JP2019082692A - Colored photosensitive resin composition, pigment dispersion, partition, organic electroluminescent element, image display device, and illumination - Google Patents

Abstract

To provide, as a first problem addressed by the present invention, a colored photosensitive resin composition that is highly reliable because the amount of outgas is little after a cured product is formed, and that provides excellent adhesion of patterns in a development step during formation of the cured product.SOLUTION: The colored photosensitive resin composition according to a first embodiment of the present invention comprises a colorant (A), a dispersant (B), a binder resin (C), a photopolymerizable monomer (D), and a photopolymerization initiator (E), where: the colorant (A) contains an organic black pigment (A1) that comprises at least one member selected from the group consisting of a compound represented by general formula (I) in the figure, a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound; the dispersant (B) contains an acrylic dispersant; and the binder resin (C) contains at least 75 mass% of an epoxy (meth)acrylate resin (C1).SELECTED DRAWING: None

Description

  The present invention relates to a colored photosensitive resin composition, and a pigment dispersion liquid used for the colored photosensitive resin composition, a partition constituted of the colored photosensitive resin composition, an organic electroluminescent device provided with the partition, and an image The present invention relates to a display device and lighting.

  A liquid crystal display (LCD) utilizes the property that the alignment of liquid crystal molecules is switched by turning on / off a voltage applied to the liquid crystal. On the other hand, each member constituting a cell of LCD is often formed by a method using a photosensitive composition represented by photolithography. The application range of the photosensitive composition tends to be further expanded in the future because the photosensitive composition can easily form a fine structure and can be easily processed on a large screen substrate.

Also, with the simplification of the panel structure and the manufacturing process, a method of forming a so-called columnar spacer, which is used to keep the distance between two substrates in a liquid crystal panel constant, is studied. Colored spacers in which the spacer and the black matrix are integrated have also been developed. However, in such a colored spacer, in addition to the usual shape and compression characteristics, a volume resistivity or a ratio of a certain value or more is prevented so as not to cause a short circuit of the electric circuit even when mounted directly on the TFT element. It is required to have a dielectric constant.
As such a colored spacer, one using a plurality of organic coloring pigments for the pigment and one using an organic black pigment have been proposed. Patent Document 1 describes a photosensitive coloring composition having excellent dispersibility and light shielding property by combining a specific organic black pigment and a dispersant, and having a low relative dielectric constant.

On the other hand, an image display apparatus including an organic electroluminescent element (also referred to as organic electroluminescence or organic EL) is excellent in visibility and responsiveness such as contrast and viewing angle, and low power consumption, thin and light weight, and It is attracting attention as a next-generation flat panel display (FPD) because the display body can be made flexible.
The organic electroluminescent element has a structure in which an organic layer including a light emitting layer or various functional layers is sandwiched between a pair of electrodes at least one of which is light transmitting. The image display apparatus displays an image by driving a panel in which an organic electroluminescent element is disposed for each pixel.
Conventionally, such an organic electroluminescent device is manufactured by laminating a light emitting layer or various functional layers in a region surrounded by a partition wall after forming the partition wall (bank) on a substrate.

  In order to form a light emitting layer or the like in a region surrounded by a partition, a vapor deposition method in which a material is sublimated in a vacuum state and deposited on a substrate to form a film is mainly applied. Further, in recent years, a method of forming a film by a wet process such as a casting method, a spin coating method, or an inkjet printing method has attracted attention. In particular, the ink jet printing method can reduce unevenness in film thickness in the case of a large area, and can achieve high definition of the display by reduction of color at the time of application, reduction of material usage, and improvement of yield. Since it becomes possible, it is suitable as a film-forming method of the organic layer in a large sized panel.

  Moreover, as a method of forming these partition walls easily, a method of forming by photolithography using a photosensitive resin composition is known.

WO 2015/046178

  In recent years, there is a demand to reduce the outgassing generated from the cured product after forming the cured product constituting the image display device and the like. In particular, in organic electroluminescent devices, there is a strong demand for reducing the outgassing generated from the partition walls at the time of device light emission. In the organic electroluminescent device, if the amount of outgas generated from the cured product such as the partition wall is large, the lifetime of the device may be reduced.

  On the other hand, among the image display devices, in a high resolution model, it is necessary to miniaturize a cured product constituting the same, and even a fine pattern is required to be sufficiently in close contact with a substrate or the like in a developing step. ing.

As a result of investigation by the present inventors, it was found that the photosensitive coloring composition described in Patent Document 1 has a large amount of outgassing and has a problem in practical use.
In addition, Patent Document 1 does not describe or suggest the application of the organic electroluminescent device to the partition, and the inventors of the present invention examined the application for forming the partition of the organic electroluminescent device and are required for a model of general resolution. It has been found that the adhesion of patterns of the same size is sufficient, but the adhesion of fine patterns as required for high resolution models is not sufficient.

The first object of the present invention is to provide a colored photosensitive resin composition which has a small amount of outgassing after formation of a cured product and is excellent in reliability, and also has good adhesion of a fine pattern in a developing step at the time of production of the cured product. It is to provide.
Another object of the present invention is to provide a partition formed using the colored photosensitive resin composition, an organic electroluminescent device provided with the partition, and an image display apparatus and illumination including the organic electroluminescent device.

A second object of the present invention is to provide a colored photosensitive resin composition for forming partition walls of an organic electroluminescent device, which has a small amount of outgassing after formation of a cured product and is excellent in reliability.
Another object of the present invention is to provide a partition formed using the colored photosensitive resin composition, an organic electroluminescent device provided with the partition, and an image display apparatus and illumination including the organic electroluminescent device.

  Furthermore, the 3rd subject of this invention is providing the pigment dispersion liquid for comprising the photosensitive resin composition which solves a 1st subject.

As a result of intensive investigations conducted by the present inventors, the present inventors have found that the above-mentioned problems can be solved by a colored photosensitive resin composition or the like containing a specific organic black pigment and further containing a specific binder resin in a certain amount or more. It reached.
That is, the gist of the present invention is as follows.

[1] A colored photosensitive resin composition comprising (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator,
The (A) coloring agent is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound Containing (A1) organic black pigment containing
The (B) dispersant contains an acrylic dispersant,
The coloring photosensitive resin composition characterized by the said (C) binder resin containing 75 mass% or more of (C1) epoxy (meth) acrylate resins.

(In formula (I), R ^a1 and R ^a6 each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are each independently a hydrogen atom, a halogen atom, R ^a11 , COOH, COOR ^a11 , COO ⁻ , CONH ₂ , CONHR ^{a11 , CONR a11 R a12, CN,} OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ^a11 or SO ₂ NR ^a11 R ^a12 is represented;
And, at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may be directly linked to each other or to each other by oxygen atoms, sulfur atoms, NH or NR ^a11 bridges;
R ^a11 and R ^a12 are each independently 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 2 to 12 alkynyl groups are represented. )
[2] The colored photosensitive resin composition according to [1], wherein the content ratio of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85% by mass or more.
[3] The (C1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and a partial structure represented by the following general formula (III) The coloring photosensitive resin composition as described in [1] or [2] which contains one or both of epoxy (meth) acrylate resin to have.

(In formula (II), R ¹¹ represents a hydrogen atom or a methyl group;
R ¹² represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (II) may be further substituted by any substituent;
* Represents a bond. )

(In formula (III), each R ¹³ independently represents a hydrogen atom or a methyl group;
R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond. )
[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the acrylic dispersant is a nitrogen-containing acrylic dispersant.
[5] The color sensitivity according to any one of [1] to [4], wherein the content ratio of the (A) colorant is 60% by mass or less based on the total solid content of the colored photosensitive resin composition. Resin composition.
[6] The colored photosensitive resin according to any one of [1] to [5], wherein the (A) colorant further contains one or both of (A2) an organic coloring pigment and (A3) carbon black Composition.
[7] The colored photosensitive resin composition according to any one of [1] to [6], wherein the content ratio of the (A1) organic black pigment in the (A) colorant is 10% by mass or more.
[8] The colored photosensitive resin composition according to any one of [1] to [7], which is used to form a partition wall of an organic electroluminescent device.

[9] For forming a partition wall of an organic electroluminescent device, which contains (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator A colored photosensitive resin composition of
The (A) coloring agent is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound Containing (A1) organic black pigment containing
The coloring photosensitive resin composition characterized by the said (C) binder resin containing 75 mass% or more of (C1) epoxy (meth) acrylate resins.

(In formula (I), R ^a1 and R ^a6 each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are each independently a hydrogen atom, a halogen atom, R ^a11 , COOH, COOR ^a11 , COO ⁻ , CONH ₂ , CONHR ^{a11 , CONR a11 R a12, CN,} OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ^a11 or SO ₂ NR ^a11 R ^a12 is represented;
And, at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may be directly linked to each other or to each other by oxygen atoms, sulfur atoms, NH or NR ^a11 bridges;
R ^a11 and R ^a12 are each independently 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 2 to 12 alkynyl groups are represented. )
[10] The colored photosensitive resin composition according to [9], wherein the content ratio of the (C1) epoxy (meth) acrylate resin in the (C) binder resin is 85% by mass or more.
[11] The (C1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and a partial structure represented by the following general formula (III) The coloring photosensitive resin composition as described in [9] or [10] which contains one or both of the epoxy (meth) acrylate resin to have.

(In formula (II), R ¹¹ represents a hydrogen atom or a methyl group;
R ¹² represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (II) may be further substituted by any substituent;
* Represents a bond. )

(In formula (III), each R ¹³ independently represents a hydrogen atom or a methyl group;
R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond. )
[12] The color sensitivity according to any one of [9] to [11], wherein the content ratio of the (A) colorant is 60% by mass or less based on the total solid content of the colored photosensitive resin composition. Resin composition.
[13] The colored photosensitive resin according to any one of [9] to [12], wherein the (A) colorant further contains one or both of (A2) an organic coloring pigment and (A3) carbon black Composition.
[14] The colored photosensitive resin composition according to any one of [9] to [13], wherein the content ratio of the (A1) organic black pigment in the (A) colorant is 10% by mass or more.

[15] A partition configured of the colored photosensitive resin composition according to any one of [1] to [14].
The organic electroluminescent element provided with the partition as described in [16] [15].
The image display apparatus containing the organic electroluminescent element as described in [17] [16].
[18] A lighting comprising the organic electroluminescent device according to [16].

[19] A pigment dispersion containing (A) a colorant, (B) a dispersant and (C) a binder resin,
The (A) coloring agent is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound Containing (A1) organic black pigment containing
The (B) dispersant contains an acrylic dispersant,
The pigment dispersion liquid characterized by said (C) binder resin containing (C1) epoxy (meth) acrylate resin.

(In formula (I), R ^a1 and R ^a6 each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are each independently a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ^a11 , COO ⁻ , CONH ₂ , CONHR ^{a11 , CONR a11 R a12, CN,} OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ^a11 or SO ₂ NR ^a11 R ^a12 is represented;
And, at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may be directly linked to each other or to each other by oxygen atoms, sulfur atoms, NH or NR ^a11 bridges;
R ^a11 and R ^a12 are each independently 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 2 to 12 alkynyl groups are represented. )
[20] The pigment dispersion according to [19], wherein the content ratio of the (B) dispersant is 10 parts by mass or more with respect to 100 parts by mass of the (A) colorant.
[21] An epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and a partial structure represented by the following general formula (III): The pigment dispersion liquid as described in [19] or [20] which contains one or both of the epoxy (meth) acrylate resin to have.

(In formula (II), R ¹¹ represents a hydrogen atom or a methyl group;
R ¹² represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (II) may be further substituted by any substituent;
* Represents a bond. )

(In formula (III), each R ¹³ independently represents a hydrogen atom or a methyl group;
R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond. )
[22] The pigment dispersion according to any one of [19] to [21], wherein the acrylic dispersant is a nitrogen-containing acrylic dispersant.
[23]
The pigment dispersion liquid of any one of [19]-[22] used in order to manufacture a coloring photosensitive resin composition.

  According to an embodiment of the present invention, there is provided a colored photosensitive resin composition which has a small amount of outgassing after formation of a cured product and is excellent in reliability, and has good adhesion of a pattern in a development step at the time of creation of the cured product. Can. In addition, the cured product formed from the colored photosensitive resin composition of the present invention has a small amount of outgassing at the time of operation, and as the light emitting element, the decrease in life is small, and the reliability is excellent.

  Moreover, according to another aspect of the present invention, it is possible to provide a colored photosensitive resin composition for forming partition walls of an organic electroluminescent device, which has a small amount of outgassing after formation of a cured product and is excellent in reliability. In addition, the cured product formed from the colored photosensitive resin composition of the present invention has a small amount of outgassing at the time of operation, and as the light emitting element, the decrease in life is small, and the reliability is excellent.

  Moreover, it becomes possible to provide the said colored photosensitive resin composition by the pigment dispersion liquid of this invention.

Hereinafter, the present invention will be described in detail. In addition, the following description is an example of embodiment of this invention, and this invention is not specified in these, unless the summary is exceeded.
In the present invention, "(meth) acrylic" means "acrylic and / or methacrylic", and "total solids" means in the colored photosensitive resin composition or pigment dispersion. It shall mean all ingredients other than the solvent. Furthermore, the numerical range represented using "-" in this invention means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.
In the present invention, "(co) polymer" is meant to include both a homopolymer (homopolymer) and a copolymer (copolymer), and "(acid) anhydride", " (Anhydride)... "Acid" is meant to include both an acid and its anhydride.
In the present invention, the partition material refers to a bank material, a wall material, and a wall material, and similarly, the partition wall refers to a bank, a wall, and a wall. The partition wall is, for example, for partitioning a functional layer (organic layer) in an active drive type organic electroluminescent device, and a material for forming the functional layer in a partitioned region (pixel region) is vapor-deposited or inkjetted. It is used in order to form the pixel etc. which consist of a functional layer and a partition by performing application and drying by etc., and so on.
In the present invention, the weight average molecular weight refers to a weight average molecular weight (Mw) in terms of polystyrene by GPC (gel permeation chromatography).
In the present invention, the term "reliability" refers to the reliability at the time of driving of the organic electroluminescent device, and particularly to the display reliability in the case of an image display device and to the luminescence reliability in the case of illumination.

  The colored photosensitive resin composition according to the first aspect of the present invention solves the first problem, and the compound (A) is a compound represented by the following general formula (I), And (B) an organic black pigment containing (A1) an organic black pigment containing at least one selected from the group consisting of a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound; An acrylic dispersant is contained, and the (C) binder resin contains 75% by mass or more of the (C1) epoxy (meth) acrylate resin.

  A colored photosensitive resin composition according to a second aspect of the present invention solves the second problem, and is a colored photosensitive resin composition for forming partition walls of an organic electroluminescent device, The (A) coloring agent is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound It is a thing containing the (A1) organic black pigment containing seed | species, and said (C) binder resin contains 75 mass% or more of (C1) epoxy (meth) acrylate resins.

  The pigment dispersion according to the third aspect of the present invention solves the third problem, and the (A) colorant is a compound represented by the general formula (I) described later, the compound A (A1) organic black pigment containing at least one member selected from the group consisting of a geometric isomer, a salt of the compound, and a salt of the geometric isomer of the compound, wherein the (B) dispersant comprises an acrylic dispersion And the (C) binder resin comprises (C1) an epoxy (meth) acrylate resin.

  Hereinafter, “the colored photosensitive resin composition of the present invention” refers to both the colored photosensitive resin composition according to the first aspect and the colored photosensitive resin composition according to the second aspect unless otherwise noted. Point to

[1] Components and composition of colored photosensitive resin composition The components constituting the colored photosensitive resin composition of the present invention and the composition thereof will be described.
The colored photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as "photosensitive resin composition") comprises (A) a colorant, (B) a dispersant, (C) a binder resin, and (D) a photopolymerization. And (E) a photopolymerization initiator, and usually also a solvent.

[1-1] (A) Colorant The (A) colorant in the colored photosensitive resin composition and the pigment dispersion of the present invention is a compound represented by the following general formula (I) (hereinafter referred to as “compound (I) (A1) organic black pigment (hereinafter referred to as "(A1)") which contains at least one member selected from the group consisting of: geometrical isomers of the compound, salts of the compound, and salts of geometrical isomers of the compound , “(A1) Organic black pigment” may be referred to.
Thus, it is considered that the high resistance, the low dielectric constant, and the high light blocking ratio can be realized by containing the (A1) organic black pigment. Furthermore, since a cured product having a color tone closer to black can be obtained, it can be suitably used as a colorant for forming partition walls of an organic electroluminescent device, which has a large area ratio in an image display area of an image display device. . In addition, the dispersibility and storage stability are also good by using the (A1) organic black pigment, and in the case of a colored photosensitive resin composition containing the same, the patterning aptitude at the time of development is also good.

In formula (I), R ^a1 and R ^a6 each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are each independently a hydrogen atom, a halogen atom, R ^a11 , COOH, COOR ^a11 , COO ⁻ , CONH ₂ , CONHR ^{a11 , CONR a11 R a12, CN,} OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ^a11 or SO ₂ NR ^a11 R ^a12 is represented;
And, at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may be directly linked to each other or to each other by oxygen, sulfur, NH or NR ¹¹ bridges;
R ^a11 and R ^a12 are each independently 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 2 to 12 alkynyl groups are represented.

  The geometric isomer of the compound represented by the general formula (I) has the following core structure (however, the substituent in the structural formula is omitted), and the trans-trans isomer is probably the most stable. .

  When the compound represented by the general formula (I) is anionic, the charge thereof may be any known suitable cation such as metal, organic, inorganic or metal organic cation, specifically alkali metal, alkaline earth metal It is preferable that the salts be compensated by a transition metal, a primary ammonium, a secondary ammonium, a tertiary ammonium such as trialkyl ammonium, a quaternary ammonium such as tetra alkyl ammonium or an organometallic complex. Moreover, when the geometric isomer of the compound represented by general formula (I) is anionic, it is preferable that it is a similar salt.

As for the substituent of the general formula (I), the followings are preferable since the shielding ratio tends to be high. This is because the following substituents have no absorption and are considered not to affect the hue of the pigment.
Each of R ^a2 , R ^a4 , R ^a5 , R ^a7 , R ^a9 and R ^a10 is preferably independently a hydrogen atom, a fluorine atom or a chlorine atom, and more preferably a hydrogen atom.
Each of R ^a3 and R ^a8 independently preferably is preferably a hydrogen atom, NO ₂ , OCH ₃ , OC ₂ H ₅ , a bromine atom, a chlorine atom, CH ₃ , C ₂ H ₅ , N (CH ₃ ) ₂ , N (CH ₂ ) _{3) (C 2 H 5)} , N (C 2 H 5) 2, α- naphthyl, beta-naphthyl, SO ₃ H or SO ₃ ^- and is, more preferably a hydrogen atom or SO ₃ H.

Each of R ¹ and R ⁶ independently is preferably a hydrogen atom, CH ₃ or CF ₃ , and more preferably a hydrogen atom.
Preferably, at least one combination selected from the group consisting of R ¹ and R ⁶ , R ² and R ⁷ , R ³ and R ⁸ , R ⁴ and R ⁹ , and R ⁵ and R ¹⁰ is identical, more preferably R ¹ is identical to R ⁶ , R ² is identical to R ⁷ , R ³ is identical to R ⁸ , R ⁴ is identical to R ⁹ , and R ⁵ is R ¹⁰ and It is the same.

  The alkyl group having 1 to 12 carbon atoms is, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, 2-methylbutyl group, n- Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl A nonyl group, a decyl group, an undecyl group or a dodecyl group.

  The cycloalkyl group having 3 to 12 carbon atoms is, for example, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, thudyl group, norbornyl group, bornyl group, norcalyl group A caryl group, a menthyl group, a norpinyl group, a pinyl group, a 1-adamantyl group or a 2-adamantyl group.

  The alkenyl group having 2 to 12 carbon atoms is, for example, vinyl group, allyl group, 2-propen-2-yl group, 2-buten-1-yl group, 3-buten-1-yl group, 1,3-butadiene -2-yl group, 2-penten-1-yl group, 3-penten-2-yl group, 2-menthyl-1-buten-3-yl group, 2-methyl-3-buten-2-yl group, 3-methyl-2-buten-1-yl group, 1,4-pentadien-3-yl group, hexenyl group, octenyl group, nonenyl group, decenyl group or dodecenyl group.

  The cycloalkenyl group having a carbon number of 3 to 12 is, for example, 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2 , 4-Cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4 (10) -tugen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene-1 -Yl group, 7,7-dimethyl-2,4-norcaradiene-3-yl group or camphenyl group.

  The alkynyl group having 2 to 12 carbon atoms is exemplified by, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl Group, 1,4-pentadiyn-3-yl group, 1,3-pentadiyn-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group Group, trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadiyn-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decin-10-yl group or 1-dodecin-12-yl group.

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

  The (A1) organic black pigment is preferably a compound represented by the following general formula (I-1) (hereinafter sometimes referred to as “compound (I-1)”), and a geometric isomer of the compound And at least one selected from the group consisting of

As a specific example of such an organic black pigment, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF Corporation) can be mentioned under the trade name.
The organic black pigment is preferably dispersed by the dispersant, solvent and method described later. Also, at the time of dispersion, the sulfonic acid derivative of the compound (I) (sulfonic acid substituted product), or the sulfonic acid derivative of the geometric isomer of the compound (I), particularly the sulfonic acid derivative of the compound (I-1), or When the sulfonic acid derivative of the geometric isomer of the compound (I-1) is present, the dispersibility and the storage stability may be improved.

  The colorant (A) used in the present invention may contain other colorants in addition to the organic black pigment (A1). As another coloring agent, it is preferable to use a pigment, and the pigment may be an organic pigment or an inorganic pigment, but it is more preferable to use an organic pigment from the viewpoint of high resistance and low dielectric constant. In particular, it is more preferable to use an organic coloring pigment (hereinafter sometimes referred to as "(A2) organic coloring pigment").

  The chemical structures of these pigments are not particularly limited, but organic pigments such as azo, phthalocyanine, quinacridone, benzimidazolone, isoindolinone, dioxazine, indanthrene and perylene pigments can be used. . Hereinafter, specific examples of usable organic pigments are shown by pigment numbers. Terms such as "CI pigment red 2" listed below mean color index (CI).

As a red pigment, C.I. I. Pigment red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 81, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 17 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235 236, 237, 238, 239, 242, 243, 245, 247, 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 can be mentioned. Among these, preferably C.I. I. Pigment red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, and more preferably C.I. I. Pigment red 177, 209, 224, 254 can be mentioned.
In terms of dispersibility and light shielding property, C.I. I. Pigment Red 177, 254, 272 are preferably used, and when the colored photosensitive resin composition of the present invention is cured by ultraviolet light, it is preferable to use a red pigment having a low ultraviolet absorptivity, From C. I. It is more preferable to use pigment red 254, 272.

  As an orange (orange) pigment, C.I. I. Pigment orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65, 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79 can be mentioned. Among these, C.I. I. Pigment Orange 13, 43, 64, 72 are preferably used, and when curing the colored photosensitive resin composition of the present invention with ultraviolet light, it is preferable to use an orange pigment having a low ultraviolet absorptivity, From such a viewpoint, C.I. I. Pigment orange 64, 72 is more preferable, and C.I. I. Pigment Orange 64 is particularly preferred.

As a blue pigment, C.I. I. Pigment blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 can be mentioned. Among these, preferably C.I. I. Pigment blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. I. Pigment blue 15: 6 can be mentioned.
In terms of dispersibility and light shielding property, C.I. I. Pigment Blue 15: 6, 16, 60 is preferably used, and when curing the colored photosensitive resin composition of the present invention with ultraviolet light, it is preferable to use a blue pigment having a low ultraviolet absorptivity, From such a viewpoint, C.I. I. It is more preferable to use pigment blue 60.

As a purple pigment, C.I. I. Pigment violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 25, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 can be mentioned. Among these, C.I. I. Pigment violet 19 and 23 are preferred, and C.I. I. It is more preferable to use pigment violet 23.
In terms of dispersibility and light shielding property, C.I. I. It is preferable to use pigment violet 23 and 29, and when curing the colored photosensitive resin composition of the present invention by ultraviolet light, it is preferable to use a violet pigment having a low ultraviolet absorptivity, from such a viewpoint C. I. It is more preferable to use pigment violet 29.

Examples of organic coloring pigments that can be used besides red pigments, orange pigments, blue pigments, and purple pigments include green pigments, yellow pigments, and the like.
As a green pigment, C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58 can be mentioned. Among these, preferably C.I. I. Pigment green 7, 36 can be mentioned.
As yellow pigments, C.I. I. Pigment yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 17 , 174, 175, 176, 180, 181, 182, 183, 185, 188, 189, 190, 191, 191, 191, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202 , 203, 204, 205, 206, 207, 208 can be mentioned. Among these, preferably C.I. I. Pigment yellow 83, 117, 129, 138, 139, 150, 154, 155, 180, 185, and more preferably C.I. I. Pigment yellow 83, 138, 139, 150, 180 can be mentioned.

  Among these pigments, it is preferable to use a combination of at least one selected from the group consisting of red pigments and orange pigments, and at least one selected from the group consisting of blue pigments and purple pigments. Thus, there is a tendency that high light-shielding property can be achieved by using a specific pigment combination.

Among these, in terms of light shielding property and color tone, it is preferable to contain at least one or more of the following pigments.
Red pigment: C.I. I. Pigment red 177, 254, 272
Orange pigment: C.I. I. Pigment orange 43, 64, 72
Blue pigment: C.I. I. Pigment blue 15: 6, 60
Purple pigment: C.I. I. Pigment violet 23, 29

  The combination of colors is not particularly limited, but from the viewpoint of light shielding, for example, a combination of a red pigment and a blue pigment, a combination of a blue pigment and an orange pigment, a combination of a blue pigment and an orange pigment and a purple pigment, etc. .

In addition to these organic coloring pigments, other black coloring agents can be used as other coloring agents.
Among the black colorants, other organic black pigments other than those represented by the above general formula (I) may be used from the viewpoint of light shielding property and color tone. Other organic black pigments include aniline black, perylene black, cyanine black and the like.

  In the present invention, inorganic black pigments can be used. As the inorganic black pigment, carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black and the like can be mentioned. Among these, carbon black (hereinafter sometimes referred to as “(A3) carbon black”) can be preferably used from the viewpoint of light shielding property and image characteristics. Examples of carbon black include the following carbon blacks.

Mitsubishi Chemical Corporation: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF 88, # 5, # 10, # 20, # 25, # 30, # 32, # 33, # 33, # 40 # 44, # 45, # 47, # 50, # 52, # 55, # 650, # 750, # 850, # 900, # 950, # 960, # 970, # 980, # 990, # 1000, ## 2200, # 2300, # 2350, # 2400, # 2600, # 2650, # 3030, # 3050, # 3150, # 3250, # 3400, # 3600, # 3750, # 3950, # 4000, # 4010, OIL 7 B, OIL 9 B , OIL11B, OIL30B, OIL31B
Made by Degussa: Printex (registered trademark, the same as the following) 3, Printex 3 OP, Printex 30, Printex 30 OP, Printex 40, Printex 45, Printex 55, Printex 60, Printex 75, Printex 80, Printex 85, Printex 90, Printex A, Printex L, Printex G, Printex P, Printex P U, Printex V, SpecialBlack 550, Special Black 350, Special Black 250, Special Black 100, Special Black 6, Special Black 5, Special Black 4, Color Black FW1, Color Black FW2, Co lor Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170
Made by Cabot: Monarch (registered trademark, the same as the following) 120, Monarch 280, Monarch 460, Monarch 800, Monarch 880, Monarch 900, Monarch 1000, Monarch 1100, Monarch 1300, Monarch 1400, Monarch 4630, REGAL (the same as the following) 99, REGAL 99R, REGAL 415, REGAL 415 R, REGAL 250, REGAL 250 R, REGAL 330, REGAL 400 R, REGAL 55 R0, REGAL 660 R, BLACK PEARLS 480, PEARLS 130, VULCAN (registered trademark, hereinafter the same) XC72R, ELFTEX (registered trademark) -8
Made by Biller: RAVEN (registered trademark) 11, RAVEN 14, RAVEN 15, RAVEN 16, RAVEN 22, RAVEN 35, RAVEN 40, RAVEN 410, RAVEN 420, RAVEN 450, RAVEN 500, RAVEN 780, RAVEN 850H, RAVEN 1000, RAVEN 1020, RAVEN 1040U, RAVEN 1060U , RAVEN 1170, RAVEN 1190U, RAVEN 1250, RAVEN 1500, RAVEN 2000, RAVEN 2500U, RAVEN 3500, RAVEN 5000, RAVEN 5250, RAVEN 5750, RAVEN 7000

  The carbon black may be coated with a resin. Use of resin-coated carbon black has the effect of improving the adhesion to a glass substrate and the volume resistance. As the carbon black coated with resin, for example, carbon black described in Japanese Patent Application Laid-Open No. 09-71733 can be suitably used. Resin-coated carbon black is preferably used in terms of volume 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 100 ppm or less. Carbon black is usually Na mixed in from the raw material oil and combustion oil (or gas) at the time of production, reaction stopped water and granulated water, and further from the furnace material of the reaction furnace, etc., Ca, K, Mg, Al, Fe Etc. is contained in the order of percent. Of these, Na and Ca are generally contained in several hundred ppm or more, respectively, but by reducing them, the permeation to the transparent electrode (ITO) and other electrodes is suppressed, and electricity is reduced. Tend to be able to prevent

  As a method of reducing the content of the ash content containing these Na and Ca, as a raw material oil and fuel oil (or gas) at the time of producing carbon black and reaction stop water, those having the smallest content of these are selected carefully It is possible by reducing the amount of addition of the alkali substance to adjust the volume and the structure as much as possible. Another method is a method of washing carbon black produced from a furnace with water, hydrochloric acid or the like to dissolve and remove Na or Ca.

  Specifically, after carbon black is mixed and dispersed in water, hydrochloric acid or hydrogen peroxide solution, a solvent which is poorly soluble in water is added, and the carbon black moves to the solvent side and is completely separated from water At the same time, most of Na and Ca present in carbon black are dissolved and removed in water and acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, there are cases where it is possible to use only the carbon black production process with carefully selected raw materials or water or acid dissolution method alone. The total amount of Na and Ca can be easily made 100 ppm or less.

  The resin-coated carbon black is preferably a so-called acidic carbon black having a pH of 6 or less. Since the dispersion diameter (agglomerate diameter) in water is reduced, coating to fine units is possible, which is preferable. Furthermore, it is preferable that the average particle diameter is 40 nm or less and the dibutyl phthalate (DBP) absorption amount is 140 mL / 100 g or less. By setting the content in the above range, a coating film having a good light shielding property tends to be obtained. The average particle size means a number average particle size, and it is a particle which measures several 2000 000 pieces of carbon black particles in the photograph obtained by photographing several fields at a magnification of several tens of thousands by electron microscope observation. It means the equivalent circle diameter obtained by image analysis.

  The method for preparing the resin-coated carbon black is not particularly limited. For example, after appropriately adjusting the amounts of carbon black and resin, 1. A resin solution prepared by mixing and heating a resin and a solvent such as cyclohexanone, toluene and xylene, and a suspension obtained by mixing carbon black and water are mixed and stirred to separate carbon black and water, 2. A method of forming a sheet obtained by removing the water and heating and kneading, forming into a sheet, pulverizing and drying it; A method of mixing and stirring the resin solution and the suspension prepared in the same manner as above to granulate the carbon black and the resin, separating the obtained granular material, and heating to remove the remaining solvent and water; 3. A carboxylic acid such as maleic acid or fumaric acid is dissolved in a solvent, carbon black is added, mixed and dried, the solvent is removed to obtain a carboxylic acid-impregnated carbon black, and a resin is added thereto to dry blend. How to do it; The reactive group-containing monomer component constituting the resin to be coated and water are stirred at high speed to prepare a suspension, cooled after polymerization, and after obtaining a reactive group-containing resin from a polymer suspension, Carbon black is added and kneaded, and a method of reacting carbon black and a reactive group (grafting of carbon black), cooling and crushing, or the like can be employed.

The type of resin to be coated is not particularly limited, but a synthetic resin is generally used, and furthermore, a resin having a benzene ring in the structure has a stronger amphoteric surfactant function. It is preferable from the viewpoint of dispersibility and dispersion stability.
Specific synthetic resins include thermosetting resins such as phenol resin, melamine resin, xylene resin, diallyl phthalate resin, glyptal resin, epoxy resin, alkylbenzene resin, polystyrene, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, modified polyphenylene Thermoplastic resins such as oxides, polysulfones, polyparaphenylene terephthalamides, polyamideimides, polyimides, polyaminobismaleimides, polyethersulfopolyphenylenesulfones, polyarylates, and polyetheretherketones can be used. The amount of the coating resin is preferably 1 to 30% by mass with respect to the total amount of carbon black and the coating resin. By setting the content to the above lower limit or more, there is a tendency that the coating can be made sufficient. On the other hand, by setting the content to the above upper limit value or less, adhesion between resins can be prevented, and the dispersibility can be made favorable.

  The carbon black thus coated with a resin can be used as a light shielding material such as a partition wall or a colored spacer according to a conventional method, and an organic light emitting element and a color filter having the partition wall and the colored spacer as components It can be created by ordinary methods. When such carbon black is used, it tends to be possible to achieve a high light blocking rate and low cost. Further, by coating the surface of the carbon black with a resin, it is possible to prepare a light shielding material such as a partition wall having a high resistance and a low dielectric constant and a colored spacer.

In addition to the above-mentioned organic coloring pigment and black coloring agent, dyes may be used as other coloring agents. Examples of dyes that can be used as colorants include azo dyes, anthraquinone dyes, phthalocyanine dyes, quinoneimine dyes, quinoline dyes, nitro dyes, carbonyl dyes, methine dyes and the like.
As an azo dye, for example, C.I. I. Acid Yellow 11, C.I. I. Acid Orange 7, C.I. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct red 28, C.I. I. Direct red 83, C.I. I. Direct Yellow 12, C.I. I. Direct orange 26, C.I. I. Direct green 28, C.I. I. Direct green 59, C.I. I. Reactive Yellow 2, C.I. I. Reactive Red 17, C.I. I. Reactive red 120, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Disperse thread 58, C.I. I. Disperse Blue 165, C.I. I. Basic Blue 41, C.I. I. Basic Red 18, C.I. I. Mordant tread 7, C.I. I. Mordant yellow 5, C.I. I. Mordant Black 7 and the like.

Examples of anthraquinone dyes include C.I. I. Bat Blue 4, C.I. I. Acid Blue 40, C.I. I. Acid Green 25, C.I. I. Reactive Blue 19, C.I. I. Reactive Blue 49, C.I. I. Disperse thread 60, C.I. I. Disperse Blue 56, C.I. I. Disperse Blue 60 and the like.
In addition to these, as a phthalocyanine dye, for example, C.I. I. Pad Blue 5 and the like are, for example, C.I. I. Basic Blue 3, C.I. I. Basic Blue 9 and the like are, for example, C.I. I. Solvent yellow 33, C.I. I. Acid Yellow 3, C.I. I. Disperse Yellow 64 and the like are, for example, C.I. I. Acid Yellow 1, C.I. I. Acid Orange 3, C.I. I. Disperse Yellow 42 and the like.

The pigments such as (A1) organic black pigment, (A2) organic coloring pigment, black colorant and the like have an average particle diameter of usually 1 μm or less, preferably 0.5 μm or less, more preferably 0.25 μm or less, It is preferable to use it dispersedly. Here, the standard of the average particle size is the number of pigment particles.
The average particle size of the pigment is a value determined from the pigment particle size measured by dynamic light scattering (DLS). Particle size measurement is a sufficiently diluted colored photosensitive resin composition (usually diluted to prepare a pigment content ratio of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by the measuring instrument , According to its concentration, and measure at 25.degree.

[1-2] (B) Dispersant In the colored photosensitive resin composition and the pigment dispersion of the present invention, it is possible to finely disperse (A) the colorant and stabilize the dispersed state of the quality. Since it is important to secure the property, it contains (B) a dispersant.

  In the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion according to the third aspect of the present invention, the (B) dispersant contains an acrylic dispersant. Since the acrylic dispersant has a flexible main skeleton having a linear molecular structure, many of the adsorptive groups are adsorbed to the colorant so that the colorant is uniformly dispersed in the colored photosensitive resin composition and the pigment dispersion. It is considered to be dispersed. By uniformly arranging the coloring agent in the coating film, the coating film becomes a dense film, and further, by uniformly arranging the coloring agent which is a component insoluble in the alkaline developer, in the coating film, Penetration of the developing solution into the inside of the coating film is suppressed at the time of development processing to improve the pattern adhesion, and it is considered that the adhesion is also improved even in the case of particularly fine patterns.

As the acrylic dispersant, a polymer dispersant having a functional group is preferable. Further, from the viewpoint of dispersion stability, a carboxyl group; a phosphoric acid group; a sulfonic acid group; or these bases; an acrylic dispersant containing a nitrogen atom is preferable, and among them, an acrylic dispersant containing a nitrogen atom is preferable. Furthermore, a polymer dispersant having a basic functional group such as a primary, secondary or tertiary amino group; a quaternary ammonium base; a group derived from a nitrogen-containing heterocycle such as pyridine, pyrimidine or pyrazine; It is particularly preferable from the viewpoint of being able to be dispersed with a small amount of dispersant when dispersing the colorant. These functional groups act as adsorptive groups that adsorb to the colorant.
Examples of commercially available acrylic dispersants include DISPERBYK-2000, DISPERBYK-2001, BYK-LPN 21116, BYK-LPN6919, etc. (all manufactured by Bick Chemie, Inc.).

  As an acrylic dispersant containing a nitrogen atom, an unsaturated group-containing unit having a functional group (the functional group as referred to herein is the functional group described above as the functional group contained in the polymer dispersant) It is preferable to use a random copolymer, a graft copolymer or a block copolymer of a body and an unsaturated group-containing monomer having no functional group. These copolymers can be produced by known methods.

  As the unsaturated group-containing monomer having a functional group, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyl oxyethyl phthalic acid, 2- (meth) acryloyl oxyethyl Unsaturated monomers having a carboxyl group such as hexahydrophthalic acid and acrylic acid dimer; dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate and tertiary amino groups such as quaternary compounds thereof, quaternary ammonium Unsaturated monomers having a base are mentioned as a specific example. One of these may be used alone, or two or more may be used in combination.

  Examples of unsaturated group-containing monomers having no functional group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate and isobutyl ( Meta) 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, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone, styrene and derivatives thereof, α-methylstyrene, N-cyclohexene N-substituted maleimide such as syl maleimide, N-phenyl maleimide, N-benzyl maleimide, acrylonitrile, vinyl acetate and polymethyl (meth) acrylate macromonomer, polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, polyethylene glycol Macromonomers, macromonomers such as polypropylene glycol macromonomers, polycaprolactone macromonomers, etc. may be mentioned. One of these may be used alone, or two or more may be used in combination. The side chains of these monomers act as solvent affinity moieties compatible with the solvent.

  The acrylic dispersant is preferably an AB or BAB block copolymer composed of an A block having a functional group and a B block having no functional group from the viewpoint of dispersibility. In this case, in the A block, in addition to the partial structure derived from the unsaturated group-containing monomer containing the functional group, a partial structure derived from the unsaturated group-containing monomer not containing the functional group is included They may be contained in the A block in any form of random copolymerization or block copolymerization. The content of the partial structure not containing a functional group in the A block is usually 80% by mass or less, preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 10% by mass or less Most preferably, it is 0% by mass.

From the viewpoint of dispersibility, the B block is preferably composed of only a partial structure derived from the unsaturated group-containing monomer not containing the above-mentioned functional group, and two or more single amounts in one B block Partial structures derived from the body may be contained, and these may be contained in any mode of random copolymerization or block copolymerization in the B block.
The A-B or B-A-B block copolymer is prepared, for example, by the living polymerization method described below.
The living polymerization method includes an anion living polymerization method, a cation living polymerization method, and a radical living polymerization method. Among these, in the anion living polymerization method, a polymerization active species is an anion, and is represented by, for example, the following scheme.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , M is a metal atom, and s and t are integers of 1 or more.

  In the radical living polymerization method, the polymerization active species is a radical, and is shown, for example, by the following scheme.

In the above scheme, Ar ¹ is a monovalent organic group, Ar ² is a monovalent organic group different from Ar ¹ , j and k are each an integer of 1 or more, and R ^a is a hydrogen atom or 1 R ^b is ^a hydrogen atom or a monovalent organic group different from R ^a .

  In order to synthesize this acrylic dispersant, JP-A-9-62002, JP-A-9-62002 and P.I. Lutz, P .; Masson et al, Polym. Bull. 12, 79 (1984), B. C. Anderson, G. D. Andrews et al, Macromolecules, 14, 1601 (1981), K. Hatada, K. Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Koichi Right Hand, Koichi Hatata, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Articles, 46, 189 (1989), M. Kuroki, T. Aida, J. Am. Chem. Sic, 109, 4737 (1987), Takizo Aida, Shohei Inoue, Synthetic Organic Chemistry, 43, 300 (1985), D., et al. Y. Sogoh, W. R. Known methods described in Hertler et al, Macromolecules, 20, 1473 (1987) may be employed.

As described above, the acrylic dispersant that can be used in the present invention may be an A-B block copolymer or a B-A-B block copolymer, and constitutes the copolymer The A block / B block ratio is also not particularly limited, and is preferably 1/99 to 80/20 (mass ratio), and more preferably 5/95 to 60/40 (mass ratio). Within this range, the balance between dispersibility and storage stability tends to be easily secured.
The amount of quaternary ammonium base in 1 g of the A-B block copolymer or B-A-B block copolymer that can be used in the present invention is preferably 0.1 to 10 mmol in general. Within this range, good dispersibility tends to be secured.

On the other hand, an amino group may be contained in such an acrylic dispersant. The amine value of the acrylic dispersant is usually about 1 to 130 mg KOH / g. 10 mg KOH / g or more is preferable, 30 mg KOH / g or more is more preferable, 50 mg KOH / g or more is more preferable, 60 mg KOH / g or more is particularly preferable, 120 mg KOH / g or less is preferable, 100 mg KOH / g or less is more preferable, 90 mg KOH / g g or less is more preferable, and 80 mg KOH / g or less is particularly preferable. By setting the content to the above lower limit or more, the dispersibility tends to be good, and by setting the content to the above upper limit or less, the storability after dispersion tends to be good. The combination of the upper limit and the lower limit is preferably 10 to 120 mg KOH / g, more preferably 30 to 100 mg KOH / g, further preferably 50 to 90 mg KOH / g, and particularly preferably 60 to 80 mg KOH / g.
Here, the amine value of the acrylic dispersant is represented by the mass of KOH equivalent to the amount of base per 1 g of the solid content excluding the solvent in the dispersant sample, and is measured by the following method.
In a 100 mL beaker, precisely weigh 0.5 to 1.5 g of the dispersant sample and dissolve with 50 mL of acetic acid. This solution is neutralized titrated with 0.1 mol / L HClO ₄ in acetic acid using an automatic titrator equipped with a pH electrode. The inflection point of the titration pH curve is taken as the titration end point, and the amine value is determined by the following equation.

Amine value [mg KOH / g] = (561 x V) / (W x S)
[Wherein W represents the amount by which the dispersant sample is weighed [g], V represents the titration amount at the titration end point [mL], and S represents the solid concentration [% by mass] of the dispersant sample. ]

  The weight average molecular weight (Mw) of the acrylic dispersant is not particularly limited, but is preferably 1000 or more, more preferably 3000 or more, still more preferably 4000 or more, particularly preferably 5000 or more, and preferably 50000 or less, 20000 or less More preferably, 15000 or less is more preferable. By setting the content to the above lower limit or more, the dispersibility tends to be good, and by setting the above upper limit or less, the viscosity change tends to be difficult to occur. As a combination of an upper limit and a lower limit, 1000-50000 are preferable, 3000-20000 are more preferable, 4000-15000 are more preferable, 5000-15000 are especially preferable.

  When the acrylic dispersant has a quaternary ammonium base as a functional group, the chemical structure of the repeating unit containing the quaternary ammonium base is not particularly limited, but from the viewpoint of dispersibility, the acrylic dispersant has the following general formula (V It is preferable to have a repeating unit (hereinafter sometimes referred to as "repeating unit (V)") represented by).

In the above formula (V), each of R ^{31 to} R ³³ independently has a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent An optionally substituted aralkyl group, and two or more of R ^{31 to} R ³³ may combine with each other to form a cyclic structure;
R ³⁴ is a hydrogen atom or a methyl group;
X is a divalent linking group;
Y ^- is a counter anion.

The carbon number of the alkyl group which may have a substituent in R ^{31 to} R ³³ in the above formula (V) is not particularly limited, but is usually 1 or more and preferably 10 or less, The following is more preferable, 4 or less is more preferable, and 2 or less is particularly preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. Among them, methyl group, ethyl group, propyl group and butyl group are mentioned. It is preferably a group, pentyl group or hexyl group, more preferably methyl group, ethyl group, propyl group or butyl group, and still more preferably methyl group or ethyl group. Further, it may be linear or branched. In addition, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The number of carbon atoms of the aryl group which may have a substituent in R ^{31 to} R ³³ in the above formula (V) is not particularly limited, but it is usually 6 or more, and preferably 16 or less, It is more preferable that Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group and the like, and among these, phenyl group, methylphenyl group, ethylphenyl group It is preferably a dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group or an ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in R ^{31 to} R ³³ in the above formula (V) is not particularly limited, but is usually 7 or more, and preferably 16 or less, The following is more preferable, 10 or less is more preferable, and 8 or less is particularly preferable. Specific examples of the aralkyl group include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group and the like, and among these, phenylmethyl group, phenylethyl group It is preferably a group, a phenylpropyl group or a phenylbutyl group, and more preferably a phenylmethyl group or a phenylethyl group.

Among these, from the viewpoint of dispersibility, R ^{31 to} R ³³ are preferably each independently an alkyl group or an aralkyl group, and specifically, R ³¹ and R ³³ are each independently a methyl group or ethyl And R ³² is preferably a phenylmethyl group or a phenylethyl group, more preferably R ³¹ and R ³³ are a methyl group, and R ³² is a phenylmethyl group.

  When the polymer dispersant has a tertiary amine as a functional group, from the viewpoint of dispersibility, the repeating unit represented by the following general formula (VI) (hereinafter referred to as "repeating unit (VI)" It is preferable to have the

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

In addition, as the alkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (VI), it is preferable to preferably employ those exemplified as R ^{31 to} R ³³ of the above formula (V) it can.
Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (VI), those exemplified as R ^{31 to} R ³³ of the above formula (V) are preferably adopted. Can. In addition, as the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ of the above formula (VI), those exemplified as R ^{31 to} R ³³ of the above formula (V) are preferably adopted. it can.

Among these, from the viewpoint of dispersibility, R ³⁵ and R ³⁶ are preferably each independently an alkyl group which may have a substituent, and more preferably a methyl group or an ethyl group.

Examples of the substituent which may be possessed by the alkyl group, the aralkyl group or the aryl group in R ^{31 to} R ³³ of the above formula (V) and R ³⁵ and R ³⁶ of the above formula (VI) include a halogen atom, an alkoxy group, A benzoyl group, a hydroxyl group etc. are mentioned.

In the above formulas (V) and (VI), as the divalent linking groups X and Z, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ⁴³ -group, -COOR ⁴⁴ -group [wherein R ⁴³ and R ^{44 each} represents a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)] is -COO-R ⁴⁴ - group, more preferably _-COO-C 2 _{H 4} - is a radical.
In the above formula (V), examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like.

  The content ratio of the repeating unit represented by the formula (V) is not particularly limited, but from the viewpoint of dispersibility, it is represented by the content ratio of the repeating unit represented by the formula (V) and the formula (VI) Preferably it is 60 mol% or less with respect to the sum total of the content rate of a repeating unit, More preferably, it is 50 mol% or less, More preferably, it is 40 mol% or less, Especially preferably, it is 35 mol% or less Preferably it is 5 mol% or more, More preferably, it is 10 mol% or more, More preferably, it is 20 mol% or more, Especially preferably, it is 30 mol% or more. As a combination of the upper limit and the lower limit, 5 to 60 mol% is preferable, 10 to 50 mol% is more preferable, 20 to 40 mol% is more preferable, and 30 to 35 mol% is particularly preferable.

  Further, the content ratio of the repeating unit represented by the above formula (V) to the total repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 1 mol% or more, 5 mol% or more Is more preferably 8 mol% or more, particularly preferably 10 mol% or more, and preferably 50 mol% or less, more preferably 30 mol% or less. The content is preferably 20 mol% or less, more preferably 15 mol% or less. The combination of the upper limit and the lower limit is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, still more preferably 8 to 20 mol%, and particularly preferably 10 to 15 mol%.

  The content of the repeating unit represented by the formula (VI) is not particularly limited, but from the viewpoint of dispersibility, it is represented by the content of the repeating unit represented by the formula (V) and the formula (VI) Preferably it is 100 mol% or less with respect to the sum total of the content rate of a repeating unit, More preferably, it is 90 mol% or less, More preferably, it is 80 mol% or less, Especially preferably, it is 70 mol% or less Preferably it is 10 mol% or more, More preferably, it is 30 mol% or more, More preferably, it is 50 mol% or more, Especially preferably, it is 60 mol% or more. The combination of the upper limit and the lower limit is preferably 10 to 100 mol%, more preferably 30 to 90 mol%, still more preferably 50 to 80 mol%, and particularly preferably 60 to 70 mol%.

  Further, the content ratio of the repeating unit represented by the formula (VI) to the total repeating units of the dispersant is not particularly limited, but from the viewpoint of dispersibility, it is preferably 5 mol% or more, 10 mol% or more Is more preferably 15 mol% or more, particularly preferably 20 mol% or more, and preferably 60 mol% or less, more preferably 40 mol% or less. The content is preferably 30 mol% or less, more preferably 25 mol% or less. The combination of the upper limit and the lower limit is preferably 5 to 600 mol%, more preferably 10 to 40 mol%, still more preferably 15 to 30 mol%, and particularly preferably 20 to 25 mol%.

  The acrylic dispersant is a repeating unit represented by the following general formula (VII) (hereinafter referred to as “repeating unit (VII) from the viewpoint of enhancing the compatibility with a binder component such as a solvent and improving the dispersion stability. It is preferable to have “)”.

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

The carbon number of the alkyl group which may have a substituent in R ⁴¹ of the above formula (VII) is not particularly limited, but it is usually 1 or more, preferably 2 or more, and 10 or less Is preferable, 6 or less is more preferable, and 4 or less is more preferable. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group and octyl group. Among them, methyl group, ethyl group, propyl group and butyl group are mentioned. It is preferably a group, pentyl group or hexyl group, more preferably methyl group, ethyl group, propyl group or butyl group. Further, it may be linear or branched. In addition, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

  Further, n in the above formula (VII) is preferably 1 or more, more preferably 2 or more, and preferably 10 or less from the viewpoint of compatibility and dispersibility with a binder component such as a solvent. And 5 or less are more preferable. As a combination of the upper limit and the lower limit, an integer of 1 to 10 is preferable, and an integer of 2 to 5 is more preferable.

  Further, the content ratio of the repeating unit represented by the above formula (VII) to the total repeating units of the dispersant is not particularly limited, but is preferably 1 mol% or more, more preferably 2 mol% or more Is more preferably 4 mol% or more, and preferably 30 mol% or less, more preferably 20 mol% or less, and still more preferably 10 mol% or less. In the case of the above range, compatibility with the compatibility with the binder component such as solvent and the dispersion stability tends to be easily achieved. The combination of the upper limit and the lower limit is preferably 1 to 30 mol%, more preferably 2 to 20 mol%, and still more preferably 4 to 10 mol%.

  In addition, from the viewpoint of enhancing the compatibility of the dispersing agent with the binder component such as the solvent of the dispersing agent and the like and improving the dispersion stability, the acrylic dispersing agent is a repeating unit represented by one or more of the following general formulas (VIII) It is preferable to have “the repeating unit (VIII)”.

In the above formula (VIII), R ³⁸ represents an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent;
R ³⁹ is a hydrogen atom or a methyl group.

The carbon number of the alkyl group which may have a substituent in R ³⁸ of the above formula (VIII) is not particularly limited, but it is usually 1 or more, preferably 2 or more, and 4 or more More preferably, it is preferably 10 or less, and more preferably 8 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, an octyl group and a 2-ethylhexyl group. Among these, a methyl group and an ethyl group are mentioned. It is preferably a propyl group, a butyl group, a pentyl group, a hexyl group, or a 2-ethylhexyl group, and more preferably a methyl group, an ethyl group, a propyl group, a butyl group or a 2-ethylhexyl group. Further, it may be linear or branched. In addition, it may contain a cyclic structure such as a cyclohexyl group or a cyclohexylmethyl group.

The carbon number of the aryl group which may have a substituent in R ³⁸ of the above formula (VIII) is not particularly limited, but it is usually 6 or more, preferably 16 or less, and 12 or less Is more preferable, and 8 or less is more preferable. Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group and the like, and among these, phenyl group, methylphenyl group, ethylphenyl group It is preferably a dimethylphenyl group or a diethylphenyl group, and more preferably a phenyl group, a methylphenyl group or an ethylphenyl group.

The carbon number of the aralkyl group which may have a substituent in R ³⁸ of the above formula (VIII) is not particularly limited, but it is usually 7 or more, preferably 16 or less, and 12 or less Is more preferably 10 or less. Specific examples of the aralkyl group include phenylmethyl group (benzyl group), phenylethyl group (phenethyl group), phenylpropyl group, phenylbutyl group, phenylisopropyl group and the like, and among these, phenylmethyl group, phenylethyl group It is preferably a group, a phenylpropyl group or a phenylbutyl group, and more preferably a phenylmethyl group or a phenylethyl group.

Among these, from the viewpoint of solvent compatibility and dispersion stability, R ³⁸ is preferably an alkyl group or an aralkyl group, and is a methyl group, an ethyl group, a butyl group, a 2-ethylhexyl group or a phenylmethyl group. Is more preferred.
As a substituent which the alkyl group in R ³⁸ may have, a halogen atom, an alkoxy group and the like can be mentioned. Moreover, as a substituent which an aryl group or an aralkyl group may have, a chain | strand-shaped alkyl group, a halogen atom, an alkoxy group etc. are mentioned. In addition, the linear alkyl group represented by R ³⁸ includes both linear and branched.

  In addition, the content ratio of the repeating unit represented by the formula (VIII) to the total repeating units of the dispersant (in the case of containing two or more repeating units represented by the formula (VIII), the total content ratio thereof) Is preferably 30 mol% or more, more preferably 40 mol% or more, still more preferably 50 mol% or more, and 80 mol% or less from the viewpoint of dispersibility. Preferably, it is 70 mol% or less. The combination of the upper limit and the lower limit is preferably 30 to 80 mol%, more preferably 40 to 70 mol%, and still more preferably 50 to 70 mol%.

  The acrylic dispersant may have repeating units other than the repeating unit (V), the repeating unit (VI), the repeating unit (VII) and the repeating unit (VIII). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylate-based monomers such as (meth) acrylic acid chloride; (meth) acrylamide, N- (Meth) acrylamide type monomers such as methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; repeating units derived from monomers such as N-methacryloyl morpholine and the like.

  The acrylic dispersant is an A block having a repeating unit (V) and a repeating unit (VI), and a B block not having a repeating unit (V) and a repeating unit (VI), from the viewpoint of further enhancing the dispersibility. It is preferable that it is a block copolymer which has The block copolymer is preferably an A-B block copolymer or a B-A-B block copolymer. Unexpectedly, the dispersing ability of the dispersant tends to be remarkably improved by introducing not only the quaternary ammonium base but also the tertiary amino group into the A block. The B block preferably has the repeating unit (VII), and more preferably has the repeating unit (VIII).

  In the A block, the repeating units (V) and the repeating units (VI) may be contained in any mode of random copolymerization and block copolymerization. In addition, two or more types of repeating units (V) and repeating units (VI) may be contained in one A block, in which case each repeating unit is a random copolymerization in the A block, You may contain in any aspect of block copolymerization.

  Moreover, repeating units other than repeating unit (V) and repeating unit (VI) may be contained in A block, As an example of such a repeating unit, the above-mentioned (meth) acrylic acid ester type single is mentioned. The repeating unit derived from a monomer etc. are mentioned. The content of the repeating unit other than the repeating unit (V) and the repeating unit (VI) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, it is not contained in the block.

Repeating units other than the repeating units (VII) and (VIII) may be contained in the B block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (Meth) acrylate based monomers such as acrylic acid chloride; (meth) acrylamide based monomers such as (meth) acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, glycidyl crotonate Ethers; repeating units derived from monomers such as N-methacryloyl morpholine. The content ratio of repeating units other than the repeating unit (VII) and the repeating unit (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%. Most preferably, it is not contained in the block.
One of these acrylic dispersants may be used alone, or two or more thereof may be used in combination.
Further, in the colored photosensitive resin composition according to the first aspect of the present invention, and the pigment dispersion according to the third aspect of the present invention, the (B) dispersant is, in addition to the above-mentioned acrylic dispersant, Other polymer dispersants shown may be included.

  Other polymer dispersants include, for example, urethane dispersants, polyethyleneimine dispersants, polyallylamine dispersants, dispersants comprising a monomer having an amino group and a macromonomer, polyoxyethylene alkyl ether dispersants, poly An oxyethylene diester type dispersing agent, a polyether phosphoric acid type dispersing agent, a polyester phosphoric acid type dispersing agent, a sorbitan aliphatic ester type dispersing agent, an aliphatic modified polyester type dispersing agent and the like can be mentioned.

  Specific examples of such dispersants are trade names EFKA (registered trademark; manufactured by BASF Corporation), DISPERBYK (registered trademark. Manufactured by BIC Chemie Co., Ltd.), Disparon (registered trademark. Manufactured by Kushimoto Chemical Co., Ltd.), SOLSPERSE (Registered trademark; manufactured by Lubrizol Corporation), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), ADISPAR (registered trademark, manufactured by Ajinomoto Co., Ltd.) and the like can be mentioned.

The weight average molecular weight (Mw) of the other polymer dispersants is usually 700 or more, preferably 1000 or more, and usually 100,000 or less, preferably 50000 or less.
Among the other polymer dispersants, urethane polymer dispersants are preferable from the viewpoint of pigment dispersibility.
Among the urethane-based polymer dispersants, polymer dispersants having a basic functional group and having a polyester bond and / or a polyether bond are preferable in terms of dispersibility and storage stability.

As a urethane type polymer dispersing agent, DISPERBYK160-167, 182 series are mentioned, for example.
If a chemical structure preferable as a urethane type polymer dispersing agent is specifically illustrated, for example, a polyisocyanate compound and a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule may be in the same molecule. And a dispersion resin having a weight average molecular weight of 1,000 to 200,000 obtained by reacting an active hydrogen with a compound having a tertiary amino group. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be converted to a quaternary ammonium base.

  Examples of the above-mentioned polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, tolidine diisocyanate, etc. Aliphatic diisocyanates such as aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, isophorone diisocyanate, 4,4'-methylene bis (cyclohexyl isocyanate), ω, ω Alicyclic diisocyanates such as '-diisocyanatodimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetrame Aliphatic diisocyanates having an aromatic ring such as lxylylene diisocyanate, lysine ester triisocyanate, 1,6,11-undecanetriisocyanate, 1,8-diisocyanate-4-isocyanatomethyloctane, 1,3,6-hexamethylene triisocyanate And triisocyanates such as bicycloheptane triisocyanate, tris (isocyanatophenylmethane) and tris (isocyanatophenyl) thiophosphate, and trimers, water adducts thereof, and polyol adducts thereof. Preferred as polyisocyanates are trimers of organic diisocyanates, and most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. One of these may be used alone, or two or more may be used in combination.

  As a method for producing a trimer of isocyanate, a portion of an isocyanate group using the above-mentioned polyisocyanate with a suitable trimerization catalyst such as tertiary amines, phosphines, alkoxides, metal oxides, carboxylates and the like After the trimerization is terminated by addition of a catalyst poison, the unreacted polyisocyanate is removed by solvent extraction and thin-film distillation to obtain a desired polyisocyanate containing isocyanurate group.

As compounds having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule, polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol etc., and one terminal hydroxyl group of these compounds have 1 to 1 carbon atoms These include those alkoxylated with 25 alkyl groups and mixtures of two or more of these.
Polyether glycols include polyether diols, polyether ester diols, and mixtures of two or more of these. As polyether diols, those obtained by homopolymerization or copolymerization of alkylene oxides, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol and those And mixtures of two or more thereof.

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

  Examples of polyester glycols include dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, Dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol , 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1 , 6-hexanediol, 2-methyl-2,4- Intandiol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 1,8-octamethylene glycol, Aliphatic glycols such as 2-methyl-1,8-octamethylene glycol and 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, aromatic glycols such as xylylene glycol and bishydroxyethoxybenzene, N -Those obtained by polycondensation of N-alkyl dialkanolamines such as methyldiethanolamine etc., such as polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate etc, or the diols or carbon number 1 to 25 single value Polylactone diol or polylactone monool obtained by using an alcohol as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone and mixtures of two or more thereof. Most preferable as the polyester glycol is polycaprolactone glycol or polycaprolactone initiated by an alcohol having 1 to 25 carbon atoms.

Polycarbonate glycols include poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, etc. Polyolefin glycols include polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated polyisoprene glycol, etc. Can be mentioned.
One of these may be used alone, or two or more may be used in combination.

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

The compound which has an active hydrogen and a tertiary amino group in the same molecule used for this invention is demonstrated.
Active hydrogen, that is, a hydrogen atom directly bonded to an oxygen atom, a nitrogen atom or a sulfur atom, includes a hydrogen atom in a functional group such as a hydroxyl group, an amino group or a thiol group, among which an amino group, especially primary Preferred is a hydrogen atom of the amino group of

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, or a heterocyclic structure, more specifically an imidazole ring or a triazole ring.
If the compound which has active hydrogen and a tertiary amino group in such a same molecule is illustrated, N, N- dimethyl- 1, 3- propane diamine, N, N- diethyl 1, 3- propane diamine, N , N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dipropylethylenediamine, N, N -Dibutylethylenediamine, N, N-dimethyl-1,4-butanediamine, N, N-diethyl-1,4-butanediamine, N, N-dipropyl-1,4-butanediamine, N, N-dibutyl-1 , 4-butanediamine and the like.

  When the tertiary amino group is a nitrogen-containing heterocyclic structure, examples of the nitrogen-containing heterocyclic ring include pyrazole ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzimidazole ring, benzo Nitrogen-containing hetero five-membered ring such as triazole ring, benzoxazole ring, benzothiazole ring, benzothiadiazole ring, etc. Pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, acridine ring, six-membered nitrogen-containing hetero ring such as isoquinoline ring There is a ring. Among these nitrogen-containing heterocycles, preferred is an imidazole ring or a triazole ring.

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

  The preferable compounding ratio of the raw material at the time of manufacturing a urethane type polymer dispersing agent is a compound of the number average molecular weights 300-10000 which has one or two hydroxyl groups in the same molecule with respect to 100 mass parts of polyisocyanate compounds. Parts by weight, preferably 20 to 190 parts by weight, more preferably 30 to 180 parts by weight, 0.2 to 25 parts by weight of a compound having active hydrogen and a tertiary amino group in the same molecule, preferably 0.3 to 24 It is a mass part.

  The urethane-based polymer dispersant can be produced according to a known polyurethane resin production method. As the solvent for production, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone and isophorone, esters such as ethyl acetate, butyl acetate and cellosolve, benzene, toluene, xylene and hexane are usually used. Some hydrocarbons such as diacetone alcohol, isopropanol, secondary butanol, tertiary butanol, chlorides such as methylene chloride and chloroform, ethers such as tetrahydrofuran and diethyl ether, dimethylformamide, N-methyl Aprotic polar solvents such as pyrrolidone and dimethyl sulfoxide are used. One of these may be used alone, or two or more may be used in combination.

  In the above production, a urethanization reaction catalyst is usually used. As this catalyst, for example, tin-based compounds such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, stannas octoate, iron-based compounds such as iron acetylacetonate and ferric chloride, and 3 such as triethylamine and triethylenediamine And the like. One of these may be used alone, or two or more may be used in combination.

  The introduced amount of the compound having active hydrogen and tertiary amino group in the same molecule is preferably controlled in the range of 1 to 100 mg KOH / g in terms of the amine value after the reaction. More preferably, it is in the range of 5 to 95 mg KOH / g. The amine value is a value obtained by neutralizing titration of a basic amino group with an acid and expressing the acid value in mg of KOH corresponding to the acid value. There is a tendency that the dispersing ability is improved by setting it to the above lower limit value, and there is a tendency that the developability becomes good by setting it to the above upper limit value.

In the case where the isocyanate group is left in the polymer dispersant in the above reaction, it is preferable to destroy the isocyanate group with an alcohol or an amino compound because the temporal stability of the product is increased.
The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1,000 to 200,000, preferably 2,000 to 100,000, and more preferably 3,000 to 50,000. When the content is at least the lower limit, the dispersibility and the dispersion stability tend to be good, and when the content is at the upper limit or less, the solubility is improved, the dispersibility is good, and the control of the reaction tends to be easy. is there.

  Further, from the viewpoint of improving the dispersion stability, it is preferable to use the (B) dispersant in combination with a pigment derivative described later.

  On the other hand, the (B) dispersant in the colored photosensitive resin composition according to the second aspect of the present invention is not particularly limited as long as the (A) colorant can be dispersed. Specifically, the above-mentioned acrylic dispersant may be used, or the above-mentioned other polymer dispersant may be used. Among these, from the viewpoint of dispersibility, it is preferable to include an acrylic dispersant or a urethane polymer dispersant.

[1-3] (C) Binder Resin The colored photosensitive resin composition and the pigment dispersion liquid of the present invention contain (C) a binder resin. (C) By including the binder resin, it becomes possible to obtain a homogeneous film. The binder resin (C) is not particularly limited as long as a homogeneous film can be obtained, but from the viewpoint of solubility in an alkali developer, an alkali-soluble resin is preferable.
In the colored photosensitive resin composition and the pigment dispersion liquid of the present invention, the (C) binder resin is characterized by containing (C1) epoxy (meth) acrylate resin from the viewpoint of reducing outgassing. (C1) Epoxy (meth) acrylate resin has a rigid skeleton, has high heat resistance and is hard to be thermally decomposed, and since the skeleton is rigid, it has an arrayed structure upon curing and a highly crosslinkable film is formed. Therefore, it is considered that the amount of outgas generated after the formation of the cured product is reduced.
Moreover, it is preferable that (C1) epoxy (meth) acrylate resin is a thing containing a carboxyl group or a hydroxyl group from a soluble viewpoint to alkaline developing solution.

The (C1) epoxy (meth) acrylate resin is preferably a resin obtained by adding an acid or an ester compound having an ethylenically unsaturated bond to an epoxy resin, and further reacting a polybasic acid or an anhydride thereof. For example, by the ring-opening addition of the carboxyl group of the acid having an ethylenically unsaturated bond to the epoxy group of the epoxy resin, the ethylenically unsaturated bond is added to the epoxy compound via an ester bond (-COO-) In addition to the above, one in which one carboxyl group of polybasic acid anhydride is added to the hydroxyl group generated at that time is mentioned. Moreover, when adding a polybasic acid anhydride, what was simultaneously added and added the polyhydric alcohol is also mentioned.
Further, a resin obtained by reacting a compound having a functional group capable of further reacting with the carboxyl group of the resin obtained by the above reaction is also included in the above (C1) epoxy (meth) acrylate resin.
Thus, the epoxy (meth) acrylate resin does not have an epoxy group substantially due to the chemical structure, and is not limited to "(meth) acrylate", but an epoxy compound (epoxy resin) is a raw material And because it is a representative example, "(meth) acrylate" is so named according to conventional practice.

Here, the term "epoxy resin" also includes raw material compounds prior to formation of a resin by heat curing, and the epoxy resin can be appropriately selected and used from known epoxy resins.
Moreover, the epoxy resin can use the compound obtained by making a phenolic compound and an epihalohydrin react. The phenolic compound is preferably a compound having a divalent or trivalent or higher phenolic hydroxyl group, and may be a monomer or a polymer.
Specifically, for example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, biphenyl novolac epoxy resin, trisphenol epoxy resin, polymerization of phenol and dicyclopentane Epoxy resin, dihydroxyl fluorene type epoxy resin, dihydroxyl alkylene oxylfluorene type epoxy resin, diglycidyl ether of 9,9-bis (4'-hydroxyphenyl) fluorene, 1,1-bis (4'-hydroxy) And the like. Examples of such a diglycidyl ether of phenyl) adamantane and the like can be given, and a compound having an aromatic ring in the main chain can be suitably used.

  Among them, from the viewpoint of high cured film strength, bisphenol A epoxy resin, phenol novolac epoxy resin, cresol novolac epoxy resin, epoxidized polymer of phenol and dicyclopentadiene, 9, 9-bis (4'-hydroxyphenyl) Epoxide compounds of fluorene (diglycidyl ether compounds), epoxy resins having an adamantyl group, and the like are preferable, epoxy compounds of polymers of phenol and dicyclopentadiene, epoxy compounds of 9,9-bis (4'-hydroxyphenyl) fluorene And epoxy resins having an adamantyl group are more preferable.

  Among the acids having an ethylenically unsaturated bond, an ethylenically unsaturated monocarboxylic acid is preferred. Examples of the acid having an ethylenically unsaturated bond include (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri (meth) acrylate, succinic anhydride adduct, pentaerythritol trihydrate. (Meth) acrylate tetrahydrophthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate tetrahydrophthalic anhydride An acid adduct, a reaction product of (meth) acrylic acid and ε-caprolactone, and the like can be mentioned. Among them, (meth) acrylic acid is preferable from the viewpoint of sensitivity.

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

By using a polyhydric alcohol, the molecular weight of the (C1) epoxy (meth) acrylate resin can be increased, branching can be introduced into the molecule, and the molecular weight and viscosity can be balanced. In addition, the introduction rate of the acid group into the molecule can be increased, and the balance of sensitivity and adhesion tends to be easily maintained.
Examples of polyhydric alcohols include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane and 1,2,3-propanetriol. Is preferred.

  The acid value of the (C1) epoxy (meth) acrylate resin is not particularly limited, but 10 mg KOH / g or more is preferable, 20 mg KOH / g or more is more preferable, 40 mg KOH / g or more is more preferable, 60 mg KOH / g or more is more preferable, 80 mg KOH / g or more is particularly preferable, 200 mg KOH / g or less is preferable, 180 mg KOH / g or less is more preferable, 150 mg KOH / g or less is more preferable, 130 mg KOH / g or less is more preferable, 120 mg KOH / g or less is particularly preferable. By setting the content to the above lower limit value, the developability of the unexposed area tends to be improved, and by setting the content to the above upper limit value, film reduction and the like tend to be suppressed. The combination of the upper limit and the lower limit is preferably 10 to 200 mg KOH / g, more preferably 20 to 180 mg KOH / g, further preferably 40 to 150 mg KOH / g, still more preferably 60 to 130 mg KOH / g, and 80 to 120 mg KOH / g It is particularly preferable.

  The weight average molecular weight (Mw) of the (C1) epoxy (meth) acrylate resin is not particularly limited, but is usually 1000 or more, preferably 2000 or more, more preferably 3000 or more, still more preferably 4000 or more, particularly preferably 5000 or more, Usually, it is 30000 or less, preferably 20000 or less, more preferably 15000 or less, still more preferably 10000 or less, particularly preferably 8000 or less. The film reduction or the like tends to be suppressed by setting it to the lower limit value or more, and the developability of the unexposed area tends to be improved by setting it to the upper limit value or less. As a combination of an upper limit and a lower limit, 1000-30000 are preferable, 2000-20000 are more preferable, 3000-15000 are more preferable, 4000-10000 are more preferable, and 5000-8000 are mentioned especially preferable.

  The (C1) epoxy (meth) acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and the acid or ester compound having an ethylenic unsaturated bond is added in the coexistence of a catalyst and a thermal polymerization inhibitor to cause addition reaction, and further a polybasic acid or the acid Anhydrous can be added to continue the reaction.

  Here, as an organic solvent used for reaction, 1 type or 2 types or more of organic solvents, such as methyl ethyl ketone, cyclohexanone, diethylene glycol ethyl ether acetate, propylene glycol monomethyl ether acetate, are mentioned. Further, as the above catalyst, tertiary amines such as triethylamine, benzyldimethylamine and tribenzylamine, tetramethylammonium chloride, methyltriethylammonium chloride, tetraethylammonium chloride, tetrabutylammonium chloride, and trimethylbenzylammonium chloride and the like One or more of quaternary ammonium salts, phosphorus compounds such as triphenyl phosphine, and stibines such as triphenyl stibine may be used. Furthermore, as a thermal polymerization inhibitor, 1 type (s) or 2 or more types, such as hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, etc. are mentioned.

  The acid or ester compound having an ethylenically unsaturated bond is usually 0.7 to 1.3 chemical equivalents, preferably 0.9 to 1.1 chemical equivalents, per 1 chemical equivalent of the epoxy group of the epoxy resin. The amount can be Moreover, as temperature at the time of addition reaction, it can be set as the temperature of 60-150 degreeC normally, Preferably it is 80-120 degreeC. Furthermore, the amount of the polybasic acid (anhydride) used is usually 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1, per 1 chemical equivalent of hydroxyl groups produced in the addition reaction. The amount can be a chemical equivalent.

The chemical structure of the (C1) epoxy (meth) acrylate resin is not particularly limited, but from the viewpoint of reducing outgassing, an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and / or the following general It is preferable to contain the epoxy (meth) acrylate resin which has a partial structure represented by Formula (III). The epoxy (meth) acrylate resin is excellent in patterning performance because of its high sensitivity, and has a hydrophobic skeleton, and its substrate adhesion is good because its dissolution rate is mild. Furthermore, unlike acrylic resin, it has a rigid skeleton, and it is considered to be able to suppress the generation of outgassing because it has an ordered structure upon curing and is closely crosslinked.
In particular, an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and / or an epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III) It is considered that the hydrophilic property such as (meth) acryloyl group is developed to the outside because of its bulky and rigid skeleton, and the developability becomes good.

In formula (II), R ¹¹ represents a hydrogen atom or a methyl group;
R ¹² represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (II) may be further substituted by any substituent;
* Represents a bond.

In formula (III), each R ¹³ independently represents a hydrogen atom or a methyl group;
R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond.

[(C1-1) epoxy (meth) acrylate resin]
Next, an epoxy (meth) acrylate resin (hereinafter, abbreviated as “(C1-1) epoxy (meth) acrylate resin”) having a repeating unit structure represented by the general formula (II) will be described in detail.

In formula (II), R ¹¹ represents a hydrogen atom or a methyl group;
R ¹² represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (II) may be further substituted by any substituent;
* Represents a bond.

(R ¹² )
In Formula (II), R ¹² represents a divalent hydrocarbon group which may have a substituent.
Examples of the divalent hydrocarbon group include a divalent aliphatic group, a divalent aromatic ring group, and a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked. It can be mentioned.

  Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among them, linear ones are preferable from the viewpoint of development solubility, and cyclic ones are preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved. As a combination of the upper limit and the lower limit, 1 to 20 are preferable, 3 to 15 are more preferable, and 6 to 10 are more preferable.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group include an iso-propyl group, a sec-butyl group, a tert-butyl group, an iso-amyl group and the like.
The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more and 2 or more, and usually 12 or less and 10 or less. By setting the lower limit value or more, a strong film tends to be obtained, and the substrate adhesion tends to be good. By setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed, and resolution There is a tendency to improve the sex. Specific examples of the divalent cyclic aliphatic group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, tricyclodecane ring, adamantane ring, cyclododecane ring, dicyclopentadiene, etc. Groups obtained by removing two hydrogen atoms from the ring of Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a tricyclodecane ring or an adamantane ring is preferable.

  As a substituent which a bivalent aliphatic group may have, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; a nitro group; a cyano group; a carboxyl group etc. are mentioned. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

  Moreover, as a bivalent aromatic ring group, a bivalent aromatic hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned. The carbon number 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 still more preferably 10 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved.

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

The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a fused ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole having two free valencies Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring etc. That.
Among these, from the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

  Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group and a glycidyl ether group. Among these, from the viewpoint of development solubility and moisture resistance, no substitution is preferable.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic groups can be used. A group in which a ring group is linked to one or more is mentioned.
The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved.

  Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the following formulas (II-A) to (II-F) Can be mentioned. Among these, the group represented by the following formula (II-A) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobicization of the film. * In the chemical formula represents a bond.

As mentioned above, the benzene ring in formula (II) may be further substituted by any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, from the viewpoint of patterning characteristics, it is preferable to be unsubstituted.

  The repeating unit structure represented by the formula (II) is preferably a repeating unit structure represented by the following formula (II-1), from the viewpoint of simplicity of synthesis.

In formula (II-1), R ¹¹ and R ¹² are as defined in the above formula (II);
R ^X represents a hydrogen atom or a polybasic acid residue;
* Represents a bond;
The benzene ring in Formula (II-1) may be further substituted by any substituent.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. As polybasic acids, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid 1 type, or 2 or more types selected from an acid, chlorendic acid, methyl tetrahydro phthalic acid, and biphenyl tetracarboxylic acid are mentioned.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are more preferable. Is tetrahydrophthalic acid or biphenyltetracarboxylic acid, more preferably tetrahydrophthalic anhydride.

(C1-1) The repeating unit structure represented by the formula (II-1) contained in one molecule of the epoxy (meth) acrylate resin may be one type or two or more types, and, for example, R ^X is a hydrogen atom And R ^X may be a mixture of polybasic acid residues.

  The number of the repeating unit structure represented by the formula (II) contained in one molecule of the (C1-1) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more. Moreover, 20 or less is preferable and 15 or less is more preferable. By setting the lower limit value or more, a strong film is easily obtained and surface roughening tends to be difficult to occur, and by setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed. There is a tendency for the resolution to be improved.

  The weight average molecular weight (Mw) in terms of polystyrene of the epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 1500 or more, 2000 or more is more preferable, 3000 or more is especially preferable, 30000 or less is preferable, 20000 or less is more preferable, 10000 or less is more preferable, 8000 or less is particularly preferable. The residual film ratio of the colored photosensitive resin composition tends to be good by setting it to the above lower limit value, and the resolution tends to become good by setting it to the above upper limit value. As a combination of an upper limit and a lower limit, 1000-30000 are preferable, 1500-20000 are more preferable, 2000-10000 are more preferable, 3000-8000 are mentioned especially.

  The acid value of the (C1-1) epoxy (meth) acrylate resin is not particularly limited, but 10 mg KOH / g or more is preferable, 20 mg KOH / g or more is more preferable, 40 mg KOH / g or more is more preferable, 50 mg KOH / g or more is more 80 mg KOH / g or more is particularly preferable, 200 mg KOH / g or less is preferable, 150 mg KOH / g or less is more preferable, 130 mg KOH / g or less is more preferable, and 100 mg KOH / g or less is particularly preferable. By setting the content to the above lower limit or more, the development solubility tends to be improved and the resolution tends to be good. By setting the content to the above upper limit or less, the residual film ratio of the colored photosensitive resin composition becomes good. Tend. The combination of the upper limit and the lower limit is preferably 10 to 200 mg KOH / g, more preferably 20 to 150 mg KOH / g, still more preferably 40 to 130 mg KOH / g, still more preferably 50 to 100 mg KOH / g, and 80 to 100 mg KOH / g. It is particularly preferable.

  The specific example of (C1-1) epoxy (meth) acrylate resin is given to the following.

[(C1-2) epoxy (meth) acrylate resin]
Next, the epoxy (meth) acrylate resin (It abbreviates as "(C1-2) epoxy (meth) acrylate resin" hereafter) which has a partial structure represented by the said General formula (III) is explained in full detail.

In formula (III), each R ¹³ independently represents a hydrogen atom or a methyl group;
R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond.

(R ¹⁴ )
In the above general formula (III), R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

The number of rings possessed by the aliphatic ring group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. By setting the lower limit value or more, a strong film is easily obtained and surface roughening tends to be difficult to occur, and by setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed. There is a tendency for the resolution to be improved. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5 and still more preferably 2 to 3.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. preferable. By setting the lower limit value or more, a strong film is easily obtained and surface roughening tends to be difficult to occur, and by setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed. The resolution tends to be improved. As a combination of the upper limit and the lower limit, 4 to 40 are preferable, 6 to 30 are more preferable, 8 to 20 are more preferable, and 8 to 15 are particularly preferable.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of the residual film ratio and resolution of the colored photosensitive resin composition.

On the other hand, the number of rings possessed by the aromatic ring group is not particularly limited, but usually 1 or more and 2 or more is preferable, 3 or more is more preferable, and usually 10 or less and 5 or less is preferable and 4 or less is more preferable. By setting the lower limit value or more, a strong film is easily obtained and surface roughening tends to be difficult to occur, and by setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed. The resolution tends to be improved. As a combination of the upper limit and the lower limit, 1 to 10 are preferable, 2 to 5 are more preferable, and 3 to 4 are more preferable.
As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group can be mentioned. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, particularly preferably 12 or more, and preferably 40 or less, 30 or less. More preferably, 20 or less is more preferable, and 15 or less is particularly preferable. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening tends to be difficult to occur, and by setting the content to the above upper limit value, patterning characteristics tend to be good. The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 30, still more preferably 8 to 20, still more 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, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, A fluorene ring etc. are mentioned. Among these, a fluorene ring is preferable from the viewpoint of patterning properties.

  Further, the divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, and, for example, a divalent aliphatic group, a divalent aromatic ring group, one or more And a group in which one or more divalent aromatic ring groups are connected to each other.

  Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among them, linear ones are preferable from the viewpoint of development solubility, and cyclic ones are preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, and still more preferably 15 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group include, as a side chain, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group as the above-mentioned divalent linear aliphatic group. The structure which has group, an iso-butyl group, a sec-butyl group, a tert- butyl group etc. is mentioned.
The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more and 2 or more, and is usually 10 or less and 5 or less, more preferably 3 or less. By setting the lower limit value or more, a strong film tends to be obtained, and the substrate adhesion tends to be good. By setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed, and resolution There is a tendency to improve the sex. Specific examples of the divalent cyclic aliphatic group include two hydrogen atoms from rings such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring and cyclododecane ring. Groups are mentioned. Among these, in view of the rigidity of the skeleton, a group in which two hydrogen atoms are removed from an adamantane ring is preferable.

  As a substituent which a bivalent aliphatic group may have, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; a nitro group; a cyano group; a carboxyl group etc. are mentioned. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

  Moreover, as a bivalent aromatic ring group, a bivalent aromatic hydrocarbon ring group and a bivalent aromatic heterocyclic group are mentioned. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, preferably 30 or less, more preferably 20 or less, and still more preferably 15 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved.

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

  The aromatic heterocyclic ring in the divalent aromatic heterocyclic group may be a single ring or a fused ring. Examples of the divalent aromatic heterocyclic group include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole having two free valencies Ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, Groups such as pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring etc. That. Among these, from the viewpoint of patterning properties, a benzene ring or a naphthalene ring having two free valences is preferable, and a fluorene ring having two free valences is more preferable.

  Examples of the substituent which the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. Among these, from the viewpoint of development solubility, no substitution is preferable.

Further, as a group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked, one or more of the above-mentioned divalent aliphatic groups and the above-mentioned divalent aromatic groups can be used. A group in which a ring group is linked to one or more is mentioned.
The number of divalent aliphatic groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved.
The number of divalent aromatic ring groups is not particularly limited, but is preferably 1 or more and 2 or more, and usually 10 or less and 5 or less, and more preferably 3 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved.

  Specific examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include the groups represented by the formulas (II-A) to (II-F), etc. Can be mentioned. Among these, the group represented by the formula (II-C) or the group represented by the formula (II-D) is preferable from the viewpoint of the rigidity of the skeleton and the hydrophobization of the film.

  Although the bonding aspect of the cyclic hydrocarbon group which is a side chain is not specifically limited with respect to these bivalent hydrocarbon groups, For example, one hydrogen atom of an aliphatic group or an aromatic ring group is substituted by this side chain. And the aspect which comprised the cyclic hydrocarbon group which is a side chain including one of the carbon atom of an aliphatic group is mentioned.

(R ^15, R ¹⁶⁾
In Formula (III), each of R ¹⁵ and R ¹⁶ independently represents a divalent aliphatic group which may have a substituent.

  Examples of the divalent aliphatic group include linear, branched and cyclic ones. Among them, linear ones are preferable from the viewpoint of development solubility, and cyclic ones are preferable from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening is less likely to occur, adhesion to the substrate tends to be good, and by setting the content to the above upper limit value, surface smoothness of the film is obtained. And it is easy to suppress the deterioration of sensitivity and the resolution tends to be improved.

Specific examples of the divalent linear aliphatic group include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group and an n-heptylene group. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.
Specific examples of the divalent branched aliphatic group include, as a side chain, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, and an n-butyl group as the above-mentioned divalent linear aliphatic group. The structure which has group, an iso-butyl group, a sec-butyl group, a tert- butyl group etc. is mentioned.
The number of rings possessed by the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more and 2 or more, and usually 12 or less and 10 or less. By setting the lower limit value or more, a strong film tends to be obtained, and the substrate adhesion tends to be good. By setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed, and resolution There is a tendency to improve the sex. Specific examples of the divalent cyclic aliphatic group include a hydrogen atom from a ring such as cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring, dicyclopentadiene, etc. Groups obtained by removing two. Among these, from the viewpoint of the rigidity of the skeleton, a group obtained by removing two hydrogen atoms from a dicyclopentadiene ring or an adamantane ring is preferable.

  As a substituent which a bivalent aliphatic group may have, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; A hydroxyl group; a nitro group; a cyano group; a carboxyl group etc. are mentioned. Among these, from the viewpoint of ease of synthesis, it is preferably unsubstituted.

(M, n)
In the said General formula (III), m and n respectively independently represent the integer of 0-2. By setting the content to the above lower limit or more, the patterning suitability becomes good, there is a tendency that surface roughening is less likely to occur, and if it is below the above upper limit, developability tends to be good. M and n are preferably 0 from the viewpoint of developability, while m and n are preferably each independently 1 or more from the viewpoint of patterning suitability and surface roughness.

  The partial structure represented by the general formula (III) is preferably a partial structure represented by the following general formula (III-1), from the viewpoint of adhesion to a substrate.

In formula (III-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n are as defined in the above formula (III);
R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent;
p is an integer of 1 or more;
The benzene ring in formula (III-1) may be further substituted by any substituent;
* Represents a bond.

(R ^α )
In the general formula (III-1), R ^α represents a monovalent cyclic hydrocarbon group.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

The number of rings contained in the aliphatic ring group is not particularly limited, but is preferably 1 or more and 2 or more, and usually 6 or less and 4 or less, and more preferably 3 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening tends to be difficult to occur, and by setting the content to the above upper limit value, patterning characteristics tend to be good. As a combination of the upper limit and the lower limit, 1 to 6 is preferable, 2 to 4 is more preferable, and 2 to 3 is more preferable.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, particularly preferably 15 or less. preferable. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening tends to be difficult to occur, and by setting the content to the above upper limit value, patterning characteristics tend to be good. As a combination of the upper limit and the lower limit, 4 to 40 are preferable, 6 to 30 are more preferable, 8 to 20 are more preferable, and 8 to 15 are particularly preferable.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of strong film properties.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, and usually 10 or less and 5 or less. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening tends to be difficult to occur, and by setting the content to the above upper limit value, patterning characteristics tend to be good. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5 and still more preferably 3 to 5.
The aromatic ring group includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, 30 or less is preferable, 20 or less is more preferable, and 15 or less is more preferable. By setting the content to the above lower limit value, a strong film is easily obtained, surface roughening tends to be difficult to occur, and by setting the content to the above upper limit value, patterning characteristics tend to be good. As a combination of the upper limit and the lower limit, 4 to 30 is preferable, 5 to 20 is more preferable, and 6 to 15 is more preferable.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, from the viewpoint of developing solubility, a fluorene ring is preferable.

  As a substituent which the cyclic hydrocarbon group may have, a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Among these, from the viewpoint of easiness of synthesis, no substitution is preferable.

  p represents an integer of 1 or more, preferably 2 or more, and preferably 3 or less. By setting the content to the above lower limit or more, the film curing degree and the residual film ratio tend to be good, and by setting the above upper limit or less, the developability tends to be favorable. As a combination of the upper limit and the lower limit, 1 to 3 is preferable, and 2 to 3 is more preferable.

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

As described above, the benzene ring in formula (III-1) may be further substituted by any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more.
Among these, from the viewpoint of patterning characteristics, it is preferable to be unsubstituted.

  The specific example of the partial structure represented by said Formula (III-1) is given to the following.

  The partial structure represented by the general formula (III) is preferably a partial structure represented by the following general formula (III-2) from the viewpoint of rigidity of the skeleton and membrane hydrophobization.

In formula (III-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n are as defined in the above formula (III);
R ^β represents a divalent cyclic hydrocarbon group which may have a substituent;
The benzene ring in formula (III-2) may be further substituted by any substituent;
* Represents a bond.

(R ^β )
In Formula (III-2), R ^β represents a divalent cyclic hydrocarbon group.
The cyclic hydrocarbon group includes an aliphatic ring group or an aromatic ring group.

The number of rings contained in the aliphatic ring group is not particularly limited, but is usually 1 or more and 2 or more, and usually 10 or less and 5 or less. By setting the lower limit value or more, a strong film is easily obtained and surface roughening tends to be difficult to occur, and by setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed. There is a tendency for the resolution to be improved. As a combination of the upper limit and the lower limit, 1 to 10 is preferable, and 2 to 5 is more preferable.
The carbon number of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. By setting the lower limit value or more, there is a tendency to suppress film roughness during development, and by setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed, and the resolution is improved. Tend to be The combination of the upper limit and the lower limit is preferably 4 to 40, more preferably 6 to 35, and still more preferably 8 to 30.
Specific examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecane ring, norbornane ring, isobornane ring, adamantane ring, cyclododecane ring and the like. Among these, an adamantane ring is preferable from the viewpoint of storage stability.

On the other hand, the number of rings contained in the aromatic ring group is not particularly limited, but is usually 1 or more and 2 or more, preferably 3 or more, and usually 10 or less and 5 or less. By setting the lower limit value or more, a strong film is easily obtained and surface roughening tends to be difficult to occur, and by setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed. There is a tendency for the resolution to be improved. The combination of the upper limit and the lower limit is preferably 1 to 10, more preferably 2 to 5 and still more preferably 3 to 5.
The aromatic ring group includes an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The carbon number of the aromatic ring group is usually 4 or more, preferably 6 or more, and more preferably 8 or more. The above is more preferable, and 40 or less is preferable, 30 or less is more preferable, 20 or less is more preferable, and 15 or less is particularly preferable. By setting the lower limit value or more, a strong film is easily obtained and surface roughening tends to be difficult to occur, and by setting the upper limit value or less, deterioration of the surface smoothness and sensitivity of the film is easily suppressed. There is a tendency for the resolution to be improved. As a combination of the upper limit and the lower limit, 4 to 40 is preferable, 6 to 30 is more preferable, 8 to 20 is more preferable, and 10 to 15 is particularly preferable.
Specific examples of the aromatic ring in the aromatic ring group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring and the like. Among these, from the viewpoint of developability, a fluorene ring is preferable.

  As a substituent which the cyclic hydrocarbon group may have, a hydroxyl group, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, Examples thereof include alkyl groups having 1 to 5 carbon atoms such as amyl group and iso-amyl group; alkoxy groups having 1 to 5 carbon atoms such as methoxy group and ethoxy group; hydroxyl group; nitro group; cyano group; Among these, from the viewpoint of simplicity of synthesis, no substitution is preferable.

Among these, in terms of storage stability and electrical properties, R ^β is preferably a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.
On the other hand, it is preferable that R ^β is a divalent aromatic ring group, and more preferably a divalent fluorene ring group, from the viewpoint of low hygroscopicity and patterning properties of the coating film.

As described above, the benzene ring in formula (III-2) may be further substituted by any substituent. Examples of the substituent include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group and a propoxy group. The number of substituents is also not particularly limited, and may be one or two or more. Moreover, two benzene rings in Formula (III-2) may be linked via these substituents.
Among these, from the viewpoint of patterning characteristics, it is preferable to be unsubstituted. Further, from the viewpoint of making it difficult to cause film loss and the like, methyl group substitution is preferable.

  The specific example of the partial structure represented by said Formula (III-2) below is given.

  On the other hand, it is preferable that the partial structure represented by said Formula (III) is a partial structure represented by following formula (III-3) from a viewpoint of a coating film residual film rate and a patterning characteristic.

In formula (III-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n are as defined in the above formula (III);
R ^Z represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or an anhydride thereof. Furthermore, one more OH group may be removed and shared with R ^Z in another molecule represented by formula (III-3), that is, a plurality of formulas (III-3) via R ^Z ) May be linked.
As polybasic acids, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid 1 type, or 2 or more types selected from an acid, chlorendic acid, methyl tetrahydro phthalic acid, and biphenyl tetracarboxylic acid are mentioned.
Among these, from the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid and biphenyltetracarboxylic acid are more preferable. And tetrahydrophthalic acid and biphenyltetracarboxylic acid.

(C1-2) The partial structure represented by the formula (III-3) contained in one molecule of the epoxy (meth) acrylate resin may be one type or two or more types. For example, R ^Z is a hydrogen atom And those in which R ^Z is a polybasic acid residue may be mixed.

  Further, the number of partial structures represented by the formula (III) contained in one molecule of the (C1-2) epoxy (meth) acrylate resin is not particularly limited, but is preferably 1 or more, more preferably 3 or more, Moreover, 20 or less is preferable, 15 or less is more preferable, and 10 or less is more preferable. By setting the lower limit value or more, a strong film is easily obtained, surface roughening is less likely to occur, the electrical characteristics tend to be good, and by setting the upper limit value or less, surface smoothness and sensitivity of the film can be obtained. The deterioration is easily suppressed, and the resolution tends to be improved.

  The weight average molecular weight (Mw) in terms of polystyrene of the (C1-2) epoxy (meth) acrylate resin measured by gel permeation chromatography (GPC) is not particularly limited, but is preferably 1000 or more, more preferably 2000 or more, 3000 or more is more preferable, 3500 or more is especially preferable, 30000 or less is preferable, 20000 or less is more preferable, 10000 or less is more preferable, 7000 or less is further more preferable, 5000 or less is particularly preferable. By setting the content to the lower limit or more, the patterning characteristics tend to be good, and by setting the content to the upper limit or less, a strong film is easily obtained, and surface roughness tends not to occur easily. As a combination of an upper limit and a lower limit, 1000-30000 are preferable, 2000-20000 are more preferable, 3000-10000 are more preferable, 3500-7000 are still more preferable, and 3500-5000 are especially preferable.

  The acid value of the (C1-2) epoxy (meth) acrylate resin is not particularly limited, but 10 mg KOH / g or more is preferable, 20 mg KOH / g or more is more preferable, 40 mg KOH / g or more is more preferable, 60 mg KOH / g or more is still more The amount is preferably 80 mg KOH / g or more, more preferably 200 mg KOH / g or less, more preferably 150 mg KOH / g or less, and still more preferably 120 g KOH / g or less. When the content is at least the lower limit, a strong film tends to be easily obtained. When the content is at most the upper limit, development solubility is improved and the resolution tends to be good. The combination of the upper limit and the lower limit is preferably 10 to 200 mg KOH / g, more preferably 20 to 150 mg KOH / g, still more preferably 40 to 150 mg KOH / g, still more preferably 60 to 120 mg KOH / g, and 80 to 120 mg KOH / g It is particularly preferable.

The binder resin (C) contained in the colored photosensitive resin composition and the pigment dispersion of the present invention is a binder resin other than the (C1) epoxy (meth) acrylate resin (hereinafter referred to as "(C2) other binder resin"). May be included.
(C2) Other binder resins include, for example, acrylic resins, carboxyl group-containing epoxy resins, carboxyl group-containing urethane resins, novolac resins, polyvinyl phenol resins, etc. These may be used alone. Also, a plurality of types may be mixed and used.

In the colored photosensitive resin composition of the present invention, the (C) binder resin contains 75% by mass or more of the (C1) epoxy (meth) acrylate resin. By containing 75% by mass or more of the (C1) epoxy (meth) acrylate resin in the binder resin (C1), it is considered that the heat resistance of the cured product can be improved, and the amount of outgas generated after formation of the cured product can be reduced.
The content ratio of the (C1) epoxy (meth) acrylate resin to the binder resin (C1) is not particularly limited as long as it is 75% by mass or more, preferably 80% by mass or more, more preferably 85% by mass or more, and 90% by mass or more Is more preferable, and 95% by mass or more is particularly preferable. Moreover, it is normally 100 mass% or less. Outgassing tends to be suppressed by setting it to the above lower limit value or more. The combination of the upper limit and the lower limit is preferably 75 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass It is particularly preferable.

[1-4] (D) Photopolymerizable Monomer The colored photosensitive resin composition of the present invention contains (D) a photopolymerizable monomer. The sensitivity is improved by containing the photopolymerizable monomer (D).
The (D) photopolymerizable monomer used in the present invention is a compound having at least one ethylenically unsaturated group in the molecule. Specifically, for example, (meth) acrylic acid, (meth) acrylic acid alkyl ester, acrylonitrile, styrene, carboxylic acid having one ethylenic unsaturated bond, ester of polyvalent or monohydric alcohol, etc. are mentioned. Be

In the present invention, in particular, it is desirable to use a polyfunctional ethylenic monomer having two or more ethylenic unsaturated groups in one molecule. The number of ethylenically unsaturated groups possessed by the polyfunctional ethylenic monomer is not particularly limited, but is usually 2 or more, preferably 4 or more, more preferably 5 or more, and preferably It is 8 or less, more preferably 7 or less. By setting the content to the above lower limit or higher, the sensitivity tends to be high, and by setting the above upper limit or below, the solubility in a solvent tends to be improved. As a combination of the upper limit and the lower limit, 2 to 8 are preferable, 4 to 8 are more preferable, and 5 to 7 are more preferable.
Examples of polyfunctional ethylenic monomers include, for example, esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids; esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids; aliphatic polyhydroxy compounds, aromatic poly The ester etc. which are obtained by the esterification reaction of polyvalent hydroxy compounds, such as a hydroxy compound, and unsaturated carboxylic acid and polybasic carboxylic acid are mentioned.

  Examples of the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid include ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate and pentaerythritol triacrylate. Acrylic esters of aliphatic polyhydroxy compounds such as pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, glycerol acrylate, etc. Methacrylates wherein acrylates of these exemplified compounds are replaced by methacrylates , Itaconic acid ester similarly substituted for itaconate Maleic acid esters in which instead of the crotonic acid ester or maleate was changed to and the like.

As esters of aromatic polyhydroxy compounds and unsaturated carboxylic acids, acrylic acid esters and methacrylic acid esters of aromatic polyhydroxy compounds such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcine diacrylate, resorcine dimethacrylate, pyrogallol triacrylate and the like Etc.
The esters obtained by the esterification reaction of polybasic carboxylic acids and unsaturated carboxylic acids with polyvalent hydroxy compounds are not necessarily single substances, but acrylic acid, phthalic acid, and acrylic acid, phthalic acid, and so on. A condensate of ethylene glycol, a condensate of acrylic acid, maleic acid and diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin, and the like can be mentioned.

In addition, as an example of the polyfunctional ethylenic monomer used in the present invention, a polyisocyanate compound and a hydroxyl group-containing (meth) acrylic acid ester or polyisocyanate compound and a polyol and a hydroxyl group-containing (meth) acrylic acid ester are reacted Urethane (meth) acrylates as obtained; epoxy acrylates such as addition reaction product of polyvalent epoxy compound and hydroxy (meth) acrylate or (meth) acrylic acid; Acrylamides such as ethylene bis acrylamide; Diallyl phthalate Allyl esters such as: vinyl group-containing compounds such as divinyl phthalate are useful.
As said urethane (meth) acrylates, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (made by Nippon Kayaku Co., Ltd.), U-2PPA, U-6LPA, U, for example -10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), and the like.

Among these, it is preferable to use (meth) acrylic acid alkyl ester as the (D) photopolymerizable monomer from the viewpoint of curability, and it is more preferable to use dipentaerythritol hexaacrylate.
One of these may be used alone, or two or more may be used in combination.

[1-5] (E) Photopolymerization Initiator The colored photosensitive resin composition of the present invention contains (E) a photopolymerization initiator. The photopolymerization initiator (E) is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen abstraction reaction, and generating a polymerization active radical. If necessary, additives such as a polymerization accelerator (chain transfer agent) and a sensitizing dye may be added and used.
As photopolymerization initiators, for example, metallocene compounds containing a titanocene compound described in JP-A-59-152396 and JP-A-61-151197; JP-A-2000-56118 Haloaryl biimidazole derivatives described in JP-A 10-39503; halomethyl-s-triazine derivatives; N-aryl-α-amino acids such as N-phenylglycine; N -Radical activators such as aryl-α-amino acid salts and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; JP-A-2000-80068, JP-A-2006-36750, etc. The oxime ester derivative etc. which are described in are mentioned.

  Specifically, for example, as titanocene derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6-pentafluoro) Phenyl-1-yl), dicyclopentadienyl titanium bis (2,3,5,6-tetrafluoropheny-1-yl), dicyclopentadienyl titanium bis (2,4,6-trifluoropheny-) 1-yl), dicyclopentadienyl titanium di (2, 6-difluoro phen- 1-yl), dicyclopenta dienyl titanium di (2, 4- difluoro phen- 1-yl), di (methyl cyclopenta) (Dienyl) titanium bis (2,3,4,5,6-pentafluorophen-1-yl), di (methylcyclo) (Pentadienyl) titanium bis (2,6-difluorophen-1-yl), dicyclopentadienyltitanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1-yl], etc. It can be mentioned.

  Moreover, as biimidazole derivatives, 2- (2'-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-chlorophenyl) -4,5-bis (3'-methoxyphenyl) imidazole Dimer, 2- (2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl 4.)-4, 5- diphenyl imidazole dimer etc. are mentioned.

  Also, as halomethylated oxadiazole derivatives, 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′- (2′-) Benzofuryl) vinyl] -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2 ′-(6 ′ ′-benzofuryl) vinyl)]-1,3,4-oxadiazole 2-trichloromethyl-5-furyl-1,3,4-oxadiazole and the like.

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

  Further, as α-aminoalkylphenone derivatives, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-) Morpholinophenyl) -butanone-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethyl benzoate, 4-dimethylaminoisoamylbenzoe 4-Diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4 -Diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone etc. It is.

As the photopolymerization initiator, oxime ester derivatives (oxime ester compounds and ketoxime ester compounds) are particularly effective in terms of sensitivity and plate-making property, and when using an alkali-soluble resin containing a phenolic hydroxyl group, etc. In particular, oxime ester derivatives (oxime ester compounds and ketoxime ester compounds) excellent in such sensitivity are useful because they are disadvantageous in terms of sensitivity.
Examples of the oxime ester compound include compounds having a partial structure represented by the following general formula (IX), and preferable examples include oxime ester compounds represented by the following general formula (IX-A).

In formula (IX), R ²² is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, or 3 carbon atoms which may be substituted. To 8 cycloalkanoyl group, alkoxycarbonylalkanoyl group having 3 to 20 carbon atoms, phenoxycarbonylalkanoyl group having 8 to 20 carbon atoms, heteroaryloxyoxycarbonylalkanoyl group having 3 to 20 carbon atoms, amino having 2 to 10 carbon atoms And an alkylcarbonyl group, an aryloyl group having 7 to 20 carbon atoms, a heteroaryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

In formula (IX-A), R ^21a is a hydrogen atom, or an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, which may be substituted, or a heteroaryl having 1 to 20 carbon atoms. An alkyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a heteroarylthioalkyl group, having 1 to 20 carbon atoms Aminoalkyl group, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, aryloyl group having 7 to 20 carbon atoms, heteroaryloyl having 1 to 20 carbon atoms Group, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, or 1 to 10 carbon atoms Represents a cycloalkylalkyl group of
R ^{21 b} represents an optional substituent containing an aromatic hydrocarbon ring or an aromatic heterocycle (heteroaromatic ring).
R ^21a may be linked to R ^21b to form a ring, and the linking group is an alkylene group having 1 to 10 carbon atoms which may have a substituent, a polyethylene group (-(CH = And CH) _r- ), a polyethynylene group (-(C≡C) _r- ), or a group formed by combining these (in addition, r is an integer of 0 to 3).

In formula (IX-A), R ^22a is an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, which may be substituted. Number 3-8 cycloalkanoyl group, C3-C20 alkoxycarbonyl alkanoyl group, C8-C20 phenoxycarbonyl alkanoyl group, C3-C20 heteroaryloxyoxycarbonyl alkanoyl group, C2-C10 carbon number And an aryloyl group having 7 to 20 carbon atoms, a hetero aryloyl group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, or an aryloxycarbonyl group having 7 to 20 carbon atoms.

The R ^22a in R ²² and the formula (IX-A) in the general formula (IX), preferably an alkanoyl group having 2 to 12 carbon atoms, heteroaryl alkanoyl group having 1 to 20 carbon atoms, 3 carbon atoms -8 cycloalkanoyl groups are mentioned.
Preferred examples of R ^21a in the above general formula (IX-A) include unsubstituted methyl group, ethyl group, propyl group and propyl group substituted with N-acetyl-N-acetoxyamino group.
In addition, R ^{21 b} in the above general formula (IX-A) is preferably a carbazoyl group which may be substituted, a fluorenyl group which may be substituted, a thioxanthonyl group which may be substituted, or may be substituted Good phenyl sulfide groups are mentioned.

In addition, as an optional substituent in the above general formulas (IX) and (IX-A), an alkyl group, an aromatic hydrocarbon ring group (aryl group), an aliphatic ring group, an aromatic heterocyclic group, a halogen group, A hydroxyl group, a carboxyl group, an amino group, an amido group etc. are mentioned.
Specific examples of the oxime ester-based compound suitable for the present invention include compounds as exemplified below, but the compounds are not limited to these compounds.

  As a keto oxime ester compound, the compound containing the partial structure shown by the following general formula (X) is mentioned, The keto oxime ester compound shown by the following general formula (X-A) is mentioned preferably.

In Formula (X), R ²⁴ has the same meaning as R ²² in Formula (IX).

In the above general formula (X-A), R ^23a is a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 25 carbon atoms, a hetero ring having 1 to 20 carbon atoms which may be substituted. An arylalkyl group, an alkoxycarbonylalkyl group having 3 to 20 carbon atoms, a phenoxycarbonylalkyl group having 8 to 20 carbon atoms, an alkylthio alkyl group having 2 to 20 carbon atoms, a heteroaryloxycarbonylalkyl group having 1 to 20 carbon atoms or a hetero Arylthio alkyl group, aminoalkyl group having 1 to 20 carbon atoms, alkanoyl group having 2 to 12 carbon atoms, alkenoyl group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, aryloyl having 7 to 20 carbon atoms Group, C1-C20 hetero aryloyl group, C2-C10 alkoxycarbonyl group, C7-C2 0 aryloxycarbonyl group or C 1 -C 10 cycloalkylalkyl group is shown;
R ^23b represents an optional substituent containing an aromatic hydrocarbon ring or an aromatic heterocycle (heteroaromatic ring).
R ^23a may be linked to R ^23b to form a ring, and the linking group is an alkylene group having 1 to 10 carbon atoms which may have a substituent, a polyethylene group (-(CH = And CH) _r- ), a polyethynylene group (-(C≡C) _r- ), or a group formed by combining these (in addition, r is an integer of 0 to 3).

In the general formula (X-A), R ^24a is an optionally substituted alkanoyl group having 2 to 12 carbon atoms, an alkenoyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 4 to 8 carbon atoms, carbon Benzoyl group having 7 to 20 atoms, heteroarylyl group having 3 to 20 carbon atoms, alkoxycarbonyl group having 2 to 10 carbon atoms, aryloxycarbonyl group having 7 to 20 carbon atoms, heteroaryl group having 2 to 20 carbon atoms, Or an alkylaminocarbonyl group having 2 to 20 carbon atoms.

The R ^24a in R ²⁴ and the formula (X-A) in the general formula (X), preferably an alkanoyl group having 2 to 12 carbon atoms, heteroaryl alkanoyl group having 1 to 20 carbon atoms, 3 carbon atoms -8 cycloalkanoyl group, a C7-C20 aryloyl group is mentioned.
Preferred examples of R ^23a in the general formula (X-A) include an unsubstituted ethyl group, a propyl group, a butyl group, and an ethyl group or a propyl group substituted with a methoxycarbonyl group.
Further, as R ^23b in the above general formula (X-A), a carbazoyl group which may be substituted, a fluorenyl group which may be substituted, and a phenyl sulfide group which may be substituted may be mentioned.

In addition, as an optional substituent in the above general formulas (X) and (XA), an alkyl group, an aromatic hydrocarbon ring group (aryl group), an aliphatic ring group, an aromatic heterocyclic group, a halogen group, A hydroxyl group, a carboxyl group, an amino group, an amido group etc. are mentioned.
Specific examples of the ketoxime ester compound suitable for the present invention include the compounds exemplified below, but the compounds are not limited to these compounds.

These oxime ester compounds and ketoxime ester compounds are compounds known per se and, for example, a series described in JP-A-2000-80068 and JP-A-2006-36750. Is a kind of compound of In the present invention, from the viewpoint of sensitivity, the (E) photopolymerization initiator is preferably an oxime ester compound and / or a ketoxime ester compound.
The said photoinitiator may be used individually by 1 type, and may use 2 or more types together.

  (E) As the photopolymerization initiator, in addition to those described above, benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether; 2-methylanthraquinone, 2-ethylanthraquinone, 2- Anthraquinone derivatives such as t-butyl anthraquinone and 1-chloroanthraquinone; benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and the like Benzophenone derivatives; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl Ton, .alpha.-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl- (4) Acetophenone derivatives such as' -methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone; thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2- Thioxanthone derivatives such as chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone; Benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate 9-fe Acridine derivatives such as nil acridine and 9- (p-methoxyphenyl) acridine; phenazine derivatives such as 9, 10-dimethyl benzphenazine; and anthrone derivatives such as benzanthrone.

  Among these photopolymerization initiators, among the oxime ester derivatives, compounds containing the partial structure represented by the general formula (IX) from the viewpoints of sensitivity, solubility in solvents, and pattern adhesion during development There are the following compounds.

  Or the following compounds which are compounds containing the partial structure shown by said general formula (X) are more preferable.

The photopolymerization initiator (E) may be used alone or in combination of two or more.
(E) The photopolymerization initiator may be mixed with a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source, as necessary, for the purpose of enhancing sensitivity. As the sensitizing dyes, xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, JP-A-3-239703 and JP-A-5-289335. , A 3-ketocoumarin compound described in JP-A-3-239703, JP-A-5-289335, a pyrometen pigment described in JP-A-6-19240, and the like, JP-A-47-2528, JP-A-54-155922, JP-B-45-37377, JP-A-48-84183, JP-A-52-112681, Japan JP-A-58-15503, JP-A-60-88005, JP-A-59-56403, JP-A-2-69, JP-A-57 No. 168,088, Japanese Patent Laid-Open No. 5-107761, Japanese Patent Laid-Open No. 5-210240, may be mentioned dyes having a dialkyl aminobenzene skeleton described in JP Japanese Patent Laid-Open No. 4-288818.

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

  Examples of the polymerization accelerator include aromatic amines such as ethyl p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later. Be The polymerization accelerators may be used alone or in combination of two or more.

[1-6] Other Compounding Components of Colored Photosensitive Resin Composition The colored photosensitive resin composition of the present invention comprises, in addition to the components described above, adhesion improvers such as silane coupling agents, coatability improvers, development Modifiers, ultraviolet light absorbers, antioxidants, surfactants, pigment derivatives and the like can be appropriately blended.

[1-6-1] Adhesion Improver The colored photosensitive resin composition of the present invention may contain an adhesion improver in order to improve the adhesion to the substrate. As the adhesion improver, silane coupling agents, phosphoric acid group-containing compounds and the like are preferable.
As a kind of a silane coupling agent, various things, such as an epoxy type, a (meth) acryl type, an amino type, can be used individually by 1 type, or in mixture of 2 or more types.

As preferable silane coupling agents, for example, (meth) acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane Epoxysilanes such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, ureidosilanes such as 3-ureidopropyltriethoxysilane, Although isocyanate silanes, such as 3-isocyanate propyl triethoxysilane, are mentioned, Especially preferably, it is a silane coupling agent of epoxy silanes.
As a phosphoric acid group containing compound, (meth) acryloyl group containing phosphates are preferable and what is represented with the following general formula (XI-A), (XI-B) or (XI-C) is preferable.

In the above general formulas (XI-A), (XI-B) and (XI-C), R ⁵¹ represents a hydrogen atom or a methyl group;
l and l 'represent an integer of 1 to 10;
m represents 1, 2 or 3;
These phosphate group-containing compounds may be used alone or in combination of two or more.

[1-6-2] Pigment Derivative The colored photosensitive resin composition of the present invention may contain a pigment derivative as a dispersing aid for the purpose of improving dispersibility and storage stability.
As a pigment derivative, azo type, phthalocyanine type, quinacridone type, benzimidazolone type, quinophthalone type, isoindolinone type, dioxazine type, anthraquinone type, indanthrene type, perylene type, perinone type, perinone type, diketopyrrolopyrrole type, dioxazine There may be mentioned derivatives of such as systems, among which phthalocyanines and quinophthalones are preferred.
As a substituent of the pigment derivative, a sulfonic acid group, a sulfonamide group and its quaternary salt, a phthalimidomethyl group, a dialkylaminoalkyl group, a hydroxyl group, a carboxyl group, an amido group etc. directly on the pigment skeleton or an alkyl group, an aryl group or a complex What is bonded via a ring group etc. is mentioned, Preferably it is a sulfonic acid group. Moreover, these substituents may be multiply substituted by one pigment frame.

  Specific examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. One of these may be used alone, or two or more may be used in combination.

[1-6-3] Photo-Acid Generator A photo-acid generator is a compound capable of generating an acid by ultraviolet light, and, for example, a crosslinking agent such as a melamine compound by the action of an acid generated upon exposure. Causes the crosslinking reaction to proceed. Among the photoacid generators, those having high solubility in solvents, particularly high solubility in solvents used for photosensitive coloring compositions, are preferred. For example, diphenyliodonium, ditollylodonium, phenyl (p-anisyl) are preferable. Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl (p-tolyl) iodonium, p -Diaryliodoniums such as isopropylphenyl (p-tolyl) iodonium, chlorides, bromides or borofluoride salts of triarylsulfoniums such as triphenylsulfonium, hexafluorophosphate salts, Sulfonium organoboron complexes such as senate salts, aromatic sulfonates, tetrakis (pentafluorophenyl) borate salts, etc., diphenylphenacylsulfonium (n-butyl) triphenylborate, or 2-methyl-4,6- Although triazine compounds, such as bis trichloromethyl triazine and 2- (4-methoxyphenyl) -4,6-bis trichloromethyl triazine, etc. can be mentioned, it is not this limitation.

[1-6-4] Crosslinking agent A crosslinking agent can be further added to the colored photosensitive resin composition of the present invention, and for example, a melamine or guanamine compound can be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XII).

In formula (XII), R ⁶¹ represents a —NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms;
One If R ⁶¹ is -NR ⁶⁶ R ⁶⁷ groups ^{R 62, R 63, R 64} , R 65, R 66 and R ^67, and when R ⁶¹ is an aryl group having 6 to 12 carbon atoms R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ each represent a —CH ₂ OR ⁶⁸ group;
The rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ each independently represent a hydrogen atom or a —CH ₂ OR ⁶⁸ group;
R ⁶⁸ represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
Here, the aryl group having 6 to 12 carbon atoms is typically a phenyl group, a 1-naphthyl group or a 2-naphthyl group, and an alkyl group, an alkoxy group, a halogen atom, etc. are exemplified as the phenyl group and the naphthyl group. The substituent of may be bonded. The alkyl group and the alkoxy group can each have about 1 to 6 carbon atoms. Among the above, the alkyl group represented by R ⁶⁸ is preferably a methyl group or an ethyl group, more preferably a methyl group.

  Examples of melamine compounds corresponding to the general formula (XII), that is, compounds of the following general formula (XII-A) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, pentamethoxymethylmelamine, tetramethoxy Methylmelamine, hexaethoxymethylmelamine and the like are included.

In the formula (XII-A), when one of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ is an aryl group, one of R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ is —CH ₂ Represents OR ⁶⁸ groups;
The rest of R ⁶² , R ⁶³ , R ⁶⁴ , R ⁶⁵ , R ⁶⁶ and R ⁶⁷ each independently represent a hydrogen atom or a —CH ₂ OR ⁶⁸ group;
R ⁶⁸ represents a hydrogen atom or an alkyl group.

In addition, guanamine compounds corresponding to general formula (XII), that is, compounds wherein R ⁶¹ in the general formula (XII) is aryl, include tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, trimethoxymethylbenzoguanamine, tetraethoxymethylbenzoguanamine Etc. are included.

Furthermore, crosslinking agents having methylol groups or methylol alkyl ether groups can also be used. An example is given below.
2,6-Bis (hydroxymethyl) -4-methylphenol, 4-tert-butyl-2,6-bis (hydroxymethyl) phenol, 5-ethyl-1,3-bis (hydroxymethyl) perhydro-1,3 3,5-Triazin-2-one (generally called N-ethyldimethylol triazone) or its dimethyl ether, dimethylol trimethylene urea or its dimethyl ether, 3,5-bis (hydroxymethyl) perhydro-1,3,5- Oxadiazin-4-one (generally called dimethylol urone) or its dimethyl ether, tetramethylol glyoxal diurein or its tetramethyl ether.

  These crosslinking agents may be used alone or in combination of two or more. The amount of the crosslinking agent to be used is preferably 0.1 to 15% by mass, and particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.

[1-6-5] Mercapto compound It is also possible to add a mercapto compound as a polymerization accelerator or for the purpose of improving the adhesion to a substrate.

  Examples of mercapto compounds include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, 1,4-dimethylmercaptobenzene, butanediol bisthiopropionate, and butanediol bis Thioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate, pentaerythritol tetrakisthiopropioate , Pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis 3-Mercaptobutyrate), butanediol bis (3-mercaptobutyrate), 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentaerythritol tetrakis (3) -Mercapto butyrate), pentaerythritol tris (3-mercapto butyrate), ethylene glycol bis (3- mercapto isobutyrate), butanediol bis (3- mercapto isobutyrate), trimethylolpropane tris (3-mercaptoiso) Butyrate), 1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -triquinone and other mercapto compounds having a heterocyclic ring Or aliphatic polyfunctional mercapto compounds etc. It is. These can be used singly or in combination of two or more.

[1-6-6] Surfactant The colored photosensitive resin composition of the present invention may contain a surfactant to improve the coating property.

As surfactant, various things, such as anionic surfactant, cationic surfactant, nonionic surfactant, and amphoteric surfactant, can be used, for example. Among them, it is preferable to use a nonionic surfactant in that the possibility of adversely affecting various properties is low, and a fluorine-based or silicone-based surfactant is particularly effective in terms of coatability.
As these commercial items, for example, “BM-1000” and “BM-1100” manufactured by BM Chemie, “Megafuck F-142D” and “Megafuck F-172”, “Megafuck F-173” manufactured by DIC “Megafuck F-183”, “Megafuck F-470”, “Megafuck F-475”, “Megafuck F-478”, “Megafuck F-554”, “Megafuck F-559” Examples include "FC 430" manufactured by 3M Japan, and "DFX-18" manufactured by Neos.

Further, examples of silicone surfactants include “DC3PA”, “SH7PA”, “DC11PA”, “SH21PA”, “SH28PA”, “SH29PA”, “8032Additive”, “SH8400”, manufactured by Toray Dow Corning, Commercial products such as BYK 300, BYK 323, BYK 325, and BYK 330 manufactured by Big Chemie, and KP 340 manufactured by Shin-Etsu Silicone Co., Ltd. can be mentioned.
As the surfactant, one other than the fluorine-based surfactant and the silicone-based surfactant may be contained, and as the other surfactant, the non-ionic surfactant, the anionic surfactant, the cationic interface Activators, amphoteric surfactants and the like can be mentioned.
In addition, surfactant may be used individually by 1 type, and may use together 2 or more types by arbitrary combinations and a ratio. Among them, a combination of silicone surfactant / fluorinated surfactant is preferable. In this combination of silicone surfactant / fluorine surfactant, for example, "BYK-300" manufactured by Bick Chemie or "F-475""F-478""F-554 manufactured by DIC". Or "F-559" and the like.

[1-6-7] Liquid-Repellent Agent The colored photosensitive resin composition of the present invention may contain a liquid-repellent agent. It is preferable to contain a liquid repellent especially when creating a partition using the colored photosensitive resin composition of this invention, and creating an organic electroluminescent element by the inkjet method. By containing a liquid repellent agent, it is possible to impart liquid repellency to the surface of the partition walls, so that the obtained partition walls can be prevented from color mixing of each pixel of the organic layer.
The liquid repellent agent includes silicone-containing compounds and fluorine-based compounds, and preferably, a liquid repellent agent having a crosslinking group (hereinafter sometimes referred to as “crosslinking group-containing liquid repellent agent”). The crosslinking group may, for example, 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.
In the case of using a crosslinking group-containing liquid repellent, when the formed coating film is exposed, the crosslinking reaction on the surface can be accelerated, and the liquid repellent is less likely to flow out in the development process, and as a result, the partition wall obtained It can be considered that it can exhibit high liquid repellency.

  When a fluorine-based compound is used as the liquid repellent agent, the fluorine-based compound tends to be oriented on the surface of the partition wall to prevent ink bleeding and color mixing. More specifically, the group having a fluorine atom tends to repel the ink and prevent ink bleeding and color mixing due to the ink passing through the partition wall and entering the adjacent region.

  Specific examples of the crosslinking group-containing liquid repellent agent, particularly the ethylenically unsaturated group-containing fluorine compound, include, for example, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoroalkyltrialkylammonium salt , An oligomer containing a perfluoroalkyl group and a hydrophilic group, an oligomer containing a perfluoroalkyl group and a lipophilic group, an oligomer containing a perfluoroalkyl group, a hydrophilic group and a lipophilic group, a urethane containing a perfluoroalkyl and a hydrophilic group, Per Mention may be made of fluorine-containing organic compounds such as fluoroalkyl esters and perfluoroalkyl phosphates.

  Commercial products of these fluorine-containing compounds include “DEFENSAMCF-300”, “DEFENSAMCF-310”, “DEFENSAMCF-312”, “DEFENSAMCF-323”, “Megafuck RS-72-K” manufactured by DIC, 3M Japan "Florard FC-431", "Florrad FC-4430", "Florrad FC-4432" manufactured by Asahi Glass, "Asahi Guard AG 710", "Surflon S-382", "Surflon SC-101", "Surflon SC- 102 "," Surflon SC-103 "," Surfron SC-104 "," Surflon SC-105 "," Surflon SC-106 ", products such as" Optool DAC-HP "," HP-650 "manufactured by Daikin Industries, Ltd. Commercially available fluorine-containing compounds It can be used.

  Thus, when using a fluorine-based compound as the liquid repellent agent, the fluorine atom content ratio in the liquid repellent agent is not particularly limited, but preferably the fluorine atom content ratio is preferably 1% by mass or more, more preferably 5% by mass or more Moreover, 50 mass% or less is preferable, and 25 mass% or less is more preferable. By setting the lower limit value or more, the contact angle tends to be high, and by setting the upper limit value or less, the outflow to the pixel portion tends to be suppressed.

  The molecular weight of the liquid repellent agent is not particularly limited, and may be a low molecular weight compound or a high molecular weight product. The liquid repellent agent of high molecular weight is preferable because the fluidity of the liquid repellent agent due to baking can be suppressed, and the liquid repellent agent can be suppressed from flowing out of the partition wall, and from such a viewpoint, the number average molecular weight of the liquid repellent agent is 100 or more is preferable, 500 or more is more preferable, 100000 or less is preferable, and 10000 or less is more preferable.

  The content ratio of the liquid repellent in the colored photosensitive resin composition of the present invention is usually 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass or more based on the total solid content. It is usually at most 1% by mass, preferably at most 0.5% by mass, more preferably at most 0.3% by mass. There is a tendency to show high liquid repellency by setting it to the above lower limit value, and there is a tendency to be able to control the outflow to the pixel part of the liquid repellent by setting it to the above upper limit value.

[1-6-8] Ultraviolet Absorber The colored photosensitive resin composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber is added for the purpose of controlling the light curing distribution by absorbing a specific wavelength of a light source used for exposure by the ultraviolet absorber. The addition of the ultraviolet absorber tends to improve the taper angle and shape after development, and eliminate the residue remaining in the non-exposed area after development. As the ultraviolet absorber, from the viewpoint of inhibition of light absorption of the initiator, for example, a compound having an absorption maximum between wavelengths 250 nm and 400 nm can be used.
As an ultraviolet absorber, a benzotriazole compound and / or a triazine compound are desirable. By including the benzotriazole compound and / or the triazine compound, the light absorptivity at the film bottom of the initiator decreases, and the difference between the cured area of the film surface and the film bottom decreases, and the effect of increasing the taper angle is obtained. It is thought that

  Examples of benzotriazole compounds include 2- (5 methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, octyl-3 [3-tert-butyl -4-Hydroxy-5- (5-chloro-2H-benzotriazol-2-yl) phenyl] propionate and 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H Of 2-benzotriazol-2-yl) phenyl] propionate, 2- [2-hydroxy-3,5-bis (α, α-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, 2- (2H-benzotriazol-2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3 -Tetramethylbutyl) phenol, benzenepropanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 side chain and linear alkyl esters It can be mentioned.

Commercially available benzotriazole compounds include, for example, Sumisorb 200, Sumisorb 250, Sumisorb 300, Sumisorb 340, Sumisorb 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF 77, JF 78, JF 79, JF 80, JF 83 (manufactured by Johoku Chemical Co., Ltd.) TINUVIN PS, TINUVIN 99, TINUVIN 109, TINUVIN 384-2, TINUVIN 326, TINUVIN 900, TINUVIN 928, TINUVIN 928, TINUVIN 1130 (manufactured by BASF Corp.), EVERSORB 70, EVERSORB 71, EVERSORB 72, EVERSORB 73, EVERSORB 74, EVERSORB 75, EVERSORB 76, EVORIB B78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Eiko Chemical Co., Ltd.), Tomisorb 100, Tomisorb 600 (manufactured by AP Corporation), SEESORB 701, SEESORB702, SEESORB 703, SEESORB 704, SEESORB 706, SEESORB 707, SEESORB 709 (manufactured by Shipro Kasei Co., Ltd.), RUVA-93 (Otsuka Chemical Co., Ltd.) and the like.
Examples of triazine compounds include 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol, 2- [4,6-bis ( 2,4-Dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxyphenyl) -4 Product of the reaction of 2,6-bis (2,4-dimethylphenyl) -1,3,5-triazine with (2-ethylhexyl-glycidic ester, 2,4-bis "2-hydroxy-4-butoxyphenyl"- 6- (2,4-dibutoxyphenyl) -1,3-5-triazine etc. Among these, a hydroxyphenyl triazine compound is preferable from a viewpoint of a taper angle and exposure sensitivity.
As a triazine type compound marketed, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (made by BASF) etc. can be mentioned, for example.

[1-6-9] Polymerization inhibitor The colored photosensitive resin composition of the present invention may contain a polymerization inhibitor. The inclusion of the polymerization inhibitor tends to inhibit radical polymerization, and thus, the taper angle of the resulting cured product tends to be able to be increased.
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, 2,6-di-tert-butyl-4-cresol (BHT) and the like. Among these, 2,6-di-tert-butyl-4-cresol, hydroquinone or methoxyphenol is preferable from the viewpoint of the polymerization inhibiting ability.

  The polymerization inhibitor preferably contains one or more kinds. Usually, when (C) binder resin is produced, a polymerization inhibitor may be contained in the resin, and in addition to the polymerization inhibitor contained in the resin, the same or different polymerization inhibitor as that is photosensitive. You may add at the time of resin composition manufacture.

  The content of the polymerization inhibitor in the colored photosensitive resin composition is usually 0.0005% by mass or more, preferably 0.001% by mass or more, and more preferably, relative to the total solid content of the colored photosensitive resin composition. It is 0.01% by mass or more, and usually 0.1% by mass or less, preferably 0.08% by mass or less, more preferably 0.05% by mass or less. There is a tendency that the taper angle can be increased by setting the lower limit value or more, and there is a tendency that high sensitivity can be maintained by setting the upper limit value or less.

[1-6-10] Inorganic Filler Further, the colored photosensitive resin composition of the present invention further improves the strength of the cured product and (C) proper interaction with the binder resin (formation of matrix structure) An inorganic filler may be contained for the purpose of improving the flatness and the taper angle of the coating film by the above. Examples of such an inorganic filler include talc, silica, alumina, barium sulfate, magnesium oxide, and those surface-treated with various silane coupling agents.

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

[1-7] Solvent The colored photosensitive resin composition and the pigment dispersion of the present invention usually contain a solvent. By including the solvent, a colorant such as a pigment can be dispersed in the solvent, and coating becomes easy.
The colored photosensitive resin composition of the present invention generally comprises (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, (E) a photopolymerization initiator and, if necessary, Various other materials to be used are used as dissolved or dispersed in a solvent. Similarly, in the pigment dispersion of the present invention, usually, (A) colorant, (B) dispersant, (C) binder resin and other various materials used as needed are dissolved or dispersed in a solvent Used in the state. Among the solvents, organic solvents are preferable from the viewpoint of dispersibility and coatability.

  Among the organic solvents, it is preferable to select one having a boiling point of 100 to 300 ° C. (pressure 1013.25 hPa conditions, hereinafter the same applies to all the boiling points) from the viewpoint of coating property, and the boiling point is 120 to 280 ° C. It is more preferable to select one in the range of

Examples of such organic solvents include the following.
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether Ether, tri Chi glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether;
Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono-n-butyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, methoxybutyl Acetate, 3-methoxybutyl acetate, methoxypentyl acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol mono-n-butyl ether acetate, dipropylene glycol monomethyl ether acetate, triethylene glycol Roh ether acetate, triethylene glycol monoethyl ether acetate, glycol alkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate;
Alkyl acetates such as cyclohexanol acetate;
Ethers such as amyl ether, diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, ethyl isobutyl ether, dihexyl ether;

Like acetone, methyl ethyl ketone, methyl amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketone, methyl nonyl ketone, methoxymethyl pentanone Ketones;
Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethyl pentanol, glycerin 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, cumene;
Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprilate, butyl stearate, ethyl benzoate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, 3-methoxypropionate Linear or cyclic esters such as butyl, γ-butyrolactone;
Alkoxycarboxylic acids such as 3-methoxypropionic acid, 3-ethoxypropionic acid;
Halogenated hydrocarbons such as butyl chloride, amyl chloride;
Ether ketones such as methoxymethyl pentanone;
Acetonitrile, nitriles such as benzonitrile, etc.

The commercially available organic solvents corresponding to the above include Mineral Spirit, Valsol # 2, Apco # 18 Solvent, Apcosynner, Socar Solvent No. 1 and No. 1 2, Solvesso # 150, Shell TS 28 Solvent, Carbitol, Ethyl Carbitol, Butyl Carbitol, Methyl Cellosolve ("Cellosorb" is a registered trademark. The same shall apply hereinafter.), Ethyl Cellosolve, Ethyl Cellosolve Acetate, Methyl Cellosolve Acetate, Diglyme (any one Are also trade names).
These organic solvents may be used alone or in combination of two or more.

  When forming a partition and a coloring spacer by the photolithographic method, it is preferable to select the thing of the range whose boiling point is 100-200 degreeC as an organic solvent. More preferably, it has a boiling point of 120 to 170 ° C.

Among the above organic solvents, glycol alkyl ether acetates are preferable in terms of good balance of coating properties, surface tension and the like and relatively high solubility of the components in the composition.
Moreover, although glycol alkyl ether acetates may be used independently, you may use another organic solvent together. Particularly preferable organic solvents to be used in combination are glycol monoalkyl ethers. Among these, propylene glycol monomethyl ether is particularly preferable in view of the solubility of the component in the composition. In addition, glycol monoalkyl ethers have high polarity, and when the amount added is too large, the pigment tends to aggregate, and the storage stability tends to decrease, for example, the viscosity of the colored photosensitive resin composition obtained later increases. Thus, the proportion of glycol monoalkyl ethers in the solvent is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

  It is also preferable to use an organic solvent having a boiling point of 150 ° C. or higher (hereinafter sometimes referred to as “high-boiling point solvent”) in combination. The combined use of such a high boiling point solvent makes it difficult to dry the colored photosensitive resin composition, but has the effect of preventing the uniform dispersion state of the pigment in the composition from being destroyed by rapid drying. . That is, for example, there is an effect of preventing the generation of foreign matter defects at the tip of the slit nozzle due to the precipitation and solidification of the coloring agent and the like. Among the various solvents described above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable from the viewpoint of such effects being high.

  3 mass%-50 mass% are preferable, as for the content rate of the high boiling point solvent in the organic solvent, 5 mass%-40 mass% is more preferable, and 5 mass%-30 mass% is especially preferable. By setting the lower limit value or more, for example, there is a tendency to be able to suppress that a coloring material etc. precipitates and solidifies at the tip of the slit nozzle and causes foreign matter defects, and by setting the upper limit value or less. There is a tendency to be able to suppress such problems as tact failure of the vacuum drying process and pin marks of prebaking.

The high boiling point solvent having a boiling point of 150 ° C. or more may be a glycol alkyl ether acetate or may be a glycol alkyl ether, and in this case, a high boiling point solvent having a boiling point of 150 ° C. or more is separately contained You don't have to.
As preferred high boiling point solvents, for example, among the various solvents described above, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, 1,6-hexanol diacetate Acetate, triacetin and the like can be mentioned.

<Composition of Component in Colored Photosensitive Resin Composition>
In the colored photosensitive resin composition of the present invention, the content ratio of the (A) colorant is preferably 20% by mass or more and 25% by mass or more based on the total solid content in the colored photosensitive resin composition. 30% by mass or more, 60% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less Even more preferred is When the content is at least the lower limit, sufficient optical density (OD) tends to be easily obtained, and when the content is at most the upper limit, sufficient image formability tends to be easily obtained. The combination of the upper limit and the lower limit is preferably 20 to 60% by mass, more preferably 25 to 50% by mass, still more preferably 30 to 45% by mass, and particularly preferably 30 to 40% by mass.

  In the colored photosensitive resin composition and the pigment dispersion of the present invention, the content ratio of the (A1) organic black pigment to the (A) colorant is usually 10% by mass or more, preferably 30% by mass or more, more preferably It is 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, particularly preferably 90% by mass or more, and usually 100% by mass or less. By setting the content ratio of the (A1) organic black pigment in the colorant to the lower limit value or more, a coating film having a more desirable black color tone is obtained, and a coating film having high strength tends to be obtained. . The combination of the upper limit and the lower limit is preferably 10 to 100% by mass, more preferably 30 to 100% by mass, still more preferably 50 to 100% by mass, still more preferably 70 to 100% by mass, and 80 to 100% by mass Particularly preferred is 90 to 100% by mass.

In the colored photosensitive resin composition and the pigment dispersion liquid of the present invention, the (A) coloring agent may contain (A2) organic coloring pigment together with (A1) organic black pigment. In that case, the content ratio of the (A1) organic black pigment to the (A) colorant is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and usually 90% by mass or less, preferably It is 80 mass% or less, more preferably 60 mass% or less. In addition, the content ratio of the (A2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, more preferably 40% by mass or more, and usually 90% by mass or less, preferably 80% by mass or less More preferably, it is 70% by mass or less. By setting the lower limit value or more, the taper angle tends to be low, and by setting the upper limit value or less, a coating film having a blacker tone tends to be obtained.
The content ratio of the (A1) organic black pigment to 100 parts by mass of the organic coloring pigment (A2) is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 900 parts by mass or less, preferably 800 parts by mass or less Preferably it is 500 mass parts or less, More preferably, it is 200 mass parts or less.

  In the colored photosensitive resin composition and the pigment dispersion of the present invention, the (A) colorant may contain (A3) carbon black together with the (A1) organic black pigment. In that case, the content ratio of the (A1) organic black pigment to the (A) colorant is usually 50% by mass or more, preferably 60% by mass or more, and usually 95% by mass or less, preferably 90% by mass or less. Further, the content ratio of (A3) carbon black is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less. A sufficient optical density (OD) tends to be obtained by setting the content to the above lower limit, and a high volume resistivity and a low dielectric constant are obtained by setting the content to the above upper limit, and wrinkles at the time of curing Etc. tend to be difficult to occur. The content ratio of the (A1) organic black pigment to 100 parts by mass of (A3) carbon black is usually 100 parts by mass or more, preferably 150 parts by mass or more, and usually 2000 parts by mass or less, preferably 1000 parts by mass or less.

  In the colored photosensitive resin composition and the pigment dispersion of the present invention, (A) the organic black pigment may be contained together with the (A1) organic black pigment in the (A) colorant. . In that case, the content ratio of the (A1) organic black pigment to the (A) coloring agent is usually 10% by mass or more, preferably 20% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less. The content ratio of the (A2) organic coloring pigment is usually 10% by mass or more, preferably 20% by mass or more, and usually 60% by mass or less, preferably 50% by mass or less. Furthermore, the content ratio of (A3) carbon black is usually 5% by mass or more, preferably 10% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less. In this case, the content ratio of the (A1) organic black pigment to 100 parts by mass of the (A2) organic coloring pigment is usually 15 parts by mass or more, preferably 20 parts by mass or more, and usually 800 parts by mass or less, preferably 700 parts by mass or less is there. The content ratio of the (A1) organic black pigment to 100 parts by mass of (A3) carbon black is usually 40 parts by mass or more, preferably 50 parts by mass or more, and usually 1000 parts by mass or less, preferably 900 parts by mass or less.

  The content ratio of the dispersant (B) is usually 1% by mass or more, preferably 3% by mass or more, more preferably 5% by mass or more, and usually 30% by mass or less in the solid content of the colored photosensitive resin composition. 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is more preferable. By setting the amount to the above lower limit or more, the dispersibility tends to be good, and by setting the amount to the above upper limit or less, the excess dispersant can be reduced, and the developability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, still more preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass.

  In addition, the content ratio of the (B) dispersant with respect to 100 parts by mass of the (A) colorant is usually 5 parts by mass or more and 10 parts by mass or more, and usually 50 parts by mass or less and 30 parts by mass or less. By setting the amount to the above lower limit or more, the dispersibility tends to be good, and by setting the amount to the above upper limit or less, the excess dispersant can be reduced, and the developability tends to be good. The combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass.

In the colored photosensitive resin composition according to the first aspect of the present invention, the content ratio of the acrylic dispersant is not particularly limited, but is usually 1% by mass or more in the solid content of the colored photosensitive resin composition, % By mass or more is preferable, 5% by mass or more is more preferable, 30% by mass or less and 20% by mass or less is preferable, 15% by mass or less is more preferable, and 10% by mass or less is more preferable. By setting the amount to the above lower limit or more, the dispersibility tends to be good, and by setting the amount to the above upper limit or less, the excess dispersant can be reduced, and the developability tends to be good. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, still more preferably 5 to 15% by mass, and particularly preferably 5 to 10% by mass.
In the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion according to the third aspect of the present invention, the content ratio of the acrylic dispersant to 100 parts by mass of the (A) colorant is Usually, 5 parts by mass or more and 10 parts by mass or more are preferable, and 50 parts by mass or less and 30 parts by mass or less are preferable. By setting the amount to the above lower limit or more, the dispersibility tends to be good, and by setting the amount to the above upper limit or less, the excess dispersant can be reduced, and the developability tends to be good. The combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, and more preferably 10 to 30 parts by mass.

  The content ratio of the binder resin (C) is not particularly limited, but generally 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass, based on the total solid content of the colored photosensitive resin composition of the present invention Or more, more preferably 30% by mass or more, particularly preferably 40% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less . By setting the lower limit value or more, a strong film tends to be easily obtained. By setting the upper limit value or less, the penetration of the developer into the exposed portion is suppressed to a low level, and the film surface smoothness and sensitivity It tends to be easy to control the deterioration. The combination of the upper limit and the lower limit is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, still more preferably 30 to 50% by mass, and 40 to 50% by mass It is particularly preferable.

  The content ratio of the (C1) epoxy (meth) acrylate resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass, based on the total solid content of the colored photosensitive resin composition of the present invention Or more, more preferably 30% by mass or more, still more preferably 35% by mass or more, particularly preferably 40% by mass or more, usually 80% by mass or less, preferably 70% by mass or less, more preferably 60% by mass or less More preferably, it is 50% by mass or less. When the content is at least the lower limit, a strong film tends to be easily obtained. When the content is at most the upper limit, deterioration in surface smoothness and sensitivity of the film tends to be suppressed. The combination of the upper limit and the lower limit is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, still more preferably 20 to 60% by mass, still more preferably 30 to 60% by mass, and 35 to 60% by mass Particularly preferred is 40 to 50% by mass.

  In the present invention, an epoxy (meth) acrylate resin having a repeating unit structure represented by the above general formula (II) in the binder resin (C) and / or an epoxy having a partial structure represented by the above general formula (III) The content ratio of the meta) acrylate resin (the content ratio of the total when both are included) is not particularly limited, but is preferably 75% by mass or more, more preferably 80% by mass or more, and 85% by mass or more Is more preferably 90% by mass or more, and particularly preferably 95% by mass or more. Moreover, it is normally 100 mass% or less. Outgassing aptitude tends to become favorable by setting it as the above-mentioned lower limit value or more. The combination of the upper limit and the lower limit is preferably 75 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass It is particularly preferable.

  The content ratio of the (D) photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, based on the total solid content of the colored photosensitive resin composition. The amount is usually 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less. By setting the content to the above lower limit value, the sensitivity tends to be high, and by setting the content to the above upper limit value, developability tends to be good. As a combination of the upper limit and the lower limit, 1 to 30% by mass is preferable, 5 to 20% by mass is more preferable, and 8 to 15% by mass is more preferable.

  The content ratio of the photopolymerization initiator (E) is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1 based on the total solid content of the colored photosensitive resin composition of the present invention. % By mass, more preferably 2% by mass, particularly preferably 3% by mass, usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 5% by mass or less It is. By setting the amount to the lower limit or more, good sensitivity tends to be obtained, and by setting the amount to the upper limit or less, the amount of the binder resin and the photopolymerizable monomer suitable for development tends to be secured. The combination of the upper limit and the lower limit is preferably 0.1 to 15% by mass, more preferably 0.5 to 10% by mass, still more preferably 1 to 8% by mass, and still more preferably 2 to 5% by mass. Particularly preferred is 5% by mass.

  When the polymerization accelerator is used together with the photopolymerization initiator (E), the content ratio of the polymerization accelerator is preferably 0.05% by mass or more based on the total solid content of the colored photosensitive resin composition of the present invention. Usually, it is 10% by mass or less, preferably 5% by mass or less. The polymerization accelerator is usually 0.1 parts by mass or more, preferably 0.2 parts by mass or more, and usually 100 parts by mass or less, preferably 50 parts by weight, per 100 parts by mass of the photopolymerization initiator (D). It is below.

When the content ratio of the polymerization accelerator is at least the lower limit value, good sensitivity tends to be obtained, and when the content ratio is at most the upper limit value, the solubility of the unexposed part in the developer tends to be good.
In addition, the blending ratio of the sensitizing dye in the colored photosensitive resin composition of the present invention is usually 0.5% by mass or more, preferably from the viewpoint of sensitivity, in the total solid content in the colored photosensitive resin composition. It is 1% by mass or less, usually 20% by mass or less, preferably 15% by mass or less, and more preferably 10% by mass or less.

  When the adhesion improver is used, its content is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, more preferably 0. to 5% by mass relative to the total solid content in the colored photosensitive resin composition. It is 4 to 2% by mass. By setting the content ratio of the adhesion improver to the above lower limit value or higher, the adhesion tends to be improved, and by setting the content ratio below the upper limit value, good sensitivity can be obtained, and residues after development are less likely to occur. Tend.

Moreover, when using surfactant, the content rate is normally 0.001-10 mass% with respect to the total solid in a coloring photosensitive resin composition, Preferably 0.005-1 mass%, More preferably, 0.01 to 0.5% by mass, most preferably 0.03 to 0.3% by mass. By setting the content ratio of the surfactant to the above lower limit value, the smoothness and uniformity of the coating film tend to be obtained, and by setting the content ratio to the upper limit value or less, the occurrence of unevenness and the like tends to be suppressed. .
The colored photosensitive resin composition of the present invention is prepared using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.

<Physical Properties of Colored Photosensitive Resin Composition>
The colored photosensitive resin composition of the present invention can be suitably used for forming a black matrix besides partition walls and colored spacers, and from such a viewpoint it is preferable to exhibit a black color, and the film thickness of the coating film is 1 μm. The optical density (OD) per unit is preferably 0.5 or more, more preferably 0.8 or more, still more preferably 1.0 or more, and particularly preferably 1.3 or more. .

  When applied to a member having a high area ratio in an image display area of an image display device, such as a partition of an organic electroluminescent element, it is preferable that the color tone be closer to black. From such a viewpoint, x of the chromaticity at the time of curing is preferably 0.20 or more, more preferably 0.25 or more, still more preferably 0.30 or more, 0. It is preferably 50 or less, more preferably 0.45 or less, and still more preferably 0.40 or less. Further, y of the chromaticity is preferably 0.20 or more, more preferably 0.25 or more, still more preferably 0.30 or more, and preferably 0.50 or less. And 0.4 or less are more preferable, and 0.40 or less is more preferable.

[2] Components and Composition of Pigment Dispersion Liquid The components constituting the pigment dispersion liquid of the present invention and the composition thereof will be described.
The pigment dispersion of the present invention (hereinafter sometimes simply referred to as "pigment dispersion") contains (A) a colorant, (B) a dispersant and (C) a binder resin. Usually, it also contains a solvent. Moreover, the pigment dispersion liquid of this invention can be suitably used as one of the raw materials used when manufacturing a coloring photosensitive resin composition so that it may mention later.

  As the (A) colorant, the (B) dispersant, the (C) binder resin and the solvent used in the pigment dispersion, those mentioned as the ones used in the colored photosensitive resin composition can be suitably used. .

In the pigment dispersion of the present invention, the (A) colorant contains the aforementioned (A1) organic black pigment. (A1) A coating film obtained by applying a colored photosensitive resin composition produced using a pigment dispersion containing an organic black pigment can realize high resistance, low dielectric constant and high light blocking ratio, and is more black It tends to be a cured product of similar color tone.
In addition, the (B) dispersant contains an acrylic dispersant. By producing a colored photosensitive resin composition using a pigment dispersion containing an acrylic dispersant, pattern adhesion during development tends to be good.
Moreover, (C) binder resin contains (C1) epoxy (meth) acrylate resin. (C1) By producing a colored photosensitive resin composition using a pigment dispersion containing an epoxy (meth) acrylate resin, the amount of outgas generated after forming a cured product tends to be small.

<Composition of Component in Pigment Dispersion>
In the pigment dispersion of the present invention, the content ratio of the (A) colorant is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, based on the total solid content in the pigment dispersion. More preferably 40% by mass or more, still more preferably 50% by mass or more, particularly preferably 55% by mass or more, usually 100% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, more preferably Is 60 mass% or less. By setting it as the said lower limit or more, a coloring photosensitive resin composition can be manufactured by a suitable solid content concentration, and there exists a tendency for dispersibility to become favorable by setting it below the said upper limit. The combination of the upper limit and the lower limit is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, still more preferably 30 to 70% by mass, still more preferably 40 to 70% by mass, and 50 to 60% by mass Particularly preferred is 55 to 60 mass.

  In the pigment dispersion of the present invention, the content ratio of the (B) dispersant is usually 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content in the pigment dispersion. The content is usually 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less. By setting the content to the above lower limit or more, the dispersibility tends to be good, and by setting the content to the above upper limit or less, the excess dispersant can be reduced, and the developability of the obtained colored photosensitive resin composition becomes good. Tend. The combination of the upper limit and the lower limit is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and 10 to 15% by mass It is particularly preferable.

  In the pigment dispersion of the present invention, the content ratio of the acrylic dispersant is usually 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, based on the total solid content in the pigment dispersion. Usually, it is 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 20% by mass or less, and particularly preferably 15% by mass or less. While the dispersibility is improved by setting the content to the above lower limit or more, the pattern adhesion tends to be good during development of the cured product, and the colored photosensitive resin composition obtained by setting the content to the above upper limit or less The developability tends to be good. The combination of the upper limit and the lower limit is preferably 2 to 50% by mass, more preferably 5 to 40% by mass, still more preferably 5 to 30% by mass, still more preferably 5 to 20% by mass, and 10 to 15% by mass It is particularly preferable.

  In the pigment dispersion of the present invention, the content ratio of the (C) binder resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, based on the total solid content in the pigment dispersion. More preferably, it is 20% by mass or more, particularly preferably 25% by mass or more, and usually 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less. By setting the content to the above lower limit or more, the dispersibility tends to be good, and by setting the content to the above upper limit or less, the amount of the colorant in the colored photosensitive resin composition obtained can be optimized, and the light shielding property is sufficient. Tend to be secured. The combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass, still more preferably 20 to 35% by mass, and 25 to 30% by mass It is particularly preferable.

  In the pigment dispersion of the present invention, the content ratio of the (C1) epoxy (meth) acrylate resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass with respect to the total solid content in the pigment dispersion. % By mass, more preferably 20% by mass or more, particularly preferably 25% by mass or more, usually 50% by mass or less, preferably 40% by mass or less, more preferably 35% by mass or less, still more preferably 30% by mass or less It is. The outgassing aptitude of the cured product tends to be good by setting the content to the above lower limit value, and the amount of coloring agent in the colored photosensitive resin composition obtained by setting the content to the above upper limit value can be optimized. There is a tendency to secure good light shielding. The combination of the upper limit and the lower limit is preferably 5 to 50% by mass, more preferably 10 to 40% by mass, still more preferably 15 to 35% by mass, still more preferably 20 to 35% by mass, and 25 to 30% by mass It is particularly preferable.

  The pigment dispersion of the present invention is prepared using the above-mentioned organic solvent so that the solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.

[3] Production Method of Colored Photosensitive Resin Composition The colored photosensitive resin composition (hereinafter sometimes referred to as “resist”) of the present invention is produced according to a conventional method.
In general, the colorant (A) is preferably dispersed in advance using a paint conditioner, a sand grinder, a ball mill, a roll mill, a stone mill, a jet mill, a homogenizer, and the like. Since the (A) colorant is micronized by the dispersion treatment, the coating characteristics of the resist are improved.

The dispersion treatment is usually carried out preferably in a system in which a part or all of (A) a colorant, an organic solvent, and (B) a dispersant, and (C) a binder resin are used in combination (hereinafter referred to as dispersion treatment) Mixture, and composition obtained by the treatment may be referred to as "ink" or "pigment dispersion". In particular, using a polymer dispersant as the dispersant (B) is preferable because thickening of the obtained ink and resist over time is suppressed (the dispersion stability is excellent).
Thus, in the step of producing the resist, it is preferable to produce a pigment dispersion containing at least (A) a colorant, an organic solvent, and (B) a dispersant.

In addition, when a dispersion process is performed with respect to the liquid which contains all the components mix | blended with a coloring photosensitive resin composition, there exists a possibility that a highly reactive component may modify | denature due to the heat_generation | fever which arises at the time of dispersion processing. Therefore, it is preferable to carry out dispersion treatment in a system containing a polymer dispersant.
When the colorant (A) is dispersed by a sand grinder, glass beads or zirconia beads having a diameter of about 0.1 to 8 mm are preferably used. Dispersion treatment conditions are usually a temperature of 0 ° C. to 100 ° C., preferably in the range of room temperature to 80 ° C. The dispersion time may be appropriately adjusted because the appropriate time varies depending on the composition of the liquid, the size of the dispersion treatment apparatus, and the like. It is a standard of dispersion to control the gloss of the ink so that the 20 degree specular gloss (JIS Z8741) of the resist is in the range of 50 to 300. By setting the glossiness of the resist to the lower limit value or more, the dispersion process is not sufficient and the residual of coarse pigment (coloring agent) particles can be suppressed, and the developability, adhesion, resolution and the like tend to be sufficient. . Further, by setting the gloss value to the upper limit value or less, it is possible to avoid that the pigment is crushed and a large number of ultrafine particles are generated, and the dispersion stability tends to be easily maintained.

  The dispersed particle size of the pigment dispersed in the ink is usually 0.03 to 0.3 μm, and is measured by a dynamic light scattering method or the like. Next, the ink obtained by the dispersion process and the other components contained in the resist are mixed to form a uniform solution. In the resist manufacturing process, it is desirable to filter the obtained resist with a filter or the like because fine dust is often mixed in the solution.

[4] Cured Product and Method of Forming the Same [4-1] Cured Product A cured product can be obtained by curing the colored photosensitive resin composition of the present invention. A cured product composed of a colored photosensitive resin composition can be suitably used as a partition wall or a colored spacer.

[4-1-1] Partition The colored photosensitive resin composition of the present invention can be suitably used to form a partition, particularly a partition for partitioning the organic layer of the organic electroluminescent device. As an organic layer used for an organic electroluminescent element, the hole transport layer on a hole injection layer, a hole transport layer, or a hole injection layer which is described, for example in Japan Unexamined-Japanese-Patent No. 2016-165396 is mentioned. The organic layer to be used may be mentioned.

[4-1-2] Colored Spacer In addition to the partition walls, the colored photosensitive resin composition of the present invention can be suitably used as a resist for a colored spacer. When a spacer is used in a TFT type LCD, light incident on the TFT may cause the TFT to malfunction as a switching element, and a colored spacer is used to prevent this (for example, JP-A-8-234212). No. 2).

[4-2] Forming Method Next, the partition wall and the colored spacer using the colored photosensitive resin composition of the present invention will be described according to the manufacturing method. A black matrix and other cured products can also be formed by the same method.

[4-2-1] Support As a support for forming partition walls and colored spacers, the material is not particularly limited as long as it has appropriate strength. A transparent substrate is mainly used, but as the material, for example, polyester resin such as polyethylene terephthalate, polyolefin resin such as polypropylene and polyethylene, thermoplastic resin sheet such as polycarbonate, polymethyl methacrylate and polysulfone, epoxy resin And thermosetting resin sheets such as unsaturated polyester resin and poly (meth) acrylic resin, or various glasses. Among these, glass and heat resistant resin are preferable from the viewpoint of heat resistance. In addition, a transparent electrode such as ITO or IZO may be formed on the surface of the substrate. It is also possible to form on a TFT array other than a transparent substrate.

The support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film formation treatment of various resins such as urethane resin, etc., if necessary, for improvement of surface physical properties such as adhesiveness. .
The thickness of the transparent substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. Moreover, when performing the thin film formation process of various resin, the film thickness is the range of 0.01-10 micrometers normally, Preferably it is 0.05-5 micrometers.

[4-2-2] Coating of Colored Photosensitive Resin Composition Coating of the colored photosensitive resin composition on a substrate is carried out by a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating It can be done by law. Above all, according to the die coating method, the amount of coating solution used is significantly reduced, and there is no influence of mist etc. adhering when using the spin coating method, and the generation of foreign matter is suppressed, and so on. It is preferable from

  When the thickness of the coating film is too thick, pattern development may become difficult, and when too thin, it may be difficult to increase the pigment concentration and desired color development may become impossible. The thickness of the coating film is preferably in the range of usually 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, still more preferably in the range of 1 to 4 μm, as the film thickness after drying. is there.

[4-2-3] Drying of Coating Film Drying of the coating film after applying the colored photosensitive resin composition to the substrate is preferably performed by a drying method using a hot plate, an IR oven, or a convection oven. The drying conditions can be appropriately selected according to the type of the solvent component, the performance of the dryer used, and the like. The drying time is usually selected in the range of 15 seconds to 5 minutes at a temperature of 40 to 200 ° C., preferably at a temperature of 50 to 130 ° C., depending on the type of solvent component and the performance of the dryer used. It is selected in the range of 30 seconds to 3 minutes.
The higher the drying temperature, the better the adhesion of the coating film to the transparent substrate, but if it is too high, the binder resin (C) may be decomposed to induce thermal polymerization to cause development failure. In addition, the drying process of this coating film may be a reduced pressure drying method in which drying is performed in a reduced pressure chamber without raising the temperature.

[4-2-4] Exposure Image exposure is performed by overlapping a negative mask pattern on a coating film of a colored photosensitive resin composition, and irradiating a light source of ultraviolet light or visible light through the mask pattern. Under the present circumstances, in order to prevent the fall of the sensitivity of the photopolymerizable layer by oxygen as needed, you may expose after forming oxygen blocking layers, such as a polyvinyl alcohol layer, on a photopolymerizable coating film. The light source used for the above-mentioned image exposure is not particularly limited. Examples of light sources include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, ultra high pressure mercury lamps, metal halide lamps, medium pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, lamp light sources such as fluorescent lamps, argon ion lasers, YAG lasers, Laser light sources such as excimer lasers, nitrogen lasers, helium cadmium lasers, semiconductor lasers and the like can be mentioned. An optical filter can also be used when irradiating and using the light of a specific wavelength.

[4-2-5] Development The partition wall and colored spacer according to the present invention are exposed to an image of a coating film made of a colored photosensitive resin composition by the above light source, and then an organic solvent or surfactant and alkaline An image can be formed on a substrate by development using an aqueous solution containing a compound. The aqueous solution may further contain an organic solvent, a buffer, a complexing agent, a dye or a pigment.

  As the alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium hydrogencarbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate Inorganic alkaline compounds such as sodium hydrogen phosphate, potassium hydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-.di- or triethanolamine, mono-.di- or trimethylamine Mono-.di- or triethylamine, mono- or diisopropylamine, n-butylamine, mono-.di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), choline, etc. Machine alkaline compounds. These alkaline compounds may be a mixture of two or more.

  Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and alkyl benzene sulfonic acid Anionic surfactants such as salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts, and amphoteric surfactants such as alkyl betaines and amino acids.

  Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, diacetone alcohol and the like. The organic solvent may be used alone or in combination with an aqueous solution.

  The conditions for development are not particularly limited, and the development temperature is usually in the range of 10 to 50 ° C., preferably 15 to 45 ° C., particularly preferably 20 to 40 ° C., and the development method is immersion development, spray development, brush It can be by any method such as a developing method or an ultrasonic developing method.

[4-2-6] Thermal Curing Treatment The substrate after development is subjected to a thermal curing treatment or a light curing treatment, preferably a thermal curing treatment. In this case, the temperature of the thermosetting treatment is selected in the range of 100 to 280 ° C., preferably in the range of 150 to 250 ° C., and the time is selected in the range of 5 to 60 minutes.

[5] Organic Electroluminescent Device, Image Display Device, and Illumination [5-1] Organic Electroluminescent Device The organic electroluminescent device of the present invention comprises a cured product composed of the above-described colored photosensitive resin composition, for example, a partition wall .
For example, various organic electroluminescent devices are manufactured using the substrate provided with the barrier rib pattern manufactured by the method described above. Although the method of forming the organic electroluminescent device is not particularly limited, preferably, after forming a pattern of partition walls on the substrate by the above method, the functional material is sublimated in a vacuum state, and within the region surrounded by the partition walls on the substrate An organic electroluminescent element is manufactured by forming organic layers, such as a pixel, by wet processes, such as the vapor deposition method which makes it form into a film, and a cast method, a spin coat method, and an inkjet printing method, to make it form into a film.

When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent the light of the light emitting layer of one pixel from leaking to the other pixel. Since it is necessary to prevent the deterioration of the image quality caused by the reflection of light, it is preferable to provide the partition walls constituting the organic electroluminescent element with a light shielding property.
In addition, in the organic electroluminescent element, it is necessary to provide electrodes on the upper surface and the lower surface of the partition wall, and therefore the partition wall preferably has a high resistance and a low dielectric constant from the viewpoint of insulation. Therefore, when using a coloring agent in order to provide a light-shielding property to a partition, it is preferable to use said (A1) organic black pigment which is a high resistance and a low dielectric constant.

[5-2] Image Display Device The image display device of the present invention is not particularly limited as long as it is a device for displaying an image or a video, but a liquid crystal display device, an organic EL display device, etc. may be mentioned. For example, a liquid crystal display device including the above-described colored spacer, an organic EL display device including the above-described organic electroluminescent element, and the like can be mentioned.

[5-2-1] Liquid Crystal Display Device The liquid crystal display device is not particularly limited in its type or structure as long as it contains the above-mentioned colored spacer. For example, the black matrix of the present invention is provided on a TFT element substrate to form red, green and blue pixels, and if necessary, an overcoat layer is formed, and then ITO, IZO and the like are further formed thereon. Etc., and used as a part of parts, such as a color display and a liquid crystal display. In addition, in some applications such as a planar orientation drive method (IPS mode), the transparent electrode may not be formed.

  In general, an alignment film is formed on a color filter, a photo spacer is formed on the alignment film, and then a liquid crystal cell is formed by bonding to a counter substrate. Liquid crystal is injected into the formed liquid crystal cell and connected to the counter electrode And complete. As the alignment film, a resin film such as polyimide is suitable. For forming the alignment film, usually, a gravure printing method and / or a flexo printing method is adopted, and the thickness of the alignment film is several tens nm. After curing treatment of the alignment film by thermal baking, the alignment film is subjected to surface treatment by irradiation with ultraviolet light or treatment with a rubbing cloth to be processed into a surface state capable of adjusting the inclination of the liquid crystal.

[5-2-2] Organic EL Display Device The organic EL display device is not particularly limited as to the type and structure of the image display device as long as it includes the above-described organic electroluminescent device, and, for example, active drive type organic electroluminescent The device can be assembled according to a conventional method. For example, the image display device of the present invention is formed by the method as described in "Organic EL display" (Am Co., published on August 20, 2004, Shimizu Toki, Chiya Adachi, Hideyuki Murata) can do. For example, an image may be displayed by combining an organic electroluminescent element emitting white light and a color filter, or an image may be displayed by combining organic electroluminescent elements having different luminescent colors such as RGB.

[5-3] Illumination The illumination of the present invention includes the organic electroluminescent device described above. There is no particular limitation on the type and the structure, and the organic electroluminescent device of the present invention can be assembled according to a conventional method. As an organic electroluminescent element, it is good also as a simple matrix drive system, and good also as an active matrix drive system.
In order for the illumination of the present invention to emit white light, an organic electroluminescent device that emits white light may be used. In addition, organic electroluminescent elements of different luminescent colors may be combined, and each color may be mixed to be white, or the color mixing ratio may be adjusted to provide a toning function.

EXAMPLES Next, the present invention will be more specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.
The components of the colored photosensitive resin composition used in the following examples and comparative examples are as follows.

<Binder resin-I>
Nippon Kayaku "ZCR-1642H" (weight average molecular weight (Mw) 6500, acid value 98 mg KOH / g, carboxyl group-containing epoxy (meth) acrylate resin). This resin corresponds to (C1-1) and has a repeating unit structure represented by the chemical formula (II-1), wherein R ¹¹ is a methyl group, and R ¹² is a group represented by the above formula (II-A). R ^X is a tetrahydrophthalic acid residue.

<Binder resin-II>

50 parts by mass of the epoxy compound having the above structure (epoxy equivalent 264), 13.65 parts by mass of acrylic acid, 60.5 parts by mass of 3-methoxybutyl acetate, 0.936 parts by mass of triphenylphosphine, and 0.032 parts by mass of paramethoxyphenol The part was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and allowed to react with stirring until the acid value became 5 mgKOH / g or less at 90 ° C. The reaction took 12 hours to obtain an epoxy acrylate solution.
25 parts by mass of the above epoxy acrylate solution, 0.74 parts by mass of trimethylolpropane (TMP), 3.95 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA), 2.7 parts by mass of tetrahydrophthalic anhydride (THPA) The mixture was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and the temperature was raised to 105.degree. C. with stirring to cause a reaction.
When the resin solution becomes transparent, dilute with 3-methoxybutyl acetate to prepare a solid content of 50% by mass, and a carboxyl group-containing epoxy (meth) having an acid value of 112 mg KOH / g and a weight average molecular weight (Mw) 4100 An acrylate resin was obtained. This resin corresponds to (C1-2).

<Binder resin-III>

  Epoxy compound (EPICLON HP7200HH manufactured by DIC, polyglycidyl ether of dicyclopentadiene-phenol polymer, weight average molecular weight 1000, epoxy equivalent 270) 155 parts by mass, acrylic acid 41 parts by mass, p-methoxy 0.1 parts by mass of phenol, 2.5 parts by mass of triphenylphosphine and 130 parts by mass of propylene glycol monomethyl ether acetate were charged in a reaction vessel, and heated and stirred at 100 ° C. until the acid value became 3.0 mg KOH / g or less. It took 9 hours for the acid value to reach the target (acid value 2.9 mg KOH / g). Subsequently, 74 parts by mass of tetrahydrophthalic anhydride was further added, and reaction was carried out at 120 ° C. for 4 hours to obtain a binder resin-III solution having an acid value of 98 mg KOH / g and a weight average molecular weight (Mw) 3500. This resin corresponds to (C1-1).

<Binder resin-IV>

  98.0 parts by mass of an epoxy compound (epoxy equivalent 245) represented by the above structural formula, 28.8 parts by mass of acrylic acid, 113.0 parts by mass of 3-methoxybutyl acetate, 1.1 parts by mass of triphenylphosphine, and para 0.02 parts by mass of methoxyphenol was placed in a flask equipped with a thermometer, a stirrer, and a condenser, and allowed to react with stirring until the acid value became 5 mgKOH / g or less at 90 ° C. The reaction required 15 hours to obtain an epoxy acrylate solution.

In 189.1 parts by mass of the above epoxy acrylate solution, 11.8 parts by mass of biphenyltetracarboxylic acid dianhydride (BPDA) and 30.4 parts by mass of tetrahydrophthalic anhydride (THPA) are added, and the temperature is raised to 105 ° C. while stirring. The temperature was slowly raised to react.
When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate to prepare a solid content of 55% by mass, thereby obtaining Binder Resin-IV having an acid value of 110 mg KOH / g and a weight average molecular weight (Mw) of 2800. This resin corresponds to (C1-2).

<Binder resin-V>
It stirred, nitrogen-substituting 145 mass parts of propylene glycol monomethyl ether acetate, and it heated up at 120 degreeC. To this, 10 parts by mass of styrene, 85.2 parts by mass of glycidyl methacrylate and 66 parts by mass of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) having a tricyclodecane skeleton are dropped, and 2,2'-azobis-2-methyl 8.47 mass parts of butyronitrile were dripped over 3 hours, and also stirring was continued at 90 degreeC for 2 hours. Next, the inside of the reaction vessel was changed to air displacement, 0.7 parts by mass of trisdimethylaminomethylphenol and 0.12 parts by mass of hydroquinone were added to 43.2 parts by mass of acrylic acid, and the reaction was continued at 100 ° C. for 12 hours. Thereafter, 56.2 parts by mass of tetrahydrophthalic anhydride (THPA) and 0.7 parts by mass of triethylamine were added and reacted at 100 ° C. for 3.5 hours. The weight average molecular weight (Mw) of the binder resin-V thus obtained was about 8400, the acid value was 80 mg KOH / g, and the double bond equivalent was 480 g / mol.

<Colorant-I>
BASF AG, Irgaphor (registered trademark) Black S 0100 CF (having a chemical structure represented by the following formula (I-1))

<Dispersant-I>
BYK-LPN 21116 manufactured by BYK-Chemie Co., Ltd. (acrylic A-B block copolymer comprising an A block having a quaternary ammonium base and a tertiary amino group in a side chain, and a B block having no quaternary ammonium base and a tertiary amino group) Polymer: Amine value: 70 mg KOH / g, Acid value: 1 mg KOH / g or less)
The A block of Dispersant-I contains repeating units of the following formulas (1a) and (2a), and the B block contains repeating units of the following formula (3a). The content ratio of repeating units of the following formulas (1a), (2a), and (3a) to the total repeating units of Dispersant-I is 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively. is there.

<Dispersant-II>
Big Chemie made DISPERBYK-167 (urethane based polymer dispersant)
<Solvent-I>
PGMEA: Propylene glycol monomethyl ether acetate <solvent-II>
MB: 3-methoxy-1-butanol <solvent-III>
MBA: 3-methoxybutyl acetate

<Photoinitiator-I>
<Diketone body>
Ethyl carbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) are dissolved in 30 mL of dichloromethane, cooled to 2 ° C. with an ice water bath and stirred, AlCl ₃ (3. 3). 41 g, 25.61 mmol) were added. After further stirring for 3 hours at room temperature, 15 mL of a solution of crotonoyl chloride (2.81 g, 26.89 mmol) in dichloromethane was added to the reaction solution, AlCl ₃ (4.1 g, 30.73 mmol) was added, and 30 more hours. Stirred for a minute. The reaction solution was poured into 200 mL of ice water, 200 mL of dichloromethane was added, and the organic layer was separated. The collected organic layer was dried over anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a white solid diketone (10 g).

<Oxime body>
Diketone body (3.00 g, 7.19 mmol), NH ₂ OH.HCl (1.09 g, 15.81 mmol), and sodium acetate (1.23 g, 15.08 mmol) were mixed in 30 mL of isopropanol and refluxed for 3 hours .
After completion of the reaction, the reaction solution was concentrated, and 30 mL of ethyl acetate was added to the obtained residue, and the mixture was washed with 30 mL of saturated aqueous sodium hydrogen carbonate solution and 30 mL of saturated brine and dried over anhydrous magnesium sulfate. After filtration, the organic layer was concentrated under reduced pressure to obtain 3.01 g of a solid. The product was purified by column chromatography to obtain 2.22 g of a pale yellow solid oxime.

<Oxime ester form>
Add oxime compound (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) to 20 mL of dichloromethane and cool on ice, add triethylamine (1.77 g, 17.5 mmol) dropwise, It reacted for time. After confirming the disappearance of the raw materials by thin layer chromatography, water was added to stop the reaction. The reaction solution was washed twice with 5 mL of saturated aqueous sodium hydrogen carbonate solution, twice with 5 mL of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic layer is concentrated under reduced pressure, and the obtained residue is purified by column chromatography (ethyl acetate / hexane = 2/1 by volume) to give 0.79 g of a light yellow solid photopolymerization initiator -I (compound of the following chemical structure) was obtained. The chemical shifts of Photoinitiator-I are shown below.

¹ H NMR (CDCl ₃ ): δ 1.17 (d, 3 H), 1.48 (t, 3 H), 1.81 (s, 3 H), 2.16 (s, 3 H), 2.30 (s, 3) 3H), 3.17-3.22 (m, 2H), 4.42 (q, 2H), 4.78-4.94 (br, 1H), 7.45-7.59 (m, 5H) , 7.65 (dd, 1 H), 7.95 (m, 2 H), 8.04 (m, 2 H), 8. 14 (dd, 1 H), 8.42 (d, 1 H), 8.64 ( d, 1H)

<Photopolymerizable monomer>
DPHA: Nippon Kayaku Co., Ltd. dipentaerythritol hexaacrylate <surfactant>
DIC Corporation Megafuck F-559
<Additives>
Nippon Kayaku Co., Ltd. KAYAMER PM-21 (methacryloyl group-containing phosphate)

Preparation of Pigment Dispersions 1 to 6
A coloring agent (pigment), a dispersing agent, and a binder resin were added such that the proportions in the solid content thereof were as described in Table 1 and were further mixed such that the solvent had a mass ratio described in Table 1. The solution was dispersed for 3 hours in the range of 25 to 45 ° C. with a paint shaker. As beads, 0.5 mm diameter zirconia beads were used, and 2.5 times the mass of the dispersion were added. After completion of the dispersion, the beads and the dispersion were separated by a filter to prepare pigment dispersions 1 to 6.

[Examples 1 to 6, Reference Example 1, and Comparative Example 1]
Using the prepared pigment dispersions 1 to 6, each component is added so that the proportion in the solid content becomes the blending proportion in Table 2, and further, PGMEA is added so that the content proportion of the total solid content becomes 22 mass%. In addition, the mixture was stirred and dissolved to prepare a colored photosensitive resin composition. Using the obtained colored photosensitive resin composition, a pattern was prepared and evaluated by the method described later.

<Method of making bulkhead substrate>
Each colored photosensitive resin composition was applied on an ITO substrate (a glass substrate on which ITO having a film thickness of 1500 Å was vapor-deposited) using a spinner. Next, the coated film was formed by heating and drying on a hot plate at 100 ° C. for 80 seconds.
The resulting coated film was subjected to an exposure process using an exposure mask having linear openings with various widths of 5 to 50 μm (every 5 to 20 μm: every 1 μm, every 25 to 50 μm: every 5 μm). The exposure gap (the distance between the exposure mask and the coated surface) was 5 μm. The irradiation light intensity at a wavelength 365nm is used ultraviolet is 32 mW / cm ^2, the exposure amount was 60 mJ / cm ^2. Moreover, ultraviolet irradiation was performed under air.

Subsequently, after performing shower development with a water pressure of 0.05 MPa at 25 ° C. using a developing solution consisting of a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution, the development is stopped with pure water and washed with water It wash | cleaned by the spray. The shower development time was adjusted between 10 and 120 seconds, which was 1.2 times the time required for dissolution and removal of the unexposed film.
By these operations, a pattern from which unnecessary portions were removed was obtained. The substrate on which the pattern was formed was heated in an oven at 230 ° C. for 45 minutes to cure the pattern to obtain a linear pattern (pattern 1) having a film thickness of 2.5 μm. Further, an entire surface covering pattern (pattern 2) having a film thickness of 2.5 μm was also produced by the same procedure except that the exposure mask was not used.

<Evaluation of substrate adhesion>
Among the patterns corresponding to 5 to 50 μm line-like openings, among the patterns with high resolution, those with the smallest width are shown in Table 2 as the value of the mask opening width (μm) of the smallest one. The The smaller the value, the better the adhesion to the substrate, and if the minimum adhesion is 20 μm or less, the development adhesion to development is practically sufficient. If it is 10 μm or less, the development adhesion to development is excellent.

<Method of evaluating outgassing>
About 3 mg of the coating film was scraped from the substrate of pattern 2 to obtain a sample for outgassing measurement.
Using TG-DTA 6300 (manufactured by Hitachi High-Tech Science Co., Ltd.), the sample was heated from room temperature to 500 ° C. at 10 ° C./min under an air atmosphere (Flow 200 ml / min), and the weight loss at that time was measured. The amount of weight loss (% by mass) when the temperature is raised from room temperature to 400 ° C. is shown in Table 2 with respect to the total amount of binder resin contained in each colored photosensitive resin composition. In addition, the weight loss amount (mass%) at the time of raising from room temperature to 400 degreeC with respect to the total solid of each coloring photosensitive resin composition is Example 1: 26.8, Example 2: 30.2, implementation Example 3: 29.7, Example 4: 27.9, Example 5: 30.8, Example 6: 31.9, Reference Example 1: 25.6, Comparative Example 1: 33.7.

<Chromaticity>
Using the substrate of pattern 2 of Example 1, using an aluminum deposition plate as a reference plate with a spectrophotometer UV-3100 (manufactured by Shimadzu Corporation), the mirror reflectance of 5 degrees at a wavelength of 380 to 780 nm is coated It measured from the side and computed the chromaticity (D65 light source) in XYZ color system.
The substrate of Example 1 had sx = 0.323 and sy = 0.329.

The application | coating board | substrate using the coloring photosensitive resin composition of Examples 1-6 and the reference example 1 was confirmed to be excellent in an outgassing characteristic.
On the other hand, it was confirmed that the coated substrate using the colored photosensitive resin composition of Comparative Example 1 had poor outgassing properties.
Compared with the colored photosensitive resin composition of Comparative Example 1, the colored photosensitive resin compositions of Examples 1 to 6 and Reference Example 1 have a high content ratio of epoxy (meth) acrylate resin in the binder resin. Epoxy (meth) acrylate resin is hard to be decomposed by heat because it has a rigid skeleton, and since the skeleton is rigid to form an ordered structure upon curing to form a highly crosslinkable film, epoxy (meta) in the binder resin It is considered that the outgassing characteristics are improved by increasing the content of the acrylate resin.

On the other hand, in comparison with the coated substrate using the colored photosensitive resin composition of Reference Example 1, the coated substrate using the colored photosensitive resin composition of Examples 1 to 6 is excellent in the development adhesion of the fine line pattern. Was confirmed. Even the colored photosensitive resin composition of Reference Example 1 can be sufficiently applied as a partition of an organic electroluminescent device having a general resolution, but high resolution can be obtained with the colored photosensitive resin composition of Examples 1 to 6 It is suggested that it can apply also to the partition of organic electroluminescent element of
Since the dispersant contained in the colored photosensitive resin composition of Reference Example 1 is not an acrylic dispersant, the developer easily penetrates into the film at the time of development, and it is considered that the fine line pattern was hard to remain on the substrate.
On the other hand, since the dispersing agent contained in the colored photosensitive resin composition of Examples 1 to 6 is an acrylic dispersing agent, it has a flexible main skeleton having a linear molecular structure, and therefore many of the adsorptive groups are By adsorbing to the coloring agent, the coloring agent is uniformly dispersed in the colored photosensitive resin composition, and the coloring agent which is an insoluble component of the developing solution is uniformly arranged even in the obtained coated film, to form a dense film, It is considered that penetration of the developer into the film was suppressed at the time of development, and even a fine line pattern could be formed on the substrate.

  Moreover, in the coloring photosensitive resin composition of Examples 1-6, the coloring photosensitive resin composition obtained by having prepared using the pigment dispersions 1-5 containing an epoxy (meth) acrylate resin as binder resin The content ratio of the epoxy (meth) acrylate resin contained in the substance could be increased.

Claims (23)

A colored photosensitive resin composition comprising (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator,
The (A) coloring agent is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound Containing (A1) organic black pigment containing
The (B) dispersant contains an acrylic dispersant,
The coloring photosensitive resin composition characterized by the said (C) binder resin containing 75 mass% or more of (C1) epoxy (meth) acrylate resins.

(In formula (I), R ^a1 and R ^a6 each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are each independently a hydrogen atom, a halogen atom, R ^a11 , COOH, COOR ^a11 , COO ⁻ , CONH ₂ , CONHR ^{a11 , CONR a11 R a12, CN,} OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ^a11 or SO ₂ NR ^a11 R ^a12 is represented;
And, at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may be directly linked to each other or to each other by oxygen atoms, sulfur atoms, NH or NR ^a11 bridges;
R ^a11 and R ^a12 are each independently 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 2 to 12 alkynyl groups are represented. )   The coloring photosensitive resin composition of Claim 1 whose content rate of said (C1) epoxy (meth) acrylate resin in said (C) binder resin is 85 mass% or more. The (C1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy having a partial structure represented by the following general formula (III) The coloring photosensitive resin composition of Claim 1 or 2 which contains one or both of meta-acrylate resin.

(In formula (II), R ¹¹ represents a hydrogen atom or a methyl group;
R ¹² represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (II) may be further substituted by any substituent;
* Represents a bond. )

(In formula (III), each R ¹³ independently represents a hydrogen atom or a methyl group;
R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond. )   The coloring photosensitive resin composition according to any one of claims 1 to 3, wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.   The coloring photosensitive resin composition of any one of Claims 1-4 whose content rate of the said (A) coloring agent is 60 mass% or less per total solid of the said coloring photosensitive resin composition.   The coloring photosensitive resin composition of any one of Claims 1-5 in which the said (A) coloring agent contains one or both of (A2) organic color pigment and (A3) carbon black further.   The coloring photosensitive resin composition of any one of Claims 1-6 whose content rate of (A1) organic black pigment in said (A) coloring agent is 10 mass% or more.   The coloring photosensitive resin composition of any one of Claims 1-7 used in order to form the partition of an organic electroluminescent element. Coloring sensitization for forming a partition of an organic electroluminescent element containing (A) coloring agent, (B) dispersing agent, (C) binder resin, (D) photopolymerizable monomer and (E) photopolymerization initiator Resin composition, and
The (A) coloring agent is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound Containing (A1) organic black pigment containing
The coloring photosensitive resin composition characterized by the said (C) binder resin containing 75 mass% or more of (C1) epoxy (meth) acrylate resins.

(In formula (I), R ^a1 and R ^a6 each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are each independently a hydrogen atom, a halogen atom, R ^a11 , COOH, COOR ^a11 , COO ⁻ , CONH ₂ , CONHR ^{a11 , CONR a11 R a12, CN,} OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ^a11 or SO ₂ NR ^a11 R ^a12 is represented;
And, at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may be directly linked to each other or to each other by oxygen atoms, sulfur atoms, NH or NR ^a11 bridges;
R ^a11 and R ^a12 are each independently 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 2 to 12 alkynyl groups are represented. )   The coloring photosensitive resin composition of Claim 9 whose content rate of said (C1) epoxy (meth) acrylate resin in said (C) binder resin is 85 mass% or more. The (C1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy having a partial structure represented by the following general formula (III) The colored photosensitive resin composition according to claim 9 or 10, comprising one or both of the meta) acrylate resins.

(In formula (II), R ¹¹ represents a hydrogen atom or a methyl group;
R ¹² represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (II) may be further substituted by any substituent;
* Represents a bond. )

(In formula (III), each R ¹³ independently represents a hydrogen atom or a methyl group;
R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond. )   The coloring photosensitive resin composition of any one of Claims 9-11 whose content rate of the said (A) coloring agent is 60 mass% or less per total solid of the said coloring photosensitive resin composition.   The coloring photosensitive resin composition of any one of Claims 9-12 in which the said (A) coloring agent contains one or both of (A2) organic color pigment and (A3) carbon black further.   The coloring photosensitive resin composition of any one of Claims 9-13 whose content rate of (A1) organic black pigment in said (A) coloring agent is 10 mass% or more.   The partition comprised with the coloring photosensitive resin composition of any one of Claims 1-14.   The organic electroluminescent element provided with the partition of Claim 15.   An image display apparatus comprising the organic electroluminescent device according to claim 16.   An illumination comprising the organic electroluminescent device according to claim 16. A pigment dispersion comprising (A) a colorant, (B) a dispersant and (C) a binder resin,
The (A) coloring agent is at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound Containing (A1) organic black pigment containing
The (B) dispersant contains an acrylic dispersant,
The pigment dispersion liquid characterized by said (C) binder resin containing (C1) epoxy (meth) acrylate resin.

(In formula (I), R ^a1 and R ^a6 each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ^a2 , R ^a3 , R ^a4 , R ^a5 , R ^a7 , R ^a8 , R ^a9 and R ^a10 are each independently a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ^a11 , COO ⁻ , CONH ₂ , CONHR ^{a11 , CONR a11 R a12, CN,} OH, OR a11, COCR a11, OOCNH 2, OOCNHR a11, OOCNR a11 R a12, NO 2, NH 2, NHR a11, NR a11 R a12, NHCOR a12, NR a11 COR a12, N = CH ₂ , N = CHR ^a11 , N = CR ^a11 R ^a12 , SH, SR ^a11 , SOR ^a11 , SO ₂ R ^a11 , SO ₃ R ^a11 , SO ₃ H, SO ₃ ⁻ , SO ₂ NH ₂ , SO ₂ NHR ^a11 or SO ₂ NR ^a11 R ^a12 is represented;
And, at least one combination selected from the group consisting of R ^a2 and R ^a3 , R ^a3 and R ^a4 , R ^a4 and R ^a5 , R ^a7 and R ^a8 , R ^a8 and R ^a9 , and R ^a9 and R ^a10 is They may be directly linked to each other or to each other by oxygen atoms, sulfur atoms, NH or NR ^a11 bridges;
R ^a11 and R ^a12 are each independently 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 2 to 12 alkynyl groups are represented. )   The pigment dispersion liquid according to claim 19, wherein a content ratio of the (B) dispersant is 10 parts by mass or more with respect to 100 parts by mass of the (A) colorant. The (C1) epoxy (meth) acrylate resin is an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy having a partial structure represented by the following general formula (III) 21. A pigment dispersion according to claim 19 or 20 comprising one or both of the meta) acrylate resins.

(In formula (II), R ¹¹ represents a hydrogen atom or a methyl group;
R ¹² represents a divalent hydrocarbon group which may have a substituent;
The benzene ring in formula (II) may be further substituted by any substituent;
* Represents a bond. )

(In formula (III), each R ¹³ independently represents a hydrogen atom or a methyl group;
R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain;
R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent;
m and n each independently represent an integer of 0 to 2;
* Represents a bond. )   The pigment dispersion according to any one of claims 19 to 21, wherein the acrylic dispersant is a nitrogen-containing acrylic dispersant.   The pigment dispersion liquid of any one of Claims 19-22 used in order to manufacture a coloring photosensitive resin composition.