KR20200029058A - Colored photosensitive resin composition, pigment dispersion, partition, organic electroluminescent element, image display device, and illumination - Google Patents

Abstract

The first object of the present invention is to provide a colored photosensitive resin composition having a small amount of outgas after formation of a cured product, excellent reliability, and good adhesion of a pattern in the development process at the time of manufacturing the cured product. The coloring photosensitive resin composition of this invention which concerns on 1st aspect contains (A) coloring agent, (B) dispersing agent, (C) binder resin, (D) photopolymerizable monomer, and (E) photopolymerization initiator, and said ( (A1) The organic coloring agent containing at least 1 sort (s) selected from the group which consists of a compound represented by the following general formula (I), the geometric isomer of the said compound, the salt of the said compound, and the salt of the geometric isomer of the said compound The black pigment is included, and the dispersant (B) includes an acrylic dispersant, and the binder resin (C) contains 75% by mass or more of the epoxy resin (C1).

Description

Color photosensitive resin composition, pigment dispersion, partition wall, organic electroluminescent device, image display device and lighting {COLORED PHOTOSENSITIVE RESIN COMPOSITION, PIGMENT DISPERSION, PARTITION, ORGANIC ELECTROLUMINESCENT ELEMENT, IMAGE DISPLAY DEVICE, AND ILLUMINATION}

The present invention relates to a colored photosensitive resin composition, and further includes a pigment dispersion used in the colored photosensitive resin composition, a partition wall composed of the colored photosensitive resin composition, an organic electroluminescent device having the partition wall, an image display device, and lighting. It is about.

The liquid crystal display (LCD) utilizes the property that the arrangement method of liquid crystal molecules is changed by turning on / off the applied voltage to the liquid crystal. On the other hand, each member constituting the cell of the LCD is often formed by a method using a photosensitive composition, typified by photolithography. The reason why the photosensitive composition is easy to form a fine structure and is easy to process with respect to a substrate for a large screen is that the range of application of the photosensitive composition tends to become wider in the future.

In addition, with the simplification of the panel structure and the manufacturing process, a method of forming a so-called columnar spacer by photolithography, which is used to keep the spacing of two substrates in a liquid crystal panel constant, has been studied and recently In addition, a colored spacer in which a photo spacer and a black matrix are integrated is also being developed. However, such a colored spacer is required to have a volume resistivity above a certain level or a relative dielectric constant below a certain level so as not to cause a short circuit of an electric circuit even when mounted directly on a TFT element, in addition to the usual shape and compression characteristics.

As such a colored spacer, a plurality of types of organic colored pigments are used for the pigments, or an organic black pigment is proposed. Patent Document 1 discloses a photosensitive coloring composition having excellent dispersibility, light blocking property, and low relative dielectric constant by combining a specific organic black pigment and a dispersing agent.

On the other hand, an image display device including an organic electroluminescent element (also referred to as organic electroluminescence, organic EL) is excellent in visibility and responsiveness such as contrast and viewing angle, low power consumption, thinner and lighter weight, and the display body. Because it is flexible, it is receiving attention as a next-generation flat panel display (FPD).

The organic electroluminescent element has a structure in which at least one of a pair of electrodes has light-transmitting properties, and organic species including a light-emitting layer or various functional layers are interposed. The image display device performs image display by driving a panel in which an organic electroluminescent element is disposed for each pixel.

Conventionally, such an organic electroluminescent device is manufactured by forming a partition (bank) on a substrate, and then laminating a light emitting layer or various functional layers in an area surrounded by the partition.

In order to form a light emitting layer or the like in an area surrounded by a partition wall, a vapor deposition method in which a material is sublimed in a vacuum state and attached to a substrate to form a film is mainly applied. In addition, recently, a method of forming a film by a wet process such as a cast method, a spin coat method, and an inkjet printing method has attracted attention. Particularly, in the inkjet printing method, it is possible to reduce unevenness in film thickness when a large area is achieved, and to achieve high-precision display, reduced material usage, and improved yield by dividing and coating during application. Since it becomes possible, it is suitable as a method for forming organic species in a large panel.

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

International Publication No. 2015/046178

Recently, after forming a cured product constituting an image display device or the like, there is a desire to reduce outgas generated from the cured product. In particular, in the organic electroluminescent device, there is a strong desire to reduce the outgas generated from the partition walls when the device emits light. This is because, in the organic electroluminescent device, if the amount of outgas generated from a cured product such as a partition wall is large, the life of the device may decrease.

On the other hand, among the image display devices, in a high-resolution model, it is necessary to refine the cured product constituting it, and even a fine pattern is required to sufficiently adhere to a substrate or the like in the development process.

When the present inventors examined, the photosensitive coloring composition described in patent document 1 found that there were many outgases and there existed a problem practically.

In addition, Patent Document 1 has no description or suggestion about the application of the organic electroluminescent device to the partition wall, and the inventors have investigated the use of the organic electroluminescent device to form the partition wall. Although this sufficient was found, it was found that the adhesion of the fine pattern required for the high-resolution model was not sufficient.

The first object of the present invention is to provide a colored photosensitive resin composition having a small amount of outgas after formation of a cured product, excellent reliability, and good adhesion of a fine pattern in a developing process at the time of producing the cured product.

Moreover, it is providing the partition wall formed using the coloring photosensitive resin composition, the organic electroluminescent element provided with the partition, the image display apparatus containing the organic electroluminescent element, and illumination.

Moreover, the 2nd subject of this invention is providing the coloring photosensitive resin composition for forming the partition wall of the organic electroluminescent element which is excellent in reliability with little outgas amount after formation of a hardened | cured material.

Moreover, it is providing the partition wall formed using the coloring photosensitive resin composition, the organic electroluminescent element provided with the partition, the image display apparatus containing the organic electroluminescent element, and illumination.

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

As a result of earnest examination by the present inventors, it has been found that the above-mentioned problems can be solved by a colored photosensitive resin composition containing a specific organic black pigment and further containing a specific amount of a specific binder resin or more, to reach the present invention.

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

[1] A colored photosensitive resin composition containing (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator,

The (A) coloring agent contains (A1) at least one selected from the group consisting of a compound represented by the following general formula (I), a geometrical isomer of the compound, a salt of the compound, and a salt of the geometrical isomer of the compound. ) Contains an organic black pigment,

The dispersant (B) includes an acrylic dispersant,

The said (C) binder resin contains (C1) epoxy (meth) acrylate resin 75 mass% or more, The coloring photosensitive resin composition characterized by the above-mentioned.

[Formula 1]

(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 ;

Further, 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 , They may be directly bonded to each other, or may be bonded to each other by an oxygen atom, a sulfur atom, NH or an NR ^a11 bridge;

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 an alkynyl group having 2 to 12 carbon atoms. Indicates.)

[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 epoxy (meth) acrylate resin (C1) having a repeating unit structure represented by the following general formula (II) and the epoxy having a partial structure represented by the following general formula (III) The colored photosensitive resin composition as described in [1] or [2], containing one or both of (meth) acrylate resins.

[Formula 2]

(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 also be substituted with an arbitrary substituent;

* Represents a bonding hand.)

[Formula 3]

(In formula (III), R ¹³ each 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 bonding hand.)

[4] The colored photosensitive resin composition according to any one of [1] to [3], wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.

[5] The colored photosensitive resin composition according to any one of [1] to [4], wherein the content ratio of the colorant (A) is 60% by mass or less per total solid content of the colored photosensitive resin composition.

[6] The colored photosensitive resin composition according to any one of [1] to [5], wherein the colorant (A) further comprises (A2) an organic coloring pigment and (A3) one or both of carbon black.

[7] The colored photosensitive resin composition according to any one of [1] to [6], wherein the content ratio of the organic black pigment (A1) in the colorant (A) 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 partition walls of an organic electroluminescent element.

[9] A colored photosensitive resin for forming a partition wall of an organic electroluminescent device containing (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator. As a composition,

The (A) coloring agent contains (A1) at least one selected from the group consisting of a compound represented by the following general formula (I), a geometrical isomer of the compound, a salt of the compound, and a salt of the geometrical isomer of the compound. ) Contains an organic black pigment,

The said (C) binder resin contains (C1) epoxy (meth) acrylate resin 75 mass% or more, The coloring photosensitive resin composition characterized by the above-mentioned.

[Formula 4]

(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 ;

Further, 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 , They may be directly bonded to each other, or may be bonded to each other by an oxygen atom, a sulfur atom, NH or an NR ^a11 bridge;

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 an alkynyl group having 2 to 12 carbon atoms. Indicates.)

[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 epoxy (meth) acrylate resin (C1) having a repeating unit structure represented by the following general formula (II) and the epoxy having a partial structure represented by the following general formula (III) The colored photosensitive resin composition according to [9] or [10], comprising one or both of the (meth) acrylate resins.

[Formula 5]

(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 also be substituted with an arbitrary substituent;

* Represents a bonding hand.)

[Formula 6]

(In formula (III), R ¹³ each 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 bonding hand.)

[12] The colored photosensitive resin composition according to any one of [9] to [11], wherein the content ratio of the colorant (A) is 60% by mass or less per total solid content of the colored photosensitive resin composition.

[13] The colored photosensitive resin composition according to any one of [9] to [12], wherein the colorant (A) further comprises (A2) an organic coloring pigment and (A3) one or both of carbon black.

[14] The colored photosensitive resin composition according to any one of [9] to [13], wherein the content ratio of the organic black pigment (A1) in the colorant (A) is 10% by mass or more.

[15] A partition wall composed of the colored photosensitive resin composition according to any one of [1] to [14].

[16] An organic electroluminescent device comprising the partition wall according to [15].

[17] An image display device comprising the organic electroluminescent element according to [16].

[18] An illumination comprising the organic electroluminescent element according to [16].

[19] A pigment dispersion containing (A) a colorant, (B) a dispersant, and (C) a binder resin,

The (A) coloring agent contains (A1) at least one selected from the group consisting of a compound represented by the following general formula (I), a geometrical isomer of the compound, a salt of the compound, and a salt of the geometrical isomer of the compound. ) Contains an organic black pigment,

The dispersant (B) includes an acrylic dispersant,

The pigment dispersion, characterized in that the (C) binder resin comprises (C1) epoxy (meth) acrylate resin.

[Formula 7]

(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 ;

Further, 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 , They may be directly bonded to each other, or may be bonded to each other by an oxygen atom, a sulfur atom, NH or an NR ^a11 bridge;

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 an alkynyl group having 2 to 12 carbon atoms. Indicates.)

[20] The pigment dispersion according to [19], wherein the content ratio of the dispersant (B) is 10 parts by mass or more with respect to 100 parts by mass of the colorant (A).

[21] The epoxy (meth) acrylate resin (C1) having a repeating unit structure represented by the following general formula (II) and the epoxy having a partial structure represented by the following general formula (III) The pigment dispersion according to [19] or [20], containing one or both of the (meth) acrylate resins.

[Formula 8]

(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 also be substituted with an arbitrary substituent;

* Represents a bonding hand.)

[Formula 9]

(In formula (III), R ¹³ each 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 bonding hand.)

[22] The pigment dispersion according to any one of [19] to [21], wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom.

[23] The pigment dispersion according to any one of [19] to [22], used for producing a colored photosensitive resin composition.

According to one aspect of the present invention, it is possible to provide a colored photosensitive resin composition having a small amount of outgas after formation of a cured product, excellent reliability, and good adhesion of a pattern in a developing process at the time of producing the cured product. In addition, the cured product formed from the colored photosensitive resin composition of the present invention has a small amount of outgas during operation, a small decrease in life, and excellent reliability in a light emitting element.

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

Moreover, it becomes possible to provide the said coloring photosensitive resin composition with 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 to these unless the gist is exceeded.

In addition, in this invention, "(meth) acrylic" means "acrylic and / or methacrylic", and "all solid content" means other than a solvent in a coloring photosensitive resin composition or a pigment dispersion liquid. It shall mean the whole component of. In addition, in this invention, the numerical range shown using "-" means the range containing the numerical value described before and after "-" as a lower limit and an upper limit.

In addition, in the present invention, "(co) polymer" means that both a homopolymer (homopolymer) and a copolymer (copolymer) are included, and "(acid) anhydride" and "(anhydrous) … Acid "means containing both an acid and its anhydride.

In the present invention, the partition wall material refers to the bank material, the wall material, and the wall material, and similarly, the partition wall refers to the bank, wall, and wall material. The partition wall, for example, is for partitioning the functional layer (organic type) in the active-driven organic electroluminescent device, and a material for constructing the functional layer in the partitioned region (pixel region) is deposited or applied by inkjet or the like. , It is used to form a pixel or the like composed of a functional layer and a partition by performing drying.

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

In the present invention, the reliability means the reliability at the time of driving the organic electroluminescent element, in particular, the display reliability for the image display device and the light emission reliability for illumination.

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

The colored photosensitive resin composition according to the second aspect of the present invention solves the second problem and is a colored photosensitive resin composition for forming a partition wall of an organic electroluminescent device, wherein the colorant (A) is a general formula described later. And (A1) an organic black pigment containing at least one member selected from the group consisting of the compound represented by (I), the geometrical isomer of the compound, the salt of the compound, and the salt of the geometrical isomer of the compound, wherein ( C) Binder resin contains 75 mass% or more of (C1) epoxy (meth) acrylate resin.

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

Hereinafter, unless otherwise specified, "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.

[1] Components and composition of colored photosensitive resin composition

The components constituting the colored photosensitive resin composition of the present invention and its composition will be described.

The colored photosensitive resin composition of the present invention (hereinafter sometimes simply referred to as a "photosensitive resin composition") includes (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E ) It contains a photoinitiator, and also usually contains a solvent.

[1-1] (A) Coloring agent

The coloring agent (A) coloring agent in the coloring photosensitive resin composition of this invention and a pigment dispersion liquid is a compound represented by the following general formula (I) (Hereinafter, it may be called "compound (I)."), The geometric isomer of the said compound , (A1) organic black pigment containing at least one member selected from the group consisting of a salt of the compound and a salt of the geometrical isomer of the compound (hereinafter sometimes referred to as "(A1) organic black pigment".) It includes.

In this way, it is considered that by including the organic black pigment (A1), high resistance, low dielectric constant, and high light-shielding rate can be realized. Further, since a cured product having a color tone closer to black is obtained, it can be suitably used as a colorant for forming a partition wall of an organic electroluminescent element having a large area ratio in the image display area of the image display device. Moreover, dispersibility and storage property are also favorable by using (A1) organic black pigment, and the patterning aptitude at the time of development is also favorable in the coloring photosensitive resin composition containing this.

[Formula 10]

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 ;

Further, 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 , They may be directly bonded to each other, or may be bonded to each other by an oxygen atom, a sulfur atom, NH or an NR ^a11 bridge;

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 an alkynyl group having 2 to 12 carbon atoms. Shows.

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

[Formula 11]

When the compound represented by the general formula (I) is anionic, its charge is any known suitable cation such as a metal, organic, inorganic or metal organic cation, specifically alkali metal, alkaline earth metal, transition metal It is preferably a salt compensated by a quaternary ammonium such as primary ammonium, secondary ammonium, trialkylammonium, quaternary ammonium such as tetraalkylammonium or an organic metal complex. Moreover, when the geometrical isomer of the compound represented by general formula (I) is anionic, it is preferable that it is the same salt.

As for the substituents of the general formula (I), the following are preferable because the shielding ratio tends to be high. This is because the following substituents are considered to have no absorption and do not affect the color of the pigment.

R ^a2 , R ^a4 , R ^a5 , R ^a7 , R ^a9 and R ^a10 are each independently, preferably a hydrogen atom, a fluorine atom, or a chlorine atom, and more preferably a hydrogen atom.

R ^a3 and R ^a8 are each independently, 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 ( is, more preferably a hydrogen atom or _{^{SO 3 H - CH 3) (}} C 2 H 5), N (C 2 H 5) 2, α- naphthyl, β- naphthyl, SO ₃ H or SO _3.

R ¹ and R ⁶ are each independently, 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 the same, more preferably Preferably, R ¹ is the same as R ⁶ , R ² is the same as R ⁷ , R ³ is the same as R ⁸ , R ⁴ is the same as R ^9, and R ⁵ is the same as R ¹⁰ .

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- Ethyl hexyl group, nonyl group, decyl group, undecyl group or dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms is, for example, cyclopropyl group, cyclopropylmethyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl group, trimethylcyclohexyl group, dialysis group, norbornyl group, boron It is a nil group, a norcaryl group, a carbonyl group, a menthyl group, a norfinyl group, a finyl group, a 1-adamantyl group or a 2-adamantyl group.

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

The cycloalkenyl group having 3 to 12 carbon atoms 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-cyclohexadiene-1-yl group, 1-p-menten-8-yl group, 4 (10) -tuzen-10-yl group, 2-norbornene-1-yl group, 2,5-norbornadi It is an en-1-yl group, a 7,7-dimethyl-2,4-norcaradien-3-yl group or a camphenyl group.

An alkynyl group having 2 to 12 carbon atoms is, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentin-5-yl group, 2-methyl-3-butyn-2-yl group, 1,4-pentadiin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexin-6-yl group, cis-3-methyl-2-penten-4-in-1-yl group, Trans-3-methyl-2-penten-4-in-1-yl group, 1,3-hexadiin-5-yl group, 1-octin-8-yl group, 1-nonin-9-yl group, 1-decine- 10-day or 1-dodecine-12-day.

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

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

[Formula 12]

As a specific example of such an organic black pigment, Irgaphor (trademark) Black S 0100 CF (made by BASF Corporation) is mentioned as a brand name.

The organic black pigment is preferably used by being dispersed by a dispersing agent, a solvent, and a method described later. Further, upon dispersion, the sulfonic acid derivative of the compound (I) (sulfonic acid substituent) or the sulfonic acid derivative of the geometric isomer of the compound (I), in particular the sulfonic acid derivative of the compound (I-1), or the compound (I-1) When the sulfonic acid derivative of the geometric isomer of is present, the dispersibility and preservability may be improved.

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

The chemical structure of these pigments is not particularly limited, but organic pigments such as azo-based, phthalocyanine-based, quinacridone-based, benzimidazone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based are available. Hereinafter, the specific example of the organic pigment which can be used is shown with a pigment number. "C.I. The term "pigment red 2" means a color index (C.I.).

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

In addition, in terms of dispersibility and light-shielding property, C.I. It is preferable to use Pigment Red 177, 254, 272, and when the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use those having a low UV absorption rate as a red pigment, and from this viewpoint, C.I. It is more preferable to use Pigment Red 254, 272.

As an orange (orange) pigment, C.I. Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65 , 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79. Among these, C.I. It is preferable to use Pigment Orange 13, 43, 64, 72, and when the colored photosensitive resin composition of the present invention is cured with ultraviolet rays, it is preferable to use those having a low ultraviolet absorption rate as an orange pigment, and from this viewpoint CI It is more preferable to use Pigment Orange 64, 72, and C.I. Pigment Orange 64 is particularly preferred.

As a blue pigment, C.I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33 , 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79. Among these, C.I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, more preferably C.I. Pigment Blue 15: 6 is mentioned.

In addition, in terms of dispersibility and light-shielding property, C.I. It is preferable to use Pigment Blue 15: 6, 16, 60, and when curing the colored photosensitive resin composition of the present invention with ultraviolet rays, it is preferable to use those having a low UV absorption rate as a blue pigment, and from this viewpoint CI It is more preferable to use Pigment Blue 60.

As a purple pigment, C.I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, 50. Among these, C.I. It is preferable to use pigment violet 19, 23, and C.I. It is more preferable to use Pigment Violet 23.

In addition, in terms of dispersibility and light-shielding property, C.I. It is preferable to use Pigment Violet 23, 29, and when curing the colored photosensitive resin composition of the present invention with ultraviolet rays, it is preferable to use those having a low ultraviolet absorption rate as the purple pigment, and from this viewpoint, C.I. It is more preferable to use Pigment Violet 29.

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

As a green pigment, C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58. Among these, C.I. Pigment green 7, 36.

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

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. As described above, by using a specific combination of pigments, there is a tendency to achieve high light-shielding properties.

Among these, from a viewpoint of light-shielding property and color tone, it is preferable to contain at least 1 type or more of the following pigments.

Red pigment: C.I. Pigment Red 177, 254, 272

Orange pigment: C.I. Pigment Orange 43, 64, 72

Blue pigment: C.I. Pigment Blue 15 ： 6, 60

Purple pigment: C.I. Pigment Violet 23, 29

In addition, the combination of colors is not particularly limited, but from the viewpoint of light-shielding properties, 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. You can.

Moreover, other black coloring agents other than these organic coloring pigments can be used as another coloring agent.

Among the black colorants, other organic black pigments other than those represented by the general formula (I) may be used from the viewpoint of light shielding properties and color tone. Other organic black pigments include aniline black, perylene black, and cyanine black.

Moreover, in this invention, an inorganic black pigment can be used. Carbon black, acetylene black, lamp black, bone black, graphite, iron black, titanium black, etc. are mentioned as an inorganic black pigment. Among these, carbon black (hereinafter sometimes referred to as "(A3) carbon black") can be preferably used from the viewpoint of light-shielding properties and image characteristics. The following carbon black is mentioned as an example of carbon black.

Manufactured by Mitsubishi Chemical: MA7, MA8, MA11, MA77, MA100, MA100R, MA100S, MA220, MA230, MA600, MCF88, ＃ 5, ＃ 10, ＃ 20, ＃ 25, ＃ 30, ＃ 32, ＃ 33, ＃ 40 , ＃ 44, ＃ 45, ＃ 47, ＃ 50, ＃ 52, ＃ 55, ＃ 650, ＃ 750, ＃ 850, ＃ 900, ＃ 950, ＃ 960, ＃ 970, ＃ 980, ＃ 990, ＃ 1000, ＃ 2200, ＃ 2300, ＃ 2350, ＃ 2400, ＃ 2600, ＃ 2650, ＃ 3030, ＃ 3050, ＃ 3150, ＃ 3250, ＃ 3400, ＃ 3600, ＃ 3750, ＃ 3950, ＃ 4000, ＃ 4010, OIL7B, OIL9B , OIL11B, OIL30B, OIL31B

Manufactured by Degussa: Printex (registered trademark. Same as below) 3, Printex3OP, Printex30, Printex30OP, Printex40, Printex45, Printex55, Printex60, Printex75, Printex80, Printex85, Printex90, Printex A, Printex L, Printex G, Printex P, Printex U, Printex V, SpecialBlack550, SpecialBlack350, SpecialBlack250, SpecialBlack100, SpecialBlack6, SpecialBlack5, SpecialBlack4, Color Black FW1, Color Black FW2, Color Black FW2V, Color Black FW18, Color Black FW200, Color Black S160, Color Black S170

Manufactured by Cabot: Monarch (registered trademark. Same as below) 120, Monarch280, Monarch460, Monarch800, Monarch880, Monarch900, Monarch1000, Monarch1100, Monarch1300, Monarch1400, Monarch4630, REGAL (registered trademark. Same as below) 99, REGAL99R, REGAL415 , REGAL415R, REGAL250, REGAL250R, REGAL330, REGAL400R, REGAL55R0, REGAL660R, BLACK PEARLS480, PEARLS130, VULCAN (registered trademark. Same as below.) XC72R, ELFTEX (registered trademark) -8

Manufactured by Birla: RAVEN (registered trademark. Same as below.) RAVEN1060U, RAVEN1080U, RAVEN1170, RAVEN1190U, RAVEN1250, RAVEN1500, RAVEN2000, RAVEN2500U, RAVEN3500, RAVEN5000, RAVEN5250, RAVEN5750, RAVEN7000

Carbon black may be used that is coated with a resin. When carbon black coated with a resin is used, there is an effect of improving adhesion to a glass substrate or volume resistance value. As the carbon black coated with the resin, for example, carbon black or the like described in JP-A-09-71733 can be suitably used. In terms of volume resistance and dielectric constant, a resin-coated carbon black is suitably used.

It is preferable that the total content of Na and Ca is 100 ppm or less as carbon black to be provided for the coating treatment with resin. Carbon black is usually Na, Ca, or K mixed from raw material oil or combustion oil (or gas) at the time of manufacture, reaction stop water or granulated water, and further, furnace material of the reaction furnace. , Mg, Al, Fe, etc. are contained as a percentage order. Among these, Na and Ca are generally contained in hundreds of ppm or more, respectively, but by reducing these, penetration into the transparent electrode (ITO) and other electrodes is suppressed, and electric short circuit tends to be prevented. .

As a method for reducing the content of ash containing Na or Ca, raw material oil or fuel oil (or gas) when producing carbon black, and reaction stop water are carefully selected from those with the smallest content and structure. This is possible by dramatically reducing the amount of the alkali substance to be adjusted. As another method, a method of washing carbon black produced from a furnace with water or hydrochloric acid or the like and dissolving and dissolving Na or Ca may be mentioned.

Specifically, when carbon black is mixed and dispersed in water, hydrochloric acid, or hydrogen peroxide water, when a poorly soluble solvent is added, carbon black shifts to the solvent side, and is completely separated from water, and most of Na present in the carbon black B. Ca is dissolved and removed in water or acid. In order to reduce the total amount of Na and Ca to 100 ppm or less, the carbon black production process using carefully selected raw materials or the water or acid dissolution method alone may be possible, but the combined amount of Na and Ca can be more easily achieved by using both methods together. Can be made 100 ppm or less.

Moreover, it is preferable that resin-coated carbon black is what is called acidic carbon black of pH 6 or less. Since the dispersion diameter (agglomerate diameter) in water becomes small, coating to a fine unit is possible and is suitable. Moreover, it is preferable that the average particle diameter is 40 nm or less and the dibutylphthalate (DBP) absorption amount is 140 ml / 100 g or less. By setting it within the said range, there exists a tendency for the coating film with favorable light-shielding property to be obtained. The average particle diameter means a number average particle diameter, and is used for particle image analysis in which 2000 to 3,000 carbon black particles in the obtained photograph are measured by an image processing apparatus, which is taken several minutes at a magnification of tens of times by electron microscope observation. It means a circle equivalent diameter obtained by.

The method for preparing the carbon black coated with the resin is not particularly limited, but, for example, after properly adjusting the blending amount of the carbon black and the resin, 1. Mixing the resin with a solvent such as cyclohexanone, toluene, or xylene After mixing and stirring the resin solution dissolved in heat and the suspension mixed with carbon black and water, and separating the carbon black and water, removing the water and kneading the composition obtained by heating and kneading to form a sheet, pulverized and dried How to make; 2. 3. After mixing and stirring the prepared resin solution and suspension in the same manner as above to granulate the carbon black and resin, the obtained granular material is separated and heated to remove residual solvent and water; 3. A method of dry blending by dissolving a carboxylic acid such as maleic acid or fumaric acid in a solvent, adding and mixing carbon black, drying, removing the solvent to obtain a carbon black impregnated with a carboxylic acid, and adding a resin to it; 4. After the monomer component and the water constituting the resin to be coated are stirred at high speed to prepare a suspension, and after polymerization, cooled to obtain a resin containing a reactive group from the polymer suspension, carbon black is added thereto to knead, and kneaded with carbon black. Reactive groups can be reacted (grafted with carbon black), and cooled and pulverized.

Although the type of the resin to be coated is not particularly limited, synthetic resins are common, and since the resin having a benzene ring in the structure has a stronger amphoteric surfactant function, it is preferable in terms of dispersibility and dispersion stability. Do.

Specific synthetic resins include phenol resins, melamine resins, xylene resins, diallyl phthalate resins, phthalic resins, epoxy resins, alkyl benzene resins, thermosetting resins, polystyrene, polycarbonate, polyethylene terephthalate, and polybutylene tere Phthalate, modified polyphenylene oxide, polysulfone, polyparaphenylene terephthalamide, polyamideimide, polyimide, polyaminobismaleimide, polyether sulfopolyphenylene sulfone, polyarylate, polyether ether ketone, etc. Thermoplastic resins can be used. The amount of the coating resin is preferably 1 to 30% by mass relative to the total amount of carbon black and the coating resin. When it is more than the said lower limit, there exists a tendency for coating to be sufficient. On the other hand, by setting it below the said upper limit, there exists a tendency to prevent adhesion between resins and to make it excellent in dispersibility.

Carbon black formed by coating with a resin in this way can be used as a light blocking material such as a partition wall or a colored spacer according to a conventional method. It can be manufactured by a phosphorus method. When such a carbon black is used, there is a tendency that it is possible to achieve high light-shielding rate and low cost. Moreover, the light-shielding material, such as a partition wall of a high resistance and a low dielectric constant, a coloring spacer, can be manufactured by coating the carbon black surface with resin.

Moreover, you may use dye other than the organic coloring pigment and black coloring agent mentioned above as another coloring agent. Examples of the dye that can be used as a colorant include azo-based dyes, anthraquinone-based dyes, phthalocyanine-based dyes, quinoneimine-based dyes, quinoline-based dyes, nitro-based dyes, carbonyl-based dyes, and methine-based dyes.

As an azo dye, it is C.I. Acid Yellow 11, C.I. Acid Orange 7, C.I. Acid Red 37, C.I. Acid Red 180, C.I. Acid Blue 29, C.I. Direct Red 28, C.I. Direct Red 83, C.I. Direct Yellow 12, C.I. Direct Orange 26, C.I. Direct Green 28, C.I. Direct Green 59, C.I. Reactive Yellow 2, C.I. Reactive Red 17, C.I. Reactive Red 120, C.I. Reactive Black 5, C.I. Disperse Orange 5, C.I. Disperse Red 58, C.I. Disperse Blue 165, C.I. Basic Blue 41, C.I. Basic Red 18, C.I. Mordant Red 7, C.I. Mordant Yellow 5, C.I. Mordant black 7 and the like.

As an anthraquinone dye, C.I. Bat Blue 4, C.I. Acid Blue 40, C.I. Acid Green 25, C.I. Reactive Blue 19, C.I. Reactive Blue 49, C.I. Disperse Red 60, C.I. Disperse Blue 56, C.I. And Disperse Blue 60.

In addition, as a phthalocyanine-based dye, for example, C.I. Bat Blue 5 and the like are quinoneimine dyes, for example, C.I. Basic Blue 3, C.I. Basic blue 9 and the like are quinoline-based dyes, for example, C.I. Solvent Yellow 33, C.I. Acid Yellow 3, C.I. Disperse Yellow 64 and the like are nitro-based dyes, for example, C.I. Acid Yellow 1, C.I. Acid Orange 3, C.I. And Dispers Yell 42.

These (A1) organic black pigments, (A2) organic colored pigments, and pigments such as black colorants are dispersed such that the average particle size is usually 1 µm or less, preferably 0.5 µm or less, and more preferably 0.25 µm or less. It is preferred to use. Here, the standard for the average particle diameter is the number of pigment particles.

In addition, the average particle diameter of this pigment is a value calculated | required from the pigment particle diameter measured by dynamic light scattering (DLS). Particle diameter measurement is carried out on a sufficiently diluted colored photosensitive resin composition (normally diluted and prepared at about 0.005 to 0.2% by mass of the pigment content. However, if there is a concentration recommended by the measuring device, it is dependent on the concentration). , Measured at 25 ° C.

[1-2] (B) Dispersant

In the colored photosensitive resin composition and pigment dispersion of the present invention, (A) dispersing the colorant finely and stabilizing the dispersing state are important for ensuring stability of quality, and therefore (B) a dispersing agent is included.

In the colored photosensitive resin composition according to the first aspect of the present invention and the pigment dispersion liquid according to the third aspect of the present invention, the dispersant (B) includes an acrylic dispersant. Since the acrylic dispersant has a flexible main skeleton with a linear molecular structure, it is believed that the colorant is uniformly dispersed in the colored photosensitive resin composition and the pigment dispersion by adsorbing most of the adsorber to the colorant. By uniformly disposing the colorant in the coating film, the coating film becomes a dense film, and the colorant, which is a component insoluble in the alkali developer, is uniformly disposed in the coating film, so that the penetration of the developer into the coating film during development is suppressed. As a result, it is considered that the pattern adhesiveness becomes good, and even if it is a fine pattern, the adhesiveness becomes good.

Further, as the acrylic dispersant, a polymer dispersant having a functional group is preferable. Moreover, from the viewpoint of dispersion stability, an acrylic dispersant containing a carboxyl group; a phosphate group; a sulfonic acid group; or a base thereof; a nitrogen atom is preferable, and an acrylic dispersant containing a nitrogen atom is preferable. Furthermore, polymer dispersants having basic functional groups such as primary, secondary, or tertiary amino groups; quaternary ammonium bases; groups derived from nitrogen-containing heterocycles such as pyridine, pyrimidine, and pyrazine, and dispersing colorants such as pigments It is particularly preferable from the viewpoint of dispersing with a small amount of dispersant. These functional groups act as adsorbers adsorbing to the colorant.

Commercially available acrylic dispersants include, for example, DISPERBYK-2000, DISPERBYK-2001, BYK-LPN21116, and BYK-LPN6919 (all of which are manufactured by BICK Chemical).

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

As the unsaturated group-containing monomer having a functional group, (meth) acrylic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethylphthalic acid, 2- (meth) acryloyloxyethylhexa Unsaturated monomers having carboxyl groups such as hydrophthalic acid and acrylic acid dimers; Unsaturated monomers having tertiary amino groups such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and quaternates thereof, and quaternary ammonium bases And as specific examples. These may be used individually by 1 type and may use 2 or more types together.

As a monomer containing an unsaturated group having no functional group, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, iso Butyl (meth) acrylate, t-butyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxymethyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, N-vinylpyrrolidone , N-substituted maleimides such as styrene and derivatives thereof, α-methylstyrene, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide, acrylonitrile, vinyl acetate, and polymethyl (meth) acrylic Rate macro Nomeo, there may be mentioned polystyrene macromonomer, poly 2-hydroxyethyl (meth) acrylate macromonomer, the macromonomer polyethylene glycol, polypropylene glycol macromonomer, polycaprolactone macromonomer such as a macromonomer or the like. These may be used individually by 1 type and may use 2 or more types together. The side chain of these monomers acts as a solvent affinity portion compatible with the solvent.

The acrylic dispersant is an A-B or B-A-B block copolymer composed of an A block having a functional group and a B block having no functional group, 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 may be included, and these may be randomly copolymerized in the A block or It may be contained in any aspect of the block copolymerization. Moreover, the content rate in A block of the partial structure which does not contain a functional group is 80 mass% or less normally, Preferably it is 50 mass% or less, More preferably, it is 30 mass% or less, More preferably, it is 10 mass%. Hereinafter, it is most preferably 0% by mass.

From the viewpoint of dispersibility, it is preferable that the B block is composed of only a partial structure derived from an unsaturated group-containing monomer not containing the functional group, and one B block may contain partial structures derived from two or more types of monomers, These may be contained in either the random copolymerization or the block copolymerization in the B block.

The A-B or B-A-B block copolymer is prepared by the living polymerization method shown below, for example.

The living polymerization method includes an anionic living polymerization method, a cationic living polymerization method, and a radical living polymerization method, of which the anionic living polymerization method is an anion that is not a polymerization active species, and is represented by, for example, the following scheme.

[Formula 13]

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 each an integer of 1 or more.

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

[Formula 14]

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, R ^a is a hydrogen atom or a monovalent organic group, R ^b is ^a hydrogen atom different from R ^a or a monovalent organic group.

When synthesizing this acrylic dispersant, Japanese Patent Application Laid-open No. Hei 9-62002, P.Lutz, P.Masson et al, Polym. Bull. 12, 79 (1984), B.C. Anderson, G.D.Andrews et al, Macromolecules, 14, 1601 (1981), K.Hatada, K.Ute, et al, Polym. J. 17, 977 (1985), 18, 1037 (1986), Ute Koichi, Kota Hatada, Polymer Processing, 36, 366 (1987), Toshinobu Higashimura, Mitsuo Sawamoto, Polymer Journal, 46, 189 (1989) , M.Kuroki, T.Aida, J. Am. Chem. Sic, 109, 4737 (1987), Ida Takuzo, Inoue Shohei, Organic Synthetic Chemistry, 43, 300 (1985), DYSogoh, WRHertler et al, Macromolecules, 20, 1473 (1987), employ known methods, etc. can do.

As described above, the acrylic dispersant that can be used in the present invention may be an AB block copolymer, a BAB block copolymer, or an A block / B block ratio constituting the copolymer is not particularly limited, and 1/99 to 80 It is preferable that it is / 20 (mass ratio), and it is more preferable that it is 5/95 to 60/40 (mass ratio). By setting it within this range, there exists a tendency for the balance of dispersibility and storage stability to be easy to take.

Moreover, it is preferable that the quantity of the quaternary ammonium base in 1 g of A-B block copolymer and B-A-B block copolymer which can be used by this invention is 0.1-10 mmol normally. By setting it within this range, it tends to be easy to ensure good dispersibility.

On the other hand, an amino group may be contained in such an acrylic dispersing agent. The amine value of the acrylic dispersant is usually about 1 to 130 mgKOH / g. 10 mgKOH / g or more is preferable, 30 mgKOH / g or more is more preferable, 50 mgKOH / g or more is more preferable, 60 mgKOH / g or more is particularly preferable, and 120 mgKOH / g or more The following is preferable, 100 mgKOH / g or less is more preferable, 90 mgKOH / g or less is more preferable, and 80 mgKOH / g or less is particularly preferable. When it is more than the said lower limit, there exists a tendency for dispersibility to become favorable, and when it is below the said upper limit, there exists a tendency for the preservation property after dispersion to become favorable. As a combination of an upper limit and a lower limit, 10 to 120 mgKOH / g is preferable, 30 to 100 mgKOH / g is more preferable, 50 to 90 mgKOH / g is more preferable, and 60 to 80 mgKOH / g It is particularly preferable.

Here, the amine value of the acrylic dispersant is expressed by the mass of the base amount and the equivalent of KOH per 1 g of solid content excluding the solvent in the dispersant sample, and is measured by the following method.

0.5 to 1.5 g of the dispersant sample is precisely weighed into a 100 ml beaker and dissolved in 50 ml of acetic acid. This solution is neutralized and titrated with an acetic acid solution of 0.1 mol / L HClO ₄ 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 [mgKOH / g] = (561 × V) / (W × S)

[However, W: Dispersant sample balance amount [g], V: Appropriate amount at the proper end point [ml], S: Solid component concentration [mass%] of dispersant sample.]

Although the weight average molecular weight (Mw) of an acrylic dispersing agent is not specifically limited, 1000 or more are preferable, 3000 or more are more preferable, 4000 or more are more preferable, 5000 or more are especially preferable, and 50000 or less are preferable, 20000 or less is more preferable, and 15000 or less is still more preferable. When it is more than the said lower limit, there exists a tendency for dispersibility to become favorable, and when it is below the said upper limit, there exists a tendency for a viscosity change to hardly occur. As a combination of an upper limit and a lower limit, 1000-50000 is preferable, 3000-20000 is more preferable, 4000-15000 is more preferable, and 5000-15000 is 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 is a repeating unit represented by the following general formula (V) (hereinafter, It is preferable to have "repeating unit (V)."

[Formula 15]

In the formula (V), R ³¹ to R ³³ are each independently a hydrogen atom, 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, and R ³¹ to R ³³ Two or more of them 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 the counter anion.

Although the number of carbon atoms of the alkyl group which may have a substituent in R ³¹ to R ³³ of the formula (V) is not particularly limited, it is usually 1 or more, preferably 10 or less, more preferably 6 or less, It is more preferably 4 or less, and particularly preferably 2 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and the like, and among these, methyl group, ethyl group, propyl group, butyl group, pentyl group, Or it is preferably a hexyl group, more preferably a methyl group, an ethyl group, a propyl group, or a butyl group, and more preferably a methyl group or an ethyl group. Moreover, either a linear chain or a branch chain may be sufficient. Moreover, what may contain cyclic structures, such as a cyclohexyl group and a cyclohexyl methyl group, may be sufficient.

The carbon number of the aryl group which may have a substituent in R ³¹ to R ³³ of the formula (V) is not particularly limited, but is usually 6 or more, more preferably 16 or less, and more preferably 12 or less. . Specific examples of the aryl group include phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, diethylphenyl group, naphthyl group, anthracenyl group, and the like. Among these, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, or di It is preferably an ethylphenyl group, and more preferably a phenyl group, methylphenyl group, or ethylphenyl group.

Although carbon number of the aralkyl group which may have a substituent in R ³¹ -R ³³ of the formula (V) is not particularly limited, it is usually 7 or more, preferably 16 or less, more preferably 12 or less. , It is more preferably 10 or less, and particularly preferably 8 or less. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group, a phenylethyl group, a phenyl It is preferably a propyl 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, specifically, R ³¹ and R ³³ are each independently a methyl group or an ethyl group, and R ³² Is preferably a phenylmethyl group or a phenylethyl group, R ³¹ and R ³³ are methyl groups, and more preferably R ³² is a phenylmethyl group.

Moreover, when the said polymer dispersing agent has a tertiary amine as a functional group, from a dispersibility viewpoint, what has a repeating unit represented by the following general formula (VI) (it may be hereafter called a "repeating unit (VI)"). desirable.

[Formula 16]

In the formula (VI), R ³⁵ and R ³⁶ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an aralkyl group which may have a substituent, and R ³⁵ and R ³⁶ You 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.

Moreover, as the alkyl group which may have a substituent in R ³⁵ and R ³⁶ of the formula (VI), those exemplified as R ³¹ to R ³³ of the formula (V) can be preferably employed.

Similarly, as the aryl group which may have a substituent in R ³⁵ and R ³⁶ in the formula (VI), those exemplified as R ³¹ to R ^{33 in} the formula (V) can be preferably employed. Moreover, as the aralkyl group which may have a substituent in R ³⁵ and R ³⁶ of the formula (VI), those exemplified as R ³¹ to R ³³ of the formula (V) can be preferably employed.

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

As a substituent which the alkyl group, aralkyl group, or aryl group in R ³¹ -R ³³ of the formula (V) and R ³⁵ and R ³⁶ of the formula (VI) may have, a halogen atom, an alkoxy group, a benzoyl group, a hydroxyl group And the like.

In the formulas (V) and (VI), divalent linking groups X and Z include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, -CONH-R ⁴³ -group, -COOR ⁴⁴ -group [where R ⁴³ and R ⁴⁴ are a single bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)] and the like, and preferably -COO- R ⁴⁴ -group, more preferably -COO-C ₂ H ₄ -group.

Further, in the above formula (V), the counter anion Y ^- roneun, Cl ^-, and the like ^-, Br ^-, I ^-, ClO ₄ ^-, BF ₄ ^-, CH ₃ COO-, PF _6.

The content ratio of the repeating unit represented by the formula (V) is not particularly limited, but from the viewpoint of dispersibility, the total content of the repeating unit represented by the formula (V) and the repeating unit represented by the formula (VI) It is preferably 60 mol% or less, more preferably 50 mol% or less, more preferably 40 mol% or less, particularly preferably 35 mol% or less, and preferably 5 mol% or more Is, more preferably 10 mol% or more, still more preferably 20 mol% or more, and particularly preferably 30 mol% or more. The combination of the upper limit and the lower limit is preferably 5 to 60 mol%, more preferably 10 to 50 mol%, still more preferably 20 to 40 mol%, and particularly preferably 30 to 35 mol%.

Moreover, although the content rate of the repeating unit represented by said Formula (V) in all the repeating units of a dispersing agent is not specifically limited, From a dispersibility viewpoint, it is preferable that it is 1 mol% or more, More preferably, it is 5 mol% or more, 8 It is more preferable that it is mol% or more, particularly preferably 10 mol% or more, further preferably 50 mol% or less, more preferably 30 mol% or less, still more preferably 20 mol% or less, and 15 mol% or less Especially preferred. The combination of the upper limit and the lower limit is preferably 1 to 50 mol%, more preferably 5 to 30 mol%, further preferably 8 to 20 mol%, and particularly preferably 10 to 15 mol%.

The content ratio of the repeating unit represented by the formula (VI) is not particularly limited, but from the viewpoint of dispersibility, the sum of the content of the repeating unit represented by the formula (V) and the repeating unit represented by the formula (VI) With respect to, it is preferably 100 mol% or less, more preferably 90 mol% or less, further preferably 80 mol% or less, particularly preferably 70 mol% or less, and preferably 10 mol% or more Is, more preferably 30 mol% or more, still more preferably 50 mol% or more, and particularly preferably 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%.

Moreover, although the content ratio of the repeating unit represented by said Formula (VI) in all the repeating units of a dispersing agent is not specifically limited, From a dispersibility viewpoint, it is preferable that it is 5 mol% or more, It is more preferable that it is 10 mol% or more, 15 More preferably, it is more preferably 20 mol% or more, more preferably 60 mol% or less, more preferably 40 mol% or less, still more preferably 30 mol% or less, and more preferably 25 mol% or less Especially preferred. 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%.

Moreover, an acrylic dispersing agent is a repeating unit represented by the following general formula (VII) (hereinafter referred to as "repeating unit (VII)" in view of improving compatibility with a binder component such as a solvent and improving dispersion stability. It is preferred to have.)

[Formula 17]

In the 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 1-20.

In R ⁴¹ of the formula (VII), the number of carbon atoms of the alkyl group which may have a substituent is not particularly limited, but is usually 1 or more, preferably 2 or more, and preferably 10 or less, more preferably 6 or less. It is preferable, and it is more preferable that it is 4 or less. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and the like, and among these, methyl group, ethyl group, propyl group, butyl group, pentyl group, Or it is preferable that it is a hexyl group, and it is more preferable that it is a methyl group, an ethyl group, a propyl group, or a butyl group. Moreover, either a linear chain or a branch chain may be sufficient. Moreover, you may contain cyclic structures, such as a cyclohexyl group and a cyclohexyl methyl group.

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

Moreover, although the content rate of the repeating unit represented by said Formula (VII) in all the repeating units of a dispersing agent is not specifically limited, It is preferable that it is 1 mol% or more, it is more preferable that it is 2 mol% or more, and it is more preferable that it is 4 mol% or more. Preferably, it is preferably 30 mol% or less, more preferably 20 mol% or less, and even more preferably 10 mol% or less. When it is within the above range, there is a tendency that compatibility with a binder component such as a solvent is easily compatible with dispersion stability. As a combination of an upper limit and a lower limit, 1 to 30 mol% is preferable, 2 to 20 mol% is more preferable, and 4 to 10 mol% is more preferable.

Moreover, an acrylic dispersing agent is a repeating unit (hereinafter referred to as "repeating unit (VIII)" represented by one or more of the following general formula (VIII) from the viewpoint of improving compatibility with a binder component such as a solvent of the dispersing agent and improving dispersion stability. It may be called.) It is preferable to have.

[Formula 18]

In said formula (VIII), R ³⁸ is 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.

Although carbon number of the alkyl group which may have a substituent in R ³⁸ of said Formula (VIII) is not specifically limited, Usually, it is 1 or more, 2 or more are preferable, 4 or more are more preferable, and 10 or less It is preferable, and it is more preferable that it is 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, an ethyl group, a propyl group, It is preferably a butyl group, pentyl group, hexyl group, or 2-ethylhexyl group, and more preferably a methyl group, ethyl group, propyl group, butyl group, or 2-ethylhexyl group. Moreover, either a linear chain or a branch chain may be sufficient. Moreover, you may contain cyclic structures, such as a cyclohexyl group and a cyclohexyl methyl group.

The carbon number of the aryl group which may have a substituent in R ³⁸ in the formula (VIII) is not particularly limited, but is usually 6 or more, more preferably 16 or less, more preferably 12 or less, and more preferably 8 or less. It 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. Among these, phenyl group, methylphenyl group, ethylphenyl group, dimethylphenyl group, or di It is preferably an ethylphenyl group, and more preferably a phenyl group, methylphenyl group, or ethylphenyl group.

The number of carbon atoms in the aralkyl group which may have a substituent in R ³⁸ in the formula (VIII) is not particularly limited, but is usually 7 or more, more preferably 16 or less, more preferably 12 or less, and more preferably 10 or less. It is more preferable. Specific examples of the aralkyl group include a phenylmethyl group (benzyl group), a phenylethyl group (phenethyl group), a phenylpropyl group, a phenylbutyl group, and a phenylisopropyl group. Among these, a phenylmethyl group, a phenylethyl group, a phenyl It is preferably a propyl 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 more preferably a methyl group, ethyl group, butyl group, 2-ethylhexyl group or phenylmethyl group.

A halogen atom, an alkoxy group, etc. are mentioned as a substituent which R ³⁸ may have in an alkyl group. Moreover, a chain-type alkyl group, a halogen atom, an alkoxy group, etc. are mentioned as a substituent which the aryl group or aralkyl group may have. Further, it is an alkyl group of chain represented by R ³⁸ includes both straight-chain and branched.

Moreover, the content ratio of the repeating unit represented by the said formula (VIII) in all the repeating units of a dispersing agent (the content ratio of the sum total when it contains 2 or more types of repeating units represented by said formula (VIII)) is a viewpoint of dispersibility. In, it is preferable that it is 30 mol% or more, more preferably 40 mol% or more, further preferably 50 mol% or more, further preferably 80 mol% or less, and more preferably 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 repeating unit (V), repeating unit (VI), repeating unit (VII) and repeating unit (VIII). Examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylate monomers such as (meth) acrylic acid chloride; (meth) acrylamide, and (meth) acrylic compounds such as N-methylolacrylamide. ) Acrylamide-based monomers; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; repeating units derived from monomers such as N-methacryloyl morpholine.

The acrylic dispersant is a block having 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 increasing dispersibility. It is preferably a copolymer. It is preferable that the block copolymer is an A-B block copolymer or a B-A-B block copolymer. By introducing not only a quaternary ammonium base but also a tertiary amino group into the A block, the dispersing ability of the dispersant tends to be remarkably improved. Moreover, it is preferable that a B block has a repeating unit (VII), and it is more preferable to have a repeating unit (VIII).

In the A block, the repeating unit (V) and the repeating unit (VI) may be contained in either random copolymerization or block copolymerization. Moreover, 2 or more types of repeating units (V) and repeating units (VI) may be contained in one A block, and in this case, each repeating unit may be random copolymerization or block copolymerization in the A block. It may contain in an aspect.

Moreover, repeating units other than repeating unit (V) and repeating unit (VI) may be contained in the A block, and examples of such repeating units include repeating units derived from the aforementioned (meth) acrylic acid ester monomers, etc. You can. The content of the repeating units other than the repeating unit (V) and repeating unit (VI) in the A block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but these repeating units are in the A block. It is most preferably not contained.

Repeat units other than repeat units (VII) and (VIII) may be contained in the B block, and examples of such repeat units include styrene-based monomers such as styrene and α-methylstyrene; (meth) acrylic acid chloride (meth ) Acrylic acid-based monomers; (meth) acrylamide-based monomers such as (meth) acrylamide and N-methylol acrylamide; vinyl acetate; acrylonitrile; allyl glycidyl ether, crotonic acid glycidyl ether; N- And repeating units derived from monomers such as methacryloyl morpholine. The content ratio of the repeating units other than the repeating unit (VII) and repeating unit (VIII) in the B block is preferably 0 to 50 mol%, more preferably 0 to 20 mol%, but such repeating units are B blocks It is most preferably not contained in.

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

Moreover, in the coloring photosensitive resin composition which concerns on 1st aspect of this invention, and the pigment dispersion liquid which concerns on 3rd aspect of this invention, (B) dispersing agent contains other polymer dispersing agents shown below besides the acrylic dispersing agent mentioned above. You may have.

Other polymer dispersants include, for example, urethane-based dispersants, polyethyleneimine-based dispersants, polyallylamine-based dispersants, dispersants consisting of amino group-containing monomers and macromonomers, polyoxyethylene alkyl ether-based dispersants, and polyoxyethylene diester-based dispersants. , Polyether phosphate dispersants, polyester phosphate dispersants, sorbitan aliphatic ester dispersants, aliphatic modified polyester dispersants, and the like.

Specific examples of such dispersants include EFKA (registered trademark. BASF Corporation.), DISPERBYK (registered trademark. BICKCHEMI Corporation.), Disperon (registered trademark. KUSMOTO Hwasung Corporation.), SOLSPERSE under the trade name. (Registered trademark. Manufactured by Lubrizol.), KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), Azisper (registered trademark. Manufactured by Ajinomoto).

The weight average molecular weight (Mw) of other polymer dispersants is usually 700 or more, preferably 1000 or more, and is usually 100000 or less, preferably 50000 or less.

Among other polymer dispersants, urethane-based polymer dispersants are preferably mentioned from the viewpoint of dispersibility of the pigment.

Moreover, among the urethane-based polymer dispersants, polymer dispersants having a basic functional group and having a polyester bond and / or a polyether bond are preferred from the viewpoint of dispersibility and storage.

As a urethane type polymer dispersing agent, DISPERBYK 160-167, 182 series are mentioned, for example.

If the preferred chemical structure is specifically illustrated as a urethane-based polymer dispersant, for example, a polyisocyanate compound, a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the molecule, and an active hydrogen in the same molecule and a tertiary grade And dispersion resins having a weight average molecular weight of 1000 to 200,000 obtained by reacting a compound having an amino group. By treating these with a quaternizing agent such as benzyl chloride, all or part of the tertiary amino group can be used as a quaternary ammonium base.

Examples of the polyisocyanate compound include paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, naphthalene-1,5-diisocyanate, Aromatic diisocyanates such as tolidine diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, aliphatic diisocyanates such as 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, isophorone diisocyanate, 4,4 Alicyclic diisocyanates such as '-methylene bis (cyclohexyl isocyanate), ω, ω'-diisocyanate dimethylcyclohexane, xylylene diisocyanate, α, α, α', α'-tetramethyl xylylene diisocyanate, etc. Aliphatic diisocyanate, lysine ester triisocyanate having 1,6,11-luck Decantriisocyanate, 1,8-diisocyanate-4-isocyanatemethyloctane, 1,3,6-hexamethylenetriisocyanate, bicycloheptanetriisocyanate, tris (isocyanatephenylmethane), tris (isocyanatephenyl) thiophosphate, etc. And triisocyanates, trimers thereof, water adducts, and polyol adducts thereof. Preferred polyisocyanates are trimers of organic diisocyanates, and most preferred are trimers of tolylene diisocyanate and trimers of isophorone diisocyanate. These may be used individually by 1 type and may use 2 or more types together.

As a method for producing a trimer of isocyanate, the polyisocyanates are partially prepared of an isocyanate group using a suitable trimerization catalyst, for example, tertiary amines, phosphines, alkoxides, metal oxides, carboxylic acid salts, and the like. A method of obtaining a desired isocyanurate-containing polyisocyanate by performing a trimerization and stopping the trimmerization by adding a catalyst poison, and then removing the unreacted polyisocyanate by solvent extraction and thin film distillation You can.

Examples of the compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule include polyether glycol, polyester glycol, polycarbonate glycol, polyolefin glycol, and the like, and the terminal hydroxyl groups of these compounds have 1 to 25 carbon atoms. And alkoxylated alkyl groups and mixtures of two or more of these.

As polyether glycol, polyether diol, polyether ester diol, and mixtures of these two or more types are mentioned. Examples of the polyetherdiol include alkylene oxides alone or by copolymerization, such as polyethylene glycol, polypropylene glycol, polyethylene-propylene glycol, polyoxytetramethylene glycol, polyoxyhexamethylene glycol, polyoxyoctamethylene glycol, and And mixtures of two or more of them.

The polyether ester diol is obtained by reacting a mixture of an ether group-containing diol or other glycol with a dicarboxylic acid or anhydride thereof, or by reacting alkylene oxide with polyester glycol, for example, poly (poly And oxytetramethylene) adipates. The most preferred polyether glycol is polyethylene glycol, polypropylene glycol, polyoxytetramethylene glycol, or a compound in which one terminal hydroxyl group of these compounds is alkoxylated with an alkyl group having 1 to 25 carbon atoms.

As the polyester glycol, dicarboxylic acids (succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, phthalic acid, etc.) or their anhydrides and glycols (ethylene glycol, diethylene glycol, triethylene glycol, Propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1, 6-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2, Aliphatic glycols, such as 5-hexanediol, 1,8-octamethylene glycol, 2-methyl-1,8-octamethylene glycol, and 1,9-nonanediol, alicyclic glycols, such as bishydroxymethylcyclohexane, and xylylene Aromatic glycerides such as glycol and bishydroxyethoxybenzene , N-alkyldialkanolamines such as N-methyldiethanolamine)), for example, polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, polyethylene / propylene adipate, etc. Or polylactone diols or polylactone monools obtained by using the diols or monohydric alcohols having 1 to 25 carbons as an initiator, for example, polycaprolactone glycol, polymethyl valerolactone, and mixtures of two or more thereof You can. The most preferred polyester glycol is polycaprolactone glycol or polycaprolactone using an alcohol having 1 to 25 carbon atoms as an initiator.

As polycarbonate glycol, poly (1,6-hexylene) carbonate, poly (3-methyl-1,5-pentylene) carbonate, etc., polyolefin glycol is polybutadiene glycol, hydrogenated polybutadiene glycol, hydrogenated poly And isoprene glycol.

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

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.

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

Active hydrogen, that is, a hydrogen atom directly attached 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 them, the hydrogen value of an amino group, particularly a primary amino group desirable.

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, and the like.

If the compound having an active hydrogen and a tertiary amino group in the same molecule is exemplified, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-di Propyl-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 And N-dibutyl-1,4-butanediamine.

Moreover, when the tertiary amino group is a nitrogen-containing heterocyclic structure, the nitrogen-containing heterocyclic ring includes a pyrazole ring, an imidazole ring, a triazole ring, a tetrazole ring, an indole ring, a carbazole ring, an indazole ring, and a benz Nitrogen-containing hetero 5-membered rings such as imidazole rings, benzotriazole rings, benzoxazole rings, benzothiazole rings, benzothiadiazole rings, pyridine rings, pyridazine rings, pyrimidine rings, triazine rings, quinoline rings , A nitrogen-containing hetero 6-membered ring such as an acridine ring and an isoquinoline ring. Preferred of these nitrogen-containing hetero rings 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, and 1- (2-aminoethyl) imidazole. Moreover, if a compound having a triazole ring and an amino group is specifically illustrated, 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 And -1,4-diphenyl-1,2,3-triazole, 3-amino-1-benzyl-1H-2,4-triazole, and the like. Among them, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1- (3-aminopropyl) imidazole, 3-amino-1,2,4 -Triazoles are preferred.

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

When the urethane-based polymer dispersant is prepared, the preferred mixing ratio of the raw materials is 10 to 200 parts by mass, preferably 100 to 100 parts by mass of the polyisocyanate compound, and a compound having a number average molecular weight of 300 to 10000 having one or two hydroxyl groups in the same molecule. Preferably, it is 20 to 190 parts by mass, more preferably 30 to 180 parts by mass, and the compound having active hydrogen and a tertiary amino group in the same molecule is 0.2 to 25 parts by mass, preferably 0.3 to 24 parts by mass.

The production of the urethane-based polymer dispersant can be carried out according to a known polyurethane resin production method. As a solvent at the time of preparation, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and isophorone, esters such as ethyl acetate, butyl acetate, and cellosolve acetate , Hydrocarbons such as benzene, toluene, xylene, hexane, some alcohols such as diacetone alcohol, isopropanol, second butanol, and third butanol, chlorides such as methylene chloride and chloroform, tetrahydrofuran, diethyl ether, etc. Aprotic polar solvents such as ethers, dimethylformamide, N-methylpyrrolidone, and dimethyl sulfoxide are used. These may be used individually by 1 type and may use 2 or more types together.

In the above production, usually, a urethanization reaction catalyst is used. As this catalyst, for example, tin systems such as dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin dioctoate, and stannas octoate, iron-based iron acetylacetonate, ferric chloride, and tri And tertiary amines such as ethylamine and triethylenediamine. These may be used alone or in combination of two or more.

It is preferable to control the introduction amount of a compound having an active hydrogen and a tertiary amino group in the same molecule in the range of 1 to 100 mgKOH / g by the amine value after reaction. More preferably, it is in the range of 5 to 95 mgKOH / g. The amine value is a value represented by the number of mg of KOH by neutralizing titration of a basic amino group with an acid and corresponding to the acid value. The dispersibility tends to be improved by setting it to the lower limit or higher, and the developability tends to be improved by setting the lower limit or lower.

In addition, when the isocyanate group remains in the polymer dispersant by the above reaction, it is preferable because the breakdown of the isocyanate group with an alcohol or amino compound increases the stability of the product over time.

The weight average molecular weight (Mw) of the urethane-based polymer dispersant is usually in the range of 1000 to 200000, preferably 2000 to 100000, more preferably 3000 to 50000. The dispersibility and the dispersion stability tend to be improved by setting the amount to the lower limit or more, and the solubility is improved, the dispersibility is improved, and the control of the reaction tends to be easy to be made below the upper limit.

Moreover, it is preferable to use a dispersing agent (B) together with the pigment derivative mentioned later from a viewpoint of improving dispersion stability.

Meanwhile, the dispersant (B) in the colored photosensitive resin composition according to the second aspect of the present invention is not limited at all as long as it can disperse the colorant (A). Specifically, the acrylic dispersant described above may be used, or other polymer dispersants described above 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 pigment dispersion of the present invention contain (C) a binder resin. (C) By including a binder resin, it becomes possible to obtain a homogeneous film. (C) The binder resin is not particularly limited as long as a homogeneous film is obtained, but is preferably an alkali-soluble resin from the viewpoint of solubility in an alkali developer.

In the colored photosensitive resin composition and pigment dispersion of the present invention, the (C) binder resin is characterized by containing (C1) an epoxy (meth) acrylate resin from the viewpoint of reducing outgassing. (C1) Since the epoxy (meth) acrylate resin has a rigid skeleton, has high heat resistance, does not undergo thermal decomposition, and because the skeleton is rigid, an array structure is taken upon curing to form a high crosslinking film. It is considered that the amount of outgas generated after formation of the cured product decreases.

Moreover, it is preferable that (C1) epoxy (meth) acrylate resin contains a carboxyl group or a hydroxyl group from a viewpoint of solubility to an alkali developer.

(C1) It is preferable that the epoxy (meth) acrylate resin is a resin obtained by adding an acid or ester compound having an ethylenically unsaturated bond to the epoxy resin, and reacting a polybasic acid or anhydride thereof. For example, by adding a ring-opening addition of an carboxyl group of an acid having an ethylenically unsaturated bond to the epoxy group of the epoxy resin, an ethylenically unsaturated bond is added to the epoxy compound through an ester bond (-COO-), and the hydroxyl group generated at that time , What added a carboxyl group of polybasic acid anhydride is mentioned. Moreover, when adding a polybasic acid anhydride, the thing added by adding polyhydric alcohol simultaneously is mentioned.

Moreover, the resin obtained by reacting the carboxyl group of the resin obtained by the above reaction with a compound having a functional group capable of reacting is also included in the (C1) epoxy (meth) acrylate resin.

As described above, the epoxy (meth) acrylate resin has substantially no epoxy group on the chemical structure, and is not limited to "(meth) acrylate", but an epoxy compound (epoxy resin) is a raw material, and also, "(meth ) Acrylate is a representative example, and is thus named according to convention.

Here, an epoxy resin is said to include the raw material compound before forming a resin by thermal curing, and the epoxy resin can be appropriately selected from known epoxy resins and used.

Moreover, as the epoxy resin, a compound obtained by reacting a phenolic compound with epihalohydrin can be used. As the phenolic compound, a compound having a divalent or trivalent or higher phenolic hydroxyl group is preferable, 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, phenol and dish Polymeric epoxy resin of clopentane, dihydrooxylfluorene type epoxy resin, dihydrooxylalkyleneoxylfluorene type epoxy resin, diglycidyl etherified product of 9,9-bis (4'-hydroxyphenyl) fluorene , Diglycidyl etherified products of 1,1-bis (4'-hydroxyphenyl) adamantane, and the like, and those 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, epoxide of polymers of phenol and dicyclopentadiene, 9,9-bis (4'-hydride Epoxyides of oxyphenyl) fluorene (diglycidyl etherates), epoxy resins having an adamantyl group, and the like are preferred, and epoxides of polymers of phenol and dicyclopentadiene, 9,9-bis (4'- More preferred is an epoxy resin of hydroxyphenyl) fluorene, an epoxy resin having an adamantyl group.

Among the acids having ethylenically unsaturated bonds, ethylenically unsaturated monocarboxylic acids are preferred. As an acid having an ethylenically unsaturated bond, for example, (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, pentaerythritol tri (meth) acrylate succinic anhydride adduct, pentaerythrate Litol tri (meth) acrylate tetrahydro phthalic anhydride adduct, dipentaerythritol penta (meth) acrylate succinic anhydride adduct, dipentaerythritol penta (meth) acrylate phthalic anhydride adduct, dipentaerythritol penta ( And meth) acrylate tetrahydro phthalic anhydride adducts, reaction products of (meth) acrylic acid and ε-caprolactone, and the like. Especially, from a viewpoint of sensitivity, (meth) acrylic acid is preferable.

As a polybasic acid (anhydride), for example, succinic acid, maleic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, 3-methyltetrahydrophthalic acid, 4-methyltetrahydrophthalic acid, 3-ethyltetrahydrophthalic acid, 4-ethyltetra Hydrophthalic acid, hexahydrophthalic acid, 3-methylhexahydrophthalic acid, 4-methylhexahydrophthalic acid, 3-ethylhexahydrophthalic acid, 4-ethylhexahydrophthalic acid, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid, And biphenyltetracarboxylic acids and anhydrides thereof. Among them, from the viewpoint of reducing outgas, succinic anhydride, maleic anhydride, tetrahydrophthalic anhydride, or hexahydrophthalic anhydride is preferred, succinic anhydride or tetrahydrophthalic anhydride is more preferred, and tetrahydrophthalic anhydride is more preferred. Do.

By using a polyhydric alcohol, the molecular weight of the (C1) epoxy (meth) acrylate resin is increased, branching can be introduced into the molecule, and the molecular weight and viscosity tend to be balanced. Moreover, the introduction rate of an acidic radical into a molecule | numerator can be increased, and there exists a tendency to balance balance, such as sensitivity and adhesiveness.

Examples of the polyhydric alcohol include one or more polyhydric alcohols selected from trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol. It is preferred.

(C1) Although the acid value of the epoxy (meth) acrylate resin is not particularly limited, 10 mgKOH / g or more is preferable, 20 mgKOH / g or more is more preferable, and 40 mgKOH / g or more is more preferable, 60 mgKOH / g or more is more preferable, 80 mgKOH / g or more is particularly preferable, and 200 mgKOH / g or less is preferable, 180 mgKOH / g or less is more preferable, 150 mgKOH / g or less g or less is more preferable, 130 mgKOH / g or less is more preferable, and 120 mgKOH / g or less is particularly preferable. When it is more than the said lower limit, there exists a tendency for the developability of an unexposed part to be good, and when it is below the said upper limit, there exists a tendency which can suppress film reduction etc. As the combination of the upper limit and the lower limit, 10 to 200 mgKOH / g is preferable, 20 to 180 mgKOH / g is more preferable, 40 to 150 mgKOH / g is more preferable, and 60 to 130 mgKOH / g It is more preferable than this, and 80-120 mgKOH / g is especially 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, even more preferably 4000 or more, particularly preferably Preferably it is 5000 or more, and it is 30000 or less normally, Preferably it is 20000 or less, More preferably, it is 15000 or less, More preferably, it is 10000 or less, Especially preferably, it is 8000 or less. When it is more than the said lower limit, there exists a tendency which can suppress film reduction etc., and when it is below the said upper limit, there exists a tendency for the developability of an unexposed part to improve. As a combination of an upper limit and a lower limit, 1000-30000 is preferable, 2000-20000 is more preferable, 3000-15000 is more preferable, 4000-10000 is more preferable, and 5000-8000 is particularly preferable.

(C1) Epoxy (meth) acrylate resin can be synthesized by a conventionally known method. Specifically, the epoxy resin is dissolved in an organic solvent, and an acid or ester compound having the ethylenically unsaturated bond is added to react with it in the presence of a catalyst and a thermal polymerization inhibitor, and polybasic acid or anhydride thereof is added thereto. A method of continuing the reaction can be used.

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

Moreover, as an acid or ester compound which has an ethylenically unsaturated bond, it can be set as the amount which becomes 0.7-1.3 chemical equivalent normally, Preferably 0.9-1.1 chemical equivalent with respect to 1 chemical equivalent of the epoxy group of an epoxy resin. Moreover, as a temperature at the time of addition reaction, it can be set to the temperature of 60-150 degreeC normally, Preferably it is 80-120 degreeC. In addition, the amount of polybasic acid (anhydride) used may be 0.1 to 1.2 chemical equivalents, preferably 0.2 to 1.1 chemical equivalents, relative to 1 chemical equivalent of the hydroxyl group produced by the addition reaction.

The chemical structure of the (C1) epoxy (meth) acrylate resin is not particularly limited, but from the viewpoint of reducing outgas, an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and / or It is preferable to contain the epoxy (meth) acrylate resin which has a partial structure represented by general formula (III). Since the epoxy (meth) acrylate resin is highly sensitive, it has good patterning performance, has a small number of skeletons, and has a mild dissolution rate, so that substrate adhesion is good. In addition, unlike an acrylic resin, it has a rigid skeleton, and it is thought that it is possible to suppress the generation of outgas because it takes an arrangement structure during curing and is densely crosslinked.

In particular, the epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and / or the epoxy (meth) acrylate resin having a partial structure represented by the following general formula (III) has a volume in the central portion. Since it has a large and rigid skeleton, hydrophilic sites such as a (meth) acryloyl group are formed to develop outward, and developability is considered to be improved.

[Formula 19]

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 also be substituted with an arbitrary substituent;

* Represents a bonding hand.

[Formula 20]

In formula (III), R ¹³ each 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 bonding hand.

[(C1-1) Epoxy (meth) acrylate resin]

Next, the 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. .

[Formula 21]

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 also be substituted with an arbitrary substituent;

* Represents a bonding hand.

(R ¹² )

In the 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 connected.

Examples of the divalent aliphatic group include linear, branched, and cyclic ones. Among these, a straight-chain type is preferable from the viewpoint of developing solubility, while a cyclic type is preferred from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, 3 or more is preferable, 6 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is still more preferable. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved. As a combination of an upper limit and a lower limit, 1-20 are preferable, 3-15 are more preferable, and 6-10 are more preferable.

As a specific example of a bivalent linear aliphatic group, a methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, etc. are mentioned. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.

As a specific example of a bivalent branched-chain aliphatic group, iso-propyl group, sec-butyl group, tert-butyl group, iso-amyl group, etc. are mentioned.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but usually 1 or more and 2 or more are preferable, and usually 12 or less and 10 or less are preferable. By setting it as more than the said lower limit, it becomes a strong film, and there exists a tendency for the board | substrate adhesiveness to become favorable, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and there exists a tendency for resolution to improve. As a specific example of a bivalent cyclic aliphatic group, a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecan ring, a norbornane ring, an isobornane ring, a tricyclodecane ring, an adamantane ring, And a group in which two hydrogen atoms are removed from a ring such as a cyclododecane ring or dicyclopentadiene. Among these, from the viewpoint of the rigidity of the skeleton, a group in which two hydrogen atoms are removed from a tricyclodecane ring or an adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. Among these, it is preferable that it is unsubstituted from a viewpoint of ease of synthesis.

Moreover, a bivalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, furthermore preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring may be either a monocyclic ring or a condensed ring. As the divalent aromatic hydrocarbon ring group, for example, a benzene ring, a naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences , Triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and other groups.

Moreover, as an aromatic heterocyclic ring in a divalent aromatic heterocyclic group, a monocyclic ring or a condensed ring may be sufficient as it. Divalent aromatic heterocyclic groups include, for example, furan rings, benzofuran rings, thiophene rings, benzothiophen rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings having two free valences. , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoox Sazol ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, synnoline ring, quinoxaline ring, phenanthridine And groups such as rings, benzoimidazole rings, perimidine rings, quinazolin rings, quinazolinone rings, and azulene rings.

Among these, from the viewpoint of the 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 that the divalent aromatic ring group may have include a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, and a glycidyl ether group. Among these, unsubstituted is preferable from the viewpoint of developing solubility and moisture resistance.

Moreover, as a group which connected the 1 or more bivalent aliphatic group and the 1 or more bivalent aromatic ring group, the group which connected 1 or more of the above-mentioned divalent aliphatic groups and 1 or more of the above-mentioned divalent aromatic ring groups is mentioned.

The number of divalent aliphatic groups is not particularly limited, but usually 1 or more and 2 or more are preferable, and usually 10 or less and 5 or less are preferable, and 3 or less is more preferable. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved.

The number of divalent aromatic ring groups is not particularly limited, but usually 1 or more and 2 or more are preferable, and usually 10 or less and 5 or less are preferable, and 3 or less are more preferable. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved.

Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are connected include groups represented by the following formulas (II-A) to (II-F). Among these, the group represented by the following formula (II-A) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the film. * In the formula represents a bonding hand.

[Formula 22]

As described above, the benzene ring in formula (II) may be further substituted with an arbitrary substituent. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group and propoxy group. The number of substituents is not particularly limited, and may be one or two or more.

Among these, it is preferable to be unsubstituted from a viewpoint of a patterning characteristic.

Moreover, it is preferable that the repeating unit structure represented by said formula (II) is a repeating unit structure represented by following formula (II-1) from a viewpoint of synthetic simplicity.

[Formula 23]

In Formula (II-1), R ¹¹ and R ¹² have the same meanings as in Formula (II) above;

R ^X represents a hydrogen atom or a polybasic acid residue;

* Represents a bonding hand;

The benzene ring in formula (II-1) may also be substituted with an arbitrary substituent.

The polybasic acid residue means a monovalent group in which one OH group is removed from a polybasic acid or anhydride thereof. Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid and chlorendic acid. And 1 or 2 or more types selected from acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

Among these, from the viewpoint of the patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, more preferably , Tetrahydrophthalic acid, 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, for example, R ^X is hydrogen Atoms and R ^X may be mixed with polybasic acid residues.

Moreover, the number of repeating unit structures 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 it to more than the said lower limit, a firm film tends to be obtained and surface roughness tends to hardly occur, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and the tendency to improve resolution There is this.

(C1-1) The weight average molecular weight (Mw) of polystyrene conversion 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 Preferably, 2000 or more are more preferable, 3000 or more are particularly preferable, 30000 or less are preferable, 20000 or less are more preferable, 10000 or less are more preferable, and 8000 or less are particularly preferable. By setting it as more than the said lower limit, there exists a tendency for the residual film rate of a coloring photosensitive resin composition to become favorable, and when it is below the said upper limit, resolution tends to become favorable. As a combination of an upper limit and a lower limit, 1000-30000 is preferable, 1500-20000 is more preferable, 2000-10000 is more preferable, and 3000-8000 are particularly preferable.

(C1-1) Although the acid value of the epoxy (meth) acrylate resin is not particularly limited, 10 mgKOH / g or more is preferable, 20 mgKOH / g or more is more preferable, and 40 mgKOH / g or more is more It is preferable, 50 mgKOH / g or more is more preferable, 80 mgKOH / g or more is particularly preferable, and 200 mgKOH / g or less is preferable, 150 mgKOH / g or less is more preferable, 130 MGKOH / g or less is more preferable, and 100 mgKOH / g or less is particularly preferable. By setting it as more than the said lower limit, there exists a tendency for the developing solubility to improve, and resolution tends to become favorable, and when it is below the said upper limit, the residual film rate of a coloring photosensitive resin composition tends to become favorable. As the combination of the upper limit and the lower limit, 10 to 200 mgKOH / g is preferable, 20 to 150 mgKOH / g is more preferable, 40 to 130 mgKOH / g is more preferable, and 50 to 100 mgKOH / g More preferably, 80-100 mgKOH / g is particularly preferable.

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

[Formula 24]

[Formula 25]

[Formula 26]

[Formula 27]

 [(C1-2) Epoxy (meth) acrylate resin]

Next, the epoxy (meth) acrylate resin (hereinafter abbreviated as "(C1-2) epoxy (meth) acrylate resin") having a partial structure represented by the general formula (III) will be described in detail.

[Formula 28]

In formula (III), R ¹³ each 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 bonding hand.

(R ¹⁴ )

In the general formula (III), R ¹⁴ represents a divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain.

As a cyclic hydrocarbon group, an aliphatic cyclic group or an aromatic cyclic group is mentioned.

Although the number of rings which an aliphatic cyclic group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, and normally 10 or less and 5 or less are preferable, and 3 or less are more preferable. By setting it to more than the said lower limit, a firm film tends to be obtained and surface roughness tends to hardly occur, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and the tendency to improve resolution There is this. As a combination of an upper limit and a lower limit, 1-10 are preferable, 2-5 are more preferable, and 2-3 are more preferable.

Moreover, the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and more preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less, 15 The following are particularly preferred. By setting it to more than the said lower limit, a firm film tends to be obtained and surface roughness tends to hardly occur, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and the tendency to improve resolution There is this. As a combination of an upper limit and a lower limit, 4-40 are preferable, 6-30 are more preferable, 8-20 are more preferable, and 8-15 are especially preferable.

Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecan ring, norbornane ring, isobornane ring, adamantane ring, cyclododecan ring, and the like. Can be lifted. Among these, the adamantane ring is preferable from the viewpoint of the residual film rate and resolution of the colored photosensitive resin composition.

On the other hand, the number of aromatic ring groups is not particularly limited, but is usually 1 or more, 2 or more is preferable, 3 or more is more preferable, and usually 10 or less, 5 or less is preferable, and 4 or less is more desirable. By setting it to more than the said lower limit, a firm film tends to be obtained and surface roughness tends to hardly occur, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and the tendency to improve resolution There is this. As a combination of an upper limit and a lower limit, 1-10 are preferable, 2-5 are more preferable, and 3-4 are more preferable.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Moreover, carbon number of an aromatic ring group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 10 or more are more preferable, 12 or more are especially preferable, and 40 or less are preferable, 30 or less is more preferable, 20 or less is more preferable, and 15 or less is particularly preferable. When it is more than the above-mentioned lower limit, a firm film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when it is equal to or less than the above-mentioned upper limit, patterning characteristics tend to be improved. As a combination of an upper limit and a lower limit, 4-40 are preferable, 6-30 are more preferable, 8-20 are more preferable, 10-15 are more preferable, and 12-15 are especially preferable. .

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, And an acenaphthene ring, a fluoranthene ring, and a fluorene ring. Among these, a fluorene ring is preferred from the viewpoint of patterning properties.

Moreover, in the bivalent hydrocarbon group which has a cyclic hydrocarbon group as a side chain, a bivalent hydrocarbon group is not specifically limited, For example, a bivalent aliphatic group, a bivalent aromatic ring group, 1 or more divalent aliphatic groups, and 1 or more 2 The group which connected the valent aromatic ring group is mentioned.

Examples of the divalent aliphatic group include linear, branched, and cyclic ones. Among these, a straight-chain type is preferable from the viewpoint of developing solubility, while a cyclic type is preferred from the viewpoint of reducing the penetration of the developer into the exposed portion. The number of carbon atoms is usually 1 or more, preferably 3 or more, more preferably 6 or more, furthermore preferably 25 or less, more preferably 20 or less, and even more preferably 15 or less. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved.

As a specific example of a bivalent linear aliphatic group, a methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, etc. are mentioned. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.

As a specific example of a bivalent branched-chain aliphatic group, the above-mentioned divalent straight-chain aliphatic group, as a side chain, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, and structures having a sec-butyl group, tert-butyl group, and the like.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but usually 1 or more and 2 or more are preferable, and usually 10 or less, 5 or less, and more preferably 3 or less. By setting it as more than the said lower limit, it becomes a strong film, and there exists a tendency for the board | substrate adhesiveness to become favorable, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and there exists a tendency for resolution to improve. As a specific example of a bivalent cyclic aliphatic group, cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecan ring, norbornane ring, isobornane ring, adamantane ring, cyclododecan ring, etc. And a group in which two hydrogen atoms have been removed from the ring. Among these, from the viewpoint of the rigidity of the skeleton, a group in which two hydrogen atoms are removed from the adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. Among these, it is preferable that it is unsubstituted from a viewpoint of ease of synthesis.

Moreover, a bivalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group are mentioned as a bivalent aromatic ring group. The carbon number is usually 4 or more, 5 or more is preferable, 6 or more is more preferable, 30 or less is preferable, 20 or less is more preferable, and 15 or less is still more preferable. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring may be either a monocyclic ring or a condensed ring. As the divalent aromatic hydrocarbon ring group, for example, a benzene ring, a naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring having two free valences , Triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and other groups.

Moreover, as an aromatic heterocyclic ring in a divalent aromatic heterocyclic group, a monocyclic ring or a condensed ring may be sufficient as it. Divalent aromatic heterocyclic groups include, for example, furan rings, benzofuran rings, thiophene rings, benzothiophen rings, pyrrole rings, pyrazole rings, imidazole rings, oxadiazole rings having two free valences. , Indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoox Sazol ring, benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, synnoline ring, quinoxaline ring, phenanthridine And groups such as rings, benzoimidazole rings, perimidine rings, quinazolin rings, quinazolinone rings, and azulene rings. 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.

As a substituent which the bivalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, a propoxy group, etc. are mentioned. Among them, unsubstituted is preferable from the viewpoint of developing solubility.

Moreover, as a group which connected the 1 or more bivalent aliphatic group and the 1 or more bivalent aromatic ring group, the group which connected 1 or more of the above-mentioned divalent aliphatic groups and 1 or more of the above-mentioned divalent aromatic ring groups is mentioned.

The number of divalent aliphatic groups is not particularly limited, but usually 1 or more and 2 or more are preferable, and usually 10 or less and 5 or less are preferable, and 3 or less is more preferable. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved.

The number of divalent aromatic ring groups is not particularly limited, but usually 1 or more and 2 or more are preferable, and usually 10 or less and 5 or less are preferable, and 3 or less are more preferable. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved.

As a specific example of the group which connected the 1 or more bivalent aliphatic group and the 1 or more divalent aromatic ring group, group represented by said Formula (II-A)-(II-F) etc. are 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 hydrophobicity of the film.

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

(R ¹⁵ , R ¹⁶ )

In the general formula (III), R ¹⁵ and R ¹⁶ each independently represent a divalent aliphatic group which may have a substituent.

Examples of the divalent aliphatic group include linear, branched, and cyclic ones. Among these, a straight-chain type is preferable from the viewpoint of developing solubility, while a cyclic type is preferred from the viewpoint of reducing the penetration of the developer into the exposed portion. The carbon number is usually 1 or more, 3 or more is preferable, 6 or more is more preferable, 20 or less is preferable, 15 or less is more preferable, and 10 or less is still more preferable. By setting it to more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and adhesiveness with respect to a board | substrate tends to become favorable, and when it is below the said upper limit, it is easy to suppress the surface smoothness and deterioration of sensitivity of a film, Resolution tends to be improved.

As a specific example of a bivalent linear aliphatic group, a methylene group, ethylene group, n-propylene group, n-butylene group, n-hexylene group, n-heptylene group, etc. are mentioned. Among these, a methylene group is preferable from the viewpoint of the rigidity of the skeleton.

As a specific example of a bivalent branched-chain aliphatic group, the above-mentioned divalent straight-chain aliphatic group, as a side chain, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, and structures having a sec-butyl group, tert-butyl group, and the like.

The number of rings of the bivalent cyclic aliphatic group is not particularly limited, but usually 1 or more and 2 or more are preferable, and usually 12 or less and 10 or less are preferable. By setting it as more than the said lower limit, it becomes a strong film, and there exists a tendency for the board | substrate adhesiveness to become favorable, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and there exists a tendency for resolution to improve. Specific examples of the divalent cyclic aliphatic group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecan ring, norbornane ring, isobornane ring, adamantane ring, cyclododecan ring, And groups in which two hydrogen atoms have been removed from rings such as dicyclopentadiene. Among these, from the viewpoint of the rigidity of the skeleton, a group in which two hydrogen atoms are removed from a dicyclopentadiene ring or an adamantane ring is preferable.

Examples of the substituent which the divalent aliphatic group may have include an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. Among these, it is preferable that it is unsubstituted from a viewpoint of ease of synthesis.

(m, n)

In the general formula (III), m and n each independently represent an integer of 0 to 2. Patterning titration becomes favorable by making it more than the said lower limit, and surface roughness tends to become less likely to occur, and developability tends to become favorable by making it below this upper limit. It is preferable that m and n are 0 from a viewpoint of developability, while it is preferable that m and n are each independently 1 or more from a viewpoint of patterning titration and surface roughness.

Moreover, it is preferable that the partial structure represented by said general formula (III) is a partial structure represented by the following general formula (III-1) from a viewpoint of adhesiveness to a board | substrate.

[Formula 29]

In formula (III-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in formula (III) above;

R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent;

p is an integer greater than or equal to 1;

The benzene ring in formula (III-1) may also be substituted with an arbitrary substituent;

* Represents a bonding hand.

(R ^α )

In the general formula (III-1), R ^α represents a monovalent cyclic hydrocarbon group.

As a cyclic hydrocarbon group, an aliphatic cyclic group or an aromatic cyclic group is mentioned.

Although the number of rings which an aliphatic cyclic group has is not specifically limited, Usually 1 or more and 2 or more are preferable, and 6 or less and 4 or less are preferable normally, and 3 or less are more preferable. When it is more than the above-mentioned lower limit, a firm film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when it is equal to or less than the above-mentioned upper limit, patterning characteristics tend to be improved. As a combination of an upper limit and a lower limit, 1-6 are preferable, 2-4 are more preferable, and 2-3 are more preferable.

Moreover, the number of carbon atoms of the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and more preferably 40 or less, more preferably 30 or less, and even more preferably 20 or less, 15 The following are particularly preferred. When it is more than the above-mentioned lower limit, a firm film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when it is equal to or less than the above-mentioned upper limit, patterning characteristics tend to be improved. As a combination of an upper limit and a lower limit, 4-40 are preferable, 6-30 are more preferable, 8-20 are more preferable, and 8-15 are especially preferable.

Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecan ring, norbornane ring, isobornane ring, adamantane ring, cyclododecan ring, and the like. Can be lifted. Among these, adamantane rings are preferred from the viewpoint of strong membrane properties.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but usually 1 or more, 2 or more are preferable, 3 or more are more preferable, and usually 10 or less and 5 or less are preferable. When it is more than the above-mentioned lower limit, a firm film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when it is equal to or less than the above-mentioned upper limit, patterning characteristics tend to be improved. As a combination of an upper limit and a lower limit, 1-10 are preferable, 2-5 are more preferable, and 3-5 are more preferable.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Moreover, carbon number of an aromatic ring group is 4 or more normally, 5 or more are preferable, 6 or more are more preferable, 30 or less are preferable, 20 or less are more preferable, and 15 or less are still more preferable. When it is more than the above-mentioned lower limit, a firm film tends to be easily obtained, and surface roughness tends to be less likely to occur, and when it is equal to or less than the above-mentioned upper limit, patterning characteristics tend to be improved. As a combination of an upper limit and a lower limit, 4-30 are preferable, 5-20 are more preferable, and 6-15 are more preferable.

A benzene ring, a naphthalene ring, anthracene ring, a phenanthrene ring, a fluorene ring etc. are mentioned as a specific example of an aromatic ring in an aromatic ring group. Among these, from the viewpoint of developing solubility, a fluorene ring is preferable.

As a substituent which the cyclic hydrocarbon group may have, hydroxyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, iso-ah And an alkyl group having 1 to 5 carbon atoms such as a push group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. Among these, unsubstituted is preferable from the viewpoint of the ease of synthesis.

p represents an integer of 1 or more, but 2 or more is preferable, and 3 or less is preferable. When it is more than the said lower limit, there exists a tendency for a film hardening degree and a residual film rate to become favorable, and when it is below the said upper limit, developability tends to become favorable. As a combination of an upper limit and a lower limit, 1-3 are preferable, and 2-3 are more preferable.

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

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

Among these, it is preferable to be unsubstituted from a viewpoint of a patterning characteristic.

Below, the specific example of the partial structure represented by said Formula (III-1) is given.

[Formula 30]

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

Moreover, it is preferable that the partial structure represented by said general formula (III) is a partial structure represented by the following general formula (III-2) from a viewpoint of rigidity of a skeleton and membrane hydrophobicity.

[Formula 35]

In formula (III-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in formula (III) above;

R ^β represents a divalent cyclic hydrocarbon group which may have a substituent;

The benzene ring in formula (III-2) may also be substituted with an arbitrary substituent;

* Represents a bonding hand.

(R ^β )

In the formula (III-2), R ^β represents a divalent cyclic hydrocarbon group.

As a cyclic hydrocarbon group, an aliphatic cyclic group or an aromatic cyclic group is mentioned.

Although the number of rings which an aliphatic ring group has is not specifically limited, Usually, 1 or more and 2 or more are preferable, and normally 10 or less and 5 or less are preferable. By setting it to more than the said lower limit, a firm film tends to be obtained and surface roughness tends to hardly occur, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and the tendency to improve resolution There is this. As a combination of an upper limit and a lower limit, 1-10 are preferable, and 2-5 are more preferable.

Moreover, carbon number of an aliphatic ring group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 40 or less are preferable, 35 or less are more preferable, and 30 or less are still more preferable. When it is more than the said lower limit, there exists a tendency to suppress the film roughness at the time of image development, and when it is less than the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and there exists a tendency for resolution to improve. As a combination of an upper limit and a lower limit, 4-40 are preferable, 6-35 are more preferable, and 8-30 are still more preferable.

Specific examples of the aliphatic ring in the aliphatic ring group include cyclohexane ring, cycloheptane ring, cyclodecane ring, cyclododecan ring, norbornane ring, isobornane ring, adamantane ring, cyclododecan ring, etc. Can be mentioned. Among these, an adamantane ring is preferred from the viewpoint of storage stability.

On the other hand, the number of rings of the aromatic ring group is not particularly limited, but usually 1 or more, 2 or more are preferable, 3 or more are more preferable, and usually 10 or less and 5 or less are preferable. By setting it to more than the said lower limit, a firm film tends to be obtained and surface roughness tends to hardly occur, and when it is below the said upper limit, it is easy to suppress the deterioration of surface smoothness and sensitivity of a film, and the tendency to improve resolution There is this. As a combination of an upper limit and a lower limit, 1-10 are preferable, 2-5 are more preferable, and 3-5 are more preferable.

Examples of the aromatic ring group include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. Moreover, the carbon number of an aromatic ring group is 4 or more normally, 6 or more are preferable, 8 or more are more preferable, 10 or more are more preferable, 40 or less are preferable, 30 or less are more preferable, 20 The following are more preferable, and 15 or less are particularly preferable. By setting it above the said lower limit, a firm film tends to be obtained, and surface roughness tends to be less likely to occur, and when it is below the upper limit, it is easy to suppress deterioration of surface smoothness and sensitivity of the film, and tends to improve resolution There is this. As a combination of an upper limit and a lower limit, 4-40 are preferable, 6-30 are more preferable, 8-20 are more preferable, and 10-15 are especially preferable.

A benzene ring, a naphthalene ring, anthracene ring, a phenanthrene ring, a fluorene ring etc. are mentioned as a specific example of an aromatic ring in an aromatic ring group. Among these, from the viewpoint of developability, a fluorene ring is preferable.

As a substituent which the cyclic hydrocarbon group may have, hydroxyl group, methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, sec-butyl group, tert-butyl group, amyl group, iso-ah And an alkyl group having 1 to 5 carbon atoms such as a push group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group and an ethoxy group; a hydroxyl group; a nitro group; a cyano group; and a carboxyl group. Among these, unsubstituted is preferable from the viewpoint of the simplicity of synthesis.

Among these, from the viewpoint of storage stability and electrical properties, it is preferable that R ^β is a divalent aliphatic ring group, and more preferably a divalent adamantane ring group.

On the other hand, from the viewpoint of low hygroscopicity and patterning characteristics of the coating film, R ^β is preferably a divalent aromatic ring group, and more preferably a divalent fluorene ring group.

As described above, the benzene ring in formula (III-2) may also be substituted with an arbitrary substituent. Examples of the substituent include hydroxyl group, methyl group, methoxy group, ethyl group, ethoxy group, propyl group and propoxy group. The number of substituents is not particularly limited, and may be one or two or more. Moreover, two benzene rings in Formula (III-2) may be connected through these substituents.

Among these, it is preferable to be unsubstituted from a viewpoint of a patterning characteristic. Moreover, it is preferable that it is a methyl group substitution from a viewpoint which does not produce reduction etc. easily.

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

[Formula 36]

[Formula 37]

[Formula 38]

[Formula 39]

On the other hand, the partial structure represented by the formula (III) is preferably a partial structure represented by the following formula (III-3) from the viewpoint of the coating film residual rate and patterning characteristics.

[Formula 40]

In formula (III-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n have the same meanings as in formula (III) above;

R ^Z represents a hydrogen atom or a polybasic acid residue.

The polybasic acid residue means a monovalent group in which one OH group is removed from a polybasic acid or anhydride thereof. Further, another OH group is further removed, and may be shared with R ^Z in other molecules represented by formula (III-3), i.e., plural formulas (III-3) are connected via R ^Z It may be.

Examples of polybasic acids include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, methylhexahydrophthalic acid, endomethylenetetrahydrophthalic acid and chlorendic acid. And 1 or 2 or more types selected from acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid.

Among these, from the viewpoint of the patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, more preferably , Tetrahydrophthalic acid, biphenyltetracarboxylic acid.

(C1-2) The partial structure represented by the said Formula (III-3) contained in 1 molecule of an epoxy (meth) acrylate resin may be 1 type, or 2 or more types, for example, R ^Z is a hydrogen atom And those of R ^Z having polybasic acid residues may be mixed.

Moreover, although the number of partial structures represented by said Formula (III) contained in one molecule of (C1-2) epoxy (meth) acrylate resin is not specifically limited, 1 or more are preferable and 3 or more are more preferable, Moreover, 20 or less is preferable, 15 or less is more preferable, and 10 or less is still more preferable. By setting it as more than the said lower limit, a firm film is easy to be obtained, surface roughness does not arise easily, and electrical properties tend to become favorable, and when it is below the said upper limit, it is easy to suppress the deterioration of the surface smoothness and sensitivity of a film, and resolution. This tends to improve.

(C1-2) The weight average molecular weight (Mw) of polystyrene conversion of the 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 It is preferable, 3000 or more are more preferable, 3500 or more are particularly preferable, 30000 or less are preferable, 20000 or less are more preferable, 10000 or less are more preferable, 7000 or less are more preferable, 5000 or less Especially preferred. When it is more than the said lower limit, there exists a tendency for a patterning characteristic to become favorable, and when it is less than the said upper limit, a strong film tends to be obtained and surface roughness tends to become less likely to occur. The combination of the upper limit and the lower limit is preferably 1000 to 30000, more preferably 2000 to 20000, more preferably 3000 to 10000, still more preferably 3500 to 7000, and particularly preferably 3500 to 5000. .

(C1-2) Although the acid value of the epoxy (meth) acrylate resin is not particularly limited, 10 mgKOH / g or more is preferable, 20 mgKOH / g or more is more preferable, and 40 mgKOH / g or more is more preferable. And more preferably 60 mgKOH / g or more, particularly preferably 80 mgKOH / g or more, further preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and 120 mg or less KOH / g or less is more preferable. By setting it as more than the said lower limit, there exists a tendency for a firm film to be easy to be obtained, and when it is less than the said upper limit, the developing solubility improves and there exists a tendency for resolution to become favorable. As a combination of an upper limit and a lower limit, 10 to 200 mgKOH / g is preferable, 20 to 150 mgKOH / g is more preferable, 40 to 150 mgKOH / g is more preferable, and 60 to 120 mgKOH / g It is more preferable than this, and 80-120 mgKOH / g is especially preferable.

The (C) binder resin contained in the coloring photosensitive resin composition of this invention and a pigment dispersion liquid is abbreviated as (C1) binder resin other than an epoxy (meth) acrylate resin (hereinafter "(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, novolak-based resins, and polyvinylphenol-based resins. You may use a mixture of multiple types.

In the coloring photosensitive resin composition of this invention, (C) binder resin contains (C1) epoxy (meth) acrylate resin 75 mass% or more. It is considered that by including (C1) an epoxy (meth) acrylate resin in the binder resin (C) 75% by mass or more, the heat resistance of the cured product is also improved, and the amount of outgas generated after formation of the cured product can be reduced.

The content ratio of (C1) epoxy (meth) acrylate resin to (C) binder resin is not particularly limited as long as it is 75% by mass or more, preferably 80% by weight or more, more preferably 85% by weight or more, and 90% by weight % Or more is more preferable, and 95 mass% or more is particularly preferable. Moreover, it is 100 mass% or less normally. When it is more than the said lower limit, outgas tends to be suppressed. As a combination of an upper limit and a lower limit, 75-100 mass% is preferable, 80-100 mass% is more preferable, 85-100 mass% is more preferable, 90-100 mass% is more preferable, and 95- 100 mass% is especially preferable.

[1-4] (D) Photopolymerizable monomer

The coloring photosensitive resin composition of this invention contains (D) photopolymerizable monomer. (D) By including a photopolymerizable monomer, sensitivity is improved.

The photopolymerizable monomer (D) used in the present invention is a compound having at least one ethylenically unsaturated group in a molecule. Specifically, examples thereof include (meth) acrylic acid, (meth) acrylic acid alkyl esters, acrylonitrile, styrene, and esters of carboxylic acids having one ethylenically unsaturated bond and polyhydric or monohydric alcohols, and the like. have.

In the present invention, it is particularly preferable to use a polyfunctional ethylenic monomer having two or more ethylenically unsaturated groups in one molecule. The number of ethylenically unsaturated groups of 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 8 It is the following, More preferably, it is seven or less. When it is more than the said lower limit, it tends to become high sensitivity, and when it is below the said upper limit, solubility in a solvent tends to improve. As a combination of an upper limit and a lower limit, 2-8 pieces are preferable, 4-8 pieces are more preferable, and 5-7 pieces 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 polyhydroxy compounds, etc. The ester etc. which are obtained by the esterification reaction of polyhydric hydroxy compound, and unsaturated carboxylic acid and polybasic carboxylic acid are mentioned.

As the ester of the aliphatic polyhydroxy compound and the unsaturated carboxylic acid, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, Acrylic acid of aliphatic polyhydroxy compounds such as pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Esters, methacrylic acid esters with acrylates of these exemplary compounds replaced with methacrylates, itaconic acid esters with itaconate, crotonic acid esters with chronate or maleic acid esters with maleate Field There.

As an ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid, aromatic poly, such as hydroquinone diacrylate, hydroquinone dimethacrylate, resorcin diacrylate, resorcin dimethacrylate, pyrogallol triacrylate, etc. And acrylic acid esters and methacrylic acid esters of hydroxy compounds.

The ester obtained by the esterification reaction of polybasic carboxylic acid and unsaturated carboxylic acid with a polyvalent hydroxy compound is not necessarily a single product, but typical examples include condensates of acrylic acid, phthalic acid, and ethylene glycol, acrylic acid, And condensates of maleic acid and diethylene glycol, condensates of methacrylic acid, terephthalic acid and pentaerythritol, condensates of acrylic acid, adipic acid, butanediol and glycerin.

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

As the urethane (meth) acrylates, for example, DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Gunpowder Co., Ltd.), U-2PPA, U-6LPA , U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Industries Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisa Chemical Ltd.), UV-1700B , UV-7600B, UV-7605B, UV-7630B, UV7640B (manufactured by Nippon Synthetic Chemical Industries, Ltd.) and the like.

Among these, it is preferable to use (meth) acrylic-acid alkylester as (D) photopolymerizable monomer from a viewpoint of curability, and it is more preferable to use dipentaerythritol hexaacrylate.

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

 [1-5] (E) Photopolymerization initiator

The colored photosensitive resin composition of this invention contains (E) photoinitiator. (E) The photopolymerization initiator is a component having a function of absorbing light directly, causing a decomposition reaction or a hydrogen drawing reaction, and generating a polymerization active radical. If necessary, an additive such as a polymerization accelerator (chain transfer agent) or a sensitizing dye may be added and used.

Examples of the photopolymerization initiator include a metallocene compound containing the titanocene compound described in JP-A-59-152396 and JP-A-61-151197; JP 2000-2000; Hexaaryl biimidazole derivatives described in 56118; N-aryl-α-amino acids such as halomethylated oxadiazole derivatives, halomethyl-s-triazine derivatives, and N-phenylglycine described in Japanese Patent Application Laid-open No. Hei 10-39503 Radical activators such as compounds, N-aryl-α-amino acid salts, and N-aryl-α-amino acid esters, α-aminoalkylphenone derivatives; Japanese Laid-Open Patent Publication No. 2000-80068, Japanese Laid-Open Patent Publication No. 2006-36750, etc. And oxime ester derivatives described.

Specifically, for example, as the titanocene derivatives, dicyclopentadienyl titanium dichloride, dicyclopentadienyl titanium bisphenyl, dicyclopentadienyl titanium bis (2,3,4,5,6) -Pentafluorophen-1--1-yl), dicyclopentadienyltitanium bis (2,3,5,6-tetrafluoropheny-1-yl), dicyclopentadienyltitanium bis (2,4,6) -Trifluoropheny-1-yl), dicyclopentadienyltitanium di (2,6-difluoropheny-1-yl), dicyclopentadienyltitanium di (2,4-difluoropheny- 1-yl), di (methylcyclopentadienyl) titanium bis (2,3,4,5,6-pentafluoropheny-1-yl), di (methylcyclopentadienyl) titanium bis (2,6) -Difluorophen-1--1-yl), dicyclopentadienyl titanium [2,6-di-fluoro-3- (pyro-1-yl) -phen-1--1-yl], and the like.

Moreover, as the 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-diphenyl Imidazole dimer, (4'-methoxyphenyl) -4,5-diphenylimidazole dimer, and the like.

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

Moreover, as the halomethyl-s-triazine derivatives, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-e And methoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine.

Moreover, 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-dimethylaminoethylbenzoate, 4-dimethylamino Isoamylbenzoate, 4-diethylamino acetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexa Paddy, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, and the like.

As a photopolymerization initiator, in particular, oxime ester derivatives (oxime ester-based compounds and ketooxime ester-based compounds) are effective from the viewpoint of sensitivity and plate making, and when an alkali-soluble resin containing a phenolic hydroxyl group is used, etc. Since it is disadvantageous in terms of sensitivity, oxime ester derivatives (oxime ester-based compounds and ketooxime ester-based compounds) excellent in such sensitivity are particularly useful.

As an oxime ester type compound, the compound containing the partial structure represented by the following general formula (IX) is mentioned, Preferably, the oxime ester type compound represented by the following general formula (IX-A) is mentioned.

[Formula 41]

In Formula (IX), R ²² may be substituted with an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkane oil group having 1 to 20 carbon atoms, an alkenyl oil group having 3 to 25 carbon atoms, or 3 to 8 carbon atoms. Cycloalkane oil group, alkoxycarbonyl alkane oil group having 3 to 20 carbon atoms, phenoxycarbonyl alkane oil group having 8 to 20 carbon atoms, heteroaryloxycarbonyl alkane oil group having 3 to 20 carbon atoms, amino having 2 to 10 carbon atoms It represents an alkylcarbonyl group, an arylloyl 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.

[Formula 42]

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, a heteroaryl alkyl group having 1 to 20 carbon atoms, or 3 to 20 carbon atoms, which may each be substituted. Alkoxycarbonylalkyl group, 8-20 phenoxycarbonylalkyl group, 1-20 carbon atoms heteroaryloxycarbonylalkyl group or heteroarylthioalkyl group, 1-20 carbon atoms aminoalkyl group, 2-12 carbon atoms alkanoyl group , An alkenyl group having 3 to 25 carbon atoms, a cycloalkanoyl group having 3 to 8 carbon atoms, an arylloyl 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, 7 to 7 carbon atoms Represents an aryloxycarbonyl group of 20 or a cycloalkylalkyl group having 1 to 10 carbon atoms;

R ^21b represents any substituent including an aromatic hydrocarbon ring or an aromatic heterocycle (heteroaromatic ring).

In addition, R ^21a may be connected to R ^21b to form a ring, and the linking groups may each have a substituent group having 1 to 10 alkylene groups, polyethylene groups (-(CH = CH) _r- ), polyethynyl And a group formed by combining a ren group (-(C≡C) _r- ) or a combination thereof (where r is an integer from 0 to 3).

In Formula (IX-A), R ^22a may be substituted with an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, an alkenyl oil group having 3 to 25 carbon atoms, or 3 to carbon atoms, respectively. 8 cycloalkane oil group, 3 to 20 carbon atoms alkoxycarbonyl alkane oil group, 8 to 20 carbon atoms phenoxycarbonyl alkane oil group, 3 to 20 carbon atoms heteroaryloxycarbonyl alkane oil group, 2 to 10 carbon atoms Represents an aminocarbonyl group, a C7-20 arylloyl group, a C1-20 heteroaryloyl group, a C2-10 alkoxycarbonyl group, or a C7-20 aryloxycarbonyl group.

As R ^{22 in} the general formula (IX) and R ^22a in the general formula (IX-A), preferably, an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms And a cycloalkanoyl group having 3 to 8 carbon atoms.

As R ^21a in the general formula (IX-A), preferably, an unsubstituted methyl group, ethyl group, propyl group, or a propyl group substituted with an N-acetyl-N-acetoxyamino group.

In addition, the roneun formula R ^21b of the (IX-A), preferably a carbazolyl group that may be substituted, a fluorenyl group which may be optionally substituted, phenyl that may be substituted thio janto group, an optionally substituted alcohol A firefighter is mentioned.

Moreover, as arbitrary substituents in the said general formula (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, And amino groups and amide groups.

Although the compound as illustrated below is mentioned specifically as an oxime ester type compound suitable for this invention, It is not limited to these compounds at all.

[Formula 43]

[Formula 44]

As a ketooxime ester type compound, the compound containing the partial structure represented by the following general formula (X) is mentioned, Preferably, the ketooxime ester type compound represented by the following general formula (X-A) is mentioned.

[Formula 45]

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

[Formula 46]

In the said general formula (XA), R ^23a may be respectively substituted, a phenyl group, a C1-C20 alkyl group, a C2-C25 alkenyl group, a C1-C20 heteroaryl alkyl group, a C3-C20 Alkoxycarbonylalkyl groups, phenoxycarbonylalkyl groups having 8 to 20 carbon atoms, alkylthioalkyl groups having 2 to 20 carbon atoms, heteroaryloxycarbonylalkyl groups having 1 to 20 carbon atoms or heteroarylthioalkyl groups, aminoalkyl groups having 1 to 20 carbon atoms, Alkanoyl group having 2 to 12 carbon atoms, alkene oil group having 3 to 25 carbon atoms, cycloalkanoyl group having 3 to 8 carbon atoms, arylloyl group having 7 to 20 carbon atoms, heteroaryloyl group having 1 to 20 carbon atoms, 2 to 2 carbon atoms An alkoxycarbonyl group of 10, an aryloxycarbonyl group of 7 to 20 carbon atoms, or a cycloalkylalkyl group of 1 to 10 carbon atoms;

R ^23b represents any substituent including an aromatic hydrocarbon ring or an aromatic heterocycle (heteroaromatic ring).

In addition, R ^23a may be connected to R ^23b to form a ring, and the linking group may be an alkylene group having 1 to 10 carbon atoms, a polyethylene group (-(CH = CH) _r- ), or polyethynyl, respectively. And a group formed by combining a ren group (-(C≡C) _r- ) or a combination thereof (where r is an integer from 0 to 3).

In General Formula (XA), R ^24a may be substituted with an alkane oil group having 2 to 12 carbon atoms, an alkenyl oil group having 3 to 25 carbon atoms, a cycloalkane oil group having 4 to 8 carbon atoms, or 7 to 20 carbon atoms. It represents a benzoyl group, a heteroaryloyl group having 3 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a heteroaryl group having 2 to 20 carbon atoms, or an alkylaminocarbonyl group having 2 to 20 carbon atoms. .

As R ²⁴ in the general formula (X) and R ^24a in the general formula (XA), preferably, an alkanoyl group having 2 to 12 carbon atoms, a heteroaryl alkanoyl group having 1 to 20 carbon atoms, or carbon number And 3 to 8 cycloalkanoyl groups and 7 to 20 carbon atoms.

As R ^23a in the general formula (XA), preferably an unsubstituted ethyl group, a propyl group, a butyl group, or an ethyl group substituted with a methoxycarbonyl group or a propyl group.

Moreover, as R ^23b in the said general formula (XA), Preferably, the carbazoyl group which may be substituted, the fluorenyl group which may be substituted, and the phenyl sulfide group which may be substituted are mentioned.

Moreover, as arbitrary substituents in the said general formula (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, And amide groups.

As a ketoxime ester-based compound suitable for the present invention, specifically, the compounds exemplified below can be mentioned, but are not limited to these compounds at all.

[Formula 47]

[Formula 48]

These oxime ester-based compounds and ketooxime ester-based compounds are compounds known per se, and are, for example, a type of a series of compounds described in JP 2000-80068 A or JP 2006-36750 A. to be. From the viewpoint of sensitivity, in the present invention, it is preferable that the photopolymerization initiator (E) is an oxime ester-based compound and / or a ketooxime ester-based compound.

As for the said photoinitiator, 1 type may be used individually and 2 or more types may be used together.

(E) Examples of the photopolymerization initiator include benzoin alkyl ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether; 2-methyl anthraquinone; Anthraquinone derivatives, such as 2-ethyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone; Benzophenone, Mihiler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone , Benzophenone derivatives such as 2-chlorobenzophenone, 4-bromobenzophenone, and 2-carboxybenzophenone; 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1- Hydroxycyclohexylphenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl ) Acetophenone derivatives such as ketone, 2-methyl- (4'-methylthiophenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) ketone Thiothioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, etc. Thioxanthone derivatives; benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate; acrisies such as 9-phenylacridine and 9- (p-methoxyphenyl) acridine Dean derivatives; phenazine derivatives such as 9,10-dimethylbenzphenazine; and anthrone derivatives such as benzanthrone.

Among these photopolymerization initiators, the following compounds, which are compounds containing a partial structure represented by the general formula (IX), among oxime ester derivatives, from the viewpoint of sensitivity, solubility to a solvent, and pattern adhesion during development,

[Formula 49]

[Formula 50]

Or, the following compound which is a compound containing the partial structure represented by said general formula (X) is more preferable.

[Formula 51]

[Formula 52]

[Formula 53]

(E) Photopolymerization initiator may be used individually by 1 type, or may be used in combination of 2 or more type.

(E) As needed, a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source can be blended, for the purpose of increasing the sensitivity of the photosensitive initiator, if necessary. Examples of the sensitizing dye include xanthene dyes described in Japanese Patent Application Laid-Open No. Hei 4-221958, Japanese Patent Laid-Open No. Hei 4-219756, Japanese Patent Laid-Open No. Hei 3-239703, and Japanese Patent Laid-Open No. Hei 5-289335. Coumarin pigment having a heterocyclic ring, Japanese Patent Application Publication No. Hei 3-239703, Japanese Patent Publication No. Hei 5-289335 3-keto coumarin compound, Japanese Patent Application Publication No. Hei 6-19240, pyromethene pigment, In addition, Japanese Patent Publication No. 47-2528, Japanese Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681 , Japanese Patent Application Publication No. 58-15503, Japanese Patent Application Publication No. 60-88005, Japanese Patent Application Publication No. 59-56403, Japanese Patent Application Publication No. 2-69, Japanese Patent Application Publication No. 57-168088 , Japanese Patent Application Publication No. Hei 5-107761, Japanese Patent Application Publication No. 5-210240, Japanese Patent Application Publication And dyes having a dialkylaminobenzene skeleton as described in Hei 4-288818.

Preferred of these sensitizing dyes are amino group-containing sensitizing dyes, and more preferred are compounds having an amino group and a phenyl group in the same molecule. Especially preferred are, for example, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone, 2-aminobenzophenone, 4-aminobenzophenone, 4,4'-diaminobenzo Benzophenone compounds such as phenone, 3,3'-diaminobenzophenone, and 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-diethylaminophenyl) benzothiazole, 2- (p-dimethylaminophenyl) ) Benzimidazole, 2- (p-diethylaminophenyl) benzimidazole, 2,5-bis (p-diethylaminophenyl) -1,3,4-thiadiazole, (p-dimethylaminophenyl) Pyridine, (p-diethylaminophenyl) pyridine, (p-dimethylaminophenyl) quinoline, (p-diethylaminophenyl) quinoline, (p-dimethylaminophenyl) And p-dialkylaminophenyl group-containing compounds such as pyrimidine and (p-diethylaminophenyl) pyrimidine. The most preferable of these is 4,4'-dialkylaminobenzophenone.

The sensitizing dye 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. Is used. One type of polymerization accelerator may be used alone, or two or more types may be used in combination.

[1-6] Other compounding components of the colored photosensitive resin composition

In addition to the components described above, the colored photosensitive resin composition of the present invention can be appropriately blended with an adhesion enhancer such as a silane coupling agent, a coating property improving agent, a developing improver, an ultraviolet absorber, an antioxidant, a surfactant, and a pigment derivative.

[1-6-1] Adhesion enhancer

In order to improve the adhesiveness with a board | substrate, you may contain the adhesion improving agent in the colored photosensitive resin composition of this invention. As an adhesion improver, a silane coupling agent, a phosphoric acid group containing compound, etc. are preferable.

As a kind of silane coupling agent, various things, such as an epoxy type, (meth) acrylic type, and amino type, can be used individually or in mixture of 2 or more types.

As a preferable silane coupling agent, for example, (meth) acryloxysilanes, such as 3-methacryloxypropyl methyl dimethoxysilane and 3-methacryloxypropyl trimethoxysilane, 2- (3,4-epoxycyclo Hexyl) Epoxysilanes such as ethyl trimethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyl diethoxysilane, and 3-glycidoxypropyl triethoxysilane, 3-ureid Ureide silanes such as propyl triethoxysilane and isocyanate silanes such as 3-isocyanate propyl triethoxysilane, and the like, are particularly preferably silane coupling agents of epoxy silanes.

As the phosphoric acid group-containing compound, (meth) acryloyl group-containing phosphates are preferred, and are preferably represented by the following general formulas (XI-A), (XI-B) or (XI-C).

[Formula 54]

In the general formulas (XI-A), (XI-B) and (XI-C), R ⁵¹ represents a hydrogen atom or a methyl group;

l and l 'represent the integer of 1-10;

m represents 1, 2 or 3.

These phosphoric acid group-containing compounds may be used alone or in combination of two or more.

 [1-6-2] Pigment derivatives

In the colored photosensitive resin composition of the present invention, in order to improve dispersibility and preservation, a pigment derivative may be contained as a dispersion aid.

Pigment derivatives include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, perinone-based, diketopyrrolo And derivatives such as pyrrole-based and dioxazine-based, among others, phthalocyanine-based and quinophthalone-based are preferable.

As the substituent of the pigment derivative, sulfonic acid groups, sulfonamide groups and quaternary salts thereof, phthalimidemethyl groups, dialkylaminoalkyl groups, hydroxyl groups, carboxyl groups, amide groups, etc. are directly on the pigment skeleton or alkyl groups, aryl groups, heterocyclic groups, etc. What is bonded through is mentioned, Preferably it is a sulfonic acid group. Moreover, these substituents may be substituted by multiple in one pigment skeleton.

Specific examples of the pigment derivatives 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, sulfonic acid derivatives of dioxazine, and the like. . These may be used individually by 1 type and may use 2 or more types together.

[1-6-3] Light acid generator

The photo acid generator is a compound capable of generating acid by ultraviolet rays, and the crosslinking reaction proceeds by the presence of a crosslinking agent such as a melamine compound, for example, by the action of the acid generated when exposure is performed. Among these photo acid generators, those having a high solubility in a solvent, particularly in a solvent used in a photosensitive coloring composition, are preferred, for example, diphenyl iodonium, ditolyl iodonium, and phenyl (p-anisil). Iodonium, bis (m-nitrophenyl) iodonium, bis (p-tert-butylphenyl) iodonium, bis (p-chlorophenyl) iodonium, bis (n-dodecyl) iodonium, p-isobutylphenyl Diaryl iodonium such as (p-tolyl) iodonium, p-isopropylphenyl (p-tolyl) iodonium, or triarylsulfonium such as triphenylsulfonium chloride, bromide, or boride fluoride, hexafluoro Phosphate salts, hexafluoroarsenate salts, aromatic sulfonic acid salts, tetrakis (pentafluorophenyl) borate salts, sulfonium organic boron complexes such as diphenylphenacylsulfonium (n-butyl) triphenylborate, Or, 2-methyl-4,6-bistrichloromethyltria , 2-triazine and the like compounds, such as (4-methoxyphenyl) methyl-4,6-bis-trichloro-triazine as, but not limited to this.

[1-6-4] Crosslinking agent

A crosslinking agent may also be added to the colored photosensitive resin composition of the present invention, and for example, melamine or guanamin compounds may be used. Examples of these crosslinking agents include melamine or guanamine compounds represented by the following general formula (XII).

[Formula 55]

In formula (XII), R ⁶¹ represents a -NR ⁶⁶ R ⁶⁷ group or an aryl group having 6 to 12 carbon atoms;

When R ⁶¹ is -NR ⁶⁶ R ⁶⁷ group, the ^{R 62, R 63, R 64} , R 65, R 66 and R ⁶⁷ when one, and R ⁶¹ is an aryl group having 6 to 12 it is of the R ^62, R ^63, One of R ⁶⁴ and R ⁶⁵ represents 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 substituents such as an alkyl group, an alkoxy group, and a halogen atom may be bonded to these phenyl groups or naphthyl groups. The alkyl group and the alkoxy group may 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, and more preferably a methyl group.

The melamine-based compounds corresponding to the general formula (XII), that is, the compounds of the following general formula (XII-A) include hexamethylolmelamine, pentamethylolmelamine, tetramethylolmelamine, hexamethoxymethylmelamine, and pentamethoxymethyl Melamine, tetramethoxymethylmelamine, hexaethoxymethylmelamine, and the like.

[Formula 56]

In 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 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.

Moreover, to the guanamine-based compound corresponding to the general formula (XII), that is, the compound in which R ⁶¹ in the general formula (XII) is aryl, tetramethylolbenzoguanamine, tetramethoxymethylbenzoguanamine, and trimethoxymethylbenzo Guanamine, tetraethoxymethylbenzoguanamine, and the like.

Further, a crosslinking agent having a methylol group or a methylol alkyl ether group can also be used. The 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 -1,3,5-triazine-2-one (collectively N-ethyldimethyloltriazone) or its dimethyl ether body, dimethyloltrimethylene urea or its dimethyl ether body, 3,5-bis (hydroxymethyl) Perhydro-1,3,5-oxadiazin-4-one (commonly known as dimethyloluron) or its dimethyl ether body, tetramethylolglyoxaldiurene or its tetramethyl ether body.

Moreover, these crosslinking agents may be used individually by 1 type, or may be used in combination of 2 or more type. The amount when a crosslinking agent is used is preferably 0.1 to 15% by mass, particularly preferably 0.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition.

[1-6-5] Mercapto Compound

As a polymerization accelerator, it is also possible to add a mercapto compound to improve adhesion to a substrate.

As a kind of mercapto compound, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol Bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane tristhioglycolate, butanediol bisthiopropionate, trimethylolpropane tristhiopropionate, trimethylolpropane tristhioglycolate , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyltristhiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediolbis (3-mercaptobutyrate) , 1,4-bis (3-mercaptobutyryloxy) butane, trimethylolpropane tris (3-mercaptobutyrate), pentae Tritoltetrakis (3-mercaptobutyrate), pentaerythritol tris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), trimethyl All propane tris (3-mercaptoisobutyrate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H And a mercapto compound having a heterocycle such as) -trione or an aliphatic polyfunctional mercapto compound. These can be used individually by 1 type or in mixture of 2 or more types.

[1-6-6] Surfactant

The colored photosensitive resin composition of the present invention may contain a surfactant in order to improve the coatability.

As surfactant, various things, such as an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant, can be used, for example. Among them, it is preferable to use a nonionic surfactant from the viewpoint of low possibility of adversely affecting various properties, and among them, a fluorine-based or silicone-based surfactant is effective in terms of applicability.

As these commercial items, for example, "BM-1000", "BM-1100" manufactured by BM Chemie, "MegaPak F-142D" manufactured by DIC, "MegaPak F-172", "MegaPak F-173" "," MegaPak F-183 "," MegaPak F-470 "," MegaPak F-475 "," MegaPak F-478 "," MegaPak F-554 "," MegaPak F-559 ", 3M Japan Corporation "FC430", Neos Corporation "DFX-18", etc. are mentioned.

Moreover, as a silicone surfactant, For example, "DC3PA", "SH7PA", "DC11PA", "SH21PA", "SH28PA", "SH29PA", "8032 Additive", "SH8400" manufactured by Toray Dao Corning Corporation , Commercial products such as "BYK300", "BYK323", "BYK325", "BYK330" manufactured by BICK Chemical, and "KP340" manufactured by Shin-Etsu Silicone.

As the surfactant, other than fluorine-based surfactants and silicone-based surfactants may be included, and other surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. have.

Moreover, surfactant may be used individually by 1 type, and 2 or more types may be used together in arbitrary combinations and ratios. Especially, the combination of a silicone surfactant / fluorine surfactant is preferable. In the combination of this silicone-based surfactant / fluorine-based surfactant, for example, "BYK-300" manufactured by BICKCHEMI Corporation or "BYK-330" / "F-475" "F-478" manufactured by DIC Corporation "F-554" Or "F-559" etc. are mentioned.

 [1-6-7] Liquid repellent

The colored photosensitive resin composition of the present invention may contain a liquid repellent agent. Particularly, when a partition wall is formed using the colored photosensitive resin composition of the present invention and an organic electroluminescent element is formed by an inkjet method, it is preferable to contain a liquid repellent agent. Since the liquid repellent can be imparted to the surface of the partition by containing a liquid repellent, the resulting partition can be prevented from mixing in each pixel of the organic species.

Examples of the liquid repellent include a silicone-containing compound and a fluorine-based compound, and preferably a liquid repellent having a crosslinking group (hereinafter sometimes referred to as "crosslinking group-containing liquid repellent"). An epoxy group or an ethylenically unsaturated group is mentioned as a bridge | crosslinking group, It is an ethylenically unsaturated group from a viewpoint of suppressing the outflow of the liquid repellent component of a developing solution.

In the case of using a crosslinking group-containing liquid repellent agent, when exposing the formed coating film, the crosslinking reaction on its surface can be accelerated, and the repellent agent becomes difficult to flow out by developing treatment, and as a result, the resulting partition walls have high liquid repellency. It seems that it can be done by indicating.

When a fluorine-based compound is used as the liquid repellent, the fluorine-based compound tends to function on the surface of the partition wall and prevent the ink from spreading or mixing. In addition, in detail, a group having a fluorine atom tends to function to prevent ink bleeding and color mixing due to splashing of the ink and ink entering the adjacent region beyond the partition wall.

As a specific example of a crosslinking group-containing liquid repellent agent, especially an ethylenically unsaturated group-containing fluorine-based compound, for example, perfluoroalkylsulfonic acid, perfluoroalkylcarboxylic acid, perfluoroalkylalkylene oxide adduct, perfluoro Alkyl trialkyl ammonium salts, oligomers containing perfluoroalkyl groups and hydrophilic groups, oligomers containing perfluoroalkyl groups and lipophilic groups, oligomers containing perfluoroalkyl groups and hydrophilic groups and hydrophilic groups, urethanes containing perfluoroalkyl and hydrophilic groups , Fluorine-containing organic compounds such as perfluoroalkyl esters and perfluoroalkyl phosphate esters.

As commercially available products of these fluorine-containing compounds, "DEFENSAMCF-300", "DEFENSAMCF-310", "DEFENSAMCF-312", "DEFENSAMCF-323", "Megapac RS-72-K" manufactured by DIC, and 3M Japan `` Fluoride FC-431 '', `` Fluoride FC-4430 '', `` Fluoride FC-4432 '', `` AsahiGuard AG710 '' manufactured by Asahi Garas Co., `` Surflon S-382 '', `` Surflon SC-101 '', "Sufflon SC-102", "Sufflon SC-103", "Sufflon SC-104", "Sufflon SC-105", "Sufflon SC-106", "Optool DAC-HP" manufactured by Daikin Corporation , A commercially available fluorine-containing compound such as "HP-650" can be used.

As described above, in the case where a fluorine-based compound is used as the liquid repellent, the proportion of fluorine atoms in the liquid repellent is not particularly limited, but preferably the content of fluorine atoms is preferably 1% by mass or more, and more preferably 5% by mass or more. It is preferable, and 50 mass% or less is preferable, and 25 mass% or less is more preferable. When it is more than the said lower limit, there exists a tendency to show a high contact angle, and when it is less than the said upper limit, there exists a tendency which can suppress leakage to a pixel part.

The molecular weight of the liquid repellent is not particularly limited, and may be a low molecular weight compound or a high molecular weight body. The high molecular weight liquid repellent is preferable because the fluidity of the liquid repellent by firing is suppressed, and it is preferable because the liquid repellent tends to be suppressed from flowing out of the partition wall. In this respect, the number average molecular weight of the liquid repellent is , 100 or more are preferable, 500 or more are more preferable, 100000 or less are preferable, and 10000 or less are more preferable.

The content ratio of the liquid repellent agent 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, more preferably 0.1% by mass or more, and usually 1% by mass or less, based on the total solid content. Preferably it is 0.5 mass% or less, More preferably, it is 0.3 mass% or less. When it is more than the said lower limit, there exists a tendency to show high liquid repellency, and when it is below the said upper limit, there exists a tendency which can suppress the liquid repellent agent from leaking into the pixel part.

[1-6-8] UV 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 the light source used for exposure with the ultraviolet absorber. By adding an ultraviolet absorber, effects such as improving the taper angle and shape after development or removing residues remaining on the non-exposed portion after development tend to be obtained. As the ultraviolet absorber, from the viewpoint of inhibiting light absorption of the initiator, for example, a compound having a maximum absorption between the wavelengths of 250 nm to 400 nm can be used.

As the ultraviolet absorber, benzotriazole-based compounds and / or triazine-based compounds are preferred. It is considered that the inclusion effect of the benzotriazole-based compound and / or the triazine-based compound reduces the light absorption at the membrane bottom of the initiator and decreases the difference in the curing area of the membrane surface layer and the membrane bottom, thereby increasing the taper angle. .

As a benzotriazole type compound, 2- (5methyl-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-hydride Mixture of hydroxy-5- (5-chloro-2H-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-hydride 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 There may be mentioned a chain alkyl ester.

Commercially available benzotriazole compounds include, for example, Sumib 200, Sumib 250, Sumib 300, Sumib 340, Sumib 350 (manufactured by Sumitomo Chemical Co., Ltd.), JF77, JF78, JF79, JF80 , JF83 (manufactured by Johor Chemical Industries), TINUVIN PS, TINUVIN99-2, TINUVIN109, TINUVIN384-2, TINUVIN 326, TINUVIN900, TINUVIN 928, TINUVIN928, TINUVIN1130 (manufactured by BASF), EVERSORB70, EVERSORB71, EVERSORB72, EVERSORB72 EVERSORB75, EVERSORB76, EVERSORB234, EVERSORB77, EVERSORB78, EVERSORB80, EVERSORB81 (manufactured by Taiwan Yeonggwang Chemical Industry), TOMISOV 100, TOMISOB 600 (manufactured by AFIA Corporation), SEESORB701, SEESORB702, SEESORB703, SEESORB706, SEESORB703, SEESORB707 And SEESORB709 (produced by Cipro Chemicals), RUVA-93 (produced by Otsuka Chemical Co., Ltd.), and the like.

As the triazine-based compound, 2- [4,6-di (2,4-xylyl) -1,3,5-triazin-2-yl] -5-octyloxyphenol, 2- [4,6- Bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4 -Dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and reaction product of (2-ethylhexylglycidic acid ester, 2,4-bis [2- Hydroxy-4-butoxyphenyl] -6- (2,4-dibutoxyphenyl) -1,3-5-triazine, etc. Among these, from the viewpoint of taper angle and exposure sensitivity, hydroxy Phenyltriazine compounds are preferred.

As a commercially available triazine-type compound, TINUVIN400, TINUVIN405, TINUVIN460, TINUVIN477, TINUVIN479 (made by BASF) etc. are mentioned, for example.

[1-6-9] Polymerization inhibitor

The colored photosensitive resin composition of the present invention may contain a polymerization inhibitor. Since it inhibits radical polymerization by containing a polymerization inhibitor, there is a tendency that the taper angle of the resulting cured product can be increased.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methylhydroquinone, 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 preferred from the viewpoint of the ability to inhibit polymerization.

It is preferable that a polymerization inhibitor contains 1 type or 2 or more types. Usually, when manufacturing (C) a binder resin, a polymerization inhibitor may be contained in the said resin, and the same or different polymerization inhibitors other than the polymerization inhibitor contained in the resin may be used when manufacturing the photosensitive resin composition. You may add.

The content ratio of the polymerization inhibitor in the colored photosensitive resin composition is usually 0.0005 mass% or more, preferably 0.001 mass% or more, more preferably 0.01 mass% or more, and is usually more than the total solid content of the colored photosensitive resin composition. Therefore, it is 0.1 mass% or less, preferably 0.08 mass% or less, and more preferably 0.05 mass% or less. When it is more than the said lower limit, there is a tendency to increase the taper angle, and if it is less than the upper limit, there is a tendency to maintain high sensitivity.

[1-6-10] Inorganic filler

The colored photosensitive resin composition of the present invention is also intended to improve the strength of a cured product or to improve the flatness and taper angle of a coated film by appropriate interaction with (C) a binder resin (formation of a matrix structure). Thus, it may contain an inorganic filler. Examples of such inorganic fillers include talc, silica, alumina, barium sulfate, magnesium oxide, or 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 diameter referred to in the present embodiment is a value measured by a laser diffraction scattering particle size distribution measuring device manufactured by Beckman Coulter. Among these inorganic fillers, silica sol and silica sol-modified product are particularly preferably blended because dispersion stability and the effect of improving the taper angle tend to be excellent. When the colored photosensitive resin composition of the present invention contains these inorganic fillers, in terms of the content thereof, from the viewpoint of sensitivity, it is usually 5% by mass or more, preferably 10% by mass or more, usually It is 80 mass% or less, preferably 70 mass% or less.

[1-7] Solvent

The colored photosensitive resin composition and pigment dispersion of the present invention usually contain a solvent. By including a solvent, coloring agents, such as a pigment, can be disperse | distributed in a solvent, and application becomes easy.

The colored photosensitive resin composition of the present invention is usually (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, (E) a photopolymerization initiator, and others used as necessary. Various materials are used in a state dissolved or dispersed in a solvent. Similarly, the pigment dispersion of the present invention is usually used in a state in which (A) a colorant, (B) a dispersant, (C) a binder resin, and other various materials used as necessary are dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coatability.

Among the organic solvents, it is preferable to select those having a boiling point of 100 to 300 ° C (under pressure 1013.25 hPa conditions. Hereinafter, all of the boiling points are the same.) From the viewpoint of coatability, and those having a boiling point of 120 to 280 ° C. It is more preferable to choose.

As such an organic solvent, the following are mentioned, for example.

Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-butyl ether, propylene glycol-t- Butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethylpentanol, dipropylene glycol monoethyl ether, dipropylene glycol monomethyl ether, 3-me Glycol monoalkyl ethers such as methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and tripropylene glycol methyl ether;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, and 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 mono Glycol alkyl ether acetates such as methyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, and 3-methyl-3-methoxybutyl acetate;

Glycol diacetates such as ethylene glycol diacetate, 1,3-butylene glycol diacetate, and 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, and dihexyl ether;

Acetone, methyl ethyl ketone, methyl amyltone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl Ketones such as hexyl ketone, methylnonyl ketone, and methoxymethylpentanone;

Monohydric or polyhydric alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol, triethylene glycol, methoxymethylpentanol, glycerin, benzyl alcohol Ryu;

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

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

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

Amyl formate, ethyl formate, ethyl acetate, butyl acetate, propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl Caprylate, butylstearate, ethylbenzoate, 3-ethoxypropionate methyl, 3-ethoxypropionate ethyl, 3-methoxypropionate methyl, 3-methoxypropionate ethyl, 3-methoxypropionate propyl, 3-meth Chain or cyclic esters such as butyl propionate and γ-butyrolactone;

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

Halogenated hydrocarbons such as butyl chloride and amyl chloride;

Ether ketones such as methoxymethylpentanone;

Nitriles such as acetonitrile and benzonitrile.

Commercially available organic solvents corresponding to the above are: mineral spirits, barsol # 2, apco # 18 solvent, apco thinner, solvate solvent No.1 and No.2, Solvesso # 150, shell TS28 solvent, carbitol , Ethyl carbitol, butyl carbitol, methyl cellosolve ("Cellosolve" is a registered trademark. The same applies hereinafter), ethyl cellosolve, ethyl cellosolve acetate, methyl cellosolve acetate, diglyme (all brand names) And the like.

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

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

Among the organic solvents, glycol alkyl ether acetates are preferred from the viewpoints of good balance of coatability, surface tension, etc., and relatively high solubility of constituents in the composition.

Moreover, although glycol alkyl ether acetates may be used independently, you may use together other organic solvents. As the organic solvent to be used in combination, glycol monoalkyl ethers are particularly preferred. Especially, propylene glycol monomethyl ether is preferable from the solubility of the component in a composition. In addition, glycol monoalkyl ethers have high polarity, and when the amount of addition is too large, the pigment tends to aggregate, and the storage stability, such as the viscosity of the colored photosensitive resin composition obtained later, tends to decrease, and thus glycol monoalkyl ethers in the solvent. The proportion of is preferably 5% by mass to 30% by mass, and more preferably 5% by mass to 20% by mass.

Moreover, it is also preferable to use together the organic solvent which has a boiling point of 150 degreeC or more (it may be called "high boiling point solvent" hereafter.). By using such a high boiling point solvent together, the colored photosensitive resin composition becomes difficult to dry, but there is an 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 occurrence of foreign matter defects due to precipitation and solidification of a colorant or the like at the tip of the slit nozzle. Among these various solvents, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferable from the above-mentioned various solvents.

The content ratio of the high boiling point solvent in the organic solvent is preferably 3% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and particularly preferably 5% by mass to 30% by mass. By setting it as more than the said lower limit, it tends to suppress that a coloring material etc. precipitates and solidifies at the tip of a slit nozzle, for example, and it can suppress that it causes a foreign material defect, and when it is below the said upper limit, it suppresses that the drying temperature of a composition becomes slow. There is a tendency to suppress problems such as poor tact in the vacuum drying process and pin marks of the prebaking.

Further, the high boiling point solvent having a boiling point of 150 ° C or higher may be a glycol alkyl ether acetate or a glycol alkyl ether, and in this case, it is not necessary to separately contain a high boiling point solvent having a boiling point of 150 ° C or higher.

Preferred high boiling point solvents include, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, and 1,3-butylene glycol diacetate among the various solvents described above. , 1,6-hexanol diacetate, triacetin, and the like.

<Component blending amount in the colored photosensitive resin composition>

In the colored photosensitive resin composition of the present invention, the content ratio of the colorant (A) is preferably 20% by mass or more, preferably 25% by mass or more, and more preferably 30% by mass or more with respect to the total amount of solids in the colored photosensitive resin composition. Preferably, it is preferably 60% by mass or less, more preferably 50% by mass or less, more preferably 45% by mass or less, and even more preferably 40% by mass or less. When it is more than the said lower limit, sufficient optical density (OD) tends to be easy to obtain, and when it is below the said upper limit, sufficient image formability tends to be easily secured. 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.

Further, in the colored photosensitive resin composition and pigment dispersion of the present invention, the content ratio of the organic black pigment (A1) to the colorant (A) is usually 10% by mass or more, preferably 30% by mass or more, and more preferably Is 50 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, particularly preferably 90 mass% or more, and is usually 100 mass% or less. When the content ratio of the organic black pigment (A1) in the colorant (A) is equal to or more than the above lower limit, a coating film having a more desired 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, even more preferably 50 to 100% by mass, even more preferably 70 to 100% by mass, and 80 to 80% by mass. 100 mass% is especially preferable and 90-100 mass% is most preferable.

In the colored photosensitive resin composition and pigment dispersion of the present invention, in the colorant (A), the organic color pigment (A2) may be contained together with the organic black pigment (A1). In that case, the content ratio of the (A) organic black pigment to the colorant (A) is usually 10 mass% or more, preferably 20 mass% or more, more preferably 30 mass% or more, and usually 90 mass% Hereinafter, it is preferably 80 mass% or less, and more preferably 60 mass% or less. Moreover, the content rate of (A2) organic coloring pigment is 10 mass% or more normally, Preferably it is 20 mass% or more, More preferably, it is 40 mass% or more, Moreover, it is 90 mass% or less normally, Preferably it is 80 It is mass% or less, More preferably, it is 70 mass% or less. The taper angle tends to be lowered by setting it to the lower limit or more, and a blacker color coating film tends to be obtained by setting the lower limit to the upper limit or less.

Moreover, the content ratio of (A1) organic black pigment to 100 mass parts of (A2) organic coloring pigment 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 It is below mass parts, more preferably below 500 parts by mass, still more preferably below 200 parts by mass.

In the colored photosensitive resin composition and pigment dispersion of the present invention, (A) the colorant may contain (A3) carbon black together with the (A1) organic black pigment. In that case, the content ratio of the organic black pigment (A1) to the colorant (A) is usually 50% by mass or more, preferably 60% by mass or more, and usually 95% by mass or less, preferably 90% by mass Is below. Moreover, the content rate of (A3) carbon black is 5 mass% or more normally, Preferably it is 10 mass% or more, Moreover, it is 50 mass% or less normally, Preferably it is 40 mass% or less. When it is more than the above-mentioned lower limit, a sufficient optical density (OD) tends to be obtained, and if it is below the above-mentioned upper limit, a high volume resistivity value or a low relative dielectric constant is obtained, and wrinkles and the like during curing are less likely to occur. have. In addition, the content ratio of (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 Less than wealth.

Moreover, in the coloring photosensitive resin composition of this invention and a pigment dispersion liquid, (A) organic coloring pigment and (A2) organic coloring pigment and (A3) carbon black may be contained in a coloring agent. In that case, the content ratio of the organic black pigment (A1) to the colorant (A) is usually 10 mass% or more, preferably 20 mass% or more, and usually 80 mass% or less, preferably 70 mass% or less to be. Moreover, the content rate of (A2) organic coloring pigment is 10 mass% or more normally, Preferably it is 20 mass% or more, Moreover, it is 60 mass% or less normally, Preferably it is 50 mass% or less. 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 (A1) organic black pigment to 100 parts by mass of (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. In addition, the content ratio of (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 Less than wealth.

(B) The content ratio of the dispersant 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, among 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. When it is more than the said lower limit, there exists a tendency for dispersibility to become favorable, and when it is less than the said upper limit, a dispersing agent which is excess can reduce and there exists a tendency for developability to become favorable. The combination of the upper limit and the lower limit is preferably 1 to 30 mass%, more preferably 3 to 20 mass%, still more preferably 5 to 15 mass%, and particularly preferably 5 to 10 mass%.

In addition, the content ratio of the dispersant (B) to 100 parts by mass of the colorant (A) is preferably 5 parts by mass or more, preferably 10 parts by mass or more, and usually 50 parts by mass or less and preferably 30 parts by mass or less. The dispersibility tends to be improved by setting the amount to the lower limit or more, and the dispersant that is excessive can be reduced to be less than the upper limit, and the developability tends to be improved. The combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, 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 preferably 1 mass% or more, preferably 3 mass% or more, among the solid content of the colored photosensitive resin composition, 5 mass% or more is more preferable, and normally 30 mass% or less, 20 mass% or less is preferable, 15 mass% or less is more preferable, and 10 mass% or less is more preferable. The dispersibility tends to be improved by setting the amount to the lower limit or more, and the dispersant that is excessive can be reduced to be less than the upper limit, and the developability tends to be improved. The combination of the upper limit and the lower limit is preferably 1 to 30 mass%, more preferably 3 to 20 mass%, still more preferably 5 to 15 mass%, and particularly preferably 5 to 10 mass%.

Moreover, in the coloring photosensitive resin composition which concerns on 1st aspect of this invention and the pigment dispersion liquid which concerns on 3rd aspect of this invention, (A) The content rate of the acrylic dispersing agent with respect to 100 mass parts of coloring agents is 5 mass parts or more normally. , 10 parts by mass or more is preferable, and usually 50 parts by mass or less and 30 parts by mass or less are preferable. The dispersibility tends to be improved by setting the amount to the lower limit or more, and the dispersant that is excessive can be reduced to be less than the upper limit, and the developability tends to be improved. The combination of the upper limit and the lower limit is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass.

(C) Although the content ratio of the binder resin is not particularly limited, it is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass or more with respect to the total solid content of the colored photosensitive resin composition of the present invention. , More preferably 30 mass% or more, particularly preferably 40 mass% or more, usually 80 mass% or less, preferably 70 mass% or less, more preferably 60 mass% or less, still more preferably 50 mass% % Or less. When it is more than the above-mentioned lower limit, a strong film tends to be easily obtained, and if it is below the above-mentioned upper limit, penetration of the developer into the exposed portion is suppressed low, and surface smoothness and deterioration in sensitivity of the film tend to be easily suppressed. . The combination of the upper limit and the lower limit is preferably 5 to 80 mass%, more preferably 10 to 70 mass%, still more preferably 20 to 60 mass%, even more preferably 30 to 50 mass%, and 40 to 50 mass% is especially preferable.

The content ratio of the (C1) epoxy (meth) acrylate resin is usually 5% by mass or more, preferably 10% by mass or more, and more preferably 20% by mass with respect to the total solid content of the colored photosensitive resin composition of the present invention. Above, more preferably 30% by mass or more, even 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 It is 60 mass% or less, More preferably, it is 50 mass% or less. When it is more than the said lower limit, a strong film tends to be easy to obtain, and when it is less than the said upper limit, it tends to become easy to suppress the deterioration of surface smoothness and sensitivity of a film. The combination of the upper limit and the lower limit is preferably 5 to 80 mass%, more preferably 10 to 70 mass%, still more preferably 20 to 60 mass%, even more preferably 30 to 60 mass%, and 35 to 60 mass% is especially preferable, and 40-50 mass% is most preferable.

In the present invention, the epoxy (meth) acrylate resin having a repeating unit structure represented by the general formula (II) occupied by the binder resin (C) and / or the epoxy (meth) having a partial structure represented by the general formula (III) The content ratio of the acrylate resin (when both are included, the total content ratio) is not particularly limited, but is preferably 75% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more , More preferably 90% by mass or more, and particularly preferably 95% by mass or more. Moreover, it is 100 mass% or less normally. When it is more than the said lower limit, outgas aptitude tends to become favorable. As a combination of an upper limit and a lower limit, 75-100 mass% is preferable, 80-100 mass% is more preferable, 85-100 mass% is more preferable, 90-100 mass% is more preferable, and 95- 100 mass% is especially preferable.

(D) The content ratio of the photopolymerizable monomer is usually 1% by mass or more, preferably 5% by mass or more, and more preferably 8% by mass or more, and usually with respect to the total solid content of the colored photosensitive resin composition. Therefore, it is 30% by mass or less, preferably 20% by mass or less, and more preferably 15% by mass or less. When it is more than the said lower limit, it tends to become high sensitivity, and when it is less than the said upper limit, developability tends to become favorable. The combination of the upper limit and the lower limit is preferably 1 to 30% by mass, more preferably 5 to 20% by mass, and more preferably 8 to 15% by mass.

(E) The content ratio of the photopolymerization initiator is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably, based on the total solid content of the colored photosensitive resin composition of the present invention. It is 2 mass% or more, especially preferably 3 mass% or more, and is usually 15 mass% or less, preferably 10 mass% or less, more preferably 8 mass% or less, still more preferably 5 mass% or less. . When it is more than the said lower limit, there exists a tendency for favorable sensitivity to be obtained, and when it is below the said upper limit, there exists a tendency which can ensure the quantity of binder resin suitable for image development and a photopolymerizable monomer. The combination of the upper limit and the lower limit is preferably 0.1 to 15 mass%, more preferably 0.5 to 10 mass%, still more preferably 1 to 8 mass%, still more preferably 2 to 5 mass%, and 3 to 5 mass% is especially preferable.

(E) When using a polymerization accelerator together with a photopolymerization initiator, the content rate of the polymerization accelerator is preferably 0.05 mass% or more, and usually 10 mass% or less, based on the total solid content of the colored photosensitive resin composition of the present invention , Preferably 5% by mass or less. Moreover, with respect to 100 mass parts of photopolymerization initiators (D), 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 or less.

When the content ratio of the polymerization accelerator is more than the lower limit, good sensitivity tends to be obtained, and when the content ratio is less than or equal to the upper limit, solubility of the unexposed portion in the developer tends to be good.

Moreover, the blending ratio of the sensitizing dye occupied in the colored photosensitive resin composition of the present invention is usually 0.5 mass% or more, preferably 1 mass% or less, among the total solids in the colored photosensitive resin composition from the viewpoint of sensitivity, and is usually It is 20 mass% or less, preferably 15 mass% or less, and more preferably 10 mass% or less.

When the adhesion improver is used, the content ratio thereof is usually 0.1 to 5% by mass, preferably 0.2 to 3% by mass, and more preferably 0.4 to 2% by mass relative to the total solid content in the colored photosensitive resin composition. When the content ratio of the adhesion promoter is more than the lower limit, there is a tendency to improve adhesion, and when the content ratio is less than or equal to the upper limit, good sensitivity is obtained, and the residue after development tends to be less likely to occur.

Moreover, when using surfactant, the content rate is 0.001-10 mass% normally with respect to the whole solid content in a coloring photosensitive resin composition, Preferably it is 0.005-1 mass%, More preferably, it is 0.01-0.5 mass%, Most preferably, it is 0.03 to 0.3 mass%. When the content ratio of the surfactant is greater than or equal to the above lower limit, the smoothness and uniformity of the coating film tends to be obtained, and when the content is less than or equal to the upper limit, occurrence of unevenness or the like tends to be suppressed.

In addition, the colored photosensitive resin composition of the present invention is prepared by using the above-described organic solvent so that its solid content concentration is usually 5 to 50% by mass, preferably 10 to 30% by mass.

<Physical properties of the colored photosensitive resin composition>

The colored photosensitive resin composition of the present invention can be suitably used for forming a black matrix in addition to partition walls and colored spacers, and preferably exhibits black in this respect, and has an optical density (OD) per 1 µm of the film thickness of the coating film. It 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.

In addition, when applied to a member having a high area ratio occupied in the image display area of the image display device, such as a partition wall of an organic electroluminescent element, the color tone is preferably closer to black. From this viewpoint, it is preferable that x of the chromaticity when cured is 0.20 or more, more preferably 0.25 or more, further preferably 0.30 or more, further preferably 0.50 or less, more preferably 0.45 or less, and more preferably 0.40 or less It is more preferable. Moreover, it is preferable that y of chromaticity is 0.20 or more, it is more preferable that it is 0.25 or more, it is more preferable that it is 0.30 or more, it is preferable that it is 0.50 or less, it is more preferable that it is 0.45 or less, and it is still more preferable that it is 0.40 or less.

[2] composition and composition of pigment dispersion

The components constituting the pigment dispersion of the present invention and its composition 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 used suitably as one of the raw materials used when manufacturing a coloring photosensitive resin composition, as mentioned later.

As (A) coloring agent used for a pigment dispersion liquid, (B) dispersing agent, (C) binder resin, and a solvent, what was illustrated as what is used for a coloring photosensitive resin composition can be used conveniently.

In the pigment dispersion of the present invention, the colorant (A) contains the organic black pigment (A1) described above. (A1) A coating film obtained by applying a colored photosensitive resin composition prepared using a pigment dispersion liquid containing an organic black pigment can achieve high resistance, low dielectric constant and high light shielding ratio, and becomes a cured product of a color closer to black Tend to

Moreover, (B) dispersing agent contains an acrylic type dispersing agent. When a colored photosensitive resin composition is produced using a pigment dispersion liquid containing an acrylic dispersant, pattern adhesion during development tends to be good.

Moreover, (C) binder resin contains (C1) epoxy (meth) acrylate resin. (C1) By using a pigment dispersion liquid containing an epoxy (meth) acrylate resin to prepare a colored photosensitive resin composition, the amount of outgas generated after formation of the cured product tends to decrease.

<The amount of ingredients in the pigment dispersion>

In the pigment dispersion of the present invention, the content ratio of the colorant (A) is usually 10% by mass or more, preferably 20% by mass or more, more preferably 30% by mass or more, and even more preferably with respect to the total solid content in the pigment dispersion. Preferably, it is 40 mass% or more, even more preferably 50 mass% or more, particularly preferably 55 mass% or more, and usually 100 mass% or less, preferably 80 mass% or less, more preferably 70 mass% or more Hereinafter, it is more preferably 60% by mass or less. By making it more than the said lower limit, a colored photosensitive resin composition can be manufactured at a suitable solid content concentration, and when it is below the said upper limit, dispersibility tends to become favorable. The combination of the upper limit and the lower limit is preferably 10 to 80% by mass, more preferably 20 to 80% by mass, even more preferably 30 to 70% by mass, even more preferably 40 to 70% by mass, and 50 to 50% by mass. 60 mass% is especially preferable and 55-60 mass% is most preferable.

In the pigment dispersion of the present invention, the content ratio of the dispersant (B) is usually 2% by mass or more, preferably 5% by mass or more, more preferably 10% by mass or more, and It 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, particularly preferably 15% by mass or less. When it is more than the said lower limit, there exists a tendency for dispersibility to become favorable, and when it is below the said upper limit, there exists a tendency for the dispersing agent which is excess to be reduced, and the developability of the obtained colored photosensitive resin composition tends to become favorable. The combination of the upper limit and the lower limit is preferably 2 to 50 mass%, more preferably 5 to 40 mass%, still more preferably 5 to 30 mass%, even more preferably 5 to 20 mass%, and 10 to 15 mass% is especially 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, and usually, based on the total solid content in the pigment dispersion. It is 50 mass% or less, preferably 40 mass% or less, more preferably 30 mass% or less, still more preferably 20 mass% or less, particularly preferably 15 mass% or less. When it is more than the said lower limit, dispersibility becomes favorable and there exists a tendency for pattern adhesiveness to become favorable at the time of image development of a hardened | cured material, and there exists a tendency for the developability of the colored photosensitive resin composition obtained by making it below the said upper limit to become favorable. The combination of the upper limit and the lower limit is preferably 2 to 50 mass%, more preferably 5 to 40 mass%, still more preferably 5 to 30 mass%, even more preferably 5 to 20 mass%, and 10 to 15 mass% is especially preferable.

In the pigment dispersion of the present invention, the content ratio of (C) the binder resin is usually 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, and more preferably with respect to the total solid content in the pigment dispersion Preferably 20 mass% or more, particularly preferably 25 mass% or more, and usually 50 mass% or less, preferably 40 mass% or less, more preferably 35 mass% or less, still more preferably 30 mass% Is below. The dispersibility tends to be improved by setting the amount to the lower limit or more, and the amount of the colorant in the colored photosensitive resin composition obtained by setting the amount to the upper limit or less tends to be appropriate, and there is a tendency to ensure sufficient light shielding properties. As a combination of an upper limit and a lower limit, 5-50 mass% is preferable, 10-40 mass% is more preferable, 15-35 mass% is more preferable, 20-35 mass% is more preferable, and 25- 30 mass% is especially 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 with respect to the total solid content in the pigment dispersion. Mass% or more, more preferably 20 mass% or more, particularly preferably 25 mass% or more, and usually 50 mass% or less, preferably 40 mass% or less, more preferably 35 mass% or less, further preferably It is 30 mass% or less. By setting it as more than the said lower limit, the outgas suitability of a hardened | cured material tends to become favorable, and the amount of the coloring agent in the coloring photosensitive resin composition obtained by making it below the said upper limit tends to be suitable, and there exists a tendency which can ensure sufficient light-shielding property. As a combination of an upper limit and a lower limit, 5-50 mass% is preferable, 10-40 mass% is more preferable, 15-35 mass% is more preferable, 20-35 mass% is more preferable, and 25- 30 mass% is especially preferable.

Moreover, the pigment dispersion liquid of this invention is adjusted so that the solid content concentration may be 5-50 mass% normally, Preferably it is 10-30 mass% using the above-mentioned organic solvent.

[3] Method for producing colored photosensitive resin composition

The colored photosensitive resin composition of the present invention (hereinafter sometimes referred to as "resist") is produced according to a conventional method.

Usually, the colorant (A) is preferably subjected to dispersion treatment using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer, or the like. Since the colorant (A) becomes fine particles by the dispersion treatment, the coating properties of the resist are improved.

It is preferable to perform the dispersion treatment in a system in which part or all of (A) a colorant, an organic solvent, and (B) a dispersant and (C) a binder resin are usually used (hereinafter, a mixture provided for the dispersion treatment) And, the composition obtained by the treatment may be referred to as "ink" or "pigment dispersion". Particularly, the use of a polymer dispersant (B) as a dispersant is preferable because the time-dependent thickening of the obtained ink and resist is suppressed (excellent dispersion stability).

Thus, in the process of manufacturing a resist, it is preferable to manufacture a pigment dispersion liquid containing at least (A) a colorant, an organic solvent, and (B) a dispersant.

In addition, when a dispersion treatment is performed on a liquid containing all the components to be blended in the colored photosensitive resin composition, there is a possibility that a highly reactive component is denatured due to heat generated during dispersion treatment. Therefore, it is preferable to perform the dispersion treatment in a system containing a polymer dispersant.

When dispersing the colorant (A) with a sand grinder, glass beads or zirconia beads with a diameter of about 0.1 to 8 mm are preferably used. The dispersion treatment conditions, the temperature is usually from 0 ° C to 100 ° C, preferably in the range from room temperature to 80 ° C. Since the appropriate time varies depending on the composition of the liquid and the size of the dispersion processing device, the dispersion time may be appropriately adjusted. Controlling the gloss of the ink is the basis of dispersion so that the 20-degree specular glossiness of the resist (JIS Z8741) is in the range of 50 to 300. When the glossiness of the resist is set to be more than the above lower limit, the dispersion treatment is not sufficient and the residual of coarse pigment (coloring agent) particles can be suppressed, and tends to be easy to sufficiently develop, develop adhesiveness, and resolution. Moreover, when the glossiness value is below the above-mentioned upper limit, it is possible to avoid a large number of ultrafine particles due to crushing of the pigment, and tends to be easy to maintain dispersion stability.

Further, the dispersed particle diameter of the pigment dispersed in the ink is usually 0.03 to 0.3 µm, and is measured by dynamic light scattering or the like. Next, the ink obtained by the dispersion treatment is mixed with the above-mentioned other components contained in the resist to obtain a uniform solution. In the manufacturing process of a resist, since fine dust is often mixed in a liquid, it is preferable to filter the obtained resist with a filter or the like.

[4] Cured product and method for forming the same

[4-1] Cured product

A cured product can be obtained by curing the colored photosensitive resin composition of the present invention. The cured product composed of the colored photosensitive resin composition can be suitably used as a partition wall and a colored spacer.

[4-1-1] Bulkhead

The colored photosensitive resin composition of the present invention can be suitably used to form partition walls, particularly partition walls for partitioning organic species of organic electroluminescent devices. Examples of the organic species used in the organic electroluminescent device include organic species used in the hole injection layer, the hole transport layer or the hole transport layer on the hole injection layer, as described in JP 2016-165396, for example. .

[4-1-2] Color spacer

Moreover, the coloring photosensitive resin composition of this invention can be used conveniently as a resist for colored spacers other than a partition wall. When a spacer is used for a TFT type LCD, the TFT may malfunction as a switching element due to light incident on the TFT, and a colored spacer is used to prevent this (for example, Japanese Patent Application Publication No. Hei 8- 234212).

[4-2] Formation 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 production method. Moreover, a black matrix or other hardened | cured material can also be formed by the same method.

[4-2-1] Support

As a support for forming the partition wall and the colored spacer, the material is not particularly limited as long as it has a suitable strength. Although a transparent substrate is mainly used, as the material, for example, polyester-based resins such as polyethylene terephthalate, polyolefin-based resins such as polypropylene and polyethylene, polycarbonates, polymethyl methacrylates, and thermoplastic resins such as polysulfones A thermosetting resin sheet, such as a 1st sheet, an epoxy resin, an unsaturated polyester resin, and a poly (meth) acrylic-type resin, various glass, etc. are mentioned. 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.

In order to improve the surface physical properties such as adhesion, the support may be subjected to corona discharge treatment, ozone treatment, silane coupling agent, thin film forming treatment of various resins such as urethane-based resin, and the like, if necessary.

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 thin film formation process of various resin, the film thickness is normally 0.01-10 micrometers, Preferably it is the range of 0.05-5 micrometers.

[4-2-2] Application of colored photosensitive resin composition

The coloring photosensitive resin composition can be applied to the substrate by a spinner method, a wire bar method, a flow coat method, a die coat method, a roll coat method, or a spray coat method. Among them, according to the die coating method, the amount of the coating solution is greatly reduced, and there is no influence of mist or the like adhered when the spin coating method is followed.

When the thickness of the coating film is too thick, pattern development may be difficult, and when it is too thin, it is difficult to increase the pigment concentration, and sometimes desired color expression cannot be achieved. The thickness of the coating film is, as a film thickness after drying, usually in the range of 0.2 to 10 μm, more preferably in the range of 0.5 to 6 μm, and more preferably in the range of 1 to 4 μm.

[4-2-3] Drying of coating film

It is preferable to dry the coating film after apply | coating a coloring photosensitive resin composition to a board | substrate by the drying method using a hot plate, an IR oven, or a convection oven. Drying conditions can be appropriately selected depending on the type of the solvent component, the performance of the dryer used, and the like. The drying time depends on the type of the solvent component, the performance of the dryer to be used, and the like, and is usually selected within a range of 15 to 5 minutes at a temperature of 40 to 200 ° C, preferably 30 at a temperature of 50 to 130 ° C It is selected in the range of 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, (C) the binder resin decomposes, causing thermal polymerization, which may cause poor development. Moreover, 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 increasing the temperature.

[4-2-4] Exposure

An image exposure is performed by superimposing a negative mask pattern on the coating film of a coloring photosensitive resin composition, and irradiating a light source of ultraviolet light or visible light through this mask pattern. At this time, if necessary, exposure may be performed after forming an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable coating film in order to prevent deterioration of the sensitivity of the photopolymerizable layer by oxygen. The light source used for the above image exposure is not particularly limited. As the light source, for example, a lamp light source such as a xenon lamp, halogen lamp, tungsten lamp, high pressure mercury lamp, ultra high pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp, carbon arc, fluorescent lamp, argon ion laser, YAG laser , Laser light sources such as excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser. When irradiating and using light of a specific wavelength, an optical filter can also be used.

[4-2-5] Phenomenon

The partition wall and the colored spacer according to the present invention are developed by using an organic solvent or an aqueous solution containing a surfactant and an alkaline compound after image exposure of the coating film with a colored photosensitive resin composition using the light source described above. , Can be produced by forming an image on a substrate. An organic solvent, a buffer, a complexing agent, a dye, or a pigment can be further included in this aqueous solution.

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

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. And anionic surfactants such as alkylbenzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, alkyl sulfonates, and sulfosuccinic 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, and diacetone alcohol. The organic solvent may be used alone or in combination with an aqueous solution.

The conditions of the developing treatment are not particularly limited, and usually, the developing temperature is in the range of 10 to 50 ° C, particularly 15 to 45 ° C, particularly preferably 20 to 40 ° C, and the developing method is immersion developing method, spray developing. Method, brush developing method, ultrasonic developing method, or the like.

[4-2-6] Heat curing treatment

The substrate after development is subjected to a thermal curing treatment or a photo curing treatment, preferably a thermal curing treatment. The temperature for the heat curing treatment at this time is 100 to 280 ° C, preferably 150 to 250 ° C, and the time is 5 to 60 minutes.

[5] organic electroluminescent devices, image displays and lighting

[5-1] Organic electroluminescent device

The organic electroluminescent element of the present invention includes 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 a substrate having a partition wall pattern manufactured by the method described above. The method for forming the organic electroluminescent element is not particularly limited, but preferably, after forming the pattern of the partition wall on the substrate by the above method, the functional material is sublimed in a vacuum state, and within the area surrounded by the partition wall on the substrate. An organic electroluminescent element is manufactured by forming organic species such as pixels by a wet process such as a deposition method to deposit and form a film, a cast method, a spin coat method, or an inkjet printing method.

When an organic electroluminescent element is used as a pixel of an image display device, it is necessary to prevent light of a light emitting layer of one pixel from leaking to another pixel, and when an electrode or the like is a metal, it is accompanied by reflection of external light Since it is necessary to prevent deterioration of image quality, it is preferable to impart light shielding properties to the partition walls constituting the organic electroluminescent element.

Moreover, in the organic electroluminescent element, since it is necessary to provide electrodes on the upper and lower surfaces of the partition, it is preferable that the partition has a high resistance and a low dielectric constant from the viewpoint of insulation. Therefore, when using a coloring agent in order to provide light-shielding property to a partition, it is preferable to use the said (A1) organic black pigment which has high resistance and 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 an image or video display device, and examples thereof include a liquid crystal display device and an organic EL display device. 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 form and structure as long as it includes the colored spacers described above. For example, after preparing the black matrix of the present invention on a TFT element substrate, forming red, green, and blue pixels, and forming an overcoat layer, if necessary, further over thereon, ITO, IZO on the image It forms a transparent electrode such as, and is used as part of parts such as color displays and liquid crystal displays. Moreover, in some uses, such as a plane-oriented drive system (IPS mode), a transparent electrode may not be formed.

Usually, an alignment film is formed on a color filter, and after forming a photo spacer on the alignment film, a liquid crystal cell is formed by bonding with an opposing substrate, liquid crystal is injected into the formed liquid crystal cell, and a counter electrode Completed by wiring. As the alignment film, a resin film such as polyimide is suitable. In order to form an alignment film, a gravure printing method and / or a flexo printing method is usually employed, and the thickness of the alignment film is several 10 nm. After the alignment film is cured by heat firing, it is subjected to surface treatment by irradiation with ultraviolet rays or treatment with a rubbing cloth, and 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 in the form and structure of the image display device as long as it includes the above-described organic electroluminescent element, and can be assembled according to a conventional method using, for example, an active driving type organic electroluminescent element. have. For example, the image display device of the present invention can be formed by the method described in "Organic EL Display" (Oumsa, published on August 20, 2007, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata). have. For example, an image may be displayed by combining an organic electroluminescent element that emits white light and a color filter, or an image may be displayed by combining an organic electroluminescent element having different emission colors such as RGB.

[5-3] Lighting

The lighting of the present invention includes the above-described organic electroluminescent element. The form and structure are not particularly limited, and the organic electroluminescent device of the present invention can be used to assemble according to a conventional method. As the organic electroluminescent element, a simple matrix driving method or an active matrix driving method may be used.

In order for the illumination of the present invention to emit white light, an organic electroluminescent element that emits white light may be used. Further, the organic electroluminescent elements having different luminescence colors may be combined to be configured such that each color is mixed to become white, or may be configured such that the mixing ratio can be adjusted to impart a color matching function.

Example

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless the gist is exceeded.

The constituent components of the colored photosensitive resin composition used in the following Examples and Comparative Examples are as follows.

<Binder resin-I>

"ZCR-1642H" manufactured by Nippon Chemical Co., Ltd. (weight average molecular weight (Mw) 6500, acid value 98 mgKOH / g, carboxyl group-containing epoxy (meth) acrylate resin). This resin corresponds to (C1-1), has a repeating unit structure represented by formula (II-1), R ¹¹ is a methyl group, R ¹² is a group represented by formula (II-A), and R ^X Is a tetrahydrophthalic acid residue.

<Binder resin-II>

[Formula 57]

50 parts by weight of the epoxy compound of the above structure (epoxy equivalent 264), 13.65 parts by weight of acrylic acid, 60.5 parts by weight of 3-methoxybutyl acetate, 0.936 parts by weight of triphenylphosphine, and 0.032 parts by weight of paramethoxyphenol, thermometer, stirrer, The mixture was placed in a flask equipped with a cooling tube and reacted with stirring until the acid value became 5 mgKOH / g or less at 90 ° C. The reaction required 12 hours, and an epoxy acrylate solution was obtained.

25 parts by weight of the epoxy acrylate solution, 0.74 parts by weight of trimethylolpropane (TMP), 3.95 parts by weight of biphenyltetracarboxylic anhydride (BPDA), 2.7 parts by weight of tetrahydrophthalic anhydride (THPA), thermometer, stirrer, The flask was placed in a flask equipped with a cooling tube, and the mixture was slowly heated to 105 ° C while stirring to react.

When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate, prepared to be 50% by mass of solid content, and carboxyl group-containing epoxy (meth) acryl having an acid value of 112 mgKOH / g and a weight average molecular weight (Mw) of 4100. A rate resin was obtained. This resin corresponds to (C1-2).

<Binder resin-III>

[Formula 58]

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

<Binder resin-IV>

[Formula 59]

Epoxy compound represented by the above structural formula (epoxy equivalent 245) 98.0 parts by weight, acrylic acid 28.8 parts by weight, 3-methoxybutyl acetate 113.0 parts by weight, triphenylphosphine 1.1 parts by weight, and paramethoxyphenol 0.02 parts by weight, thermometer, stirrer , It was placed in a flask equipped with a cooling tube and reacted with stirring until the acid value became 5 mgKOH / g or less at 90 ° C. The reaction required 15 hours, and an epoxy acrylate solution was obtained.

189.1 parts by mass of the epoxy acrylate solution, 11.8 parts by mass of biphenyltetracarboxylic acid anhydride (BPDA), and 30.4 parts by mass of tetrahydrophthalic anhydride (THPA) were added, and the mixture was slowly heated to 105 ° C while stirring to react.

When the resin solution became transparent, it was diluted with 3-methoxybutyl acetate, prepared to have a solid content of 55 mass%, and a binder resin-IV having an acid value of 110 mgKOH / g and a weight average molecular weight (Mw) of 2800 was obtained. This resin corresponds to (C1-2).

<Binder resin -V>

145 parts by mass of propylene glycol monomethyl ether acetate was stirred while nitrogen substitution, and the temperature was raised to 120 ° C. 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 were added dropwise, and 2,2'-azobis 8.47 parts by mass of 2-methylbutyronitrile was added dropwise over 3 hours, and stirring was continued at 90 ° C 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 tetrahydro phthalic 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 thus obtained binder resin-V was about 8400, the acid value was 80 mgKOH / g, and the double bond equivalent was 480 g / mol.

<Colorant-I>

Manufactured by BASF, Irgaphor (registered trademark) Black S 0100 CF (has a chemical structure represented by the following formula (I-1))

[Formula 60]

<Dispersant-I>

BYK-LPN21116 manufactured by BICKCHEMI (Acrylic AB block copolymer consisting of A block having a quaternary ammonium base and a tertiary amino group in the side chain, and B block not having a quaternary ammonium base and a tertiary amino group. The amine value is 70 MgKOH / g.The acid value is 1 mgKOH / g or less.)

The repeating units of the following formulas (1a) and (2a) are included in the A block of the dispersant-I, and the repeating units of the following formula (3a) are included in the B block. The content ratio of the repeating units of the following formulas (1a), (2a), and (3a) in the total repeating units of the dispersant-I is 11.1 mol%, 22.2 mol%, and 6.7 mol%, respectively.

[Formula 61]

<Dispersant-II>

DISPERBYK-167, manufactured by BIC Chemie (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

<Photopolymerization initiator-I>

<Diketone body>

Ethylcarbazole (5 g, 25.61 mmol) and o-naphthoyl chloride (5.13 g, 26.89 mmol) were dissolved in 30 ml of dichloromethane, cooled to 2 ° C in an ice-water bath, stirred, and AlCl ₃ (3.41 g, 25.61 mmol). Further, after stirring at room temperature for 3 hours, a 15 ml dichloromethane solution of crotonoyl chloride (2.81 g, 26.89 mmol) was added to the reaction solution, AlCl ₃ (4.1 g, 30.73 mmol) was added, and further 1 hour. Stir for 30 minutes. The reaction solution was emptied into 200 ml of ice water, 200 ml of dichloromethane was added, and the organic species was separated. The recovered organic species were dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain a diketone body (10 g) as a white solid.

<Oxy Core>

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, 30 ml of ethyl acetate was added to the obtained residue, 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 species was concentrated under reduced pressure to obtain 3.01 g of a solid. This was purified by column chromatography to obtain 2.22 g of a pale yellow solid oxime body.

<Oxime ester body>

The oxime body (2.22 g, 4.77 mmol) and acetyl chloride (1.34 g, 17.0 mmol) were added to 20 mL of dichloromethane to ice-cool, triethylamine (1.77 g, 17.5 mmol) was added dropwise, and left to stand for 1 hour. Reacted. 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, and twice with 5 ml of saturated brine, and dried over anhydrous sodium sulfate. After filtration, the organic species was concentrated under reduced pressure, and the obtained residue was purified by column chromatography (ethyl acetate / hexane = volume ratio 2/1) to obtain 0.79 g of a light yellow solid photopolymerization initiator-I (the following chemical structure: Compound). The chemical shift of photoinitiator-I is shown below.

[Formula 62]

<Photopolymerizable monomer>

DPHA: Dipentaerythritol hexaacrylate manufactured by Nippon Gunpowder Co., Ltd.

<Surfactant>

Megapac F-559 manufactured by DIC

<Additive>

KAYAMER PM-21 manufactured by Nippon Gunpowder (phosphate containing methacryloyl groups)

<Preparation of pigment dispersions 1-6>

The coloring agent (pigment), dispersing agent, and binder resin were added so that the ratio in the solid content became the compounding ratio of Table 1, and the solvent was mixed so that it might become the mass ratio of Table 1. The solution was subjected to dispersion treatment for 3 hours in the range of 25 to 45 ° C by a paint shaker. As beads, zirconia beads of 0.5 mmφ were used, and a mass of 2.5 times the dispersion was added. After the dispersion was completed, beads and 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 was added so that the proportion in the solid content was the blending ratio of Table 2, and PGMEA was added, stirred and dissolved to make the total solid content content to be 22 mass%, A colored photosensitive resin composition was prepared. Using the obtained colored photosensitive resin composition, a pattern was created and evaluated by a method described later.

<Method for manufacturing bulkhead substrate>

Each colored photosensitive resin composition was coated on an ITO substrate (a glass substrate on which ITO having a film thickness of 1500 mm 2 was deposited) using a spinner. Subsequently, the coating film was formed by heating and drying at 100 ° C. for 80 seconds on a hot plate.

The obtained coating film was subjected to exposure treatment using an exposure mask having line-like openings of various widths of 5 to 50 µm (5 to 20 µm: 1 µm spacing, 25 to 50 µm to 5 µm spacing). . The exposure gap (distance between the exposure mask and the coated surface) was 5 µm. As the irradiation light, ultraviolet rays having an intensity at a wavelength of 365 nm of 32 mW / cm 2 were used, and the exposure amount was 60 mJ / cm 2. Moreover, ultraviolet irradiation was performed under air.

Subsequently, a developer composed of a 2.38% by mass aqueous solution of TMAH (tetramethylammonium hydroxide) was used, after performing a shower development at a pressure of 0.05 MPa at 25 ° C, development was stopped with pure water and washed with a water spray. The shower development time was adjusted between 10 and 120 seconds, and was set to 1.2 times the time during which the unexposed coating film was dissolved and removed.

A pattern in which unnecessary portions were removed was obtained by these operations. The substrate on which the pattern was formed was heated in an oven at 230 ° C. for 45 minutes to cure the pattern, thereby obtaining a line pattern (pattern 1) having a film thickness of 2.5 μm. In addition, an entire surface covering pattern (pattern 2) having a film thickness of 2.5 μm was also produced in the same order except that no exposure mask was used.

<Evaluation of substrate adhesion>

In the pattern corresponding to the line-shaped opening of 5 to 50 µm, the value of the mask opening width (µm) of which the pattern remains on the substrate with good resolution is shown in Table 2 as the minimum adhesion. . It can be said that the smaller this value is, the better the adhesion to the substrate is, and the minimum adhesion is 20 µm or less, the sufficient development adhesion to development is practical, and particularly, 10 µm or less, the development adhesion to development is excellent.

<Evaluation method of outgas>

About 3 mg of the coating film was scraped off from the substrate of pattern 2 to obtain a sample for outgas measurement.

Using TG-DTA6300 (manufactured by Hitachi High-Tech Science), the sample was heated to 10 ° C./min from room temperature to 500 ° C. under air atmosphere (Flow 200 mL / min), and the weight loss at that time was measured. Table 2 shows the weight loss amount (% by mass) when the temperature was increased from room temperature to 400 ° C with respect to the total amount of binder resin contained in each colored photosensitive resin composition. Moreover, the weight loss amount (mass%) when it rose from room temperature to 400 degreeC with respect to the total solid content of each coloring photosensitive resin composition is Example 1: 26.8, Example 2: 30.2, Example 3: 29.7, Example It was 4: 27.9, Example 5: 30.8, Example 6: 31.9, Reference example 1: 25.6, and Comparative example 1: 33.7.

<Chromaticity>

Using the substrate of pattern 2 of Example 1, a spectrophotometer UV-3100 (manufactured by Shimadzu Corporation) was used as an aluminum deposition plate as a reference plate, and a specular reflectance of 5 degrees at a wavelength of 380 to 780 nm was measured from the coating film side. Then, chromaticity (D65 light source) in the XYZ colorimeter was calculated.

The substrate of Example 1 was sx = 0.323 and sy = 0.329.

It was confirmed that the coated substrates using the colored photosensitive resin compositions of Examples 1 to 6 and Reference Example 1 had excellent outgas characteristics.

On the other hand, it was confirmed that the coated substrate using the colored photosensitive resin composition of Comparative Example 1 had poor outgas characteristics.

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 of epoxy (meth) acrylate resin in the binder resin. Since epoxy (meth) acrylate resins have a rigid skeleton, it is difficult to be thermally decomposed, and because the skeleton is rigid, an array structure is formed upon curing to form a high crosslinking film, and thus epoxy (meth) acrylic in the binder resin is formed. It is considered that the outgas characteristics are improved by increasing the content ratio of the rate resin.

On the other hand, it was confirmed that, compared to the coated substrate using the colored photosensitive resin composition of Reference Example 1, the coated substrate using the colored photosensitive resin compositions of Examples 1 to 6 was superior in developing adhesion of the thin wire pattern. Even if the colored photosensitive resin composition of Reference Example 1 can be sufficiently applied as a partition wall of an organic electroluminescent device of general resolution, the colored photosensitive resin compositions of Examples 1 to 6 can also be applied to partition walls of a high resolution organic electroluminescent device. Was suggested.

Since the dispersing agent contained in the colored photosensitive resin composition of Reference Example 1 is not an acrylic dispersing agent, it is believed that the developer easily penetrates into the film at the time of development, and the thin wire pattern does not easily remain on the substrate.

On the other hand, since the dispersing agent contained in the colored photosensitive resin compositions of Examples 1 to 6 is an acrylic dispersing agent, since it has a flexible main skeleton with a linear molecular structure, the coloring agent in the coloring photosensitive resin composition is absorbed by most of the adsorbers It is thought that even in the coating film obtained by uniformly dispersing, a colorant serving as a developer-insoluble component is uniformly arranged to form a dense film, and the penetration of the developer into the film during development is suppressed, and even a thin wire pattern can be formed on the substrate. .

Moreover, in the colored photosensitive resin composition of Examples 1-6, it was prepared using the pigment dispersion liquids 1-5 containing an epoxy (meth) acrylate resin as a binder resin, and the epoxy (meth) contained in the obtained colored photosensitive resin composition ) It was possible to increase the content ratio of the acrylate resin.

Claims (11)

A colored photosensitive resin composition used to form partition walls of an organic electroluminescent device, comprising (A) a colorant, (B) a dispersant, (C) a binder resin, (D) a photopolymerizable monomer, and (E) a photopolymerization initiator. as,
The (A) coloring agent contains (A1) at least one selected from the group consisting of a compound represented by the following general formula (I), a geometrical isomer of the compound, a salt of the compound, and a salt of the geometrical isomer of the compound. ) Contains an organic black pigment,
The dispersant (B) includes an acrylic dispersant,
The said (C) binder resin contains (C1) epoxy (meth) acrylate resin 75 mass% or more, The coloring photosensitive resin composition characterized by the above-mentioned.

(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 ;
Further, 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 , They may be directly bonded to each other, or may be bonded to each other by an oxygen atom, a sulfur atom, NH or an NR ^a11 bridge;
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 an alkynyl group having 2 to 12 carbon atoms. Indicates.) According to claim 1,
The coloring photosensitive resin composition whose content rate of the said (C1) epoxy (meth) acrylate resin in the said (C) binder resin is 85 mass% or more. According to claim 1,
The (C1) epoxy (meth) acrylate resin has an epoxy (meth) acrylate resin having a repeating unit structure represented by the following general formula (II) and an epoxy (meth) having a partial structure represented by the following general formula (III). A colored photosensitive resin composition comprising one or both of the 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 also be substituted with an arbitrary substituent;
* Represents a bonding hand.)

(In formula (III), R ¹³ each 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 bonding hand.) According to claim 1,
The colored photosensitive resin composition, wherein the acrylic dispersant is an acrylic dispersant containing a nitrogen atom. According to claim 1,
The coloring photosensitive resin composition in which the content rate of the said (A) coloring agent is 60 mass% or less per total solid content of the said coloring photosensitive resin composition. According to claim 1,
The coloring photosensitive resin composition in which the said (A) coloring agent further contains one or both of (A2) organic coloring pigment and (A3) carbon black. According to claim 1,
The coloring photosensitive resin composition whose content rate of the (A1) organic black pigment in the said (A) coloring agent is 10 mass% or more. The partition wall which consists of the coloring photosensitive resin composition in any one of Claims 1-7. An organic electroluminescent device comprising the partition wall according to claim 8. An image display device comprising the organic electroluminescent element according to claim 9. An illumination comprising the organic electroluminescent element according to claim 9.