amount 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, still more preferably 10 to 70 parts by mass, yet more preferably 15 to 50 parts by mass, and particularly preferably 20 to 40 parts by mass.

[1-1-4] (D) colorant

The photosensitive colored resin composition of the present invention contains (D) a colorant. By containing the colorant (D), appropriate light absorption can be obtained, and particularly, appropriate light blocking properties can be obtained when the composition is used for applications in which a light blocking member such as a colored partition wall is formed.

The type of the colorant (D) used in the present invention is not particularly limited, and a pigment or a dye may be used. Among these, pigments are preferably used from the viewpoint of durability.

(D) The pigment contained in the colorant may be one kind alone or two or more kinds. In particular, two or more kinds are preferable from the viewpoint of uniformly shielding light in the visible region.

The type of pigment that can be used as the colorant (D) is not particularly limited, and examples thereof include organic pigments and inorganic pigments. Among these, organic pigments are preferably used from the viewpoint of controlling the transmission wavelength of the photosensitive colored resin composition to efficiently perform curing.

Examples of the organic pigment include an organic coloring pigment and an organic black pigment. The organic coloring pigment is an organic pigment that exhibits a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a violet pigment, a green pigment, and a yellow pigment.

Among the organic pigments, organic coloring pigments are preferably used from the viewpoint of light-shielding properties and ultraviolet absorptivity.

One kind of organic coloring pigment may be used alone, but two or more kinds may also be used in combination. In particular, when the pigment is used for light-shielding applications, it is more preferable to use organic color pigments having different colors in combination, and it is further preferable to use organic color pigments that exhibit a color close to black in combination.

The chemical structure of these organic pigments is not particularly limited, and examples thereof include: azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, bisindolinone

Azines, indanthrene, perylene, etc. Specific examples of pigments that can be used are shown below by the pigment numbers. The terms "c.i. pigment red 2" and the like listed below refer to the pigment index (c.i.).

As the red pigment, there can be mentioned: 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, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:2, 53:1, 53:2, 53:3, 57:1, 57:2, 58:4, 60, 63:1, 63:2, 64:1, 68, 69, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101:1, 104, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 169, 151, 166, 168, 149, 170, 172, 176, 187, 188, 207, 188, 194, 185, 194, 187, 185, 194, 187, 194, 185, 194, 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 them, from the viewpoint of light-shielding properties and dispersibility, c.i. pigment red 48:1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254 are preferable, and c.i. pigment red 177, 209, 224, 254 are more preferable. In addition, c.i. pigment red 177, 254, 272 is preferably used from the viewpoint of dispersibility and light-shielding properties, and when the photosensitive colored resin composition is cured by ultraviolet light, it is preferable to use a red pigment having a low ultraviolet absorption rate, and from the viewpoint of the above, c.i. pigment red 254, 272 is more preferably used.

As orange (orange) pigments, mention may be made of: 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 them, c.i. pigment orange 13, 43, 64, 72 is preferably used from the viewpoint of dispersibility and light-shielding property, and when the photosensitive colored resin composition is cured by ultraviolet light, it is preferable to use a pigment having a low ultraviolet absorption rate as the orange pigment, and from the viewpoint of the above, c.i. pigment orange 64, 72 is more preferably used.

As the blue pigment, there can be mentioned: pigment blue 1, 1:2, 9, 14, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56:1, 60, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among them, from the viewpoint of light-shielding properties, c.i. pigment blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, and 60 are preferable, and c.i. pigment blue 15:6 is more preferable.

From the viewpoint of dispersibility and light-shielding properties, c.i. pigment blue 15:6, 16, and 60 is preferably used, and when the photosensitive colored resin composition is cured by ultraviolet light, it is preferable to use a blue pigment having a low ultraviolet absorption rate, and from the viewpoint of the above, c.i. pigment blue 60 is more preferably used.

As the violet pigment, there can be mentioned: c.i. pigment violet 1, 1:1, 2:2, 3:1, 3:3, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50. Among them, from the viewpoint of light-shielding properties, c.i. pigment violet 19 and 23 are preferable, and c.i. pigment violet 23 is more preferable.

From the viewpoint of dispersibility and light-shielding properties, c.i. pigment violet 23 and 29 are preferably used, and when the photosensitive colored resin composition is cured by ultraviolet light, a violet pigment having a low ultraviolet absorption rate is preferably used, and from the viewpoint of the above, c.i. pigment violet 29 is more preferably used.

Examples of the organic coloring pigment that can be used in addition to the red pigment, the orange pigment, the blue pigment, and the violet pigment include a green pigment and a yellow pigment.

As the green pigment, there can be mentioned: 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 them, c.i. pigment green 7 and 36 are preferably used.

As the yellow pigment, there can be mentioned: pigment yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35:1, 36:1, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 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, 127:1, 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, 188, 193, 198, 195, 185, 188, 193, 194, 198, 197, 200, 204, 197, 200, 194, 204, 199, 204, 197, 200, 204, 199, 204, 197, 204, 200, 199, 204, 200, 207. 208. Among them, c.i. pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185 are preferable, and c.i. pigment yellow 83, 138, 139, 150, 180 are more preferable.

Among these, at least one selected from the group consisting of a red pigment, an orange pigment, a blue pigment and a violet pigment is preferably used from the viewpoint of light-shielding properties and shape control.

Among these, at least one or more of the following pigments are preferably contained from the viewpoint of light-shielding properties and shape control.

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

A violet pigment: c.i. pigment violet 23, 29

In addition, the combination of the organic color pigments when two or more organic color pigments are used in combination is not particularly limited, but from the viewpoint of light-shielding properties, it is preferable to contain at least one selected from a red pigment and an orange pigment, and at least one selected from a blue pigment and a violet pigment.

The combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, for example, the following are listed: combinations of red pigments with blue pigments, combinations of blue pigments with orange pigments with violet pigments, and the like.

Further, in addition to these organic coloring pigments, a black pigment may also be used. In addition, a black pigment may be further used in addition to the organic coloring pigment.

The black pigment may be an inorganic black pigment or an organic black pigment, but preferably contains either or both of carbon black and an organic black pigment from the viewpoint of light-shielding properties.

Among the black pigments, from the viewpoint of suppressing absorption of ultraviolet rays and thereby facilitating shape control, it is preferable to use an organic black pigment, and particularly from the viewpoint of light-shielding properties, it is preferable to use an organic black pigment (hereinafter, also referred to as "organic black pigment represented by the general formula (1)) containing at least one selected from the group consisting of a compound represented by the following general formula (1) (hereinafter, also referred to as" compound (1) "), a geometric isomer of the compound (1), a salt of the compound (1), and a salt of the geometric isomer of the compound (1).

[ chemical formula 49]

In the formula (1), R¹¹And R¹⁶Each independently represents a hydrogen atom, CH₃、CF₃Fluorine atom or chlorine atom;

Is selected from R¹²And R¹³、R¹³And R¹⁴、R¹⁴And R¹⁵、R¹⁷And R¹⁸、R¹⁸And R¹⁹And R¹⁹And R²⁰Optionally bonded directly to each other, or through an oxygen atom, a sulfur atom, NH or NR²¹Bridging to bond to each other;

R²¹and R²²Each independently represents 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 an alkynyl group having 2 to 12 carbon atoms.

The compound (1) and the geometric isomer of the compound (1) have the following core structure (in which a substituent in the structural formula is omitted), and the trans-trans isomer may be the most stable.

[ chemical formula 50]

When the compound (1) is anionic, it is preferably a salt obtained by compensating the charge of any known suitable cation, for example, a metal, organic, inorganic or metal organic cation, specifically a tertiary amine such as an alkali metal, alkaline earth metal, transition metal, primary amine, secondary amine or trialkylamine, or a quaternary ammonium or organometallic complex compound such as tetraalkylammonium. When the geometric isomer of the compound (1) is anionic, the same salt is preferable.

Among the substituents of the general formula (1) and their definitions, the following substituents are preferred from the viewpoint of having a tendency to increase the shielding rate. This is because the following substituents are not absorbed and do not affect the hue of the pigment.

R¹²、R¹⁴、R¹⁵、R¹⁷、R¹⁹And R²⁰Each independently represents preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.

R¹³And R¹⁸Each independently preferably represents a hydrogen atom or NO₂、OCH₃、OC₂H₅Bromine atom, chlorine atom, CH₃、C₂H₅、N(CH₃)₂、N(CH₃)(C₂H₅)、N(C₂H₅)₂Alpha-naphthyl, beta-naphthyl, SO₃H or SO ₃ ^-More preferably a hydrogen atom or SO₃H is particularly preferably a hydrogen atom.

R¹¹And R¹⁶Each independently preferably represents a hydrogen atom or CH₃Or CF₃Further, a hydrogen atom is preferable.

Preferably selected from R¹¹And R¹⁶、R¹²And R¹⁷、R¹³And R¹⁸、R¹⁴And R¹⁹And R¹⁵And R²⁰Is the same, more preferably R¹¹And R¹⁶Same, R¹²And R¹⁷Same, R¹³And R¹⁸Same, R¹⁴And R¹⁹Are identical and R¹⁵And R²⁰The same is true.

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

Cycloalkyl having 3 to 12 carbon atoms is, for example, cyclopropyl, cyclopropylmethyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, trimethylcyclohexyl, thujyl, norbornyl, norcarane, carane-yl, methyl-ethyl, methyl-propyl, methyl-,

Alkyl, norpinanyl, pinanyl, adamantan-1-yl, or adamantan-2-yl.

Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl, allyl, 2-propen-2-yl, 2-buten-1-yl, 3-buten-1-yl, 1, 3-butadien-2-yl, 2-penten-1-yl, 3-penten-2-yl and 2-

The radical-1-buten-3-yl, 2-methyl-3-buten-2-yl, 3-methyl-2-buten-1-yl, 1, 4-pentadien-3-yl, hexenyl, octenyl, nonenyl, decenyl or dodecenyl.

Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl, 3-cyclohexen-1-yl, 2, 4-cyclohexadien-1-yl and 1-p-cyclonen

En-8-yl, 4(10) -limonene-10-yl, 2-norbornen-1-yl, 2, 5-norbornadien-1-yl, 7-dimethyl-2, 4-norcareen-diene-3-ylOr a camphyl group.

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

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

[ chemical formula 51]

Specific examples of such an organic Black pigment include those sold under the trade name Irgaphor (registered trademark) Black S0100 CF (manufactured by BASF corporation).

The organic black pigment is preferably dispersed in a dispersant or a solvent by the method described later. Further, if the sulfonic acid derivative of the compound (1), particularly the sulfonic acid derivative of the compound (2), is present during dispersion, the dispersibility and the storage stability may be improved, and therefore, it is preferable that the organic black pigment contains these sulfonic acid derivatives.

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

On the other hand, as the inorganic black pigment, there can be mentioned: carbon black, acetylene black, lamp black, bone black, graphite, iron black, Xeronine black, titanium black, and the like. Among these, carbon black is preferably used from the viewpoint of light-shielding properties and image characteristics. Examples of the carbon black include the following.

Mitsubishi chemical corporation: MA7, MA8, MA11, MA77, 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, # 30550, #3250, #3400, #3600, #3750, #3950, #4000, #4010, # 7B, OIL9B, OIL11B, OIL30B, OIL31B, and # 263033

Manufactured by Degussa: printex (registered trademark, the same below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, Printex G, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Colorack FW1, Coloracolorack FW2, Colorack 2V, Colorack 18, Colorack 18, Colorack 160, Colorack 200, Colorack 170, Colorack 200 RBorack FW

Manufactured by Cabot corporation: monarch (registered trademark, same below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark, same below) 99, REGAL99R, REGAL415R, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark, same below) 72 XC72R, ELFTEX (registered trademark) -8

Manufactured by Birror corporation: RAVEN (registered trademark, the same below) 11, RAVEN14, RAVEN15, RAVEN16, RAVEN22RAVEN30, RAVEN35, RAVEN40, RAVEN410, RAVEN420, RAVEN450, RAVEN500, RAVEN780, RAVEN850, RAVEN890H, RAVEN1000, RAVEN1020, RAVEN1040, RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black coated with a resin may be used as the carbon black. When carbon black coated with a resin is used, the adhesion to a glass substrate and the volume resistance value are improved. As the carbon black coated with a resin, for example, carbon black described in japanese patent application laid-open No. h 09-71733 can be preferably used. Resin-coated carbon black is preferably used in view of volume resistance and dielectric constant.

The carbon black to be subjected to the coating treatment with a resin preferably has a total content of Na and Ca of 100ppm or less. Carbon black generally contains ash composed of Na, Ca, K, Mg, Al, Fe, and the like, which is mixed from raw oil, fuel oil (or gas), reaction termination water, granulation water, furnace material of a reactor, and the like at the time of production. Among them, Na and Ca are usually contained in an amount of several hundred ppm or more, and by reducing these amounts, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electrical short-circuiting tends to be prevented.

As a method for reducing the content of these ashes containing Na and Ca, a method of strictly selecting as small as possible the content of Na and Ca as a raw oil, a fuel oil (or gas), and reaction terminating water in the production of carbon black, and a method of reducing as small as possible the amount of alkali substances to be added for structure adjustment can be used. As another method, there is a method of removing Na and Ca by dissolving the carbon black produced from a furnace by washing with water, hydrochloric acid, or the like.

Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide water, and then a solvent that is hardly soluble in water is added, the carbon black is transferred to the solvent side, and is completely separated from water, and almost all of Na and Ca present in the carbon black are dissolved in water or acid and removed. In order to reduce the total amount of Na and Ca to 100ppm or less, it may be possible to achieve only a carbon black production process in which the raw materials are strictly selected alone or a method in which the raw materials are dissolved in water or acid alone, but it is easier to reduce the total amount of Na and Ca to 100ppm or less by using both methods in combination.

The resin-coated carbon black is preferably so-called acidic carbon black having a pH of 6 or less. It is preferable because the dispersed particle size in water is small and the coating under fine cells can be performed. More preferably, carbon black having an average particle diameter of 40nm or less and a dibutyl phthalate (DBP) absorption of 140ml/100g or less. When the amount is within the above range, a coating film having good light-shielding properties tends to be obtained. The average particle diameter represents a number average particle diameter, and represents an equivalent circle diameter obtained by the following particle image analysis: the particle image analysis is performed by taking pictures of several tens of thousands of times in several fields of view through electron microscope observation, and measuring about 2000 to 3000 particles in the pictures by an image processing device.

The method for producing the resin-coated carbon black is not particularly limited, and for example, after the blending amounts of the carbon black and the resin are appropriately adjusted, the following method can be employed: 1. mixing a resin with a solvent such as cyclohexanone, toluene, xylene, etc., heating and dissolving the mixture to prepare a resin solution, mixing carbon black and water to prepare a suspension, mixing and stirring the resin solution and the suspension to separate the carbon black from the water, removing the water, heating and kneading the mixture to obtain a composition, forming the obtained composition into a sheet, pulverizing the sheet, and drying the sheet; 2. mixing and stirring the resin solution and the suspension prepared in the same manner as described above, granulating the carbon black and the resin, separating the obtained granules, heating, and removing the residual solvent and water; 3. dissolving carboxylic acid such as maleic acid and fumaric acid in the solvent exemplified above, adding carbon black, mixing, drying, removing the solvent to obtain carbon black to which carboxylic acid is attached (added), and then adding resin thereto and dry-mixing; 4. stirring the monomer component containing reactive group and water which form the resin to be coated at high speed to prepare suspension, cooling after polymerization, obtaining the resin containing reactive group from the polymer suspension, adding carbon black into the suspension, mixing, reacting the carbon black with the reactive group (grafting the carbon black), cooling and crushing; and so on.

The type of resin to be coated is not particularly limited, and is usually a synthetic resin, and a resin having a benzene ring in its structure is more preferable from the viewpoint of dispersibility and dispersion stability because it has a stronger action with an amphoteric surfactant.

Specific examples of the synthetic resin include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyphosate resin, epoxy resin, and alkylbenzene resin, and thermoplastic resins such as polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene ether, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyethersulfone, polyphenylsulfone, polyarylate, and polyether ether ketone. The amount of the coating resin is preferably 1 to 30% by mass based on the total amount of the carbon black and the resin. When the amount of the coating resin is not less than the lower limit, the carbon black can be sufficiently coated. On the other hand, when the amount is equal to or less than the upper limit, the adhesion between the resins tends to be prevented and the dispersibility tends to be good.

The carbon black coated with the resin in this manner can be used as a colorant for coloring partition walls according to a conventional method. When such carbon black is used, colored partition walls having a high light-shielding rate and a low surface reflectance tend to be formed at low cost. It is also presumed that coating the surface of carbon black with a resin has an effect of encapsulating ash containing Na and Ca in carbon black.

These pigments are preferably used in a dispersed state with an average particle diameter of usually 1 μm or less, preferably 0.5 μm or less, and more preferably 0.25 μm or less. Wherein the average particle diameter is based on the number of pigment particles.

The average particle diameter of the pigment is a value determined from the particle diameter of the pigment measured by Dynamic Light Scattering (DLS). The particle size measurement is carried out at 25 ℃ on a sufficiently diluted photosensitive colored resin composition (usually diluted to a pigment concentration of about 0.005 to 0.2 mass%, wherein the concentration is the concentration recommended by the measurement equipment).

In addition, a dye may be used in addition to the organic coloring pigment and the black pigment. As dyes that can be used as colorants, there can be mentioned: azo dyes, anthrone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes, and the like.

As azo dyes, there may be mentioned, for example: c.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. active yellow 2, c.i. active red 17, c.i. active red 120, c.i. active black 5, c.i. disperse orange 5, c.i. disperse red 58, c.i. disperse blue 165, c.i. basic blue 41, c.i. basic red 18, c.i. medium red 7, c.i. medium yellow 5, c.i. medium black 7, etc.

Examples of the anthrone dyes include: c.i. vat blue 4, c.i. acid blue 40, c.i. acid green 25, c.i. active blue 19, c.i. active blue 49, c.i. disperse red 60, c.i. disperse blue 56, c.i. disperse blue 60, etc.

Further, as phthalocyanine-based dyes, for example: c.i. vat blue 5, etc.; examples of the quinoneimine-based dye include: c.i. basic blue 3, c.i. basic blue 9, and the like; examples of quinoline dyes include: c.i. solvent yellow 33, c.i. acid yellow 3, c.i. disperse yellow 64, and the like; examples of the nitro dye include: c.i. acid yellow 1, c.i. acid orange 3, c.i. disperse yellow 42, and the like.

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

[1-1-5] (E) component: liquid repellent

The photosensitive colored resin composition of the present invention contains a fluorine atom-containing resin having a crosslinking group as (E) the liquid repellent. It is considered that since the surface of the partition wall obtained by containing the fluorine atom-containing resin having a crosslinking group can be imparted with ink repellency, color mixing of the obtained partition wall together with the light emitting portion (pixel) of the organic layer can be prevented.

The crosslinking group may be an epoxy group or an ethylenically unsaturated group, and is preferably an ethylenically unsaturated group from the viewpoint of suppressing the outflow of the liquid repellent component of the developer.

It is considered that the use of a liquid repellent having a crosslinking group accelerates the crosslinking reaction occurring on the surface of the coating film formed when exposed to light, and the liquid repellent hardly flows out during the development treatment, and as a result, the partition walls obtained can exhibit high ink repellency.

Further, the fluorine atom-containing resin tends to orient on the surface of the partition walls, and to prevent ink leakage and color mixing. More specifically, there is a tendency that: the group having fluorine atoms repels ink, thereby having a function of preventing ink bleeding and color mixing caused by ink entering adjacent regions across partition walls.

The fluorine-containing resin having a crosslinking group preferably has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain. By having either or both of the perfluoroalkyl group and the perfluoroalkylene ether chain, the fluorine atom-containing resin tends to be more easily aligned on the surfaces of the partition walls, to exhibit higher ink repellency, and to further prevent bleeding and color mixing of the ink.

Examples of the perfluoroalkyl group include: perfluorobutyl, perfluorohexyl, perfluorooctyl, and the like. Examples of perfluoroalkylene ether chains include: -CF₂-O-、-(CF₂)₂-O-、-(CF₂)₃-O-、-CF₂-C(CF₃)O-、-C(CF₃)-CF₂-O-and2-valent groups having their repeating units.

Specific examples of the fluorine atom-containing resin having a crosslinking group include: an acrylic copolymer resin having an epoxy group and a perfluoroalkyl group, an acrylic copolymer resin having an epoxy group and a perfluoroalkylene ether chain, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkyl group, an acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, an epoxy (meth) acrylate resin having an epoxy group and a perfluoroalkyl group, an epoxy (meth) acrylate resin having an epoxy group and a perfluoroalkylene ether chain, an epoxy (meth) acrylate resin having an ethylenically unsaturated group and a perfluoroalkyl group, an epoxy (meth) acrylate resin having an ethylenically unsaturated group and a perfluoroalkylene ether chain, and the like. Among them, acrylic copolymer resins having an ethylenically unsaturated group and a perfluoroalkyl group and acrylic copolymer resins having an ethylenically unsaturated group and a perfluoroalkylene ether chain are preferable from the viewpoint of ink repellency, and acrylic copolymer resins having an ethylenically unsaturated group and a perfluoroalkylene ether chain are more preferable.

As commercially available products of these fluorine atom-containing resins having a crosslinking group, there may be used "Megafac (registered trademark, the same applies hereinafter)" F116 "," Megafac F120 "," Megafac F142D "," Megafac F144D "," Megafac F150 "," Megafac F160 "," Megafac F171 "," Megafac F172 "," Megafac F184 "," Megafac F177 "," Megafac F178A "," Megafac F178K "," Megafac F179 "," Megafac F183 "," Megafac F184 "," Megafac F191 "," Megafac F812 "," Megafac F815 "," Megafac F824 "," Megafac F833 "," Megafac RS101 "," Megafac RS102 "," Megafac RS105 "," Megafac RS201 "," Megafac RS301 "," Megafac RS 301-301 "or" Megafac RS401 "Megafac RS" by DIC, Hereinafter, the same shall apply to the examples) of commercially available fluorine-containing organic compounds under the trade names MCF300 "," DEFENSA MCF310 "," DEFENSA MCF312 "," DEFENSA MCF323 ", Fluorad FC 430", Fluorad FC431 "," FC-4430 "," FC4432 ", ASAHI GUARD (registered trademark) AG 710", manufactured by 3M Japan, Surflon (registered trademark, the same shall apply to the same shall, and Surflon SC-101 "," Surflon SC-102 "," Surflon SC-103 "," Surflon SC-104 "," Surflon SC-105 "," Surflon SC-106 ", and the like.

Of these, as the acrylic copolymer resin having an ethylenically unsaturated group and a perfluoroalkylene group, Megafac RS-72-K, Megafac RS-78 and the like can be preferably used.

The content of fluorine atoms 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, further preferably 20% by mass or more, and further preferably 25% by mass or more in the fluorine atom-containing resin having a crosslinking group. Further, it is preferably 50% by mass or less, more preferably 35% by mass or less. When the lower limit value is not less than the above-described lower limit value, the outflow to the pixel region tends to be suppressed, and when the upper limit value is not more than the above-described upper limit value, the contact angle tends to be high. For example, the content ratio of fluorine atoms in the fluorine atom-containing resin having a crosslinking group is preferably 5 to 50% by mass, more preferably 10 to 35% by mass, further preferably 20 to 35% by mass, and particularly preferably 25 to 35% by mass of the fluorine atom-containing resin having a crosslinking group.

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 product. The high molecular weight material is preferable because it can suppress fluidity due to post baking and can suppress outflow from the partition walls, and from this viewpoint, 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 100000 or less, more preferably 10000 or less. For example, the molecular weight of the fluorine atom-containing resin having a crosslinking group is preferably 100 to 100000, more preferably 500 to 10000.

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 0.5% by mass or more, and is usually 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less in the total solid content. When the lower limit value is not less than the lower limit value, a high ink repellency tends to be exhibited, and when the upper limit value is not more than the upper limit value, a flow-out to the pixel region tends to 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 still more preferably 0.5 to 2% by mass, based on the total solid content of the photosensitive colored resin composition.

The content 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, and is usually 5% by mass or less, preferably 3% by mass or less, and more preferably 2% by mass or less in the total solid content. When the lower limit value is not less than the lower limit value, a high ink repellency tends to be exhibited, and when the upper limit value is not more than the upper limit value, a flow-out to the pixel region tends to 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 still more preferably 0.5 to 2% by mass, based on the total solid content of the photosensitive colored resin composition.

On the other hand, in the photosensitive colored resin composition of the present invention, (E) the liquid repellent may be used together with a surfactant. The surfactant can be used for the purpose of improving coatability when forming a coating solution of the photosensitive colored resin composition, developability of a coating film, and the like, and among them, a silicone-based surfactant and a fluorine-based surfactant having no crosslinking group are preferable.

In particular, the silicone surfactant is preferable, and the polyether-modified silicone surfactant is more preferable, because it has an action of removing the residue of the photosensitive colored resin composition from unexposed portions during development and a function of exhibiting wettability.

As the fluorine-based surfactant having no crosslinking group, a compound having a fluoroalkyl group or a fluoroalkylene group at least at any one of the terminal, the main chain, and the side chain is preferable.

Examples of commercially available products of these include: BM-1000 and BM-1100 manufactured by BM Chemie, Megafac F142D, Megafac F172, Megafac F173, Megafac F183, Megafac F470, Megafac F475, Megafac F554, Megafac F559, FC430 manufactured by 3M Japan, DFX-18 manufactured by Neos, and the like.

Examples of the silicone surfactant include: commercially available products such as "DC 3 PA", "SH 7 PA", "DC 11 PA", "SH 21 PA", "SH 28 PA", "SH 29 PA", "8032 Additive", "SH 8400", BYK (registered trademark, the same as below) "BYK 330", manufactured by Dow Corning Toray corporation.

The surfactant may include surfactants other than the fluorine-based surfactant and the silicone-based surfactant, and the other surfactants include nonionic, anionic, cationic, amphoteric surfactants, and the like.

Examples of the nonionic surfactant 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, polyoxyethylene sorbitol fatty acid esters, and the like. Examples of commercially available products of these include: polyoxyethylene surfactants such as "Emargen (registered trademark, the same applies hereinafter)" 104P "and" Emargen A60 "manufactured by Kao corporation.

Examples of the anionic surfactant include: alkylsulfonic acid salts, alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, polyoxyethylene alkylethersulfonic acid salts, alkylsulfuric acid ester salts, higher alcohol sulfuric acid ester salts, aliphatic alcohol sulfuric acid ester salts, polyoxyethylene alkylethersulfuric acid salts, polyoxyethylene alkylphenylether sulfuric acid salts, alkylphosphoric acid ester salts, polyoxyethylene alkyletherphosphoric acid salts, polyoxyethylene alkylphenylether phosphoric acid ester salts, special polymer surfactants, and the like. Among them, a specific polymer surfactant is preferable, and a specific polycarboxylic acid type polymer surfactant is more preferable. As such an anionic surfactant, commercially available products can be used, and examples thereof include "Emal (registered trademark, the same applies hereinafter)" manufactured by Kao corporation, alkyl sulfate salts, "Pelex (registered trademark) NB-L" manufactured by Kao corporation, alkyl naphthalene sulfonate salts, and special polymer surfactants, "Homogenol (registered trademark, the same applies hereinafter)" L-18 "and" Homogenol L-100 "manufactured by Kao corporation.

Further, the cationic surfactant may be exemplified by quaternary ammonium salts, imidazoline derivatives, alkylamine salts, and the like, and the amphoteric surfactant may be exemplified by betaine type compounds, imidazolium salts, imidazolines, amino acids, and the like. Among these surfactants, quaternary ammonium salts are preferable, and stearyl trimethylammonium salt is more preferable. Examples of commercially available products include "acetic amine (registered trademark) 24" manufactured by kao corporation, and "Quartamin (registered trademark) 24P" and "Quartamin 86W" manufactured by Kao corporation, as alkylamine salts, and quaternary ammonium salts.

The surfactant may be used in combination of two or more types, and examples thereof include: silicone surfactant/fluorine surfactant, silicone surfactant/special polymer surfactant, and a combination of fluorine surfactant/special polymer surfactant. Among these, a combination of a silicone surfactant and a fluorine surfactant is preferable. In the combination of the silicone surfactant and the fluorine surfactant, for example: "DFX-18" manufactured by Neos, "BYK-300" or "BYK-330"/S-393 manufactured by AGC Seimi Chemical, and "KP 340"/F-554 manufactured by DIC or "F-559" manufactured by shin-Etsu Silicone corporation, "SH 7 PA"/DS-401 manufactured by Dajin Corp, and "L-77"/FC 4430 manufactured by NUC/3M Japan, and the like.

[1-1-6] (F) dispersant

In the photosensitive colored resin composition of the present invention, it is preferable to include (F) a dispersant in order to finely disperse the (D) colorant and stabilize the dispersed state.

The dispersant (F) is preferably a polymer dispersant having a functional group, and further preferably a carboxyl group in view of dispersion stability; a phosphate group; a sulfonic acid group; or a base thereof; primary, secondary or tertiary amino groups; quaternary ammonium salt groups; a polymer dispersant derived from a functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine. Among these, in particular, the pigment having a primary amino group, a secondary amino group or a tertiary amino group is particularly preferable from the viewpoint that the pigment can be dispersed with a small amount of a dispersant when dispersed; quaternary ammonium salt groups; a polymer dispersant derived from a basic functional group such as a nitrogen-containing heterocyclic group such as pyridine, pyrimidine or pyrazine.

Examples of the polymeric dispersant include: urethane dispersants, acrylic dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants comprising a macromonomer and an amino group-containing monomer, polyoxyethylene alkyl ether dispersants, polyoxyethylene diester dispersants, polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Specific examples of such a dispersant include EFKA (registered trademark, manufactured by BASF corporation), DISPERBYK (registered trademark, manufactured by BYK-Chemie corporation), Disparlon (registered trademark, manufactured by Nako chemical industries, Ltd.), SOLSPERSE (registered trademark, manufactured by Lubrizol corporation), KP (manufactured by shin-Etsu chemical industries, Ltd.), Polyflow (manufactured by Kyoho chemical Co., Ltd.), Ajisper (registered trademark, manufactured by K.K.).

These polymeric 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 1000 or more, and usually 100000 or less, preferably 50000 or less. For example, the weight average molecular weight (Mw) of the polymeric dispersant is preferably 700 to 100000, more preferably 1000 to 50000.

Among these, from the viewpoint of pigment dispersibility, the dispersant (F) preferably contains either or both of a urethane-based polymer dispersant having a functional group and an acrylic polymer dispersant, and particularly preferably contains an acrylic polymer dispersant.

In addition, 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.

Examples of the urethane and acrylic polymer dispersants include DISPERBYK160 to 167, 182 series (both of urethane), DISPERBYK2000, 2001, LPN21116 and the like (both of acrylic) (all of which are manufactured by BYK-Chemie).

Specifically, the preferable chemical structure of the urethane polymer dispersant is exemplified by a dispersion resin having a weight average molecular weight of 1000 to 200000 obtained by reacting a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 and having 1 or 2 hydroxyl groups in the molecule, and a compound having an active hydrogen and a tertiary amino group in the same molecule. The dispersion resin may be treated with a quaternizing agent such as benzyl chloride to convert all or a part of the tertiary amino groups into quaternary ammonium salt groups.

Examples of the polyisocyanate compounds include: aromatic diisocyanates such as p-phenylene diisocyanate, toluene-2, 4-diisocyanate, toluene-2, 6-diisocyanate, 4,4 '-diphenylmethane diisocyanate, naphthalene-1, 5-diisocyanate, tolidine diisocyanate, etc., aliphatic diisocyanates such as hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4, 4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, etc., alicyclic diisocyanates such as isophorone diisocyanate, 4, 4' -methylenebis (cyclohexyl isocyanate), omega '-diisocyanate dimethylcyclohexane, etc., xylylene diisocyanate, aliphatic diisocyanates having an aromatic ring such as alpha, alpha' -tetramethylxylylene diisocyanate, etc., and mixtures thereof, Triisocyanates such as lysine ester triisocyanate, undecane-1, 6, 11-triisocyanate, 1, 8-diisocyanate-4-isocyanatomethyloctane, hexamethylene-1, 3, 6-triisocyanate, bicycloheptane triisocyanate, triphenylmethane triisocyanate and triphenylthiophosphate triisocyanate, and trimers, hydrides and polyol adducts thereof. As the polyisocyanate, a trimer of an organic diisocyanate is preferable, and a trimer of toluene diisocyanate and a trimer of isophorone diisocyanate are most preferable.

These compounds may be used alone or in combination of two or more.

Examples of the method for producing an isocyanate trimer include the following methods: the polyisocyanate is partially trimerized with an isocyanate group using an appropriate trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylates, etc., and the trimerization is terminated by adding a catalyst poison, and then unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain the desired polyisocyanate containing a trimerized isocyanate group.

Examples of the compound having a number average molecular weight of 300 to 10,000 and having 1 or 2 hydroxyl groups in the same molecule include polyether diols, polyester diols, polycarbonate diols, polyolefin diols, and the like, and those obtained by alkoxylating one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms, and mixtures of two or more of these compounds.

The polyether diol includes polyether diol, polyether ester diol, and a mixture of 2 or more of these diols. Examples of the polyether glycol include those obtained by homopolymerizing or copolymerizing an alkylene oxide, such as polyethylene glycol, polypropylene glycol, polyethylene glycol propylene glycol, polyoxybutylene glycol, polyoxyhexylene glycol, polyoxyoctylene glycol, and a mixture of two or more thereof.

Examples of the polyether ester diol include those obtained by reacting a diol having an ether group or a mixture thereof with another diol with a dicarboxylic acid or an acid anhydride thereof, or by reacting an alkylene oxide with a polyester diol, such as poly (polyoxybutylene) adipate. The polyether glycol is most preferably polyethylene glycol, polypropylene glycol, polyoxybutylene glycol, or a compound obtained by oxidizing one terminal hydroxyl group of these compounds with an alkyl group having 1 to 25 carbon atoms.

As the polyester diol, there may be mentioned: dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or anhydrides thereof with 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, 4-trimethyl-1, aliphatic diols such as 3-pentanediol, 2-ethyl-1, 3-hexanediol, 2, 5-dimethyl-2, 5-hexanediol, 1, 8-octanediol, 2-methyl-1, 8-octanediol, and 1, 9-nonanediol, alicyclic diols such as bis (hydroxymethyl) cyclohexane, aromatic diols such as benzenedimethanol and bis (hydroxyethoxy) benzene, and N-alkyldialkanolamines such as N-methyldiethanolamine) by polycondensation, for example, polyethylene adipate, polybutylene adipate, 1, 6-hexanediol adipate, and ethylene propylene glycol adipate, or polylactone diols or polylactone monools obtained by using the above diols or monools having 1 to 25 carbon atoms as an initiator, for example, polycaprolactone diol, polycaprolactone monool, and the like, Polymethyl valerolactone and a mixture of 2 or more thereof. The polyester diol is most preferably polycaprolactone diol or polycaprolactone obtained using an alcohol having 1 to 25 carbon atoms as an initiator.

The polycarbonate diol includes poly (1, 6-hexanediol) carbonate and poly (3-methyl-1, 5-pentanediol) carbonate, and the polyolefin diol includes polybutadiene diol, hydrogenated polyisoprene diol, and the like.

These compounds may be used alone or in combination of two or more.

The number average molecular weight of the compound having 1 or 2 hydroxyl groups in the same molecule is usually 300 to 10000, preferably 500 to 6000, and more preferably 1000 to 4000.

A compound having an active hydrogen and a tertiary amino group in the same molecule will be described.

The active hydrogen, that is, the hydrogen atom directly bonded to the oxygen atom, nitrogen atom or sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group or a mercapto group, and among them, a hydrogen atom of an amino group, particularly a primary amino group, is preferable.

The tertiary amino group is not particularly limited, and examples thereof include an amino group having an alkyl group having 1 to 4 carbon atoms, a heterocyclic structure, more specifically, an imidazole ring or a triazole ring.

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

In addition, examples of the nitrogen-containing heterocycle in the case where the tertiary amino group has a nitrogen-containing heterocycle structure include: pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzotriazole ring

Nitrogen-containing 5-membered heterocycles such as an azole ring, a benzothiazole ring and a benzothiadiazole ring, and nitrogen-containing 6-membered heterocycles such as a pyridine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an acridine ring and an isoquinoline ring. Among these nitrogen-containing heterocycles, preferred is an imidazole ring or a triazole ring.

Specific examples of the 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 such 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, and 3-amino-1-benzyl-1H-2, 4-triazole. Among them, N-dimethyl-1, 3-propanediamine, N-diethyl-1, 3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1, 2, 4-triazole are preferable.

These compounds may be used alone or in combination of two or more.

The preferable blending ratio of the raw materials for producing the urethane polymer dispersant is as follows: the amount of the compound having a number average molecular weight of 300 to 10000, which has 1 or 2 hydroxyl groups in the same molecule, is 10 to 200 parts by mass, preferably 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the amount of the compound having active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass, based on 100 parts by mass of the polyisocyanate compound.

The urethane polymer dispersant is produced by a known method for producing a polyurethane resin. As the solvent in the production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone; esters such as ethyl acetate, butyl acetate, cellosolve acetate, and the like; hydrocarbons such as benzene, toluene, xylene, and hexane; partial alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol and tert-butyl alcohol, and chlorinated substances such as methylene chloride and chloroform; ethers such as tetrahydrofuran and diethyl ether; polar aprotic solvents such as dimethylformamide, N-methylpyrrolidone and dimethylsulfoxide. These may be used alone or in combination of 2 or more.

In the above production, a urethane reaction catalyst is generally used. Examples of the catalyst include tin-based catalysts such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate and tin octylate, iron-based catalysts such as iron acetylacetonate and iron chloride, and tertiary amines such as triethylamine and triethylenediamine. These may be used alone or in combination of 2 or more.

The amount of the compound having active hydrogen and a tertiary amino group in the same molecule is preferably controlled so that the amine value after the reaction is in the range of 1 to 100mgKOH/g, more preferably 5 to 95 mgKOH/g. The amine number is a value corresponding to an acid value in mg of KOH by neutralization titration of a basic amino group with an acid. When the amine value is less than the above range, the dispersibility tends to be lowered, and when the amine value exceeds the above range, the developability tends to be lowered.

In the case where an isocyanate group remains in the polymer dispersant in the above reaction, if the isocyanate group is further deactivated with an alcohol or an amino compound, the stability of the product with time is increased, which is preferable.

The weight average molecular weight (Mw) of the urethane polymer dispersant is usually in the range of 1000 to 200000, preferably 2000 to 100000, and more preferably 3000 to 50000. When the content is not less than the lower limit, dispersibility and dispersion stability tend to be improved, and when the content is not more than the upper limit, solubility tends to be improved and dispersibility tends to be improved.

As the acrylic polymer dispersant, a random copolymer, a graft copolymer or a block copolymer of a monomer having a functional group (the functional group mentioned here is the functional group mentioned above as the functional group contained in the polymer dispersant) and containing an unsaturated group and a monomer having no functional group and containing an unsaturated group is preferably used. These copolymers can be produced by a known method.

Examples of the monomer having a functional group and containing an unsaturated group include unsaturated monomers having a carboxyl group such as (meth) acrylic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexahydrophthalic acid, and acrylic acid dimer, and unsaturated monomers having a tertiary amino group or a quaternary ammonium group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and quaternary products thereof. These monomers may be used alone or in combination of two or more.

Examples of the monomer having no functional group and containing an unsaturated group 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, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and its derivatives, α -methylstyrene, N-cyclohexylmaleimide, N-phenylimidomaleimide, N-arylimidomaleimido, N-arylimido, N-arylthio, n-substituted maleimides such as N-benzylmaleimide, macromonomers such as acrylonitrile, vinyl acetate, poly (methyl (meth) acrylate) macromonomer, polystyrene macromonomer, poly (2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol macromonomer, polypropylene glycol macromonomer and polycaprolactone macromonomer, and the like. These monomers may be used alone or in combination of two or more.

The acrylic polymer dispersant is particularly preferably an a-B or B-a-B block copolymer composed of an a block having a functional group and a B block having no functional group, and in this case, the a block may contain a partial structure derived from the monomer not having a functional group but having an unsaturated group in addition to the partial structure derived from the monomer having a functional group and having an unsaturated group, and these structures may be contained in the a block in any form of random copolymerization or block copolymerization. The content of the partial structure containing no 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 includes a partial structure derived from the above-mentioned monomer having no functional group but having an unsaturated group, and 1B block may contain a partial structure derived from 2 or more kinds of monomers, and these structures may be contained in the B block in any form of random copolymerization or block copolymerization.

The A-B or B-A-B block copolymer can be produced, for example, by the living polymerization method shown below.

The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method and a free radical living polymerization method.

For the synthesis of the acrylic polymer dispersant, the methods described in Japanese patent application laid-open No. 9-62002, 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), Right hand Haoyi-Zhan, Polymer processing, 36,366(1987), Tomura-Zhan, Zebra-Guang-Zhan, Polymer literature, 46, 189(1989), M.Kuroki, T.Aida, J.Am.Chem.sic,109,4737(1987), Zhan-Zhan, Pingpio, organic Synthesis chemistry, 43,300, D.Y.1985, Solect.W.R.147r, Hercules et al, Machil-20, Machil-Hercules et al, published methods can be adopted.

The acrylic polymer dispersant usable in the present invention may be an a-B block copolymer or a B-a-B block copolymer, and the ratio of a block/B block constituting the copolymer is preferably 1/99 to 80/20, particularly preferably 5/95 to 60/40 (mass ratio), and when the ratio is within this range, the balance between dispersibility and storage stability tends to be ensured.

In addition, in 1g of the A-B block copolymer and the B-A-B block copolymer which can be used in the present invention, the amount of the quaternary ammonium salt group is preferably 0.1 to 10mmol in general, and when the amount is in this range, good dispersibility tends to be ensured.

In such a block copolymer, an amino group generated in the production process may be contained, and the amine value thereof is about 1 to 100mgKOH/g, and from the viewpoint of dispersibility, it is preferably 10mgKOH/g or more, more preferably 30mgKOH/g or more, further preferably 50mgKOH/g or more, and preferably 90mgKOH/g or less, more preferably 80mgKOH/g or less, further preferably 75mgKOH/g or less. For example, the amine value of the block copolymer is preferably 10 to 90mgKOH/g, more preferably 30 to 80mgKOH/g, and still more preferably 50 to 75 mgKOH/g.

Here, the amine value of the dispersant such as the block copolymer is represented by a KOH mass corresponding to the amount of base corresponding to 1g of the solid content excluding the solvent in the dispersant sample, and is measured by the following method.

0.5 to 1.5g of a dispersant sample was precisely weighed in a 100mL beaker, dissolved in 50mL of acetic acid, and subjected to a 0.1mol/L HClO solution using an automatic titrator equipped with a pH electrode₄The solution was subjected to neutralization titration with acetic acid solution, and the amine value was determined by the following equation, with the inflection point of the titration pH curve being set as the titration end point.

Amine value [ mgKOH/g ] (561 XV)/(W. times.S)

[ wherein, W: the weighed amounts of the dispersant samples [ g ], V: the titration amount [ mL ] at the end of titration, S: the solid content concentration [ mass% ] of the dispersant sample is shown. ]

The acid value of the block copolymer depends on the presence or absence of an acid group which is the base of the acid value and the type thereof, and is usually preferably a lower acid value, usually 10mgKOH/g or less, and the weight average molecular weight (Mw) is preferably in the range of 1000 to 100000. When the amount is within the above range, good dispersibility tends to be ensured.

The specific structure of the polymeric dispersant having a quaternary ammonium salt group as a functional group is not particularly limited, but from the viewpoint of dispersibility, it preferably has a repeating unit represented by the following formula (i) (hereinafter, may be referred to as "repeating unit (i)").

[ chemical formula 52]

In the above formula (i), R³¹～R³³Each independently is a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent or an aralkyl group optionally having a substituent;

R³¹～R ³³2 or more of them may be bonded to each other to form a ring structure;

R³⁴is a hydrogen atomOr a methyl group;

x is a linking group having a valence of 2;

Y^-are counter anions.

R of the above formula (i)³¹～R³³The number of carbon atoms of the alkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 1 or more, and preferably 10 or less, and more preferably 6 or less. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6. Specific examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and the like, and among these, methyl, ethyl, propyl, butyl, pentyl or hexyl is preferred, and methyl, ethyl, propyl or butyl is more preferred. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl.

R of the above formula (i)³¹～R³³The number of carbon atoms of the aryl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less. For example, the number of carbon atoms of the aryl group is preferably 6 to 16, more preferably 6 to 12. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthryl group and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable.

R of the above formula (i)³¹～R³³The number of carbon atoms of the aralkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 7 or more, and preferably 16 or less, and more preferably 12 or less. For example, the number of carbon atoms of the aralkyl group is preferably 7 to 16, more preferably 7 to 12. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group, and among these, a phenylmethyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group are preferable, and a phenylmethyl group or a phenylethyl group is more preferable.

Of these, R is preferable from the viewpoint of dispersibility ³¹～R³³Each independently is alkyl or aralkyl, specifically, R is preferred³¹And R³³Each independently being methyl or ethyl, and R³²Is phenylmethyl or phenylethyl, more preferably R³¹And R³³Is methyl and R³²Is a phenylmethyl group.

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

[ chemical formula 53]

In the above formula (ii), R³⁵And R³⁶Each independently is a hydrogen atom, an alkyl group optionally having a substituent, an aryl group optionally having a substituent or an aralkyl group optionally having a substituent;

R³⁵and R³⁶May be bonded to each other to form a ring structure;

R³⁷is a hydrogen atom or a methyl group;

z is a linking group having a valence of 2.

R as the above formula (ii)³⁵And R³⁶Wherein the alkyl group optionally having a substituent(s) may be preferably used as R in the above formula (i)³¹～R³³But are exemplary groups.

R as the above formula (ii)³⁵And R³⁶Wherein the aryl group optionally having a substituent(s) may be preferably used as R in the above formula (i)³¹～R³³But are exemplary groups.

R as the above formula (ii)³⁵And R³⁶As the aralkyl group optionally having a substituent(s) in (1), R of the above-mentioned formula (i) can be preferably employed ³¹～R³³But are exemplary groups.

Of these, R³⁵And R³⁶Preferably each independently an optionally substituted alkyl group, more preferably a methyl or ethyl group.

R as the above formula (i)³¹～R³³And R of the above formula (ii)³⁵And R³⁶Examples of the substituent optionally contained in the alkyl group, aralkyl group or aryl group in (1) include a halogen atom, an alkoxy group, a benzoyl group and a hydroxyl group.

In the above formulae (i) and (ii), examples of the 2-valent linking groups X and Z include: alkylene group having 1 to 10 carbon atoms, arylene group having 6 to 12 carbon atoms, -CONH-R⁴³-radical, -COOR⁴⁴A group [ wherein, R⁴³And R⁴⁴A single bond, an alkylene group having 1 to 10 carbon atoms or an ether group having 2 to 10 carbon atoms (an alkyloxyalkyl group)]Etc., preferably-COO-R⁴⁴-a radical.

In the formula (i), Y is a counter anion^-Examples thereof include Cl^-、Br^-、I^-、ClO₄ ^-、BF₄ ^-、CH₃COO^-、PF₆ ^-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, is preferably 60 mol% or less, more preferably 50 mol% or less, further preferably 40 mol% or less, and particularly preferably 35 mol% or less, and is preferably 5 mol% or more, more preferably 10 mol% or more, further preferably 20 mol% or more, and particularly preferably 30 mol% or more, relative to the total 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). For example, the content ratio of the repeating unit represented by the formula (i) is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, further preferably 20 to 40 mol%, and particularly preferably 30 to 35 mol% with respect to the total 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).

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

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

In addition, from the viewpoint of improving compatibility with a binder component such as a solvent and improving dispersion stability, the polymer dispersant preferably has a repeating unit represented by the following formula (iii) (hereinafter, may be referred to as "repeating unit (iii)").

[ chemical formula 54]

In the above formula (iii), R⁴⁰Is ethylene or propylene;

R⁴¹is an alkyl group optionally having a substituent;

R⁴²is a hydrogen atom or a methyl group;

n is an integer of 1 to 20.

R of the above formula (iii)⁴¹The number of carbon atoms of the alkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 1 or more, preferably 2 or moreAnd is preferably 10 or less, more preferably 6 or less. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, and an octyl group, and among these, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group are preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are more preferable. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 2 to 6.

In addition, n in the formula (iii) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less, more preferably 5 or less, from the viewpoint of compatibility and dispersibility with respect to a binder component such as a solvent. For example, n is preferably 1 to 10, more preferably 2 to 5.

The content of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more, and even more preferably 4 mol% or more, and is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When the amount is within the above range, compatibility with a binder component such as a solvent and dispersion stability tend to be achieved at the same time. For example, the content ratio of the repeating unit represented by the above formula (iii) in the total repeating units of the polymer dispersant is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and further preferably 4 to 10 mol%.

In addition, from the viewpoint of improving the compatibility of the dispersant with a binder component such as a solvent and improving dispersion stability, the polymeric dispersant preferably has a repeating unit represented by the following formula (iv) (hereinafter, may be referred to as "repeating unit (iv)").

[ chemical formula 55]

In the above formula (iv), R³⁸Is an alkyl group optionally having a substituent, an aryl group optionally having a substituent or an aralkyl group optionally having a substituent;

R³⁹Is a hydrogen atom or a methyl group.

R of the above formula (iv)³⁸The number of carbon atoms of the alkyl group optionally having a substituent(s) in ((b) is not particularly limited, and is usually 1 or more, preferably 2 or more, more preferably 4 or more, and preferably 10 or less, more preferably 8 or less. Specific examples of the alkyl group include: methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl and the like, and among these, methyl, ethyl, propyl, butyl, pentyl or hexyl is preferred, and methyl, ethyl, propyl or butyl is more preferred. The polymer may be linear or branched. Further, the compound may have a cyclic structure such as cyclohexyl or cyclohexylmethyl. For example, the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 2 to 8, and further preferably 4 to 8.

R of the above formula (iv)³⁸The number of carbon atoms of the aryl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 6 or more, and is preferably 16 or less, more preferably 12 or less, and further preferably 8 or less. Specific examples of the aryl group include a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a naphthyl group, an anthryl group and the like, and among these, a phenyl group, a methylphenyl group, an ethylphenyl group, a dimethylphenyl group or a diethylphenyl group is preferable, and a phenyl group, a methylphenyl group or an ethylphenyl group is more preferable. For example, the number of carbon atoms of the aryl group is preferably 6 to 16, more preferably 6 to 12, and still more preferably 8 to 12.

R of the above formula (iv)³⁸The number of carbon atoms of the aralkyl group optionally having a substituent(s) in (1) is not particularly limited, but is usually 7 or more, and is preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. Specific examples of the aralkyl group include a phenylmethylene, a phenylethylene, a phenylpropylene, a phenylbutylene, and a phenylisopropylene, and among these, a phenylmethylene, a phenylethylene, a phenylpropylene, and a phenylbutylene are preferable, and a phenylmethylene or a phenylethylene are more preferable. For example, a carbon atom of an aralkyl groupThe number is preferably 7 to 16, more preferably 7 to 12, and still more preferably 7 to 10.

Among these, R is from the viewpoint of solvent compatibility and dispersion stability³⁸Preferably an alkyl or aralkyl group, more preferably a methyl, ethyl or phenylmethylene group.

As R³⁸Examples of the substituent optionally contained in the alkyl group in (1) include a halogen atom and an alkoxy group. Examples of the substituent optionally contained in the aryl group or the aralkyl group include a linear alkyl group, a halogen atom, and an alkoxy group. In addition, R³⁸The chain alkyl group includes both straight-chain and branched-chain alkyl groups.

From the viewpoint of dispersibility, the content ratio of the repeating unit represented by the above formula (iv) in the total repeating units of the polymer dispersant is preferably 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, and preferably 80 mol% or less, more preferably 70 mol% or less. For example, the content ratio of the repeating unit represented by the above formula (iv) in the total repeating units of the polymer dispersant is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and still more preferably 50 to 70 mol%.

The polymer dispersant may have a repeating unit other than the repeating unit (i), the repeating unit (ii), the repeating unit (iii), and the repeating unit (iv). Examples of such a repeating unit include styrene-based monomers derived from styrene, α -methylstyrene, and the like; (meth) acryloyl chloride monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, butenoic acid glycidyl ether; repeating units of monomers such as N-methacryloyl morpholine.

From the viewpoint of further improving the dispersibility, the polymeric dispersant is preferably a block copolymer having an a block having a repeating unit (i) and a repeating unit (ii) and a B block having no repeating unit (i) and no repeating unit (ii). The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. By introducing a quaternary ammonium salt group and a tertiary amino group into the a block, the dispersing ability of the dispersant tends to be remarkably improved. In addition, the B block preferably has a repeating unit (iii), and further preferably has a repeating unit (iv).

The a block may contain the repeating unit (i) and the repeating unit (ii) in any form of random copolymerization or block copolymerization. In addition, 1 a block may contain 2 or more kinds of the repeating unit (i) and the repeating unit (ii), and in this case, the a block may contain each repeating unit in any form of random copolymerization or block copolymerization.

The a block may contain a repeating unit other than the repeating unit (i) and the repeating unit (ii), and examples of such a repeating unit include a repeating unit derived from the above-mentioned (meth) acrylate monomer. The content of the repeating unit other than the repeating unit (i) and the repeating unit (ii) in the a block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably the a block does not contain the repeating unit.

The B block may contain a repeating unit other than the repeating units (iii) and (iv), and examples of such a repeating unit include styrene-based monomers derived from styrene, α -methylstyrene, and the like; (meth) acryloyl chloride monomers such as (meth) acryloyl chloride; (meth) acrylamide monomers such as (meth) acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, butenoic acid glycidyl ether; repeating units of monomers such as N-methacryloyl morpholine. The content of the repeating unit other than the repeating unit (iii) and the repeating unit (iv) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, and most preferably the B block does not contain the repeating unit.

When the photosensitive colored resin composition of the present invention contains the dispersant (F), the content thereof is not particularly limited, but is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and is preferably 8% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, and particularly preferably 2% by mass or less, of the total solid content of the photosensitive colored resin composition. When the amount is not less than the lower limit, generation of residue due to aggregates tends to be suppressed, and when the amount is not more than the upper limit, ink repellency and developability tend to be improved. For example, when the photosensitive colored resin composition contains the dispersant (F), the content of the dispersant (F) in the entire solid content of the photosensitive colored resin composition is preferably 0.1 to 8% by mass, more preferably 0.1 to 5% by mass, still more preferably 0.5 to 3% by mass, and particularly preferably 0.5 to 2% by mass.

[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 following purpose: the photocuring profile is controlled by absorbing a specific wavelength of a light source for exposure with an ultraviolet absorber. By adding the ultraviolet absorber, effects such as improvement of verticality of the side surface of the partition wall after development, elimination of residue remaining in the unexposed portion after development, and the like can be obtained. As the ultraviolet absorber, for example, a compound having a maximum absorption at a wavelength of 250nm to 400nm can be used from the viewpoint of inhibiting the light absorption of the photopolymerization initiator (a).

The ultraviolet absorber preferably contains either or both of a benzotriazole compound and a triazine compound. It is considered that the inclusion of either or both of the benzotriazole-based compound and the triazine-based compound reduces the light absorption rate of the initiator at the bottom of the film and reduces the line width at the lower portion of the coating film, thereby achieving the effect of perpendicularity of the side surfaces of the partition walls.

Examples of the benzotriazole compound include: 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl 3- [ 3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl ] propionate, ethylhexyl 3- [ 3-tert-butyl-5- (5-chloro-2H-benzotriazol-2-yl) -4-hydroxyphenyl ] propionate, 2- [ 2-hydroxy-3, 5-bis (. alpha.,. alpha. -dimethylbenzyl) phenyl ] -2H-benzotriazole, 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (3, 5-di-tert-amyl-2-hydroxyphenyl) benzotriazole, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4, 6-bis (1-methyl-1-phenylethyl) phenol, ester compounds of 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 straight and branched chain alkyl alcohols.

Examples of commercially available benzotriazole compounds include: sumisorb (registered trademark, the same below) 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo chemical Co., Ltd.), JF77, JF78, JF79, JF80, JF83 (manufactured by North City chemical industry), TINUVIN (registered trademark, the same below) PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, "TINUVIN 928", TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB73, EVERSORB74, EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, SEERSORB 81, SEORRB 702, ORRB.

Examples of the triazine compound include: 2- [4, 6-bis (2, 4-dimethylphenyl) -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, the reaction product of 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine with 2-ethylhexylglycidyl ether, 2, 4-bis [ 2-hydroxy-4-butoxyphenyl ] -6- (2, 4-dibutoxyphenyl) -1, 3-5-triazine, and the like. Among these, from the viewpoint of perpendicularity of the side surfaces of the partition walls and ink repellency, a hydroxyphenyl triazine compound is preferable.

Examples of commercially available triazine compounds include: TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (manufactured by BASF) and the like.

Examples of other ultraviolet absorbers include: benzophenone compounds, benzoate compounds, cinnamic acid derivatives, naphthalene derivatives, anthracene and its derivatives, binaphthalene compounds, phenanthroline compounds, dyes, and the like.

More specifically, examples thereof include: benzophenone compounds such as Sumisorb 130 (manufactured by Sumitomo chemical Co., Ltd.), EVERSORB10, EVERSORB11, EVERSORB12 (manufactured by Taiwan Yongshikoku industries Co., Ltd.), Tomisorb 800 (manufactured by API Co., Ltd.), SEESORB100, SEESORB101S, SEESORB102, SEESORB103, SEESORB105, SEESORB106, SEESORB107 and SEESORB151 (manufactured by Shipro Kasei); benzoic acid ester compounds such as Sumisorb 400 (manufactured by Sumitomo chemical Co., Ltd.) and phenyl salicylate; cinnamic acid derivatives such as 2-ethylhexyl cinnamate, 2-ethylhexyl p-methoxycinnamate, isopropyl methoxycinnamate, and isoamyl methoxycinnamate; naphthalene derivatives such as 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, and 2, 7-dihydroxynaphthalene; anthracene such as anthracene and 9, 10-dihydroxyanthracene, and derivatives thereof; azo dyes, benzophenone dyes, aminoketone dyes, quinoline dyes, anthraquinone dyes, diphenylcyanoacrylate dyes, triazine dyes, p-aminobenzoic acid dyes, and the like; and so on. Among these, cinnamic acid derivatives and naphthalene derivatives are preferably used from the viewpoint of ink repellency, and cinnamic acid derivatives are particularly preferably used. These light absorbers may be used alone or in combination of two or more.

Among these, from the viewpoint of the tapered shape, either one or both of the benzotriazole compound and the hydroxyphenyltriazine compound are preferable, and the benzotriazole compound is particularly preferable.

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

When the photosensitive colored resin composition of the present invention contains an ultraviolet absorber, the content thereof is not particularly limited, but is usually 0.01% by mass or more, preferably 0.05% by mass or more, more preferably 0.1% by mass or more, further preferably 0.5% by mass or more, particularly preferably 1% by mass or more, and is usually 15% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, of the total solid content of the photosensitive colored resin composition. When the lower limit value is not less than the above-described lower limit value, the verticality of the side surfaces of the partition walls tends to be good, and when the upper limit value is not more than the above-described upper limit value, the ink repellency tends to be improved. For example, when the photosensitive colored resin composition contains an ultraviolet absorber, the content ratio of the ultraviolet absorber in the entire solid content of the photosensitive colored resin composition is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass, even more preferably 0.1 to 5% by mass, even more preferably 0.5 to 3% by mass, and particularly preferably 1 to 3% by mass.

When the photosensitive colored resin composition of the present invention contains an ultraviolet absorber, the blending ratio thereof with respect to the photopolymerization initiator (a) is usually 1 part by mass or more, preferably 10 parts by mass or more, more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 80 parts by mass or more, and usually 500 parts by mass or less, preferably 300 parts by mass or less, more preferably 200 parts by mass or less, and further preferably 100 parts by mass or less, based on the blending amount of the ultraviolet absorber with respect to 100 parts by mass of the photopolymerization initiator (a). When the lower limit value is not less than the above-described lower limit value, the verticality of the side surfaces of the partition walls tends to be good, and when the upper limit value is not more than the above-described upper limit value, 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 is preferably 1 to 500 parts by mass, more preferably 10 to 300 parts by mass, still more preferably 30 to 200 parts by mass, still more preferably 50 to 100 parts by mass, and particularly preferably 80 to 100 parts by mass based on 100 parts by mass of the photopolymerization initiator (a).

[1-1-8] polymerization inhibitor

The photosensitive colored resin composition of the present invention preferably contains a polymerization inhibitor. Since the inclusion of the polymerization inhibitor inhibits radical polymerization, the taper angle of the obtained partition wall tends to be increased.

As the polymerization inhibitor, there may be mentioned: hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, methoxyphenol, 2, 6-di-tert-butyl-4-cresol (BHT), and the like. Among these polymerization inhibitors, hydroquinone or methoxyphenol are preferable, and methylhydroquinone is more preferable, from the viewpoint of polymerization inhibiting ability.

The polymerization inhibitor preferably contains one or more species. In general, when the alkali-soluble resin (B) is produced, a polymerization inhibitor may be contained in the resin, and the resin may be used as it is, or a polymerization inhibitor may be added in addition to the polymerization inhibitor contained in the resin, the same as or different from the polymerization inhibitor, in the production of the photosensitive colored resin composition.

When the photosensitive colored resin composition contains a polymerization inhibitor, the content thereof is not particularly limited, and is usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and is usually 0.1 mass% or less, preferably 0.08 mass% or less, more preferably 0.05 mass% or less, of the total solid content of the photosensitive colored resin composition. When the lower limit value is not less than the above-described lower limit value, the taper angle tends to be increased, and when the upper limit value is not more than the above-described upper limit value, the ink repellency tends to be improved. For example, when the photosensitive colored resin composition contains a polymerization inhibitor, the content of the polymerization inhibitor in the entire solid content of the photosensitive colored resin composition is preferably 0.0005 to 0.1% by mass, more preferably 0.001 to 0.08% by mass, and still more preferably 0.01 to 0.05% by mass.

[1-1-9] thermal polymerization initiator

Further, the photosensitive colored resin composition of the present invention may contain a thermal polymerization initiator. The inclusion of the thermal polymerization initiator tends to increase the degree of crosslinking of the film. Specific examples of such a thermal polymerization initiator include: azo compounds, organic peroxides, hydrogen peroxide, and the like. These thermal polymerization initiators may be used alone or in combination of two or more.

When a thermal polymerization initiator is used in combination with a photopolymerization initiator in order to improve ink repellency and increase the crosslinking density of a film, the total content of the thermal polymerization initiator and the photopolymerization initiator is preferably set to a content of the photopolymerization initiator in the photosensitive colored resin composition, and from the viewpoint of ink repellency, the thermal polymerization initiator is preferably used in a combined amount of 5 to 300 parts by mass per 100 parts by mass of the photopolymerization initiator.

[1-1-10] amino compounds

The photosensitive colored resin composition of the present invention may contain an amino compound for promoting thermal curing. In this case, the content of the amino compound is usually 40% by mass or less, preferably 30% by mass or less, of the total solid content of the photosensitive colored resin composition. The content is usually 0.5% by mass or more, preferably 1% by mass or more. When the content is not more than the upper limit, the storage stability tends to be maintained, and when the content is not less than the lower limit, sufficient thermosetting property tends to be secured. For example, when the photosensitive colored resin composition contains an amino compound, the content ratio of the amino compound in the entire solid content of the photosensitive colored resin composition is preferably 0.5 to 40% by mass, and more preferably 1 to 30% by mass.

Examples of the amino compound include: an amino compound having at least 2 functional groups selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group obtained by condensation-modifying a hydroxymethyl group with an alcohol having 1 to 8 carbon atoms. Specific examples thereof include: a melamine resin obtained by polycondensation of melamine and formaldehyde; benzoguanamine resin obtained by condensation polymerization of benzoguanamine and formaldehyde; glycoluril resin obtained by polycondensation of glycoluril with formaldehyde; urea-formaldehyde resin obtained by condensation polymerization of urea and formaldehyde; a resin obtained by copolycondensation of formaldehyde and two or more of melamine, benzoguanamine, glycoluril, urea, or the like; modified resins obtained by modifying methylol groups of the above resins by alcohol condensation. These resins may be used alone or in combination of two or more. Among these amino compounds, melamine resins and modified resins thereof are preferable, modified resins having a methylol group modification ratio of 70% or more are more preferable, and modified resins having a modification ratio of 80% or more are particularly preferable.

Specific examples of the amino compound include melamine resins and modified resins thereof, including: "CYMEL" (registered trademark, the same below) 300, 301, 303, 350, 736, 738, 370, 771, 325, 327, 703, 701, 266, 267, 285, 232, 235, 238, 1141, 272, 254, 202, 1156, 1158 manufactured by Cytec corporation and "Nicarac" (registered trademark, the same below) MW-390, MW-100LM, MX-750LM, MW-30M, MX-45, MX-302 manufactured by Sanko chemical Co., Ltd. Examples of the benzoguanamine resin and modified resins thereof include: "CYMEL" 1123, 1125, 1128, etc., manufactured by Cytec corporation. Examples of the glycoluril resin and its modified resin include: "CYMEL" 1170, 1171, 1174, 1172 available from Cytec, and "Nicarac" MX-270 available from Sanko K.K. The urea resin and the modified resin thereof include, for example: "UFR" (registered trademark) 65 and 300 manufactured by Cytec corporation, and "Nicarac" MX-290 manufactured by Sanko chemical Co., Ltd.

[1-1-11] silane coupling agent

The photosensitive colored resin composition of the present invention is preferably further added with a silane coupling agent for improving adhesion to a substrate. Various silane coupling agents such as epoxy, methacrylic, amino, and imidazole can be used as the silane coupling agent, but epoxy and imidazole silane coupling agents are particularly preferable from the viewpoint of improving adhesion. The content thereof is usually 20 mass% or less, preferably 15 mass% or less, in the entire solid content of the photosensitive colored resin composition, from the viewpoint of adhesion.

[1-1-12] inorganic Filler

The photosensitive colored resin composition of the present invention may further contain an inorganic filler for the purpose of improving strength when a cured product is produced, and improving excellent verticality, taper angle, and the like of a coating film due to a proper interaction (formation of a matrix structure) with an alkali-soluble resin. Examples of such inorganic fillers include: talc, silica, alumina, barium sulfate, magnesium oxide, titanium oxide, or a surface-treated product thereof 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 in the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring apparatus manufactured by Beckman Coulter corporation and the like. Among these inorganic fillers, silica sol and silica sol modified products are particularly preferable because they tend to have excellent dispersion stability and an excellent effect of improving the cone angle. When the photosensitive colored resin composition of the present invention contains such an inorganic filler, the content thereof is usually 5% by mass or more, preferably 10% by mass or more, usually 80% by mass or less, preferably 70% by mass or less in the total solid content from the viewpoint of ink repellency. For example, when the photosensitive colored resin composition contains an inorganic filler, the content thereof in the entire solid content of the photosensitive colored resin composition is preferably 5 to 80% by mass, and more preferably 10 to 70% by mass.

[1-1-13] Adhesivity-improving agent

The photosensitive colored resin composition of the present invention may contain an ethylenic monomer of phosphoric acid for the purpose of imparting adhesion to a substrate. The vinyl monomer of the phosphoric acid is preferably a (meth) acryloyloxy group-containing phosphate, and is preferably an adhesion improver represented by the following general formula (g1), (g2) or (g 3).

[ chemical formula 56]

[ in the above general formulae (g1), (g2) and (g3), R⁵¹Represents 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, the content thereof is usually preferably 0.02% by mass or more, more preferably 0.05% by mass or more, further preferably 0.1% by mass or more, and particularly preferably 0.2% by mass or more, of the total solid content of the photosensitive colored resin composition. Further, it is preferably 4% by mass or less, more preferably 3% by mass or less, further preferably 2% by mass or less, and particularly preferably 1% by mass or less. When the value is equal to or higher than the lower limit, the effect of improving the adhesion to the substrate tends to be sufficient, and when the value is equal to or lower than the upper limit, the deterioration of the adhesion to the substrate tends to be easily suppressed. For example, when the photosensitive colored resin composition contains a phosphoric acid-based ethylenic monomer, the content ratio thereof in the entire solid content of the photosensitive colored resin composition is preferably 0.02 to 4% by mass, more preferably 0.05 to 3% by mass, still more preferably 0.1 to 2% by mass, and particularly preferably 0.2 to 1% by mass.

[1-1-14] solvent

The photosensitive colored resin composition of the present invention usually contains a solvent, and the above-mentioned respective components can be used in a state of being dissolved or dispersed in the solvent. The solvent is not particularly limited, and examples thereof include the following organic solvents.

Glycol monoalkyl ethers such as 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 tert-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, 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, and dipropylene glycol dimethyl ether;

glycol alkyl ether acetates such as 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 monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

Glycol diacetate esters such as ethylene glycol diacetate, propylene glycol diacetate, 1, 3-butanediol diacetate, 1, 4-butanediol diacetate, and 1, 6-hexanediol diacetate;

alkyl acetates such as cyclohexanol acetate;

ethers such as amyl ether, ethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, and dihexyl ether;

ketones 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, and methoxymethyl pentanone;

monohydric or polyhydric alcohols such as methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerol, and benzyl alcohol;

aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, and dodecane;

alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, methylcyclohexene, and bicyclohexyl;

aromatic hydrocarbons such as benzene, toluene, xylene, and cumene;

Linear or cyclic esters such as amyl formate, ethyl acetate, propyl acetate, butyl acetate, amyl acetate, methyl isobutyrate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl decanoate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, and γ -butyrolactone;

alkoxycarboxylic acids such as 3-methoxypropionic acid and 3-ethoxypropionic acid;

halogenated hydrocarbons such as chlorobutane and chloropentane;

ether ketones such as methoxymethylpentanone;

nitriles such as acetonitrile and benzonitrile;

and tetrahydrofuran compounds such as tetrahydrofuran, dimethyltetrahydrofuran, and dimethoxytetrahydrofuran.

Examples of commercially available solvents corresponding to the above include: mineral spirits (Mineral spirits), Varsol #2, Apco #18 solvent, Apco triner, Socal solvent nos. 1 and 2, Solvesso #150, Shell TS28 solvent, carbitol, ethyl carbitol, butyl carbitol, methyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diethylene glycol dimethyl ether (digle) (all trade names), and the like.

The solvent is a solvent capable of dissolving or dispersing each component in the photosensitive colored resin composition, and can be selected according to the method of using the photosensitive colored resin composition of the present invention, but from the viewpoint of coatability, it is preferable to select a solvent having a boiling point in the range of 60 to 280 ℃ under atmospheric pressure. More preferably a solvent having a boiling point of 70 ℃ or higher and 260 ℃ or lower, and preferably, for example: propylene glycol monomethyl ether, 3-methoxy-1-butanol, propylene glycol monomethyl ether acetate, 3-methoxy-1-butyl acetate.

These solvents may be used singly or in combination of two or more. The solvent is preferably used so that the proportion of the total solid content in the photosensitive colored resin composition becomes usually 10% by mass or more, preferably 15% by mass or more, more preferably 20% by mass or more, further 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, further preferably 35% by mass or less. When the amount is equal to or more than the lower limit, the occurrence of coating unevenness tends to be suppressed, and when the amount is equal to or less than the upper limit, the occurrence of foreign matter, dents, and the like tends to be suppressed. For example, the solvent is preferably used so that the proportion of the total solid content in the photosensitive colored resin composition is preferably 10 to 90% by mass, more preferably 15 to 50% by mass, still more preferably 20 to 40% by mass, and particularly preferably 25 to 35% by mass.

[1-2] method for producing photosensitive colored resin composition

The photosensitive colored resin composition of the present invention can be prepared by mixing the above components with a stirrer.

For example, when a solvent-insoluble component such as a pigment is contained as the (D) colorant, it is preferable to perform a dispersion treatment in advance using a paint shaker, a sand mill, a ball mill, a roll mill, a stone mill, an air mill, a homogenizer, or the like. By the dispersion treatment, the (D) colorant is formed into fine particles, and thus the coating properties of the photosensitive colored resin composition are improved.

The dispersion treatment is usually preferably performed in a system in which (D) a colorant, a solvent, and (F) a dispersant are used in combination with (B) a part or all of an alkali-soluble resin (hereinafter, the mixture used for the dispersion treatment and the composition obtained by the treatment are also referred to as "ink" or "pigment dispersion"). In particular, when a polymer dispersant is used as the dispersant (F), the thickening of the obtained ink and photosensitive colored resin composition with time can be suppressed (excellent dispersion stability) and therefore, it is preferable.

In this way, in the step of producing the photosensitive colored resin composition, it is preferable to produce a pigment dispersion liquid containing at least (D) the colorant, the solvent, and (F) the dispersant.

As the (D) colorant, the organic solvent and the (F) dispersant which can be used in the pigment dispersion liquid, the components described as those which can be used in the photosensitive colored resin composition can be preferably used. The content ratio of the colorant (D) in the pigment dispersion liquid is preferably the ratio described as the content ratio in the photosensitive colored resin composition.

When the colorant (D) is dispersed by a sand mill, glass beads or zirconia beads having a particle diameter of about 0.1 to 8mm are preferably used. The temperature of the dispersion treatment is usually in the range of 0 ℃ to 100 ℃, preferably in the range of room temperature to 80 ℃, and the suitable time for the dispersion treatment is not the same depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like, and thus can be appropriately adjusted. The approximate criteria for dispersion are: the gloss of the ink is controlled so that the 20-degree specular gloss (JIS Z8741) of the photosensitive colored resin composition is in the range of 50 to 300.

The dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and can be measured by a dynamic light scattering method or the like.

Next, the ink obtained by the dispersion treatment is mixed with the other components contained in the photosensitive colored resin composition to prepare a uniform solution. In the production process of the photosensitive colored resin composition, since fine dust may be mixed into the liquid, it is preferable to perform a filtration treatment of the obtained photosensitive colored resin composition with a filter or the like.

[2] Spacer 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 for forming partition walls, and particularly, can be suitably used for forming partition walls for partitioning organic layers of an organic electroluminescent device.

The method for forming the partition wall using the photosensitive colored resin composition described above is not particularly limited, and a conventionally known method can be used. Examples of the method for forming the partition wall include: the method comprises a coating step of coating a substrate with a photosensitive colored resin composition to form a photosensitive colored resin composition layer, and an exposure step of exposing the photosensitive colored resin composition layer. Specific examples of the method for forming such a bank include an ink jet method and a photolithography method.

In the ink jet method, a photosensitive colored resin composition whose viscosity has been adjusted by dilution with a solvent or the like is used as an ink, and ink droplets are ejected onto a substrate by the ink jet method along a predetermined pattern of partition walls, whereby the photosensitive colored resin composition is applied onto the substrate to form a pattern of uncured partition walls. Then, the pattern of the uncured barrier ribs is exposed to light, thereby forming the cured barrier ribs on the substrate. The exposure of the pattern of the uncured partition walls is performed in the same manner as in the exposure step in the photolithography method described later, except that no mask is used.

In the photolithography method, a photosensitive colored resin composition is applied to the entire surface 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 corresponding to the pattern of the partition walls, the exposed photosensitive colored resin composition layer is developed, thereby forming the partition walls on the substrate.

In a coating step of applying a photosensitive coloring resin composition onto a substrate in a photolithography method, a photosensitive coloring resin composition is applied onto a substrate to be formed with partition walls using a contact transfer type coating apparatus such as a roll coater, a reverse coater, or a bar coater, or a non-contact type coating apparatus such as a spin coater (a spin coater) or a curtain flow coater, and the solvent is removed by drying as necessary, thereby forming a photosensitive coloring resin composition layer.

Next, in the exposure step, the photosensitive colored resin composition is irradiated with active energy rays such as ultraviolet rays or excimer laser light through a negative mask, and the photosensitive colored resin composition layer is partially exposed in accordance with the pattern of the bank. For the exposure, a light source emitting ultraviolet rays such as a high-pressure mercury lamp, an ultrahigh-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, for example, 10 to 400mJ/cm ²Left and right.

Next, in a developing step, the photosensitive colored resin composition layer exposed to light in accordance with the pattern of the partition walls is developed with a developing solution to form the partition walls. The developing method is not particularly limited, and a dipping method, a spraying method, or the like can be used. Specific examples of the developer include: organic developers such as dimethylbenzylamine, monoethanolamine, diethanolamine, and triethanolamine, or aqueous solutions of sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, and quaternary ammonium salts. In addition, a defoaming agent and a surfactant may be added to the developer.

Thereafter, the developed partition walls are post-baked and heat-cured. The post-baking is preferably carried out at 150 to 250 ℃ for 15 to 60 minutes.

The substrate for forming the partition walls is not particularly limited, and may be appropriately selected according to the kind of organic electroluminescent element manufactured using the substrate with the partition walls formed. Preferable substrate materials include glass and various resin materials. Specific examples of the resin material include: polyesters such as polyethylene terephthalate; polyolefins such as polyethylene and polypropylene; a polycarbonate; a poly (meth) acrylic resin; polysulfones; and (3) a polyimide. Among these substrate materials, glass and polyimide are preferable because of their excellent heat resistance. In addition, 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 walls are to be formed, depending on the type of the organic electroluminescent element to be manufactured.

[3] Organic electroluminescent element

The organic electroluminescent element of the present invention comprises the above-mentioned partition wall formed of the photosensitive colored resin composition.

Various organic electroluminescent elements can be manufactured using the substrate having the partition wall pattern manufactured by the above-described method. The method of forming the organic electroluminescent element is not particularly limited, but it is preferable to form an organic layer such as a pixel by injecting ink into a region surrounded by the partition walls on the substrate after forming the pattern of the partition walls on the substrate by the above-mentioned method.

When the partition walls have a skirt shape, the ink for forming an organic layer is repelled at the skirt portions of the partition walls, and therefore, the region surrounded by the partition walls may not be uniformly covered with the ink for forming an organic layer. In contrast, by forming the partition wall in a good shape without a skirt, the region surrounded by the partition wall can be sufficiently covered with the organic layer forming ink. This can eliminate, for example, the problem of halation in the organic EL display element.

As the solvent used in forming the ink for forming an organic layer, water, an organic solvent, and a mixed solvent thereof can be used. The organic solvent is not particularly limited as long as it can be removed from the formed film after the ink is injected. Specific examples of the organic solvent include: toluene, xylene, anisole, mesitylene, tetralin, cyclohexylbenzene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, isopropanol, ethyl acetate, butyl acetate, 3-phenoxytoluene, and the like. In addition, a surfactant, an antioxidant, a viscosity modifier, an ultraviolet absorber, and the like may be added to the ink.

As a method of injecting ink into the region surrounded by the partition walls, an ink jet method is preferable because a small amount of ink can be easily injected into a predetermined portion. The ink used for forming the organic layer may be appropriately selected depending on the kind of the organic electroluminescent element to be manufactured. When the ink is injected by the ink jet method, the viscosity of the ink is not particularly limited as long as the ink can be ejected well from the ink jet head, but is preferably 4 to 20mPa · s, more preferably 5 to 10mPa · 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.

Examples of the type of the organic electroluminescent element include a bottom emission type and a top emission type.

In the bottom emission type, for example, a partition wall is formed on a glass substrate on which a transparent electrode is laminated, and a hole transport layer, a light emitting layer, an electron transport layer, and a metal electrode layer are laminated in an opening surrounded by the partition wall. On the other hand, in the top emission type, for example, a partition wall is formed on a glass substrate on which a metal electrode layer is laminated, and an electron transport layer, a light emitting layer, a hole transport layer, and a transparent electrode layer are laminated in an opening surrounded by the partition wall.

The light-emitting layer may be an organic electroluminescent layer as described in japanese patent laid-open nos. 2009-146691 and 5734681. In addition, quantum dots as 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 comprises the cured product of the present invention, and particularly, an image display device comprising the organic electroluminescent element of the present invention can be exemplified. As the image display device including the organic electroluminescent element, there is no particular limitation on the model and structure of the image display device, and for example, an active-drive type organic electroluminescent element can be used and assembled by a conventional method. For example, the image display device of the present invention can be formed by a method described in "organic EL display" (OHM corporation, 16 years, 8 months, 20 days, waiter, andkyush, village english to lucky). For example, an image may be displayed by combining an organic electroluminescent element that emits white light with a color filter, or an image may be displayed by combining organic electroluminescent elements having different luminescent colors such as RGB.

[5] Illumination device

The illumination of the present invention includes the cured product of the present invention, and in particular, includes an illumination including the organic electroluminescent element of the present invention. The type and structure thereof are not particularly limited, and for example, the organic electroluminescent element of the present invention can be assembled by a conventional method. The organic electroluminescent element may be of a simple matrix driving type or an active matrix driving type.

In order to make the illumination of the present invention emit white light, an organic electroluminescent element that emits white light may be used. Further, the color mixing function may be provided by combining organic electroluminescent elements having different emission colors so that the color mixture of the respective colors becomes white, or by adjusting the ratio of the color mixture.

Examples

The photosensitive colored resin composition of the present invention will be described below with reference to specific examples, but the present invention is not limited to the following examples within the scope not exceeding the gist thereof.

< alkali-soluble resin-I >

An alkali-soluble acrylic copolymer resin obtained by adding acrylic acid to a copolymer resin containing dicyclopentyl methacrylate/styrene/glycidyl methacrylate (molar ratio: 0.3/0.1/0.6) as a constituent monomer so as to cause an equivalent addition reaction with glycidyl methacrylate, and further adding tetrahydrophthalic anhydride so as to achieve a molar ratio of 0.39 to 1 mol of the copolymer resin. The polystyrene-equivalent weight average molecular weight (Mw) measured by GPC was 9000, and the acid value was 80 mgKOH/g. PGMEA (propylene glycol monomethyl ether acetate) was added thereto so that the solid content concentration became 42.7 mass%.

< alkali-soluble resin-II >

"ZCR-1642H" (weight average molecular weight (Mw) 6500 and acid value 98mgKOH/g) manufactured by Nippon Kabushiki Kaisha. PGMEA was added thereto so that the solid content concentration reached 40.0 mass%.

< dispersant-I >

"BYK-LPN 21116" (acrylic A-B block copolymer comprising A block having quaternary ammonium salt group and tertiary amino group in the side chain and B block having no quaternary ammonium salt group and amino group, having an amine value of 70mgKOH/g and an acid value of 1mgKOH/g or less) manufactured by BYK-Chemie K.K.)

The dispersant-I contains a repeating unit represented by the following formulas (1a) and (2a) in the A block and a repeating unit represented by the following formula (3a) in the B block. The content of the repeating units represented by the following formulae (1a), (2a), and (3a) in the total repeating units of the dispersant-I was 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[ chemical formula 57]

< solvent-I >

PGMEA: propylene glycol monomethyl ether acetate

< solvent-II >

MB: 3-methoxy-1-butanol

< photopolymerizable Compound-I >

DPHA: dipentaerythritol hexaacrylate manufactured by Nippon Kabushiki Kaisha

< 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 the compound is dissolved in PGMEA so that the concentration thereof is 0.01 mass%, the absorbance at a wavelength of 400nm is determined relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm _max) Namely, the absorbance at 368nm was 34%. Corresponds to the oxime ester photopolymerization initiator (A1).

[ chemical formula 58]

< photopolymerization initiator-2 >

IRGACURE (registered trademark, the same applies hereinafter) OXE-01 manufactured by BASF corporation was used. When the compound is dissolved in PGMEA so that the concentration thereof is 0.01 mass%, the absorbance at a wavelength of 400nm is determined relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) That is, the absorbance at 329nm was 0.7%. Corresponds to the oxime ester photopolymerization initiator (A2).

[ chemical formula 59]

< photopolymerization initiator-3 >

TRONLY (registered trademark) TR-PBG-305, a product of Changzhou powerful new electronic materials, was used. The compound is brought to a concentration relative to PGMEAWhen dissolved in a range of 0.01 mass%, the absorbance at a wavelength of 400nm is relative to the maximum absorption wavelength (lambda) between 300 and 400nm_max) That is, the absorbance at 329nm was 0.6%. Corresponds to the oxime ester photopolymerization initiator (A2).

[ chemical formula 60]

< photopolymerization initiator-4 >

A compound having the following chemical structure obtained by the method described in synthetic example 2 of Japanese patent application laid-open No. 2018-002962 was used. The absorbance at 400nm of the light-absorbing material is relative to the maximum absorption wavelength (lambda) between 300 and 400nm of the light-absorbing material _max) That is, the absorbance at 368nm was 33%. Corresponds to the oxime ester photopolymerization initiator (A1).

[ chemical formula 61]

< photopolymerization initiator-5 >

A compound having the following chemical structure was used. When the compound is dissolved in PGMEA so that the concentration thereof is 0.01 mass%, the absorbance at a wavelength of 400nm is determined relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) That is, the absorbance at 328nm was 1.1%. Corresponds to the oxime ester photopolymerization initiator (A2).

[ chemical formula 62]

< photopolymerization initiator-6 >

IRGACURE OXE-02 manufactured by BASF corporation was used. When the compound is dissolved in PGMEA so that the concentration thereof is 0.01 mass%, the absorbance at a wavelength of 400nm is relative to the maximum absorption at a wavelength of 300 to 400nmWavelength (lambda)_max) Namely, the absorbance at 336nm was 0.1%. Corresponds to the oxime ester photopolymerization initiator (A2).

[ chemical formula 63]

< liquid repellent-I >

Megafac RS-72-k (fluorine atom-containing oligomer having olefinic double bond as crosslinking group) manufactured by DIC

< additive-I >

KAYAMER (registered trademark) PM-21, manufactured by Nippon Kayaku Co., Ltd

< preparation of pigment Dispersion 1 >

The pigment, the dispersant, the alkali-soluble resin, and the solvent described in table 1 were mixed in the mass ratio described in table 1. The amounts of the dispersant and the alkali-soluble resin in table 1 are solid components, and the amount of the solvent also includes the amounts of the solvent derived from the dispersant and the alkali-soluble resin.

The solution was subjected to dispersion treatment for 3 hours at 25 to 45 ℃ by a paint shaker. As the beads, 0.5 mm. phi. zirconia beads were used, and 2.5 times the mass of the dispersion was added. After the dispersion treatment was completed, the beads were separated from the dispersion by a filter to prepare a pigment dispersion 1.

[ Table 1]

< preparation of photosensitive colored resin composition >

Using the pigment dispersion liquid 1 prepared above, each component was added so that the content of the solid content of each component in the total solid content became the value shown in table 2, and a solvent was further added so that the content of the total solid content became 31 mass% and the solvent-I/solvent-II became 80/20 (mass ratio) in the total solvent, and the mixture was diluted, stirred and dissolved to prepare photosensitive colored resin compositions of examples 1 to 4 and comparative examples 1 to 3. The obtained photosensitive colored resin composition was evaluated by the method described later.

In the table, the weighted average (%) of the absorbance at 400nm represents the absorbance (%) at 400nm of the oxime ester photopolymerization initiator (A3) in embodiment 2 of the present invention.

[ Table 2]

A photosensitive colored resin composition was prepared in the same manner as in example 1 except that 22.34 parts by mass of the photopolymerizable compound I in example 1 was changed to 11.17 parts by mass of the photopolymerizable compound I and 11.17 parts by mass of the photopolymerizable compound II in example 1, and this was defined as example 5.

Hereinafter, a method of evaluating the performance will be described.

< production of substrate for measuring contact Angle >

The photosensitive colored resin composition was applied onto a glass substrate using a spin coater so as to have a thickness of 6.0 μm after heat curing. Thereafter, the film was dried by heating at 100 ℃ for 90 seconds on a hot plate to obtain a coated substrate. Next, the resulting coated substrate was not subjected to ultraviolet exposure, but was subjected to spray development at 24 ℃ using an aqueous solution in which 0.04 mass% of KOH and 0.07 mass% of emirgen a-60 (surfactant, manufactured by kao corporation) were dissolved as a developer, and the time during which the coating was completely removed by development was read and taken as a break time.

Next, a high-pressure mercury lamp was used to expose 50mJ/cm of the coated substrate prepared separately under the same conditions as above, without using a mask²Ultraviolet exposure was performed. At this time, the intensity at a wavelength of 365nm was 45mW/cm². After the development treatment was performed with a developing time 1.6 times the off time in the same developing solution and developing conditions as described above, the substrate was washed with pure water for 10 seconds. Baking the substrateThe resultant was heated and cured at 230 ℃ for 30 minutes in a chamber to obtain a substrate for measuring a contact angle.

< measurement of PGMEA contact Angle >

The contact angle after 1 second measurement was obtained by dropping 0.7. mu.L of PGMEA onto the substrate for contact angle measurement using a Drop Master 500, a contact angle measuring apparatus manufactured by Kyowa Kagaku K.K., under conditions of 23 ℃ and a humidity of 50%, and the results are shown in Table 2. A larger contact angle indicates a higher ink repellency.

< production of Linear Pattern substrate >

The photosensitive colored resin composition was applied onto a glass substrate by a spin coater so as to have a thickness of 6.0 μm after heat curing. Thereafter, the film was dried by heating at 100 ℃ for 90 seconds on a hot plate to obtain a coated substrate. Subsequently, the coated substrate obtained was subjected to ultraviolet exposure using a high-pressure mercury lamp using a photomask. The exposure amount was 50mJ/cm²The exposure gap was 130 μm. At this time, the intensity at a wavelength of 365nm was 45mW/cm². The photomask uses exposure masks having linear openings with various widths of 5-50 μm (5-20 μm: 1 μm spacing, 25-50 μm: 5 μm spacing). Then, with the above<Production of substrate for measuring contact Angle>Similarly, after the development treatment was performed with a development time 1.6 times the off-time, the substrate was washed with pure water for 10 seconds and then heated and cured at 230 ℃ for 30 minutes in an oven, to prepare a line pattern substrate on which partition walls were supposed.

< evaluation of verticality of taper >

The cross section of the pattern corresponding to the linear opening portion having an opening width of 20 μm in the linear pattern substrate was observed by SEM observation at a magnification of 5000. As shown in the schematic diagram of fig. 1, the minimum width 4 among the pattern widths parallel to the substrate surface is defined as the minimum width, and the maximum width 3 above the minimum width is defined as the maximum width. Further, the verticality of the taper of the line pattern was evaluated from 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 is, the more vertically the barrier ribs are formed.

As is clear from comparison of examples 1 to 4 and comparative examples 1 to 2 in table 2, by combining the oxime ester photopolymerization initiator (a2) and the oxime ester photopolymerization initiator (a1), it is possible to achieve both of ink repellency and perpendicularity of the taper of the partition wall, as compared with the case where each of them is used alone.

In order to ensure ink repellency, it is necessary to fix the liquid repellent to the surface of the partition wall. However, if the degree of curing of the coating film after ultraviolet exposure is insufficient, a part of the film surface is dissolved during the subsequent development treatment, and the liquid repellent flows out into the developer. When an oxime ester type photopolymerization initiator (a2) mainly using i-rays is used alone as a photopolymerization initiator, for example, as in comparative example 2, curing after ultraviolet exposure is insufficient, and thus ink repellency is impaired.

On the other hand, when a thick film pattern having a film thickness of 5 μm or more is to be formed, ultraviolet rays entering from the surface of the coating film during ultraviolet exposure are absorbed by a photopolymerization initiator, a colorant, and the like contained in the coating film, and are difficult to pass through the inside of the coating film, which tends to cause a decrease in the degree of curing in the lower part of the coating film as compared with the upper part of the coating film. Therefore, there is a problem that the lower portion of the coating film having a low degree of curing is excessively developed during the development process, and the pattern width becomes narrow.

In comparison with comparative example 2, when an oxime ester photopolymerization initiator (a2) having a higher sensitivity among oxime ester photopolymerization initiators was further used in combination as in comparative example 3, the pattern width of the lower portion of the coating film became finer and the perpendicularity of the taper became worse, although the ink repellency became good. This is considered to be because, by using an oxime ester photopolymerization initiator (a2) having a high sensitivity, curability of the upper part of the coating film becomes high, and the liquid repellent can be fixed to the surface of the partition walls, but the curability of the lower part of the coating film cannot be improved because of a material mainly using i-rays, and thus the pattern width of the upper part of the coating film becomes wider than that of the lower part of the coating film.

On the other hand, as another method for improving the curing degree by ultraviolet light exposure, there is a method of using an oxime ester photopolymerization initiator (a1) which has an absorption band for i-rays and can also utilize h-rays, that is, which has sufficiently high absorbance at a wavelength of 400 nm.

When the oxime ester photopolymerization initiator (a1) is used to ensure ink repellency, the curing degree of the upper portion of the coating film becomes high and the pattern width of the upper portion becomes wider due to high sensitivity. However, focusing on the h-ray contributing to the high sensitivity of the oxime ester photopolymerization initiator (a1), when the oxime ester photopolymerization initiator (a1) is used alone, the h-ray is absorbed by the oxime ester photopolymerization initiator (a1) in many cases at the upper part of the coating film, and the h-ray reaching the lower part of the coating film is reduced, so that the pattern width of the lower part of the coating film tends to be further narrowed, and the perpendicularity of the taper tends to be further deteriorated. This tendency is clear from the results of comparative example 1.

On the other hand, it is considered that, by using the oxime ester photopolymerization initiator (a1) in combination with the oxime ester photopolymerization initiator (a2) as in examples 1 to 4, the absorption rate of h-rays in the upper portion of the coating film can be relatively reduced as compared with the case of using the oxime ester photopolymerization initiator (a1) alone, that is, h-rays can be transmitted to the lower portion of the coating film, and the curing by h-rays in the lower portion of the coating film can be promoted by the oxime ester photopolymerization initiator (a1), so that the perpendicularity of the taper shape of the partition walls can be improved. Further, it is considered that when an oxime ester photopolymerization initiator (a1) and an oxime ester photopolymerization initiator (a2) are used in combination, curing by i-rays and h-rays occurs in the vicinity of the film surface, and the ink repellency is also sufficient.

Claims

1. A photosensitive colored resin composition comprising (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent,

wherein the photopolymerization initiator (A) contains an oxime ester photopolymerization initiator (A1) and an oxime ester photopolymerization initiator (A2), and the absorbance of the oxime ester photopolymerization initiator (A1) at a wavelength of 400nm is relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) Lower light absorptionThe oxime ester photopolymerization initiator (A2) having a degree of not less than 20% and having an absorbance at a wavelength of 400nm relative to the maximum absorption wavelength (. lamda.) between 300 and 400nm_max) The absorbance of the light beam is 10% or less,

2. The photosensitive colored resin composition according to claim 1, wherein the oxime ester photopolymerization initiator (A1) comprises an oxime ester photopolymerization initiator having a nitro group and a carbazole skeleton.

3. The photosensitive colored resin composition according to claim 1 or 2, wherein the oxime ester photopolymerization initiator (A2) comprises a compound represented by the following general formula (A2-1),

in the formula (A2-1),

R^13Arepresents an optionally substituted alkyl group or an optionally substituted aromatic ring group,

R^14ARepresents an alkyl group or an aromatic ring group,

R^15Arepresents a substituent having a valence of 1,

n represents a number of 0 or 1,

h represents an integer of 0 to 2.

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

5. A photosensitive colored resin composition comprising (A) a photopolymerization initiator, (B) an alkali-soluble resin, (C) a photopolymerizable compound, (D) a colorant, and (E) a liquid repellent,

wherein the photopolymerization initiator (A) contains an oxime ester photopolymerization initiator (A3) which is an oxime ester photopolymerization initiator (A3) having a wavelength of 40Absorbance at 0nm to the maximum absorption wavelength (lambda) between 300 and 400nm_max) The absorbance of the solution is 8-30%,

6. The photosensitive colored resin composition according to any one of claims 1 to 5, wherein the fluorine-containing resin having a crosslinking group has either or both of a perfluoroalkyl group and a perfluoroalkylene ether chain.

7. The photosensitive colored resin composition according to any one of claims 1 to 6, wherein the (D) colorant contains:

at least one selected from red pigments and orange pigments; and

At least one selected from the group consisting of blue pigments and violet pigments.

8. The photosensitive colored resin composition according to any one of claims 1 to 7, wherein the colorant (D) contains an organic black pigment comprising at least one 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,

9. The photosensitive colored resin composition according to any one of claims 1 to 8, which is a photosensitive colored resin composition for spacer wall formation.

10. A cured product obtained by curing the photosensitive colored resin composition according to any one of claims 1 to 9.

11. An image display device comprising the cured product according to claim 10.

12. An illumination comprising the cured product according to claim 10.