KR20230076816A - Photosensitive coloring composition, cured product, organic electroluminescent device and image display device - Google Patents

Abstract

A photosensitive coloring composition less likely to cause surface roughness of an electrode after heat treatment is provided.
The photosensitive coloring composition of the present invention contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant, a) The colorant contains a compound represented by a specific general formula (I), a geometric isomer of the compound, a salt of the compound, or a salt of the geometric isomer of the compound, and the dispersant (f) contains a specific formula (1) ), containing the repeating units represented by (2) and (3) and containing an acrylic copolymer (f1) having no repeating units containing a quaternary ammonium group, and the content of chlorine atoms in the photosensitive coloring composition, It is characterized in that it is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.

Description

Photosensitive coloring composition, cured product, organic electroluminescent device and image display device

The present invention relates to a photosensitive coloring composition, a cured product, an organic electroluminescent device, and an image display device.

This application claims priority based on Japanese Patent Application No. 2020-162460, filed in Japan on September 28, 2020, and Japanese Patent Application No. 2021-024490, filed in Japan on February 18, 2021, content is incorporated here.

A liquid crystal display (LCD) utilizes the property that the alignment method of liquid crystal molecules is switched by turning on/off the voltage to the liquid crystal. Each member which comprises the cell of LCD is formed by the method using the photosensitive composition represented by the photolithography method in many cases. The application range of this photosensitive composition is further widening because it is easy to form a fine structure and it is easy to process a substrate for a large screen.

An image display device including an organic electroluminescent element (also referred to as organic electroluminescence or organic EL) has excellent visibility and responsiveness such as contrast and viewing angle, and enables low power consumption, thin and light weight, and flexible display main body. , it is attracting attention as a next-generation flat panel display (FPD).

An organic electroluminescent element has a structure in which a light emitting layer or an organic layer including various functional layers is sandwiched and supported between a pair of electrodes at least one of which is light-transmitting. An image display apparatus performs image display by driving a panel on which an organic electroluminescent element is disposed for each pixel.

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

In order to form a film such as a light emitting layer in a region surrounded by barrier ribs, a deposition method in which a material is sublimated in a vacuum state and deposited on a substrate to form a film is mainly applied.

In recent years, a method of forming a film by a wet process such as a cast method, a spin coat method, or an inkjet printing method has attracted attention. In particular, the inkjet printing method can reduce unevenness in film thickness in the case of a large area, and it is possible to achieve high resolution of the display, reduction of material usage, and improvement in yield by differential coating at the time of application. For this reason, it is suitable as a film formation method of the organic layer in a large-size panel.

As a method for easily forming the barrier rib, a method of forming by a photolithography method using a photosensitive composition is known. In addition, as a method of suppressing light leakage between pixels by imparting light-shielding properties to barrier ribs, a method of containing a coloring agent in the photosensitive composition is known.

Patent Literature 1 describes a colored photosensitive resin composition that suppresses generation of outgas by using a specific organic black pigment and alkali-soluble resin.

International Publication No. 2018/101314

In the organic electroluminescent device, there are panel types of top emission type and bottom emission type. In the case of top emission, a reflective electrode such as silver is used as an electrode and a cured product such as a barrier rib is produced thereon. However, during heat treatment, components in the photosensitive composition act to cause corrosion or migration of the metal electrode. there is. When unevenness occurs on the electrode surface (hereinafter also referred to as surface roughness), a light emitting layer cannot be uniformly formed on that portion, and when an organic electroluminescent device is manufactured, there is a possibility that display defects due to short circuits or the like may occur. .

When the present inventors examined, it was discovered that in the colored photosensitive resin composition described in patent document 1, the surface roughness of an electrode generate|occur|produced, and there exists a practical problem.

The present invention has been made in view of the above circumstances, and aims to provide a highly reliable organic light emitting element and image display device with no display defects by providing a photosensitive coloring composition that rarely causes surface roughness of electrodes after heat treatment. to be

As a result of earnest examination by the present inventors, it was found that the above-mentioned problems could be solved by using a specific dispersing agent and a coloring agent, and came to complete the present invention.

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

[1] A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant,

The (a) colorant contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound,

The (f) dispersant contains at least repeating units represented by the following general formulas (1), (2) and (3) and contains an acrylic copolymer (f1) having no repeating units containing a quaternary ammonium group, ,

Further, the photosensitive coloring composition characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.

[Formula 1]

(In formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;

R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are, independently of each other, a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ^- , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N=CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ^{11 , SO 3 R 11} _, ^SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;

At least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ is directly related to each other. or may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ bridge;

R ¹¹ and R ¹² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms. .)

[Formula 2]

(In Formula (1), R ³¹ 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 ³² is a hydrogen atom or a methyl group.

* indicates a bonding hand.)

[Formula 3]

(In Formula (2), R ³³ is a methylene group, ethylene group or propylene group, R ³⁴ is an alkyl group which may have a substituent, and R ³⁵ is a hydrogen atom or a methyl group.

n is an integer from 1 to 20;

* indicates a bonding hand.)

[Formula 4]

(In Formula (3), R ³⁶ and R ³⁷ 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, R ³⁶ and R ³⁷ These may combine with each other to form a cyclic structure.

R ³⁸ is a hydrogen atom or a methyl group.

Z is a divalent linking group.

* indicates a bonding hand.)

[2] The photosensitive coloring composition according to [1], wherein the coloring agent (a) contains an organic color pigment.

[3] A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant,

The optical density per 1 μm of film thickness of the cured coating film is 0.5 or more,

The (f) dispersant contains at least repeating units represented by the following general formulas (1), (2) and (3) and contains an acrylic copolymer (f1) having no repeating units containing a quaternary ammonium group, ,

Further, the photosensitive coloring composition characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.

[Formula 5]

(In Formula (1), R ³¹ 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 ³² is a hydrogen atom or a methyl group.

* indicates a bonding hand.)

[Formula 6]

(In Formula (2), R ³³ is a methylene group, ethylene group or propylene group, R ³⁴ is an alkyl group which may have a substituent, and R ³⁵ is a hydrogen atom or a methyl group.

n is an integer from 1 to 20;

* indicates a bonding hand.)

[Formula 7]

(In Formula (3), R ³⁶ and R ³⁷ 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, R ³⁶ and R ³⁷ These may combine with each other to form a cyclic structure.

R ³⁸ is a hydrogen atom or a methyl group.

Z is a divalent linking group.

* indicates a bonding hand.)

[4] The photosensitivity described in [3], wherein the colorant (a) contains at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a violet pigment. coloring composition.

[5] The photosensitive coloring composition according to any one of [1] to [4], wherein the acrylic copolymer (f1) is a block copolymer.

[6] The photosensitive coloring composition according to any one of [1] to [5], wherein the acrylic copolymer (f1) has an amine value of 90 mgKOH/g or more.

[7] The photosensitive coloring composition according to any one of [1] to [6], wherein the coloring agent (a) is contained in an amount of 10% by mass or more based on the total solid content of the photosensitive coloring composition.

[8] The photosensitive coloring composition according to any one of [1] to [7], which is used for forming a barrier rib of an organic electroluminescent element.

[9] A cured product obtained by curing the photosensitive colored resin composition according to any one of [1] to [8].

[10] An organic electroluminescent device comprising the cured product according to [9].

[11] An image display device including the organic electroluminescent device according to [10].

ADVANTAGE OF THE INVENTION According to this invention, the photosensitive coloring composition which rarely causes surface roughness to an electrode after heat treatment can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described concretely, this invention is not limited to the following embodiment, It can implement with various changes within the scope of the summary.

In the present invention, "(meth)acryl" means "acryl and/or methacryl", and the same applies to "(meth)acrylate" and "(meth)acryloyl".

"(Co)polymer" means that includes both a homopolymer (homopolymer) and a copolymer (copolymer), and "acid (anhydride)", "(anhydride)... "Acid" means containing both an acid and its anhydride.

In the present invention, "acrylic resin" means a (co)polymer containing (meth)acrylic acid and a (co)polymer containing (meth)acrylic acid ester having a carboxy group.

In the present invention, "monomer" is a term relative to so-called high molecular substances (polymers), and is meant to include dimers, trimers, and oligomers in addition to monomers in a narrow sense.

In the present invention, "total solid content" means the total amount of components other than the solvent contained in the photosensitive coloring composition or the pigment dispersion. Even if components other than the solvent are liquid at room temperature, the components are not included in the solvent but included in the total solid content.

In this invention, "weight average molecular weight" means the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography).

In the present invention, "amine value" represents the amine value in terms of effective solid content, unless otherwise specified, and is a value expressed by the amount of base per 1 g of solid content of the dispersant and the mass of equivalent KOH. In addition, the measuring method is mentioned later. An "acid value" represents an acid value in terms of effective solid content, and is calculated by neutralization titration, unless otherwise specified.

Regarding a pigment, "C.I." means a color index.

In this specification, the percentage or part expressed by "mass" has the same meaning as the percentage or part expressed by "weight".

[Photosensitive Coloring Composition]

The photosensitive coloring composition of the present invention,

(a) colorant

(b) Alkali-soluble resin

(c) photopolymerization initiator

(d) ethylenically unsaturated compounds

(e) solvent

(f) dispersant

contains as an essential component.

As a first aspect, (a) as a colorant, a compound represented by general formula (I), a geometric isomer of a compound represented by general formula (I), a salt of a compound represented by general formula (I), or a compound represented by general formula (I) It contains at least 1 sort(s) chosen from the group which consists of salts of the geometrical isomers of the compound shown.

As a second aspect, the optical density per 1 μm of film thickness of a coating film obtained by curing the photosensitive coloring composition of the present invention is 0.5 or more.

In addition, if necessary, it contains other compounding components such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors. Components are used in a dissolved or dispersed state in a solvent.

<(a) colorant>

The photosensitive coloring composition of this invention contains (a) a coloring agent. (a) By containing a coloring agent, suitable light absorption property, especially when used for the purpose of forming light-shielding members, such as a partition, can obtain suitable light-shielding property.

In the first aspect, (a) as a colorant, a compound represented by general formula (I), a geometric isomer of a compound represented by general formula (I), a salt of a compound represented by general formula (I), and a compound represented by general formula (I) It contains at least 1 sort(s) selected from the group which consists of salts of geometric isomers of the compound represented by.

The compound represented by the general formula (I) (hereinafter also referred to as "compound (I)") is an organic black pigment. It is presumed that by having a rigid skeleton with aromatic rings, gas containing chlorine generated during heat treatment hardly penetrates the inside of the coating film. Moreover, since the transmittance|permeability of an ultraviolet-ray is high, the applied photosensitive composition becomes easy to photocur, and it is useful in these respects.

[Formula 8]

In formula (I), R ¹¹ and R ¹⁶ each independently represent a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;

R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁸ , R ¹⁹ and R ²⁰ are each independently a hydrogen atom, a halogen atom, R ²¹ , COOH, COOR ²¹ , COO ^- , CONH ₂ , CONHR ²¹ , CONR ²¹ R ²² , CN, OH, OR ²¹ , COCR ²¹ , OOCNH ₂ , OOCNHR ²¹ , OOCNR ²¹ R ²² , NO ₂ , NH ₂ , NHR ²¹ , NR ²¹ R ²² , NHCOR ²² , NR ²¹ COR ²² , N =CH ₂ , N=CHR ²¹ , N=CR ²¹ R ²² , SH, SR ²¹ , SOR ²¹ , SO ₂ R ²¹ , SO ₃ R ²¹ , SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ²¹ or SO ₂ NR ²¹ R ²² ;

At least one combination selected from the group consisting of R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , and R ¹⁹ and R ²⁰ is directly related to each other. may be bonded together, or may be bonded to each other through an oxygen atom, a sulfur atom, NH or NR ²¹ bridge;

R ²¹ and R ²² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms. indicate

Compound (I) and geometric isomers of Compound (I) have the following core structure (provided that substituents in the structural formula are omitted), and the trans-trans isomer is probably the most stable.

[Formula 9]

When compound (I) is anionic, its charge can be transferred to any known suitable cation, for example a metal, organic, inorganic or metal-organic cation, specifically an alkali metal, alkaline earth metal, transition metal, primary ammonium , Secondary ammonium, tertiary ammonium such as trialkyl ammonium, quaternary ammonium such as tetraalkyl ammonium, or salts compensated with organometallic complexes are preferred. In addition, when the geometric isomer of Compound (I) is anionic, it is preferable that it is the same salt.

In the substituents of the general formula (1) and their definitions, the following are preferable from the point in which the shielding ratio tends to increase. This is because the following substituents do not absorb and are considered to have no effect on the hue of the pigment.

R ¹² , R ¹⁴ , R ¹⁵ , R ¹⁷ , R ¹⁹ and R ²⁰ are each independently preferably a hydrogen atom, a fluorine atom or a chlorine atom, more preferably a hydrogen atom.

R ¹³ and R ¹⁸ 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( CH ₃ )(C ₂ H ₅ ), N(C ₂ H ₅ ) ₂ , α-naphthyl, β-naphthyl, SO ₃ H or SO ₃ ^— , more preferably atomic hydrogen or SO ₃ H; Especially preferably, it is a hydrogen atom.

R ¹¹ and R ¹⁶ are each independently preferably a hydrogen atom, CH ₃ or CF ₃ , more preferably a hydrogen atom.

Preferably, at least one combination selected from the group consisting of R ¹¹ and R ¹⁶ , R ¹² and R ¹⁷ , R ¹³ and R ¹⁸ , R ¹⁴ and R ¹⁹ , and R ¹⁵ and R ²⁰ is the same, more preferably R ¹¹ is the same as R ¹⁶ , R ¹² is the same as R ¹⁷ , R ¹³ is the same as R ¹⁸ , R ¹⁴ is the same as R ¹⁹ , and R ¹⁵ is the same as R ²⁰ .

Examples of the C1-C12 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, 2-methylbutyl, n -Pentyl group, 2-pentyl group, 3-pentyl group, 2,2-dimethylpropyl group, n-hexyl group, n-heptyl group, n-octyl group, 1,1,3,3-tetramethylbutyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group or dodecyl group.

The cycloalkyl group having 3 to 12 carbon atoms, for example, a cyclopropyl group, a cyclopropylmethyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group, a trimethylcyclohexyl group, a watery group, a norbornyl group, A bornyl group, norcaryl group, caryl group, menthyl group, norphinyl group, phynyl group, adamantan-1-yl group or adamantan-2-yl group.

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

Examples of the cycloalkenyl group having 3 to 12 carbon atoms include 2-cyclobuten-1-yl group, 2-cyclopenten-1-yl group, 2-cyclohexen-1-yl group, 3-cyclohexen-1-yl group, 2,4-cyclohexadien-1-yl group, 1-p-menthen-8-yl group, 4(10)-thuyen-10-yl group, 2-norbornen-1-yl group, 2,5-norbornadiene 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, for example, 1-propyn-3-yl group, 1-butyn-4-yl group, 1-pentyn-5-yl group, 2-methyl-3-butyn-2-yl group, 1,4-pentadiin-3-yl group, 1,3-pentadiin-5-yl group, 1-hexyn-6-yl group, cis-3-methyl-2-penten-4-yn-1-yl group, Trans-3-methyl-2-penten-4-yn-1-yl group, 1,3-hexadin-5-yl group, 1-octyn-8-yl group, 1-nonin-9-yl group, 1-decyne- 10-yl group or 1-dodecyn-12-yl group.

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

The compound represented by the general formula (I) is preferably selected from the group consisting of a compound represented by the following general formula (II) (hereinafter also referred to as "compound (II)") and a geometric isomer of the compound (II) It is a compound containing at least 1 type.

[Formula 10]

As such a compound, Irgaphor (registered trademark) Black S 0100 CF (manufactured by BASF) is exemplified as a trade name.

This organic black pigment is preferably used after being dispersed by the method described later. In addition, if a sulfonic acid derivative of Compound (I) or a sulfonic acid derivative of a geometric isomer of Compound (I), particularly a sulfonic acid derivative of Compound (II) or a sulfonic acid derivative of a geometric isomer of Compound (II) is present during dispersion, Acidity and preservation may be improved.

1st aspect of this invention WHEREIN: (A) The coloring agent may contain other coloring agents other than the compound of general formula (I). As another coloring agent, a pigment is preferable, and an organic pigment or an inorganic pigment may be sufficient as the pigment. From the viewpoint of high resistance and low permittivity, organic pigments are more preferred, and organic color pigments described later are particularly preferred.

Among organic color pigments, it is preferable to use compound (I) and a blue pigment from the viewpoint of making the transmittance in the high wavelength region of the visible light region uniform. Pigment Blue B60, 15:6, 16 are preferable, and Pigment Blue B60 is more preferable.

On the other hand, from the viewpoint of making the transmittance of the entire visible light region uniform, in addition to compound (I), at least one selected from the group consisting of a red pigment and an orange pigment, and at least one selected from the group consisting of a blue pigment and a violet pigment It is preferable to use

In the second aspect, the photosensitive coloring composition of the present invention has an optical density per 1 μm of film thickness of a cured coating film (hereinafter sometimes referred to as “OD per unit film thickness”) of 0.5 or more. (a) By containing a coloring agent and making OD per unit film thickness more than the said lower limit, the light-shielding property of the hardened|cured material obtained, especially a partition wall becomes high.

OD per unit film thickness can be calculated by measuring the optical density and film thickness of a coating film obtained by curing the photosensitive coloring composition, and dividing the optical density by the film thickness. The conditions for producing the coating film are not particularly limited, but, for example, the conditions described in Examples described later can be employed.

In order to make OD per unit film thickness more than the said lower limit, what is necessary is just to adjust suitably the kind of (a) colorant, and the content rate in total solid amount, for example.

2nd aspect of this invention WHEREIN: The kind of (a) colorant which can be used for the photosensitive coloring composition is not specifically limited, A pigment may be used and dye may be used. Among these, it is preferable to use a pigment from a durable viewpoint.

(a) The pigment contained in the coloring agent may be used alone or in combination of two or more. In particular, it is preferable that it is 2 or more types from a viewpoint of uniformly shielding light in a visible region and making OD per unit film thickness compatible.

(a) Although the kind of pigment which can be used as a coloring agent is not specifically limited, For example, an organic color pigment and a black pigment are mentioned. Here, an organic color pigment means an organic pigment which shows a color other than black, and examples thereof include a red pigment, an orange pigment, a blue pigment, a purple pigment, a green pigment and a yellow pigment.

Among the pigments, it is preferable to use organic color pigments from the viewpoint of high resistance and low permittivity. Moreover, from a viewpoint of light-shielding property, it is preferable to use compound (I) or another black pigment.

An organic color pigment may be used individually by 1 type, or may use 2 or more types together. In particular, from the viewpoint of setting the OD per unit film thickness to 0.5 or more, it is more preferable to use a combination of organic color pigments of different colors, and it is more preferable to use a combination of organic color pigments exhibiting a color close to black.

The chemical structure of these organic color pigments is not particularly limited, but examples thereof include azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, isoindolinone-based, dioxazine-based, indanthrene-based, and perylene-based pigments. there is. Hereinafter, specific examples of pigments that can be used are indicated by pigment numbers. The “C.I. "C.I." in "Pigment Red 2" or the like means a color index.

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. From the viewpoints of light-shielding properties and dispersibility, C.I. Pigment Red 48: 1, 122, 149, 168, 177, 179, 194, 202, 206, 207, 209, 224, 242, 254, more preferably C.I. Pigment Red 177, 209, 224, 254 can be mentioned. In terms of dispersibility and light-shielding properties, C.I. Pigment Red 177, 254, and 272 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, as the red pigment, those having low ultraviolet absorption are preferable. From this point of view, C.I. Pigment red 254 and 272 are more preferable.

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. From the viewpoint of dispersibility or light-shielding properties, C.I. Pigment Orange 13, 43, 64, and 72 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, as the orange pigment, those having low ultraviolet absorption are preferable. From this point of view, C.I. Pigment Orange 64 and 72 are more preferable.

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. From the viewpoint of light-shielding properties, preferably C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 60, more preferably C.I. Pigment Blue 15:6. In terms of dispersibility and light-shielding properties, C.I. Pigment Blue 15:6, 16, 60 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, as the blue pigment, those with low ultraviolet absorption are preferable. From this point of view, C.I. Pigment Blue 60 is more preferable.

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. From the viewpoint of light-shielding properties, preferably C.I. Pigment Violet 19, 23, 29, more preferably C.I. Pigment Violet 23 is exemplified. In terms of dispersibility and light-shielding properties, C.I. Pigment Violet 23 and 29 are preferable, and when the photosensitive coloring composition is cured with ultraviolet rays, as a purple pigment, those having low ultraviolet absorbance are preferable. From this point of view, C.I. Pigment Violet 29 is more preferable.

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, 59. . Preferably C.I. Pigment Green 7 and 36 are mentioned.

As a yellow pigment, C.I. Pigment Yellow 1, 1: 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36 : 1, 37, 37 : 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62 : 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139 ; 174 ; 03 , 204, 205, 206, 207, 208. Preferably 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 are exemplified.

At least one selected from the group consisting of red pigments, orange pigments, blue pigments, and purple pigments is preferred from the viewpoints of light-shielding properties of the cured product and control of shape and level difference.

It is preferable to contain at least 1 or more types of the following pigments from a viewpoint of the light-shielding property of hardened|cured material, and control of a shape and level difference.

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

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

Although it does not specifically limit about the combination of organic color pigments in the case of using 2 or more types of organic color pigments together, From a light-shielding viewpoint, at least 1 sort(s) selected from the group which consists of a red pigment and an orange pigment, a blue pigment, and a violet color It is preferable to use together at least 1 sort(s) selected from the group which consists of pigments.

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, and a combination of a blue pigment, an orange pigment, and a purple pigment are exemplified. .

As the pigment, organic black pigments other than organic color pigments and organic black pigments represented by general formula (I) and inorganic black pigments can be used.

As organic black pigments other than the organic black pigment represented by General formula (I), aniline black and perylene black are mentioned, for example.

As an inorganic black pigment, the inorganic black pigment described in international publication 2018/101314 is mentioned, for example.

In using these coloring agents, when chlorine atoms are contained in the coloring agent, use is possible by adjusting the addition amount so that the amount of chlorine does not increase too much.

These pigments are preferably dispersed and used so 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. Here, the standard for the average particle diameter is the number of pigment particles.

In addition, in the photosensitive coloring composition of this invention, the average particle diameter of a pigment is the value calculated|required from the pigment particle diameter measured by dynamic light scattering (DLS). Particle size measurement is carried out on a sufficiently diluted photosensitive coloring composition (usually diluted and prepared at a pigment concentration of about 0.005 to 0.2% by mass. However, if there is a concentration recommended by a measuring instrument, it is followed by that concentration), and is carried out at 25 ° C. measured in

In the photosensitive coloring composition of the second aspect of the present invention, one type of coloring agent such as an organic color pigment or a black pigment may be used alone or two or more types may be used in combination.

You may use dye other than the organic color pigment and black pigment mentioned above. As a dye which can be used as a coloring agent, the dye described in international publication 2018/101314 is mentioned, for example.

<(b) alkali-soluble resin>

The (b) alkali-soluble resin used in the present invention is not particularly limited as long as it is a resin containing a carboxyl group or a hydroxyl group, and examples thereof include epoxy (meth)acrylate-based resins, acrylic resins, carboxyl-containing epoxy resins, and carboxyl-containing resins. A urethane resin, a novolak-type resin, and a polyvinyl phenol-type resin are mentioned. inter alia,

(b1) Epoxy (meth) acrylate resin

(b2) acrylic copolymer resin

is preferably used from the viewpoint of excellent platemaking properties. These can be used individually by 1 type or in combination of 2 or more types.

<(b1) Epoxy (meth)acrylate-based resin>

(b1) Epoxy (meth)acrylate-based resin is a reaction between an epoxy compound (epoxy resin) and an α,β-unsaturated monocarboxylic acid and/or an α,β-unsaturated monocarboxylic acid ester having a carboxy group in the ester portion. It is a resin obtained by reacting the hydroxyl group produced by with a compound having two or more substituents capable of reacting with hydroxyl groups such as polybasic acids and/or their anhydrides.

A resin obtained by reacting a compound having two or more substituents capable of reacting with a hydroxyl group before reacting a polybasic acid and/or its anhydride with a hydroxyl group, and then reacting a polybasic acid and/or its anhydride with the above (b1) epoxy ( Included in meth)acrylate-based resins.

A resin obtained by reacting a compound having a functional group capable of further reacting with the carboxy group of the resin obtained by the above reaction is also included in the above (b1) epoxy (meth)acrylate-based resin.

In this way, the epoxy (meth) acrylate-based resin does not substantially have an epoxy group in terms of chemical structure, and is not limited to "(meth) acrylate", but an epoxy compound (epoxy resin) is a raw material, and " (meth)acrylate” is a representative example, so it is named as such according to convention.

As the (b1) epoxy (meth)acrylate-based resin used in the present invention, in particular, the following epoxy (meth)acrylate-based resin (b1-1) and/or epoxy (meth)acrylate-based resin (b1-2) (Hereinafter, it may be called "carboxyl group-containing epoxy (meth)acrylate-based resin") is preferably used from the viewpoint of developability and reliability.

Moreover, as (b1) epoxy (meth)acrylate-type resin, what has an aromatic ring in a principal chain can be used more preferably from a viewpoint of an outgas.

<Epoxy (meth)acrylate-based resin (b1-1)>

An α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group is added to an epoxy resin, optionally an isocyanate group-containing compound is reacted, and then a polybasic acid and/or an anhydride thereof is further reacted. Alkali-soluble resin obtained by

<Epoxy (meth)acrylate-based resin (b1-2)>

After adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, optionally reacting an isocyanate group-containing compound, further a polyhydric alcohol, and a polybasic acid and/or Alkali-soluble resin obtained by reacting with the anhydride.

Here, the epoxy resin is meant to include raw material compounds prior to forming the resin by thermal curing, and the epoxy resin can be appropriately selected from known epoxy resins and used. Moreover, the compound obtained by making a phenolic compound and epihalohydrin react can be used for an epoxy resin. As the phenolic compound, a compound having a divalent or a divalent or higher phenolic hydroxyl group is preferable, and may be a monomer or a polymer.

As a kind of epoxy resin used as a raw material, for example, cresol novolac type epoxy resin, phenol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, trisphenolmethane type epoxy resin, biphenyl furnace A rockfish-type epoxy resin, a naphthalene novolak-type epoxy resin, an epoxy resin that is a reaction product of a polyaddition reaction of dicyclopentadiene and phenol or cresol and epihalohydrin, an epoxy resin containing an adamantyl group, and a fluorene-type epoxy resin. It can be used preferably, and among these, what has an aromatic ring in a principal chain can be used more preferably.

As the epoxy resin, for example, bisphenol A type epoxy resin (for example, "jER (registered trademark, hereinafter the same) 828" manufactured by Mitsubishi Chemical Corporation, "jER1001", "jER1002", "jER1004", etc.), Epoxy resin obtained by reaction of the alcoholic hydroxyl group of bisphenol A type epoxy resin with epichlorohydrin (for example, “NER-1302” manufactured by Nippon Chemical Co., Ltd. (epoxy equivalent 323, softening point 76° C.)), bisphenol F type resin (For example, "jER807", "EP-4001", "EP-4002", "EP-4004", etc. manufactured by Mitsubishi Chemical Corporation), in the reaction between the alcoholic hydroxyl group of bisphenol F-type epoxy resin and epichlorohydrin Epoxy resin obtained by (eg, "NER-7406" manufactured by Nippon Kayaku Co., Ltd. (epoxy equivalent 350, softening point 66 ° C.), bisphenol S-type epoxy resin, biphenyl glycidyl ether (eg, manufactured by Mitsubishi Chemical Co., Ltd.) "YX-4000" of), phenol novolac type epoxy resin (for example, "EPPN-201" manufactured by Nippon Chemical Co., Ltd., "EP-152" manufactured by Mitsubishi Chemical Corporation, "EP-154" manufactured by Dow Chemical Co., Ltd. manufactured "DEN-438"), (o, m, p-) cresol novolak type epoxy resin (for example, "EOCN (registered trademark, hereinafter the same) -102S" manufactured by Nippon Chemical Co., Ltd., "EOCN-1020 ", "EOCN-104S"), triglycidyl isocyanurate (eg, "TEPIC (registered trademark)" manufactured by Nissan Chemical Industries, Ltd.), trisphenolmethane type epoxy resin (eg, manufactured by Nippon Chemical Co., Ltd. "EPPN (registered trademark, hereinafter the same) -501", "EPPN-502", "EPPN-503"), alicyclic epoxy resin ("Seloxide (registered trademark, hereinafter the same) 2021P" manufactured by Daicel, "Cellock Side EHPE”), an epoxy resin obtained by glycidylating a phenol resin by reaction of dicyclopentadiene and phenol (eg, “EXA-7200” manufactured by DIC, “NC-7300” manufactured by Nippon Kayaku Co., Ltd.) , epoxy resins represented by the following general formulas (B1) to (B4) can be preferably used. Specifically, for example, "XD-1000" manufactured by Nippon Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B1), and "NC-3000" manufactured by Nippon Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B2). "E-201" manufactured by Osaka Organic Chemical Industry Co., Ltd. as an epoxy resin represented by the following general formula (B3), and "ESF-300" manufactured by Nippon Steel Sumikin Chemical Co., Ltd. as an epoxy resin represented by the following general formula (B4) can

[Formula 11]

In the above general formula (B1), a is an average value and represents a number from 0 to 10, and R ¹¹¹ each independently represents a hydrogen atom, a halogen atom, an alkyl group of 1 to 8 carbon atoms, a cycloalkyl group of 3 to 10 carbon atoms, or a phenyl group. , a naphthyl group, or a biphenyl group. A plurality of R ¹¹¹ groups present in one molecule may be the same or different.

[Formula 12]

In the above general formula (B2), b1 and b2 are each independently an average value and represent a number of 0 to 10, and R ¹²¹ is each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 8 carbon atoms, and 3 to 10 carbon atoms. represents a cycloalkyl group, a phenyl group, a naphthyl group, or a biphenyl group. In addition, a plurality of R ¹²¹ groups present in one molecule may be the same or different.

[Formula 13]

In the above general formula (B3), X represents a linking group represented by the following general formula (B3-1) or (B3-2). However, one or more adamantane structures are included in the molecular structure. c represents 2 or 3;

[Formula 14]

In the general formulas (B3-1) and (B3-2), R ¹³¹ to R ¹³⁴ and R ¹³⁵ to R ¹³⁷ are each independently an adamantyl group which may have a substituent, a hydrogen atom, or a hydrogen atom which may have a substituent. represents an alkyl group of 1 to 12 carbon atoms or a phenyl group which may have a substituent, and * represents a bond.

[Formula 15]

In the above general formula (B4), p and q each independently represent an integer of 0 to 4, R ¹⁴¹ and R ¹⁴² each independently represent an alkyl group having 1 to 4 carbon atoms or a halogen atom, and R ¹⁴³ and R ¹⁴⁴ represents an alkylene group having 1 to 4 carbon atoms each independently, and x and y each independently represent an integer of 0 or greater.

Among these, it is preferable to use an epoxy resin represented by any of general formulas (B1) to (B4).

Examples of α,β-unsaturated monocarboxylic acids or α,β-unsaturated monocarboxylic acid esters having a carboxy group include (meth)acrylic acid, crotonic acid, o-, m- or p-vinylbenzoic acid, and (meth)acrylic acid. α-position haloalkyl, alkoxyl, halogen, nitro, monocarboxylic acids such as cyano substituents, 2-(meth)acryloyloxyethylsuccinic acid, 2-(meth)acryloyloxyethyladipic acid, 2- (meth)acryloyloxyethylphthalic acid, 2-(meth)acryloyloxyethylhexahydrophthalic acid, 2-(meth)acryloyloxyethylmaleic acid, 2-(meth)acryloyloxypropylsuccinic acid, 2 -(meth)acryloyloxypropyladipic acid, 2-(meth)acryloyloxypropyltetrahydrophthalic acid, 2-(meth)acryloyloxypropylphthalic acid, 2-(meth)acryloyloxypropylmale Acid, 2-(meth)acryloyloxybutylsuccinic acid, 2-(meth)acryloyloxybutyladipic acid, 2-(meth)acryloyloxybutylhydrophthalic acid, 2-(meth)acryloyloxy Lactones such as ε-caprolactone, β-propiolactone, γ-butyrolactone, and δ-valerolactone are added to butylphthalic acid, 2-(meth)acryloyloxybutylmaleic acid, and (meth)acrylic acid. a monomer obtained by adding an acid (anhydride) such as (anhydride) succinic acid, (anhydride) phthalic acid, or (anhydride) maleic acid to a monomer or hydroxyalkyl (meth)acrylate or pentaerythritol tri(meth)acrylate; (meth)acrylic acid dimer etc. are mentioned.

Among these, (meth)acrylic acid is particularly preferred in terms of sensitivity.

As a method for adding an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxyl group to an epoxy resin, a known method can be used. For example, an α,β-unsaturated monocarboxylic acid or an α,β-unsaturated monocarboxylic acid ester having a carboxy group and an epoxy resin can be reacted at a temperature of 50 to 150° C. in the presence of an esterification catalyst. . Examples of the esterification catalyst used herein include tertiary amines such as triethylamine, trimethylamine, benzyldimethylamine, and benzyldiethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetraethylammonium chloride, and dodecyltrimethylammonium chloride. etc. can be used.

Each component of the epoxy resin, the α,β-unsaturated monocarboxylic acid or the α,β-unsaturated monocarboxylic acid ester having a carboxy group, and the esterification catalyst may be used by selecting one of each component, or two or more types. may be used in combination.

The amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group is preferably in the range of 0.5 to 1.2 equivalents, more preferably 0.7 to 1 equivalent of the epoxy group of the epoxy resin. to 1.1 equivalents. By setting the amount of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to be used not less than the above lower limit, an insufficient amount of unsaturated groups introduced can be suppressed, and the subsequent reaction with the polybasic acid and/or its anhydride is sufficient. It tends to be easy to do. On the other hand, by setting the above upper limit or less, the remaining unreacted product of α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxy group can be suppressed, and the curing properties tend to be good. It is acknowledged.

Examples of polybasic acids and/or anhydrides thereof include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenonetetracarboxylic acid, and methylhexahydrophthalic acid. , endomethylenetetrahydrophthalic acid, chlorendic acid, methyltetrahydrophthalic acid, biphenyltetracarboxylic acid, and anhydrides thereof.

Preferably, it is maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, biphenyltetracarboxylic acid, or an anhydride thereof. Particularly preferred are tetrahydrophthalic acid, biphenyltetracarboxylic acid, tetrahydrophthalic anhydride, or biphenyltetracarboxylic dianhydride.

The addition reaction of the polybasic acid and/or its anhydride can be carried out using a known method, and the α,β-unsaturated monocarboxylic acid or α,β-unsaturated monocarboxylic acid ester having a carboxyl group to the epoxy resin. Under the same conditions as for the addition reaction, the desired product can be obtained by continuing the reaction. The added amount of the polybasic acid and/or its anhydride component is preferably such that the acid value of the resulting carboxyl group-containing epoxy (meth)acrylate-based resin is in the range of 10 to 150 mgKOH/g, and is preferably 20 to 140 mgKOH/g It is preferable that the degree to be in the range of There exists a tendency for alkali developability to become favorable by setting it as more than the said lower limit. There exists a tendency for hardening performance to become favorable by using below the said upper limit.

During the addition reaction of polybasic acids and/or their anhydrides, polyfunctional alcohols such as trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, trimethylolethane, and 1,2,3-propanetriol (polyhydric alcohols) alcohol) may be added to introduce a multi-branched structure. In this case, the order of mixing the polybasic acid and/or its anhydride with the polyfunctional alcohol is not particularly limited. By heating, polybasic acids and/or polybasic acids and/or polybasic acids and/or polybasic acids and/or their Anhydride reacts with addition.

By using a polyhydric alcohol, (b1) the molecular weight of the epoxy (meth)acrylate resin can be increased and a branch can be introduced into the molecule, so that the molecular weight and viscosity tend to be balanced. In addition, the rate of introduction of acid groups into molecules can be increased, and there is a tendency that it is easy to balance sensitivity, adhesion, and the like.

As a carboxy group-containing epoxy (meth)acrylate-type resin, in addition to what was mentioned above, what was described in Korean Unexamined Patent Publication No. 10-2013-0022955 is mentioned, for example.

The weight average molecular weight (Mw) of the carboxyl group-containing epoxy (meth)acrylate-based resin in terms of polystyrene measured by gel permeation chromatography (GPC) is usually 1000 or more, preferably 1500 or more, more preferably 2000 or more. , More preferably 3000 or more, still more preferably 4000 or more, particularly preferably 5000 or more, and usually 30000 or less, preferably 20000 or less, more preferably 15000 or less. The above upper and lower limits can be arbitrarily combined. For example, 1000 to 30000 are preferable, 1500 to 20000 are more preferable, 1500 to 15000 are still more preferable, and 2000 to 15000 are still more preferable. There exists a tendency that it can suppress too much solubility in a developing solution by setting it as more than the said lower limit. By setting it below the upper limit above, there is a tendency that the solubility to the developer is good.

The acid value of the carboxyl group-containing epoxy (meth)acrylate-based resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, still more preferably 60 mgKOH/g or more, and 80 mgKOH/g or more. g or more is more preferred, 100 mgKOH/g or more is particularly preferred, 200 mgKOH/g or less is preferred, 150 mgKOH/g or less is more preferred, 130 mgKOH/g or less is still more preferred, and 120 mgKOH/g or less is more preferred. Particularly preferred is mgKOH/g or less. The above upper and lower limits can be arbitrarily combined. For example, 20 mgKOH/g to 200 mgKOH/g are preferable, 60 mgKOH/g to 150 mgKOH/g are more preferable, 80 mgKOH/g to 130 mgKOH/g are still more preferable, and 100 mgKOH/g to 130 mgKOH/g is more preferred. There exists a tendency for developing solubility to improve and resolution to become favorable by setting it as more than the said lower limit. There exists a tendency for the remaining-film rate of the photosensitive coloring composition to become favorable by carrying out below the said upper limit.

The chemical structure of the epoxy (meth) acrylate-based resin is not particularly limited, but from the viewpoint of developability and reliability, an epoxy (meth) acrylate-based resin having a partial structure represented by the following general formula (b1-I) (hereinafter, Sometimes abbreviated as “(b1-I) epoxy (meth)acrylate resin”) and/or an epoxy (meth)acrylate resin having a partial structure represented by the following general formula (b1-II) (hereinafter, "(b1-II) Epoxy (meth)acrylate-based resin" may be abbreviated) is preferable.

[Formula 16]

In formula (b1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond.

The benzene ring in formula (b1-I) may be further substituted with an arbitrary substituent.

[Formula 17]

In formula (b1-II), 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, and R ¹⁵ and R ¹⁶ each independently represent; Represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a bond.

<(b1-I) Epoxy (meth)acrylate-based resin>

First, an epoxy (meth)acrylate-based resin having a partial structure represented by the general formula (b1-I) will be described in detail.

[Formula 18]

In formula (b1-I), R ¹¹ represents a hydrogen atom or a methyl group, R ¹² represents a divalent hydrocarbon group which may have a substituent, k represents 1 or 2, and * represents a bond.

The benzene ring in formula (b1-I) may be further substituted with an arbitrary substituent.

( ^R12 )

In the formula (b1-I), 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 aliphatic groups. Among these, from the viewpoint of developing solubility, a linear aliphatic group is preferable. On the other hand, a cyclic aliphatic group is preferable from the viewpoint of reducing permeation of the developing solution into the exposed area. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 20 are preferable, 1 to 15 are more preferable, and 1 to 10 are still more preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

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

Examples of the divalent branched chain aliphatic group include the above-mentioned divalent linear aliphatic group, as a side chain, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec -The structure which has a butyl group and a tert- butyl group is mentioned.

The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 12 are preferable, 1 to 10 are more preferable, and 2 to 10 are still more preferable. When the film is set to the above lower limit or more, a strong film tends to be formed and the adhesion to the substrate tends to be good. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

Examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and groups obtained by removing two hydrogen atoms from rings such as dicyclopentadiene rings and dicyclopentane rings. Among these, groups in which two hydrogen atoms have been removed from the dicyclopentadiene ring, dicyclopentane ring, and adamantane ring are preferable from the viewpoint of rigidity of the skeleton.

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

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The number of carbon atoms is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. The above upper and lower limits can be arbitrarily combined. For example, 4-20 are preferable, 5-15 are more preferable, and 6-10 are still more preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a tricyclic ring having two free valences. A phenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are mentioned.

Moreover, a monocyclic ring or a condensed ring may be sufficient as an aromatic heterocyclic ring in an aromatic heterocyclic group. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , Benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, A perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring are mentioned.

Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. Among these, unsubstituted is preferable from the viewpoint of developing solubility.

Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include one or more divalent aliphatic groups described above and one or more divalent aromatic ring groups described above.

The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are particularly preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are particularly preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

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 (b1-I-A) to (b1-I-F). Among these, the group represented by the following formula (b1-I-A) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.

[Formula 19]

In the formula (b1-I), k represents 1 or 2. As for k, 1 is preferable from a viewpoint of adhesiveness and patternability. As for k, 2 is preferable from a viewpoint of NMP resistance. (b1-I) Epoxy (meth)acrylate may contain both a partial structure in which k is 1 and a partial structure in which k is 2.

The benzene ring in formula (b1-I) may be further substituted with an arbitrary substituent. As a substituent permissible for the benzene ring in formula (b1-I), a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. When the benzene ring in formula (b1-I) has a substituent, the number of substituents is not particularly limited, and may be one or two or more.

From the viewpoint of patterning characteristics, the benzene ring in the formula (b1-I) is preferably unsubstituted.

The partial structure represented by the formula (b1-I) is preferably a partial structure represented by the following formula (b1-I-1) from the viewpoint of synthesis simplicity.

[Formula 20]

In the formula (b1-I-1), R ¹¹ , R ¹² and k have the same meanings as those in the formula (b1-I), R ^X represents a hydrogen atom or a polybasic acid residue, and * represents a bond.

The benzene ring in formula (b1-I-1) may be further substituted with an arbitrary substituent.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid or its anhydride. Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydro Phthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid are exemplified.

From the viewpoint of patterning properties, maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, and biphenyltetracarboxylic acid are preferred, and more preferably tetrahydrophthalic acid. Hydrophthalic acid, biphenyltetracarboxylic acid.

The benzene ring in formula (b1-I-1) may be further substituted with an arbitrary substituent. As the substituent, those exemplified for the benzene ring in the formula (b1-I) can be preferably employed.

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

The number of partial structures represented by the formula (b1-I) contained in one molecule of the (b1-I) epoxy (meth)acrylate-based resin is not particularly limited, but is preferably 1 or more, and more preferably 3 or more. It is preferable, and 20 or less is preferable, and 15 or less is more preferable. 1-20 are preferable, 1-15 are more preferable, and 3-15 are still more preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

(b1-I) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth)acrylate-based resin is not particularly limited, but is preferably 1000 or more, and is preferably 1500 or more. More preferably, 2000 or more is still more preferable, 3000 or more is even more preferable, 4000 or more is particularly preferable, 5000 or more is most preferable, usually 30000 or less, 20000 or less is preferable, and 15000 or less is more preferable. . The above upper and lower limits can be arbitrarily combined. For example, 1000 to 30000 are preferable, 1500 to 20000 are more preferable, 1500 to 15000 are still more preferable, and 2000 to 15000 are still more preferable. There exists a tendency for the remaining-film rate of the photosensitive coloring composition to become favorable by setting it as more than the said lower limit. There exists a tendency for the solubility with respect to a developing solution to become favorable by carrying out below the said upper limit.

(b1-I) The acid value of the epoxy (meth)acrylate-based resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, and still more preferably 60 mgKOH/g or more. , 80 mgKOH/g or more is more preferred, 100 mgKOH/g or more is particularly preferred, and 200 mgKOH/g or less is preferred, 150 mgKOH/g or less is more preferred, and 130 mgKOH/g or less is more preferred. More preferably, 120 mgKOH/g or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 20 mgKOH/g to 200 mgKOH/g are preferable, 60 mgKOH/g to 150 mgKOH/g are more preferable, 80 mgKOH/g to 130 mgKOH/g are still more preferable, and 100 mgKOH/g to 130 mgKOH/g is more preferred. There exists a tendency for developing solubility to improve and resolution to become favorable by setting it as more than the said lower limit. There exists a tendency for the remaining-film rate of the photosensitive coloring composition to become favorable by carrying out below the said upper limit.

Specific examples of (b1-I) epoxy (meth)acrylate-based resins are given below. In addition, * in an example represents a binding hand.

[Formula 21]

[Formula 22]

[Formula 23]

[Formula 24]

<(b1-II) Epoxy (meth)acrylate-based resin>

An epoxy (meth)acrylate-based resin having a partial structure represented by the general formula (b1-II) will be described in detail.

[Formula 25]

In formula (b1-II), 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, and R ¹⁵ and R ¹⁶ each independently represent; Represents a divalent aliphatic group which may have a substituent, m and n each independently represent an integer of 0 to 2, and * represents a bond.

( ^R14 )

In the general formula (b1-II), 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.

The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are particularly preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly 15 or less. desirable. The above upper and lower limits can be arbitrarily combined. For example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, and 8-15 are especially preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. can be heard Among these, an adamantane ring is preferable from the viewpoint of the remaining film rate and resolution of the photosensitive coloring composition.

The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less, and more preferably 4 or less. . The above upper and lower limits can be arbitrarily combined. For example, 1-10 are preferable, 1-5 are more preferable, 1-4 are still more preferable, 2-4 are still more preferable, and 3-4 are especially preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, even more preferably 10 or more, particularly preferably 12 or more, more preferably 40 or less, and 30 or more. The following is more preferable, 20 or less is still more preferable, and 15 or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 4 to 40 are preferable, 6 to 40 are more preferable, 8 to 30 are still more preferable, 10 to 20 are even more preferable, and 12 to 15 are particularly preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. Patterning characteristics tend to be good by setting it below the said upper limit.

Examples of the aromatic ring in the aromatic ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a triphenylene ring. , an acenaphthene ring, a fluoranthene ring, and a fluorene ring. Among these, a fluorene ring is preferable from a viewpoint of a patterning characteristic.

The divalent hydrocarbon group in the divalent hydrocarbon group having a cyclic hydrocarbon group as a side chain is not particularly limited, but examples include a divalent aliphatic group, a divalent aromatic ring group, one or more divalent aliphatic groups and one or more divalent aromatic groups. and groups having cyclic groups connected thereto.

Examples of the divalent aliphatic group include linear, branched and cyclic aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of developing solubility, while a cyclic aliphatic group is preferable from the viewpoint of reducing permeation of the developing solution into the exposed area. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 25 or less, more preferably 20 or less, still more preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, 1-25 are preferable, 3-20 are more preferable, and 6-15 are still more preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

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

As the divalent branched chain aliphatic group, for example, in addition to the divalent linear aliphatic group described above, as a side chain, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec- A structure having a butyl group or a tert-butyl group is exemplified.

The number of rings of the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are particularly preferable. When the film is set to the above lower limit or more, a strong film tends to be formed and the adhesion to the substrate tends to be good. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

Examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. and groups in which two hydrogen atoms have been removed from the ring. Among these, a group obtained by removing two hydrogen atoms from the adamantane ring is preferable from the viewpoint of rigidity of the skeleton.

As a substituent which a divalent aliphatic group may have, For example, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; A carboxyl group can be mentioned. Among these, unsubstituted is preferable from the viewpoint of synthetic ease.

Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The carbon number is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

The aromatic hydrocarbon ring in the divalent aromatic hydrocarbon ring group may be a monocyclic ring or a condensed ring. Examples of the aromatic hydrocarbon ring group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, and a tricyclic ring having two free valences. A phenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are mentioned.

The aromatic heterocyclic ring in the aromatic heterocyclic group may be a monocyclic ring or a condensed ring. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole ring having two free valences. ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring , Benzoisothiazole ring, benzoimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, A benzoimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring are mentioned. Among these, from the viewpoint of patterning characteristics, a benzene ring or a naphthalene ring having two free valences is preferable, and a benzene ring having two free valences is more preferable.

As a substituent which a divalent aromatic ring group may have, a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. Among these, unsubstituted is preferable from the viewpoint of developing solubility.

Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include one or more divalent aliphatic groups described above and one or more divalent aromatic ring groups described above.

The number of divalent aliphatic groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are particularly preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

The number of divalent aromatic ring groups is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less, and more preferably 3 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 to 3 are particularly preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

Examples of the group in which one or more divalent aliphatic groups and one or more divalent aromatic ring groups are linked include groups represented by the above formulas (b1-I-A) to (b1-I-F). Among these, the group represented by the above formula (b1-I-C) is preferable from the viewpoint of rigidity of the skeleton and hydrophobicity of the membrane.

Regarding these divalent hydrocarbon groups, the bonding mode of the side chain cyclic hydrocarbon group is not particularly limited, but, for example, an aspect in which one hydrogen atom of an aliphatic group or an aromatic ring group is substituted with a side chain cyclic hydrocarbon group, An embodiment comprising a cyclic hydrocarbon group as a side chain by including one of the carbon atoms of the aliphatic group is exemplified.

(R ¹⁵ , R ¹⁶ )

In the general formula (b1-II), 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 aliphatic groups. Among these, a linear aliphatic group is preferable from the viewpoint of developing solubility, while a cyclic aliphatic group is preferable from the viewpoint of reducing permeation of the developing solution into the exposed area. The carbon number is usually 1 or more, preferably 3 or more, more preferably 6 or more, and preferably 20 or less, more preferably 15 or less, still more preferably 10 or less. For example, 1-20 are preferable, 3-15 are more preferable, and 6-10 are still more preferable. By setting the film to a value equal to or greater than the lower limit, a firm film can be easily obtained, surface roughness generated during development is less likely to occur, and adhesion to the substrate tends to be improved. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

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

Examples of the divalent branched aliphatic group include the divalent linear aliphatic group as a side chain, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, Structures having a sec-butyl group and a tert-butyl group are exemplified.

The number of rings in the divalent cyclic aliphatic group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 12 or less, preferably 10 or less. For example, 1-12 are preferable and 2-10 are more preferable. When the film is set to the above lower limit or more, a strong film tends to be formed and the adhesion to the substrate tends to be good. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

Examples of the divalent cyclic aliphatic group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, a cyclododecane ring, and groups obtained by removing two hydrogen atoms from the dicyclopentadiene ring. Among these, groups in which two hydrogen atoms have been removed from the dicyclopentadiene ring or adamantane ring are preferable from the viewpoint of rigidity of the skeleton.

As a substituent which a divalent aliphatic group may have, For example, C1-C5 alkoxy groups, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; A carboxyl group can be mentioned. Among these, unsubstituted is preferable from the viewpoint of synthetic ease.

(m、n)

In the general formula (b1-II), m and n represent an integer of 0 to 2 each independently. When the value is equal to or greater than the lower limit, the patterning aptitude tends to be improved and surface roughness generated during development tends to be less likely to occur. It is preferable that m and n are 0 from a developable viewpoint. On the other hand, it is preferable that m and n are 1 or more from the viewpoint of patterning aptitude and surface roughness generated during development.

The partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-1) from the viewpoint of adhesion to the substrate.

[Formula 26]

In formula (b1-II-1), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meaning as in formula (b1-II), R ^α represents a monovalent cyclic hydrocarbon group which may have a substituent, , p represents an integer greater than or equal to 1, and * represents a bonding hand. The benzene ring in formula (b1-II-1) may be further substituted with an arbitrary substituent.

(R ^α )

In the general formula (b1-II-1), R ^? represents a monovalent cyclic hydrocarbon group which may have a substituent.

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

The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 6 or less, preferably 4 or less, and more preferably 3 or less. For example, 1-6 are preferable, 1-4 are more preferable, 1-3 are still more preferable, and 2-3 are especially preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. Patterning characteristics tend to be good by setting it below the said upper limit.

The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 30 or less, still more preferably 20 or less, and particularly 15 or less. desirable. The above upper and lower limits can be arbitrarily combined. For example, 4-40 are preferable, 4-30 are more preferable, 6-20 are still more preferable, and 8-15 are especially preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. Patterning characteristics tend to be good by setting it below the said upper limit.

Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. can be heard Among these, an adamantane ring is preferable from the viewpoint of robust film properties.

The number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 2 to 5 are still more preferable, and 3 to 5 are particularly preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. Patterning characteristics tend to be good by setting it below the said upper limit.

As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 5 or more, more preferably 6 or more, and preferably 30 or less, more preferably 20 or less, still more preferably 15 or less. The above upper and lower limits can be arbitrarily combined. For example, 4-30 are preferable, 5-20 are more preferable, and 6-15 are still more preferable. When the value is equal to or higher than the lower limit, a strong film is easily obtained and surface roughness generated during development tends to be less likely to occur, and when the value is equal to or lower than the upper limit, the patterning characteristics tend to be good.

As an aromatic ring in an aromatic ring group, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring are mentioned. Among these, a fluorene ring is preferable from a viewpoint of developing solubility.

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

Although p represents an integer greater than or equal to 1, 2 or more is preferable and 3 or less is preferable. For example, 1-3 are preferable and 2-3 are more preferable. There exists a tendency for a film hardening degree and a remaining film rate to become favorable by setting it as more than the said lower limit. There exists a tendency for developability to become favorable by carrying out below the said upper limit.

Among these, it is preferable that R ^<alpha> is a monovalent aliphatic ring group, and it is more preferable that it is an adamantyl group from a viewpoint of firm film hardening degree.

The benzene ring in formula (b1-II-1) may be further substituted with an arbitrary substituent. As a substituent permissible for the benzene ring in formula (b1-II-1), a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. When the benzene ring in formula (b1-II-1) has a substituent, the number of substituents is not particularly limited, and may be one or two or more.

From the viewpoint of patterning characteristics, the benzene ring in the formula (b1-II-1) is preferably unsubstituted.

Specific examples of the partial structure represented by the formula (b1-II-1) are given below.

[Formula 27]

[Formula 28]

[Formula 29]

[Formula 30]

[Formula 31]

The partial structure represented by the general formula (b1-II) is preferably a partial structure represented by the following general formula (b1-II-2) from the viewpoint of rigidity of the skeleton and hydrophobicity of the film.

[Formula 32]

In formula (b1-II-2), R ¹³ , R ¹⁵ , R ¹⁶ , m and n have the same meaning as in formula (b1-II), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent, , * represents a bonding hand.

The benzene ring in formula (b1-II-2) may be further substituted with an arbitrary substituent.

(R ^β )

In the formula (b1-II-2), R ^β represents a divalent cyclic hydrocarbon group which may have a substituent.

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

The number of rings in the aliphatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 10 or less, preferably 5 or less. For example, 1-10 are preferable and 2-5 are more preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

The number of carbon atoms in the aliphatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, and preferably 40 or less, more preferably 35 or less, still more preferably 30 or less. The above upper and lower limits can be arbitrarily combined. For example, 4 to 40 are preferable, 6 to 35 are more preferable, and 8 to 30 are still more preferable. There exists a tendency for film roughness at the time of development to be suppressed by setting it as more than the said lower limit. By setting it below the said upper limit, it is easy to suppress deterioration of sensitivity and film|membrane decrease at the time of development, and there exists a tendency for resolution to improve.

Examples of the aliphatic ring in the aliphatic ring group include a cyclohexane ring, a cycloheptane ring, a cyclodecane ring, a cyclododecane ring, a norbornane ring, an isobornane ring, an adamantane ring, and a cyclododecane ring. can be heard Among these, an adamantane ring is preferable from the viewpoint of film reduction and resolution during development.

On the other hand, the number of rings in the aromatic ring group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 3 or more, and usually 10 or less, preferably 5 or less. The above upper and lower limits can be arbitrarily combined. For example, 1 to 10 are preferable, 1 to 5 are more preferable, 2 to 5 are still more preferable, and 3 to 5 are particularly preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. By setting it below the said upper limit value, it is easy to suppress deterioration of sensitivity and film decrease, and there exists a tendency for resolution to improve.

As an aromatic ring group, an aromatic hydrocarbon ring group and an aromatic heterocyclic group are mentioned. The number of carbon atoms in the aromatic ring group is usually 4 or more, preferably 6 or more, more preferably 8 or more, still more preferably 10 or more, and preferably 40 or less, more preferably 30 or less, and 20 or less. is more preferred, and 15 or less is particularly preferred. The above upper and lower limits can be arbitrarily combined. For example, 4 to 40 are preferable, 6 to 30 are more preferable, 8 to 20 are still more preferable, and 10 to 15 are particularly preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. By setting it below the said upper limit value, it is easy to suppress deterioration of sensitivity and film decrease, and there exists a tendency for resolution to improve.

As an aromatic ring in an aromatic ring group, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a fluorene ring are mentioned, for example. Among these, from a developable viewpoint, a fluorene ring is preferable.

Examples of substituents that the cyclic hydrocarbon group may have include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, amyl, isoamyl, etc. an alkyl group of 1 to 5 carbon atoms; alkoxy groups having 1 to 5 carbon atoms, such as a methoxy group and an ethoxy group; hydroxyl group; nitro group; cyano group; A carboxyl group can be mentioned. Among these, unsubstituted is preferable from the viewpoint of synthesis simplicity.

Among these, from the viewpoint of suppression of film shrinkage and resolution, R ^β is preferably a divalent aliphatic cyclic group, and more preferably a divalent adamantane cyclic group.

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

The benzene ring in formula (b1-II-2) may be further substituted with an arbitrary substituent. As a substituent permissible for the benzene ring in formula (b1-II-2), a hydroxyl group, a methyl group, a methoxy group, an ethyl group, an ethoxy group, a propyl group, and a propoxy group are mentioned, for example. When the benzene ring in formula (b1-II-2) has a substituent, the number of substituents is not particularly limited, and may be one or two or more.

Moreover, two benzene rings may be connected through the substituent. Examples of the substituent in this case include divalent groups such as -O-, -S-, -NH-, and -CH ₂ -.

From the viewpoint of patterning characteristics, the benzene ring in the formula (b1-II-2) is preferably unsubstituted. Further, from the viewpoint of making film reduction less likely to occur, the benzene ring in the formula (b1-II-2) is preferably substituted with a methyl group.

Specific examples of the partial structure represented by the formula (b1-II-2) are given below. In addition, * in an example represents a binding hand.

[Formula 33]

[Formula 34]

[Formula 35]

[Formula 36]

The partial structure represented by the formula (b1-II) is preferably a partial structure represented by the following formula (b1-II-3) from the viewpoint of the coating film remaining film rate and patterning characteristics.

[Formula 37]

In formula (b1-II-3), R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , m and n have the same meaning as in formula (b1-II), and R ^Z represents a hydrogen atom or a polybasic acid residue.

A polybasic acid residue means a monovalent group obtained by removing one OH group from a polybasic acid. Further, another OH group may be removed and shared with R ^Z in another molecule represented by formula (b1-II-3), that is, ^a plurality of formulas (b1-II- 3) may be connected.

Examples of the polybasic acid include maleic acid, succinic acid, itaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, pyromellitic acid, trimellitic acid, benzophenone tetracarboxylic acid, methylhexahydrophthalic acid, and endomethylenetetrahydro Phthalic acid, chlorendic acid, methyltetrahydrophthalic acid, and biphenyltetracarboxylic acid are exemplified.

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

(b1-II) The partial structure represented by the formula (b1-II-3) contained in one molecule of the epoxy (meth)acrylate-based resin may be one type or two or more types. For example, ^RZ is What is a hydrogen atom and what is a polybasic acid residue in R ^Z may be mixed.

(b1-II) The number of partial structures represented by the formula (b1-II) contained in one molecule of the epoxy (meth)acrylate-based resin is not particularly limited, but is preferably 1 or more, and more preferably 3 or more, Moreover, 20 or less is preferable, 15 or less is more preferable, and 10 or less is still more preferable. For example, 1 to 20 are preferable, 1 to 15 are more preferable, and 3 to 10 are still more preferable. When the amount is equal to or greater than the lower limit, a firm film can be easily obtained, and surface roughness generated during development tends to be less likely to occur. By setting it below the said upper limit value, it is easy to suppress deterioration of sensitivity and film decrease, and there exists a tendency for resolution to improve.

(b1-II) The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of the epoxy (meth)acrylate-based resin is not particularly limited, but is preferably 1000 or more, and preferably 1500 or more. More preferably, 2000 or more is still more preferable, 3000 or more is even more preferable, 4000 or more is particularly preferable, 5000 or more is most preferable, usually 10000 or less, 8000 or less is preferable, and 7000 or less is more preferable. . The above upper and lower limits can be arbitrarily combined. For example, 1000 to 10000 are preferable, 1500 to 10000 are more preferable, 1500 to 8000 are still more preferable, 2000 to 8000 are even more preferable, and 2000 to 7000 are particularly preferable. There exists a tendency for the remaining-film rate of the photosensitive coloring composition to become favorable by setting it as more than the said lower limit. There exists a tendency for the solubility with respect to a developing solution to become favorable by carrying out below the said upper limit.

(b1-II) The acid value of the epoxy (meth)acrylate-based resin is not particularly limited, but is preferably 20 mgKOH/g or more, more preferably 40 mgKOH/g or more, and still more preferably 60 mgKOH/g or more, 80 mgKOH/g or more is more preferred, 100 mgKOH/g or more is particularly preferred, and 200 mgKOH/g or less is preferred, 150 mgKOH/g or less is more preferred, and 130 mgKOH/g or less is further more preferred. It is preferred, and 120 mgKOH/g or less is particularly preferred. The above upper and lower limits can be arbitrarily combined. For example, 20 mgKOH/g to 200 mgKOH/g are preferable, 60 mgKOH/g to 150 mgKOH/g are more preferable, 80 mgKOH/g to 130 mgKOH/g are still more preferable, and 100 mgKOH/g to 130 mgKOH/g is more preferred. There exists a tendency for developing solubility to improve and resolution to become favorable by setting it as more than the said lower limit. There exists a tendency for the remaining-film rate of the photosensitive coloring composition to become favorable by carrying out below the said upper limit.

The carboxyl group-containing epoxy (meth)acrylate-based resin may be used alone or in combination of two or more resins.

A part of the carboxy group-containing epoxy (meth)acrylate-based resin may be used by substituting another binder resin. That is, you may use together the carboxy group-containing epoxy (meth)acrylate type resin and other binder resin. In this case, (b) the proportion of the carboxyl group-containing epoxy (meth)acrylate-based resin in the alkali-soluble resin is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass or more. It is more preferably 80% by mass or more, particularly preferably 80% by mass or more, and usually 100% by mass or less.

(b) As the alkali-soluble resin, it is preferable to use (b2) acrylic copolymer resin from the viewpoint of compatibility with pigments, dispersants, etc., and the acrylic copolymer resin described in Japanese Unexamined Patent Publication No. 2014-137466 can be preferably used. .

As an acrylic copolymer resin, for example, an ethylenically unsaturated monomer having one or more carboxy groups (hereinafter referred to as "unsaturated monomer (b2-1)") and another copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer ( b2-2)”).

Examples of the unsaturated monomer (b2-1) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid; unsaturated dicarboxylic acids or their anhydrides such as maleic acid, maleic anhydride, fumaric acid, citraconic acid, citraconic anhydride, and mesaconic acid; Mono[(meth)acryloyloxyalkyl] of divalent or higher polyhydric carboxylic acids such as succinate mono[2-(meth)acryloyloxyethyl] and phthalate mono[2-(meth)acryloyloxyethyl] ester; Mono(meth)acrylate of the polymer which has a carboxy group and a hydroxyl group at both terminals, such as (omega)-carboxy polycaprolactone mono(meth)acrylate; and p-vinylbenzoic acid.

These unsaturated monomers (b2-1) can be used individually or in mixture of 2 or more types.

Examples of the unsaturated monomer (b2-2) include N-substituted maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide;

aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, and acenaphthylene;

Methyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, allyl (meth)acrylate, benzyl (meth)acrylate , polyethylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polypropylene glycol (polymerization degree 2-10) methyl ether (meth)acrylate, polyethylene glycol (polymerization degree 2-10) mono(meth)acrylate, poly Propylene glycol (degree of polymerization 2-10) mono(meth)acrylate, cyclohexyl(meth)acrylate, isobornyl(meth)acrylate, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl(meth) Acrylates, dicyclopentenyl(meth)acrylate, glycerol mono(meth)acrylate, 4-hydroxyphenyl(meth)acrylate, ethylene oxide-modified (meth)acrylate of paracumylphenol, glycidyl (meth)acrylate )Acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 3-[(meth)acryloyloxymethyl]oxetane, 3-[(meth)acryloyloxymethyl]oxetane, 3- (meth)acrylic acid esters such as [(meth)acryloyloxymethyl]-3-ethyloxetane;

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, 3-(vinyloxymethyl)-3-ethyloxetane Vinyl ether, such as;

and macromonomers having mono(meth)acryloyl groups at the ends of polymer molecular chains such as polystyrene, polymethyl(meth)acrylate, poly-n-butyl(meth)acrylate, and polysiloxane.

These unsaturated monomers (b2-2) can be used individually or in mixture of 2 or more types.

In the copolymer of the unsaturated monomer (b2-1) and the unsaturated monomer (b2-2), the copolymerization ratio of the unsaturated monomer (b2-1) is preferably 5 to 50% by mass, more preferably 10 to 40% by mass. % am. By copolymerizing the unsaturated monomer (b2-1) within this range, a photosensitive coloring composition excellent in alkali developability and storage stability tends to be obtained.

As a copolymer of an unsaturated monomer (b2-1) and an unsaturated monomer (b2-2), For example, Unexamined-Japanese-Patent No. 7-140654, Unexamined-Japanese-Patent No. 8-259876, Unexamined-Japanese-Patent No. 10 -31308, Japanese Unexamined Patent Publication No. Hei 10-300922, Japanese Unexamined Patent Publication No. Hei 11-174224, Japanese Unexamined Patent Publication No. Hei 11-258415, Japanese Unexamined Patent Publication No. 2000-56118, Japanese Unexamined Patent Publication 2004-101728 and the copolymers disclosed in .

Although the copolymer of an unsaturated monomer (b2-1) and an unsaturated monomer (b2-2) can be manufactured by a well-known method, For example, Unexamined-Japanese-Patent No. 2003-222717, Unexamined-Japanese-Patent No. 2006-259680 The structure, Mw, and Mw/Mn can also be controlled by a method disclosed in International Publication No. 2007/029871.

In addition, you may use resin of international publication 2016/194619 and international publication 2017/154439.

<(c) photopolymerization initiator>

(c) The photopolymerization initiator is a component having a function of directly absorbing light, causing a decomposition reaction or a hydrogen withdrawal reaction, and generating polymerization active radicals. You may add and use additives, such as a polymerization accelerator (chain transfer agent) and a sensitizing dye, as needed.

As a photoinitiator, Metallocene compounds containing the titanocene compound of Unexamined-Japanese-Patent No. 59-152396 and Unexamined-Japanese-Patent No. 61-151197, for example; Hexaaryl biimidazole derivatives described in Japanese Unexamined Patent Publication No. 2000-56118; halomethylated oxadiazole derivatives and halomethyl-s-triazine derivatives described in Japanese Unexamined Patent Publication No. 10-39503; α-aminoalkylphenone derivatives; The oxime ester type compound described in Unexamined-Japanese-Patent No. 2000-80068, Unexamined-Japanese-Patent No. 2006-36750, etc. is mentioned.

As the metallocene compound, for example, dicyclopentadienyltitanium dichloride, dicyclopentadienyltitanium bisphenyl, dicyclopentadienyltitanium bis(2,3,4,5,6-pentafluoro phenyl), dicyclopentadienyltitanium bis(2,3,5,6-tetrafluorophenyl), dicyclopentadienyltitaniumbis(2,4,6-trifluorophenyl), dicyclopentadienyl Titanium di(2,6-difluorophenyl), dicyclopentadienyltitanium di(2,4-difluorophenyl), di(methylcyclopentadienyl)titanium bis(2,3,4,5, 6-pentafluorophenyl), di(methylcyclopentadienyl)titanium bis(2,6-difluorophenyl), dicyclopentadienyltitanium[2,6-di-fluoro-3-(pyrrole- 1-yl)-phenyl].

Hexaaryl biimidazole derivatives include, for example, 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5- bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4, 5-diphenylimidazole dimer and (4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

Halomethylated oxadiazole derivatives include, for example, 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 and 2-trichloromethyl-5-furyl-1,3,4-oxadiazole.

Halomethyl-s-triazine derivatives include, for example, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaph Tyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4 -ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine.

Examples of α-aminoalkylphenone derivatives include 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- Dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis(4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3-(4-diethylaminobenzoyl)coumarin, and 4-(diethylamino)chalcone.

As the photopolymerization initiator, oxime ester-based compounds are particularly effective in terms of sensitivity and platemaking properties, and, for example, when alkali-soluble resins containing phenolic hydroxyl groups are used, oxime ester-based compounds having excellent sensitivity are particularly useful. do. Since the oxime ester compound has a structure that absorbs ultraviolet rays, a structure that transmits light energy, and a structure that generates radicals in its structure, it is highly sensitive in a small amount and is stable against thermal reaction, and is stable in a small amount. It is possible to obtain a highly sensitive photosensitive colored resin composition.

As an oxime ester type compound, the compound represented by the following general formula (IV) is mentioned, for example.

[Formula 38]

In the formula (IV), R ^21a represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aromatic ring group.

R ^21b represents an arbitrary substituent containing an aromatic ring.

R ^22a represents an alkanoyl group which may have a substituent or an aryloyl group which may have a substituent.

n represents an integer of 0 or 1;

The number of carbon atoms in the alkyl group in R ^21a is not particularly limited, but is usually 1 or more, preferably 2 or more, and usually 20 or less, preferably 15 or less, more preferably from the viewpoint of solvent solubility and sensitivity. less than 10 For example, it is 1-20, Preferably it is 1-15, More preferably, it is 2-10. As an alkyl group, a methyl group, an ethyl group, a propyl group, and a cyclopentyl ethyl group are mentioned.

As a substituent which an alkyl group may have, for example, an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, a 4-(2-methoxy-1-methyl)ethoxy-2-methylphenyl group, or N -Acetyl-N-acetoxyamino group is mentioned, and unsubstituted is preferable from the viewpoint of synthetic ease.

Examples of the aromatic ring group for R ^21a include an aromatic hydrocarbon ring group and an aromatic heterocyclic group. The number of carbon atoms in the aromatic ring group is not particularly limited, but is preferably 5 or more from the viewpoint of solubility in the photosensitive coloring composition. Moreover, from a developability viewpoint, it is preferably 30 or less, more preferably 20 or less, and still more preferably 12 or less. For example, it is 5 to 30, preferably 5 to 20, and more preferably 5 to 12 or less.

As an aromatic ring group, a phenyl group, a naphthyl group, a pyridyl group, and a furyl group are mentioned, for example, From a viewpoint of developability among these, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

As a substituent which an aromatic ring group may have, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, an alkyl group, an alkoxy group, and the group which these substituents connected are mentioned, for example, An alkyl group, an alkoxy group, these from a developable viewpoint A linked group is preferable, and a linked alkoxy group is more preferable.

Among these, from the viewpoint of developability, it is preferable that R ^21a is an aromatic ring group which may have a substituent, and it is more preferable that it is an aromatic ring group having a linked alkoxy group as a substituent.

Moreover, as ^R21b , the optionally substituted carbazolyl group, the optionally substituted thioxanthonyl group, and the optionally substituted diphenyl sulfide group are mentioned. Among these, from a viewpoint of sensitivity, the carbazolyl group which may be substituted is preferable. From the viewpoint of electrical reliability, an optionally substituted diphenyl sulfide group is preferable.

The number of carbon atoms in the alkanoyl group in R ^22a is not particularly limited, but is usually 2 or more, preferably 3 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solubility and sensitivity to solvents; More preferably, it is 10 or less, More preferably, it is 5 or less. For example, it is 2 to 20, preferably 2 to 15, more preferably 3 to 10, still more preferably 3 to 5. An acetyl group, a propanoyl group, and a butanoyl group are mentioned as an alkanoyl group.

As a substituent which an alkanoyl group may have, an aromatic ring group, a hydroxyl group, a carboxy group, a halogen atom, an amino group, and an amide group are mentioned, for example, and unsubstituted is preferable from a viewpoint of synthetic ease.

The number of carbon atoms in the aryloyl group in R ^22a is not particularly limited, but is usually 7 or more, preferably 8 or more, and usually 20 or less, preferably 15 or less, from the viewpoint of solvent solubility and sensitivity. More preferably, it is 10 or less. For example, it is 7-20, Preferably it is 7-15, More preferably, it is 8-10. A benzoyl group and a naphthoyl group are mentioned as an aryloyl group.

As a substituent which an aryloyl group may have, a hydroxyl group, a carboxy group, a halogen atom, an amino group, an amide group, and an alkyl group are mentioned, for example, and unsubstitution is preferable from a viewpoint of synthetic ease.

Among them, from the viewpoint of sensitivity, R ^22a is preferably an optionally substituted alkanoyl group, more preferably an unsubstituted alkanoyl group, and still more preferably an acetyl group.

The initiator described in Unexamined-Japanese-Patent No. 2016-133574 is also preferably used from the viewpoint that contamination of the liquid crystal layer by the coloring agent is reduced.

A photoinitiator may be used individually by 1 type, and may use 2 or more types together.

In the photopolymerization initiator, a sensitizing dye and a polymerization accelerator according to the wavelength of the image exposure light source can be blended, if necessary, for the purpose of increasing the sensitivity. As a sensitizing dye, for example, the xanthene dye of Unexamined-Japanese-Patent No. 4-221958 and Unexamined-Japanese-Patent No. 4-219756, Unexamined-Japanese-Patent No. 3-239703, and Unexamined-Japanese-Patent No. 5 Heterocyclic coumarin dye described in No. -289335, 3-ketocoumarin compound described in Japanese Unexamined Patent Publication No. Hei 3-239703 and Japanese Unexamined Patent Publication No. Hei 5-289335, Japanese Unexamined Patent Publication No. Hei 6-19240 Described pyrromethene pigment, Japanese Unexamined Patent Publication No. 47-2528, Japanese Unexamined Patent Publication No. 54-155292, Japanese Patent Publication No. 45-37377, Japanese Unexamined Patent Publication No. 48-84183, Japanese Unexamined Patent Publication No. 52 -112681, Japanese Unexamined Patent Publication No. 58-15503, Japanese Unexamined Patent Publication No. 60-88005, Japanese Unexamined Patent Publication No. 59-56403, Japanese Unexamined Patent Publication No. 2-000069, Japanese Unexamined Patent Publication No. 57 -168088, Unexamined-Japanese-Patent No. 5-107761, Unexamined-Japanese-Patent No. 5-210240, and Unexamined-Japanese-Patent No. 4-288818 include pigments having a dialkylaminobenzene skeleton.

Among these sensitizing dyes, amino group-containing sensitizing dyes are preferable, and compounds having an amino group and a phenyl group in the same molecule are more preferable. As a preferable sensitizing dye, 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]benzooxazole, 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-diethylamino and p-dialkylaminophenyl group-containing compounds such as phenyl)quinoline, (p-dimethylaminophenyl)pyrimidine, and (p-diethylaminophenyl)pyrimidine. Among these, 4,4'-dialkylamino benzophenone is particularly preferred.

A sensitizing dye may be used individually by 1 type, and may use 2 or more types together.

As the polymerization accelerator, for example, aromatic amines such as p-dimethylaminobenzoate and 2-dimethylaminoethyl benzoate, aliphatic amines such as n-butylamine and N-methyldiethanolamine, and mercapto compounds described later are used. do. A polymerization accelerator may be used individually by 1 type, and may use 2 or more types together.

<(d) ethylenically unsaturated compound>

The photosensitive coloring composition of the present invention contains (d) an ethylenically unsaturated compound. (d) Sensitivity is improved by containing an ethylenically unsaturated compound.

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

In this invention, it is especially preferable to use the polyfunctional ethylenic monomer which has 2 or more ethylenically unsaturated bonds in 1 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 or less , and more preferably 7 or less. The above upper and lower limits can be arbitrarily combined. For example, 2 to 8 are preferable, 2 to 7 are more preferable, 4 to 7 are still more preferable, and 5 to 7 are particularly preferable. There exists a tendency to become high sensitivity by setting it as more than the said lower limit. There exists a tendency for solubility to a solvent to improve by using below the said upper limit.

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; Ester obtained by esterification reaction of polyhydric hydroxy compounds, such as an aliphatic polyhydroxy compound and an aromatic polyhydroxy compound, and an unsaturated carboxylic acid and a polybasic carboxylic acid is mentioned.

Esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids include, for example, ethylene glycol diacrylate, triethylene glycol diacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, and pentaerythritol di. Aliphatic polyhydroxys such as acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and glycerol acrylate Acrylic acid esters of compounds, methacrylic acid esters obtained by converting these acrylates to methacrylates, itaconic acid esters converted to itaconate, crotonic acid esters converted to cronate, and maleic acid esters converted to maleate.

Examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, resorcinone diacrylate, resorcinone dimethacrylate, and pyrogallol triacrylate. Acrylic acid ester and methacrylic acid ester of aromatic polyhydroxy compounds, such as these, are mentioned.

Esters obtained by esterification of polybasic carboxylic acids and unsaturated carboxylic acids with polyhydric hydroxy compounds are not necessarily single substances, but examples thereof include condensates of acrylic acid, phthalic acid, and ethylene glycol, acrylic acid, and maleic acid. , and a condensate of diethylene glycol, a condensate of methacrylic acid, terephthalic acid and pentaerythritol, a condensate of acrylic acid, adipic acid, butanediol and glycerin.

In addition, as the polyfunctional ethylenic monomer used in the present invention, for example, urethane 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 ( meth)acrylates; Epoxy acrylates like addition reaction products of a polyhydric epoxy compound and hydroxy (meth)acrylate or (meth)acrylic acid; acrylamides such as ethylenebisacrylamide; allyl esters such as diallyl phthalate; Compounds containing a vinyl group such as divinyl phthalate are useful.

Examples of urethane (meth)acrylates include DPHA-40H, UX-5000, UX-5002D-P20, UX-5003D, UX-5005 (manufactured by Nippon Chemical Co., Ltd.), U-2PPA, U-6LPA, U-10PA, U-33H, UA-53H, UA-32P, UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), UA-306H, UA-510H, UF-8001G (manufactured by Kyoeisha Chemical Co., Ltd.), UV-1700B, UV-7600B, UV-7605B, UV-7630B, and UV7640B (manufactured by Mitsubishi Chemical Corporation) are exemplified.

Among these, from the viewpoint of curability, (d) as ethylenically unsaturated compounds, esters or urethane (meth)acrylates of aliphatic polyhydroxy compounds and unsaturated carboxylic acids, polyisocyanate compounds and hydroxyl group-containing (meth)acrylic acid esters, or It is preferable to use urethane (meth)acrylates obtained by reacting a polyisocyanate compound with a polyol and a hydroxyl group-containing (meth)acrylic acid ester, and it is more preferable to use a (meth)acrylic acid alkyl ester, and dipentaerythritol hexa It is more preferable to use an acrylate.

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

<(e) Solvent>

The photosensitive coloring composition of the present invention contains (e) a solvent. (e) By containing a solvent, the (a) colorant can be dispersed or dissolved in the solvent, and application becomes easy.

The photosensitive coloring composition of the present invention usually contains (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (f) a dispersant, and various other materials used as needed. The material is used in a state dissolved or dispersed in a solvent. Among the solvents, organic solvents are preferred from the viewpoint of dispersibility and coating properties.

Among the organic solvents, those having a boiling point of 100 to 300°C are preferably selected from the viewpoint of coating properties, and those of 120 to 280°C are more preferable. Note that the boiling point referred to here means the boiling point at a pressure of 1013.25 hPa, and the following boiling points are all the same.

Examples of such an organic solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether. -n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-butyl ether, methoxymethyl pentanol, dipropylene glycol monoethyl ether , dipropylene glycol monomethyl ether, 3-methoxybutanol, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, glycol monoalkyl ethers such as tripropylene glycol methyl ether ;

Glycol dialkyl ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, 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-hexanediol 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 amyl ketone, methyl isopropyl ketone, methyl isoamyl ketone, diisopropyl ketone, diisobutyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl amyl ketone, methyl butyl ketone, methyl hexyl ketones such as ketones, methyl nonyl ketones, 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, and 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, butyl stearate, ethyl benzoate, 3-ethoxymethylpropionate, 3-ethoxyethylpropionate, 3-methoxymethylpropionate, 3-methoxyethylpropionate, 3-methoxypropylpropionate, 3-methoxymethylpropionate chain or cyclic esters such as butyl oxypropionate 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; can be heard

Commercially available organic solvents include, for example, mineral spirits, Barsol #2, Afco #18 solvent, Afco thinner, Socal solvent No.1 and No.2, Solvesso #150, Shell TS28 solvent, Carbitol . can be used

These solvents may be used independently or may use 2 or more types together.

When the barrier rib is formed by photolithography, the organic solvent having a boiling point of 100 to 240°C is preferably selected, more preferably 120 to 200°C, and even more preferably 120 to 170°C.

Among the above-mentioned solvents, glycol alkyl ether acetates are preferable in terms of good balance of applicability, surface tension, and the like, and relatively high solubility of constituent components in the composition.

Glycol alkyl ether acetates may be used alone or in combination with other solvents. As the solvent used in combination, glycol monoalkyl ethers are particularly preferred. Propylene glycol monomethyl ether is preferable from the viewpoint of the solubility of constituent components in the composition. Glycol monoalkyl ethers have high polarity, and if the amount added is too large, the pigment tends to aggregate, and the storage stability of the photosensitive coloring composition obtained later, such as an increase in viscosity, tends to decrease, so the ratio of glycol monoalkyl ethers in the solvent is 5 mass % - 30 mass % are preferable, and 5 mass % - 20 mass % are more preferable.

It is also preferable to use together an organic solvent having a boiling point of 150°C or higher (hereinafter sometimes referred to as a "high boiling point solvent"). By using the high boiling point solvent together, the photosensitive coloring 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, 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, for example. Among the various solvents described above, diethylene glycol mono-n-butyl ether, diethylene glycol mono-n-butyl ether acetate, and diethylene glycol monoethyl ether acetate are particularly preferred in view of their high effect.

When a high boiling point solvent is used together, 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 5% by mass to 30% by mass. particularly preferred. By setting it above the lower limit, it tends to be able to suppress the occurrence of foreign matter defects due to precipitation and solidification of the colorant at the tip of the slit nozzle, for example, and by setting it below the above upper limit, the drying temperature of the composition is suppressed from slowing down, , problems such as tact failure in the vacuum drying process and pin marks in the prebaking tend to be suppressed.

The high boiling point solvent having a boiling point of 150°C or higher may be glycol alkyl ether acetates or glycol alkyl ethers. In this case, it is not necessary to separately contain a high boiling point solvent having a boiling point of 150°C or higher.

As a preferable high boiling point solvent, among the above-mentioned various solvents, for example, diethylene glycol mono-n-butyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol methyl ether acetate, 1,3-butylene glycol Diacetate, 1,6-hexanol diacetate, and triacetin are mentioned.

<(f) Dispersant>

The photosensitive coloring composition of the present invention contains (f) a dispersing agent. (f) By containing a dispersing agent, the (a) coloring agent can be stably dispersed.

The (f) dispersant in the photosensitive coloring composition of the present invention is an acrylic copolymer (f1) having repeating units represented by the following general formulas (1) to (3) (hereinafter referred to as “dispersant (f1)”) ) and does not have a repeating unit containing a quaternary ammonium group.

[Formula 39]

(In Formula (1), R ³¹ 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 ³² is a hydrogen atom or a methyl group.

* indicates a bonding hand.)

[Formula 40]

(In Formula (2), R ³³ is a methylene group, ethylene group or propylene group, R ³⁴ is an alkyl group which may have a substituent, and R ³⁵ is a hydrogen atom or a methyl group.

n is an integer from 1 to 20;

* indicates a bonding hand.)

[Formula 41]

(In Formula (3), R ³⁶ and R ³⁷ 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, R ³⁶ and R ³⁷ These may combine with each other to form a cyclic structure.

R ³⁸ is a hydrogen atom or a methyl group.

Z is a divalent linking group.

* indicates a bonding hand.)

The dispersing agent (f1) has a repeating unit represented by the following general formula (1) from the viewpoint of improving compatibility with solvents and alkali-soluble resins and improving dispersion stability.

[Formula 42]

(In Formula (1), R ³¹ 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 ³² is a hydrogen atom or a methyl group.

* indicates a bonding hand.)

( ^R31 )

In the formula (1), examples of the alkyl group for R ³¹ include linear, branched, or cyclic alkyl groups, and from the viewpoint of compatibility with solvents and alkali-soluble resins, linear It is preferable, and from the viewpoint of affinity to a pigment, a branched chain type is preferable.

The number of carbon atoms in the alkyl group is not particularly limited, but is usually 1 or more, preferably 2 or more, more preferably 4 or more, more preferably 10 or less, more preferably 8 or less, still more preferably 6 or less. The above upper and lower limits can be arbitrarily combined. For example, 1-10 are preferable, 2-8 are more preferable, and 4-6 are still more preferable. There exists a tendency for affinity to a pigment to be improved by setting it as more than the said lower limit. There exists a tendency for compatibility with a solvent or alkali-soluble resin to improve and to improve dispersibility by using below the said upper limit.

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 an ethylhexyl group, and from the viewpoint of compatibility with solvents and alkali-soluble resins, A methyl group and an ethyl group are preferable, and a methyl group is more preferable.

As a substituent which an alkyl group may have, For example, Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; Aryl groups, such as a phenyl group and a naphthyl group, are mentioned, It is preferable that it is unsubstituted from a viewpoint of compatibility with a solvent or alkali-soluble resin, and a phenyl group is preferable from a viewpoint of affinity to a pigment.

Examples of the aryl group for R ³¹ include a monovalent aromatic hydrocarbon ring group and a monovalent aromatic heterocyclic group.

The number of carbon atoms in the aryl group is not particularly limited, but is usually 6 or more, preferably 16 or less, more preferably 12 or less, and still more preferably 10 or less. There exists a tendency for affinity to a pigment to be improved by using below the said upper limit. As an aryl group, a phenyl group, a naphthyl group, and anthracenyl group are mentioned, for example, From a dispersible viewpoint, a phenyl group and a naphthyl group are preferable, and a phenyl group is more preferable.

As a substituent which an aryl group may have, For example, Alkyl groups, such as a methyl group and an ethyl group; Alkoxy groups, such as a methoxy group and an ethoxy group; Halogen atoms, such as a fluorine atom, a chlorine atom, and a bromine atom; Aryl groups, such as a phenyl group and a naphthyl group; Aralkyl groups, such as a benzyl group and a phenethyl group, are mentioned, and unsubstituted is preferable from a dispersible viewpoint.

Among these, from the viewpoint of compatibility with solvents and alkali-soluble resins, as R ³¹ , an alkyl group which may have a substituent is preferable, and a methyl group, a butyl group, an ethylhexyl group, or a benzyl group is more preferable.

The dispersant (f1) has a repeating unit represented by the following general formula (2) from the viewpoint of compatibility with solvents and alkali-soluble resins.

[Formula 43]

(In Formula (2), R ³³ is a methylene group, ethylene group or propylene group, R ³⁴ is an alkyl group which may have a substituent, and R ³⁵ is a hydrogen atom or a methyl group.

n is an integer from 1 to 20;

* indicates a bonding hand.)

In the formula (2), R ³³ is a methylene group, an ethylene group, or a propylene group, but an ethylene group is preferable from the viewpoint of compatibility with solvents and alkali-soluble resins.

In the formula (2), R ³⁴ is an alkyl group which may have a substituent, but is preferably a methyl group or an ethyl group from the viewpoint of compatibility with solvents and alkali-soluble resins.

In the above formula (2), n is an integer of 1 to 20, preferably 1 or more, more preferably 2 or more, more preferably 10 or less, and more preferably 5 or less. For example, 1 to 10 are preferable, 1 to 5 are more preferable, and 2 to 5 are still more preferable. There exists a tendency for the compatibility with respect to a solvent or alkali-soluble resin to improve by setting it as more than the said lower limit. There exists a tendency for affinity to a pigment to be raised and dispersibility to be quantified by setting it below the said upper limit.

The dispersant (f1) has a repeating unit represented by the general formula (3). From the viewpoint of the surface roughness of the electrode, it is preferably used.

[Formula 44]

(In Formula (3), R ³⁶ and R ³⁷ 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, R ³⁶ and R ³⁷ These may combine with each other to form a cyclic structure.

R ³⁸ is a hydrogen atom or a methyl group.

Z is a divalent linking group.

* indicates a bonding hand.)

In the formula (3), R ³⁶ and R ³⁷ each independently represent 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. As the alkyl group that may have a substituent and the aryl group that may have a substituent, those exemplified as R ³¹ in the formula (1) can be preferably employed.

In the formula (3), R ³⁶ and R ³⁷ may be bonded to each other to form a cyclic structure. Examples of the cyclic structure include a 5- to 7-membered nitrogen-containing heterocyclic monocyclic ring or a condensed ring formed by condensing two of them. It is preferable that the nitrogen-containing heterocyclic ring does not have aromaticity, and a saturated ring is more preferable. Specifically, the following are mentioned.

[Formula 45]

(These cyclic structures may further have a substituent.

* indicates a bonding hand.)

(Z)

In the formula (3), Z is a divalent linking group.

Examples of the divalent linking group include a single bond, an alkylene group having 1 to 10 carbon atoms, an arylene group having 6 to 12 carbon atoms, a -CONH-R ³⁹ - group, a -COOR ⁴⁰ - group (however, R ³⁹ and R ⁴⁰ are each independently a single bond, an alkylene group of 1 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) of 2 to 10 carbon atoms), and a -COOR ⁷ - group is preferable from the viewpoint of dispersibility. Among R ⁴⁰ , from the viewpoint of the stability over time of the dispersion, an alkylene group of 1 to 10 carbon atoms is preferable, an alkylene group of 1 to 5 carbon atoms is more preferable, and an alkylene group of 1 to 3 carbon atoms is still more preferable.

The content of the repeating unit represented by the general formula (1) in the dispersant (f1) (hereinafter sometimes referred to as "repeating unit (1)") is not particularly limited, but is 20 mol% or more in all repeating units. is preferred, 30 mol% or more is more preferred, 40 mol% or more is more preferred, 50 mol% or more is even more preferred, 60 mol% or more is particularly preferred, and 90 mol% or less is preferred. , 85 mol% or less is more preferable, 80 mol% or less is still more preferable, and 75 mol% or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 20 mol% to 90 mol% is preferable, 30 mol% to 90 mol% is more preferable, 40 mol% to 80 mol% is still more preferable, and 50 mol% to 80 mol% is still more preferable. And 60 mol% - 80 mol% are especially preferable. There exists a tendency for affinity to a pigment to be improved by setting it as more than the said lower limit. There exists a tendency for the compatibility with respect to a solvent or alkali-soluble resin to be improved by using below the said upper limit.

The content of the repeating unit represented by the general formula (2) in the dispersant (f1) (hereinafter sometimes referred to as "repeating unit (2)") is not particularly limited, but is 1 mol% in all repeating units. The above is preferable, 2 mol% or more is more preferable, 2.5 mol% or more is more preferable, 3 mol% or more is particularly preferable, 30 mol% or less is preferable, 20 mol% or less is more preferable, 15 mol% or less is more preferable, 10 mol% or less is still more preferable, and 8 mol% or less is especially preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 mol% to 30 mol% is preferable, 1 mol% to 20 mol% is more preferable, 1 mol% to 15 mol% is still more preferable, and 1 mol% to 10 mol% is still more preferable. And 2 mol% - 10 mol% are especially preferable. There exists a tendency for the compatibility with respect to a solvent or alkali-soluble resin to be improved by setting it as more than the said lower limit. There exists a tendency for affinity to a pigment to be improved by using below the said upper limit.

The content of the repeating unit represented by the general formula (3) (hereinafter sometimes referred to as "repeating unit (3)") in the dispersant (f1) is not particularly limited, but is 10 mol% in all repeating units. The above is preferable, 20 mol% or more is more preferable, 25 mol% or more is more preferable, 30 mol% or more is particularly preferable, 50 mol% or less is preferable, and 45 mol% or less is more preferable. , 40 mol% or less is more preferable, and 35 mol% or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 10 mol% to 50 mol% is preferable, 20 mol% to 40 mol% is more preferable, 25 mol% to 35 mol% is still more preferable, and 30 mol% to 35 mol% is particularly preferable. . Dispersibility tends to become good by setting it as more than the said lower limit. When it is below the above upper limit, the stability over time of the dispersion tends to be good.

The dispersant (f1) may be contained in any of random copolymerization and block copolymerization, but from the viewpoint of dispersibility, it is preferably a block copolymer, and the block copolymer is an A block containing a repeating unit having a solvent group, a pigment It is preferable to include a B block containing a repeating unit having an adsorber.

When the dispersing agent (f1) has the repeating unit (1) and the repeating unit (2), they are preferably contained in the A block, and may be contained in either mode of random copolymerization or block copolymerization. In addition, two or more types of repeating unit (1) or repeating unit (2) may be contained in the A block, respectively, in that case, each repeating unit is contained in either random copolymerization or block copolymerization in the A block it may be

Repeating units other than repeating units (1) and (2) may be contained in the A block, and examples of such repeating units include styrene-based monomers such as styrene and α-methylstyrene; (meth)acrylate type monomers such as (meth)acrylic acid chloride; (meth)acrylamide monomers such as (meth)acrylamide and N-methylolacrylamide; vinyl acetate; acrylonitrile; Allyl glycidyl ether, crotonic acid glycidyl ether; and repeating units derived from N-methacryloylmorpholine.

Among these, the block copolymer having an A block having repeating units (1) and repeating unit (2) and a B block having repeating unit (3) is more preferably an A-B block copolymer or an A-B-A block copolymer.

The amine value of the dispersant (f1) is not particularly limited, but is preferably 50 mgKOH/g or more, more preferably 80 mgKOH/g or more, still more preferably 90 mgKOH/g or more, and particularly preferably 100 mgKOH/g or more. Also, 200 mgKOH/g or less is preferable, 160 mgKOH/g or less is more preferable, 140 mgKOH/g or less is still more preferable, and 130 mgKOH/g or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 50 mgKOH/g to 200 mgKOH/g are preferable, 80 mgKOH/g to 160 mgKOH/g are more preferable, 100 mgKOH/g to 140 mgKOH/g are still more preferable, and 100 mgKOH/g to 130 mgKOH/g is particularly preferred. There exists a tendency that the surface roughness of an electrode can be suppressed by setting it more than the said lower limit. When it is below the above upper limit, the stability over time of the dispersion tends to be improved. An amine titer is represented by the mass of KOH equivalent to the amount of base per 1 g of the solid content of the dispersant (f1).

The acid value of the dispersant (f1) is not particularly limited, but from the viewpoint of dispersibility, it is preferably 10 mgKOH/g or less, more preferably 5 mgKOH/g or less, still more preferably 1 mgKOH/g, and 0 mgKOH/g or less. particularly preferred.

The weight average molecular weight of the dispersing agent (f1) is not particularly limited, but is preferably 3000 or more, more preferably 5000 or more, still more preferably 7000 or more, and preferably 100000 or less, more preferably 50000 or less, and 10000 The following is more preferable. The above upper and lower limits can be arbitrarily combined. For example, 3000 to 100000 are preferable, 5000 to 50000 are more preferable, and 7000 to 10000 are still more preferable. There exists a tendency for dispersibility to improve by setting it as more than the said lower limit. When it is below the above upper limit, the stability over time of the dispersion tends to be improved.

The content of chlorine atoms in the dispersant (f1) is not particularly limited, but is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, still more preferably 0.2% by mass or less, and substantially free of chlorine atoms. , that is, it is particularly preferably 0.1% by mass or less. There exists a tendency for surface roughness to be suppressed by carrying out below the said upper limit.

The method for producing the dispersant (f1) is not particularly limited, and a known method can be employed. For example, Japanese Unexamined Patent Publication No. Hei 01-299014, Japanese Unexamined Patent Publication No. 2017-019937, Japanese Unexamined Patent Publication No. 2018-172530, Japanese Unexamined Patent Publication No. 2018-203795, Japanese Unexamined Patent Publication No. 2019-099801, The method described in international publication 2019/079659 is mentioned.

The (f) dispersant in the photosensitive coloring composition of the present invention may contain dispersants other than the dispersant (f1) (hereinafter sometimes referred to as "other dispersants").

As another dispersing agent, it is a carboxyl group as a functional group from the point of dispersion stability, for example; or bases thereof; primary, secondary or tertiary amino groups; quaternary ammonium base; A dispersant having a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, and pyrazine is preferable. Among them, a basic functional group such as a primary, secondary or tertiary amino group; quaternary ammonium base; A dispersant having a group derived from a nitrogen-containing heterocyclic ring such as pyridine, pyrimidine, and pyrazine is more preferable.

Moreover, when dispersing a pigment, a polymeric dispersing agent is preferable from the viewpoint that it can be dispersed with a small amount of dispersing agent.

As the polymer dispersant, for example, an acrylic dispersant other than the dispersant (f1), a urethane dispersant, a polyethyleneimine dispersant, a polyallylamine dispersant, a dispersant composed of a monomer having an amino group and a macromonomer, a polyoxyethylene alkyl ether dispersant, and polyoxyethylene diester dispersants, polyether phosphoric acid dispersants, polyester phosphoric acid dispersants, sorbitan aliphatic ester dispersants, and aliphatic modified polyester dispersants.

Such polymeric dispersants include, for example, as trade names, EFKA (registered trademark, manufactured by BASF), DISPERBYK (registered trademark, manufactured by Big Chemie, Inc.), Disparon (registered trademark, manufactured by Kusumoto Chemical Co., Ltd.), SOLSPERSE (registered trademark). Trademark: Lubrizol Co., Ltd.), KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (Kyoeisha Chemical Co., Ltd.), and Ajispur (registered trademark: Ajinomoto Co., Ltd.).

Examples of the urethane-based and acrylic polymer dispersants include DISPERBYK160 to 166, 182 series (all urethane-based), DISPERBYK2000, 2001, and BYK-LPN21116 (all acrylic-based) (all of which are manufactured by Big Chemie Co., Ltd.).

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

<Other ingredients of photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, in addition to the components described above, additives such as adhesion improvers such as silane coupling agents, surfactants, pigment derivatives, photoacid generators, crosslinking agents, mercapto compounds, and polymerization inhibitors can be appropriately blended. .

(1) adhesion improver

The photosensitive coloring composition of the present invention may contain an adhesion improver in order to improve adhesion with a substrate. As the adhesion improving agent, a silane coupling agent and a phosphoric acid group-containing compound are preferable.

As a kind of silane coupling agent, various things, such as an epoxy type, a (meth)acrylic type, and an amino type, can be used individually by 1 type or in mixture of 2 or more types.

Examples of the silane coupling agent include (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane and 3-methacryloxypropyltrimethoxysilane, and 2-(3,4-epoxycyclo Epoxysilanes such as hexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, 3-ureido Isocyanate silanes, such as ureidosilanes, such as propyl triethoxysilane, and 3-isocyanate propyl triethoxysilane, are mentioned. A silane coupling agent of epoxysilanes is particularly preferred.

As the phosphoric acid group-containing compound, (meth)acryloyl group-containing phosphates are preferable, and those represented by the following general formula (g1), (g2) or (g3) are preferable.

[Formula 46]

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

These phosphoric acid group-containing compounds may be used individually by 1 type, or may use 2 or more types together.

(2) surfactant

The photosensitive coloring composition of the present invention may contain a surfactant in order to improve applicability.

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

As such a surfactant, for example, TSF4460 (manufactured by Momentive Performance Materials), DFX-18 (manufactured by Neos), BYK-300, BYK-325, BYK-330 (manufactured by Big Chemie), KP340 (manufactured by Shin-Etsu Silicon Co., Ltd.), F-470, F-475, F-478, F-554, F-559 (manufactured by DIC Corporation), SH7PA (manufactured by Dow Corning Toray), DS-401 (manufactured by Daikin Corporation), L-77 (manufactured by Nippon Unica Co., Ltd.) and FC4430 (manufactured by 3M Co., Ltd.) are exemplified.

Surfactant may use 1 type, and may use 2 or more types together by arbitrary combinations and ratios.

(3) pigment derivatives

The photosensitive coloring composition of the present invention may contain a pigment derivative as a dispersing aid in order to improve dispersibility and storage stability.

As the pigment derivative, for example, azo-based, phthalocyanine-based, quinacridone-based, benzimidazolone-based, quinophthalone-based, isoindolinone-based, dioxazine-based, anthraquinone-based, indanthrene-based, perylene-based, ferritic Rice-based, diketopyrrolopyrrole-based, and dioxazine-based derivatives are exemplified, but among these, phthalocyanine-based and quinophthalone-based derivatives are preferable.

Substituents of the pigment derivative include, for example, sulfonic acid group, sulfonamide group and quaternary salts thereof, phthalimidemethyl group, dialkylaminoalkyl group, hydroxyl group, carboxy group, amide group, etc. directly on the pigment backbone or an alkyl group or aryl group. , and those bonded through a heterocyclic group or the like, preferably a sulfonic acid group. In addition, these substituents may be substituted in multiple numbers by one pigment skeleton.

Examples of the pigment derivative include sulfonic acid derivatives of phthalocyanine, sulfonic acid derivatives of quinophthalone, sulfonic acid derivatives of anthraquinone, sulfonic acid derivatives of quinacridone, sulfonic acid derivatives of diketopyrrolopyrrole, and sulfonic acid derivatives of dioxazine. there is. These may be used individually by 1 type, and may use 2 or more types together.

(4) Mercapto compounds

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

Examples of the mercapto compound include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, hexanedithiol, decanedithiol, and 1,4-dimethylmercaptobenzene. , butanediol bisthiopropionate, butanediol bisthioglycolate, ethylene glycol bisthioglycolate, trimethylolpropane trithioglycolate, butanediol bisthiopropionate, trimethylolpropane trithiopropionate, trimethylolpropane trithio Glycolate, pentaerythritol tetrakithiopropionate, pentaerythritol tetrakithioglycolate, trishydroxyethyltrithiopropionate, ethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mer captobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, trimethylolpropanetris(3-mercaptobutyrate), pentaerythritoltetrakis(3-mercaptobutyrate), pentaeryth Litoltris (3-mercaptobutyrate), ethylene glycol bis (3-mercaptoisobutylate), butanediolbis (3-mercaptoisobutyrate), trimethylolpropanetris (3-mercaptoisobutylate) rate), 1,3,5-tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) - having a heterocyclic ring such as trione A mercapto compound and an aliphatic polyfunctional mercapto compound are mentioned. These can use various things individually by 1 type or in mixture of 2 or more types.

(5) polymerization inhibitor

You may contain a polymerization inhibitor in the photosensitive coloring composition of this invention from a viewpoint of shape control of hardened|cured material. By containing a polymerization inhibitor, it is considered that the taper angle (the angle formed by the support and the cured product in the cross section of the cured product) can be controlled since the radical polymerization of the lower layer of the coating film is inhibited by the polymerization inhibitor.

Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, methyl hydroquinone, methoxyphenol, and 2,6-di-tert-butyl-4-cresol (BHT). Among these, from the viewpoint of shape control, 2,6-di-tert-butyl-4-cresol is preferable. Moreover, from the viewpoint of being particularly excellent in safety to the human body, hydroquinone monomethyl ether and methyl hydroquinone are preferred.

A polymerization inhibitor can be used individually by 1 type or in mixture of 2 or more types.

(b) When an alkali-soluble resin is produced, a polymerization inhibitor may be contained in the resin, and it may be used as the polymerization inhibitor of the present invention, and a polymerization inhibitor other than the polymerization inhibitor in the resin, the same as or different from the polymerization inhibitor You may add at the time of preparing a photosensitive coloring composition.

When the photosensitive coloring composition contains a polymerization inhibitor, the content thereof is not particularly limited, but is usually 0.0005% by mass or more, preferably 0.001% by mass or more, more preferably 0.01% by mass with respect to the total solid content of the photosensitive coloring composition. % or more, and is usually 0.3% by mass or less, preferably 0.2% by mass or less, and more preferably 0.1% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 0.0005 mass % - 0.3 mass % are preferable, 0.001 mass % - 0.2 mass % are more preferable, and 0.01 mass % - 0.1 mass % are still more preferable. There exists a tendency for the shape of hardened|cured material to be controllable by setting it more than the said lower limit. There exists a tendency that required sensitivity can be maintained by setting it below the said upper limit.

<Content ratio of each component in the photosensitive coloring composition>

The content ratio of the (a) colorant in the photosensitive coloring composition of the present invention is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 15% by mass or more with respect to the total solid amount. It is preferably 20% by mass or more, more preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 mass% - 50 mass% are preferable, 10 mass% - 40 mass% are more preferable, 15 mass% - 40 mass% are still more preferable, 15 mass% - 30 mass% are still more preferable And 15 mass % - 25 mass % are especially preferable. There exists a tendency that light-shielding property can be ensured by setting it as more than the said lower limit. By setting it below the said upper limit, the amount of dispersant can be reduced and there exists a tendency for surface roughness to be suppressed.

In the first aspect, the content ratio of compound (I) in the photosensitive coloring composition is preferably 5 mass% or more, more preferably 10 mass% or more, and 15 mass% or more with respect to the total solid content of the photosensitive coloring composition. It is more preferably 20% by mass or more, particularly preferably 50% by mass or less, preferably 40% by mass or less, more preferably 30% by mass or less, and particularly preferably 25% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 mass % - 70 mass % are preferable, 20 mass % - 70 mass % are more preferable, 20 mass % - 60 mass % are still more preferable, 20 mass % - 50 mass % are especially preferable . There exists a tendency for light-shielding property to improve, suppressing the loss of the ultraviolet light required for hardening by setting it as more than the said lower limit. By setting it below the said upper limit, the amount of dispersant can be reduced and there exists a tendency for surface roughness to be suppressed.

In the first aspect, when the (a) colorant contains compound (I) and other pigments, the total content is not particularly limited, but (a) the content of compound (I) in the colorant is 10% by mass The above is preferable, 20 mass% or more is more preferable, 30 mass% or more is more preferable, and 90 mass% or less is preferable, 80 mass% or less is more preferable, and 70 mass% or less is particularly preferable. . The above upper and lower limits can be arbitrarily combined. For example, 10 mass % - 90 mass % are preferable, 20 mass % - 80 mass % are more preferable, and 30 mass % - 70 mass % are still more preferable. There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit, and it can make it a color tone close to black. By setting it below the said upper limit, there exists a tendency for the residue at the time of development to become small and the reliability at the time of element fabrication to become favorable.

In the first aspect, when the (a) colorant contains compound (I) and an organic color pigment, the total content is not particularly limited, but (a) the content of compound (I) in the colorant is 10 mass % or more is preferable, 20 mass% or more is more preferable, 30 mass% or more is more preferable, and 90 mass% or less is preferable, 80 mass% or less is more preferable, and 70 mass% or less is particularly preferable. do. The above upper and lower limits can be arbitrarily combined. For example, 10 mass % - 90 mass % are preferable, 20 mass % - 80 mass % are more preferable, and 30 mass % - 70 mass % are still more preferable. There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit, and it can make it a color tone close to black. By setting it below the said upper limit, there exists a tendency for the residue at the time of development to become small and the reliability at the time of element fabrication to become favorable.

When the photosensitive coloring composition contains an organic color pigment, the content thereof is not particularly limited, but is preferably 5% by mass or more, more preferably 10% by mass or more, and 15% by mass with respect to the total solid content of the photosensitive coloring composition. The above is more preferable, 20 mass% or more is particularly preferable, and is usually 50 mass% or less, preferably 40 mass% or less, more preferably 30 mass% or less, and particularly preferably 25 mass% or less. The above upper and lower limits can be arbitrarily combined. For example, 5 mass % - 70 mass % are preferable, 20 mass % - 70 mass % are more preferable, 20 mass % - 60 mass % are still more preferable, 20 mass % - 50 mass % are especially preferable . There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. By setting it below the said upper limit, the amount of dispersant can be reduced and there exists a tendency for surface roughness to be suppressed.

(a) When the colorant contains a red pigment and/or an orange pigment, the total content of the red pigment and the orange pigment is not particularly limited, but is preferably 5% by mass or more, and preferably 8% by mass or more in the colorant (a). More preferably, 10 mass% or more is more preferable, 12 mass% or more is particularly preferable, and 40 mass% or less is preferable, 30 mass% or less is more preferable, and 20 mass% or less is particularly preferable. . The above upper and lower limits can be arbitrarily combined. For example, 5 mass % - 40 mass % are preferable, 8 mass % - 40 mass % are more preferable, 10 mass % - 30 mass % are still more preferable, 12 mass % - 20 mass % are especially preferable . There is a tendency that a color tone close to black can be obtained by setting the value to be equal to or greater than the lower limit. Moreover, there exists a tendency for high sensitivity by using below the said upper limit.

(a) When the colorant contains a blue pigment and/or a purple pigment, the total content of the blue pigment and the purple pigment is not particularly limited, but is preferably 30% by mass or more, and preferably 50% by mass or more in the (a) colorant. More preferably, 70 mass% or more is more preferable, 80 mass% or more is particularly preferable, 95 mass% or less is preferable, 92 mass% or less is more preferable, and 90 mass% or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 30 mass % - 95 mass % are preferable, 50 mass % - 95 mass % are more preferable, 70 mass % - 92 mass % are still more preferable, 80 mass % - 90 mass % are especially preferable . There is a tendency that a color tone close to black can be obtained by setting the value to be equal to or greater than the lower limit. There exists a tendency for sensitivity and light-shielding property to become favorable by using below the said upper limit.

(a) When the coloring agent contains both a red pigment and/or an orange pigment and a blue pigment and/or a purple pigment, the content ratio of the red pigment and/or the orange pigment depends on the content of the blue pigment and/or the violet pigment. is not particularly limited, but is preferably 1 mass% or more, more preferably 3 mass% or more, still more preferably 5 mass% or more, particularly preferably 8 mass% or more, and preferably 300 mass% or less. And, 100 mass % or less is more preferable, and 50 mass % or less is especially preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 mass % - 300 mass % are preferable, 3 mass % - 100 mass % are more preferable, 5 mass % - 100 mass % are still more preferable, 8 mass % - 50 mass % are especially preferable . There exists a tendency for transmission of blue light to be suppressed and light-shielding property to improve by setting it more than the said lower limit. There is a tendency that a color tone close to black can be obtained by setting the value below the above upper limit.

When the photosensitive coloring composition contains an organic black pigment, the proportion thereof is not particularly limited, but is preferably 3 mass% or more, more preferably 5 mass% or more, and 10 mass% with respect to the total solid content of the photosensitive coloring composition. The above is more preferable, 20 mass% or more is particularly preferable, and 60 mass% or less is preferable, 50 mass% or less is more preferable, and 40 mass% or less is particularly preferable. The above upper and lower limits can be arbitrarily combined. For example, 3 mass % - 60 mass % are preferable, 5 mass % - 60 mass % are more preferable, 10 mass % - 50 mass % are still more preferable, 20 mass % - 40 mass % are especially preferable . There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. By setting it below the said upper limit, the amount of dispersant can be reduced and there exists a tendency for surface roughness to be suppressed.

When the photosensitive coloring composition contains carbon black as the inorganic black pigment, the content thereof is not particularly limited, but is preferably 1% by mass or more, and more preferably 3% by mass or more, based on the total solid content of the photosensitive coloring composition. 5 mass % or more is more preferable, 30 mass % or less is preferable, 20 mass % or less is more preferable, and 10 mass % or less is especially preferable. The above upper and lower limits can be arbitrarily combined. For example, 1 mass % - 30 mass % are preferable, 3 mass % - 20 mass % are more preferable, and 3 mass % - 10 mass % are still more preferable. There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit. There exists a tendency for the hardened|cured material of high resistance and low permittivity to be formed by setting it below the said upper limit.

(a) When the colorant contains a black pigment and an organic color pigment, the total content ratio is not particularly limited, but (a) the content ratio of the black pigment in the colorant is preferably 10% by mass or more, and 20% by mass or more It is more preferably 30% by mass or more, more preferably 90% by mass or less, more preferably 80% by mass or less, and particularly preferably 70% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 10 mass % - 90 mass % are preferable, 20 mass % - 80 mass % are more preferable, and 30 mass % - 70 mass % are still more preferable. There exists a tendency for light-shielding property to become high by setting it as more than the said lower limit, and it can make it a color tone close to black. By setting it below the said upper limit, there exists a tendency for the residue at the time of development to become small and the reliability at the time of element fabrication to become favorable.

(b) The content ratio of the alkali-soluble resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more with respect to the total solid content of the photosensitive coloring composition of the present invention; More preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 85% by mass or less, preferably 80% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less , more preferably 55% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, still more preferably 20% by mass to 60% by mass, and still more preferably 30% by mass to 60% by mass. And, 30 mass % - 55 mass % are especially preferable, and 40 mass % - 55 mass % are especially preferable. There exists a tendency that the fall of the solubility of an unexposed part to a developing solution can be suppressed by setting it as more than the said lower limit, and development defect can be suppressed. By setting it below the above upper limit, there is a tendency that appropriate sensitivity can be maintained, dissolution by the developing solution of the exposed area can be suppressed, and a decrease in sharpness and adhesiveness of the pattern can be suppressed.

(b1) The content of the epoxy (meth)acrylate-based resin is not particularly limited, but is usually 5% by mass or more, preferably 10% by mass or more, more preferably 10% by mass or more, based on the total solid content of the photosensitive coloring composition of the present invention. 15% by mass or more, more preferably 20% by mass or more, particularly preferably 30% by mass or more, particularly preferably 40% by mass or more, and usually 80% by mass or less, preferably 70% by mass or less, more preferably is 60% by mass or less, particularly preferably 55% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 70% by mass, still more preferably 20% by mass to 60% by mass, and still more preferably 30% by mass to 60% by mass. And, 30 mass % - 55 mass % are still more preferable, and 40 mass % - 55 mass % are especially preferable. There exists a tendency that solubility in the developing solution of an unexposed part can be ensured by setting it as more than the said lower limit. By setting it below the above upper limit, there is a tendency that appropriate sensitivity can be maintained, dissolution by the developing solution of the exposed area can be suppressed, and a decrease in sharpness and adhesiveness of the pattern can be suppressed.

(b) The content ratio of the (b1) epoxy (meth)acrylate-based resin contained in the alkali-soluble resin is not particularly limited, but is usually 20% by mass or more, preferably 30% by mass or more, and more preferably 40% by mass. or more, and is usually 100% by mass or less, preferably 90% by mass or less, and more preferably 80% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 20 mass % - 90 mass % are preferable, 30 mass % - 80 mass % are more preferable, and 40 mass % - 80 mass % are still more preferable. There exists a tendency that solubility in the developing solution of an unexposed part can be ensured by setting it as more than the said lower limit. By setting it below the above upper limit, there is a tendency that appropriate sensitivity can be maintained, dissolution by the developing solution of the exposed area can be suppressed, and a decrease in sharpness and adhesiveness of the pattern can be suppressed.

(c) The content of the photopolymerization initiator is not particularly limited, but is usually 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, with respect to the total solid content of the photosensitive coloring composition of the present invention. Preferably 2% by mass or more, still more preferably 3% by mass or more, and usually 15% by mass or less, preferably 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less. am. The above upper and lower limits can be arbitrarily combined. For example, 0.1 mass % - 15 mass % are preferable, 0.5 mass % - 15 mass % are more preferable, 1 mass % - 10 mass % are still more preferable, 2 mass % - 8 mass % are still more preferable And 3 mass % - 6 mass % are especially preferable. There exists a tendency that the sensitivity fall can be suppressed by setting it more than the said lower limit. By setting it below the said upper limit, there exists a tendency for the fall of the solubility of an unexposed part to a developing solution to be suppressed, and development failure to be suppressed.

(c) When a polymerization accelerator is used together with a photopolymerization initiator, the content of the polymerization accelerator is not particularly limited, but is preferably 0.05% by mass or more and usually 10% by mass or less relative to the total solid content of the photosensitive coloring composition of the present invention. , Preferably it is 5 mass % or less. The polymerization promoter is preferably used in an amount of usually 0.1 to 50 parts by mass, particularly 0.1 to 20 parts by mass, based on 100 parts by mass of the (c) photopolymerization initiator. When the content ratio of the polymerization accelerator is equal to or greater than the lower limit, the decrease in sensitivity to exposure light tends to be suppressed. By setting it below the said upper limit, there exists a tendency for the fall of the solubility of an unexposed part to a developing solution to be suppressed, and development failure to be suppressed.

(c) When a sensitizing dye is used together with a photopolymerization initiator, the content thereof is not particularly limited, but is usually 20% by mass or less, preferably 15% by mass or less, based on the total solid content in the photosensitive coloring composition from the viewpoint of sensitivity, More preferably, it is 10 mass % or less.

(d) The content of the ethylenically unsaturated compound is not particularly limited, but is usually 1% by mass or more, preferably 5% by mass or more, and more preferably 10% by mass or more based on the total solid content of the photosensitive coloring composition of the present invention. , more preferably 15% by mass or more, and usually 30% by mass or less, preferably 25% by mass or less, and more preferably 20% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 1 mass % - 30 mass % are preferable, 5 mass % - 20 mass % are more preferable, and 10 mass % - 20 mass % are still more preferable. There is a tendency that proper sensitivity can be maintained, dissolution by the developing solution of the exposed area can be suppressed, and deterioration of the sharpness and adhesiveness of the pattern can be suppressed by setting it to the above lower limit or more. By setting it below the above upper limit, it tends to suppress an increase in permeability of the developing solution into the exposed portion and to obtain a good image easily.

The photosensitive coloring composition of the present invention has a content ratio of the total solid content of preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, by using (e) a solvent. , preferably 50% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, it is preferably 5% by mass to 50% by mass, more preferably 10% by mass to 30% by mass, still more preferably 15% by mass to 25% by mass.

(f) The content of the dispersant is not particularly limited, but is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 20% by mass with respect to the total solid content of the photosensitive coloring composition. % or less, preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 1 mass % - 20 mass % are preferable, 2 mass % - 15 mass % are more preferable, 3 mass % - 10 mass % are still more preferable, 3 mass % - 7 mass % are especially preferable . There exists a tendency for sufficient dispersibility to be easily obtained by setting it as more than the said lower limit. There exists a tendency that the surface roughness of the electrode surface can be suppressed by setting it below the said upper limit.

Although the content ratio of the dispersant (f1) is not particularly limited, it is usually 1% by mass or more, preferably 2% by mass or more, more preferably 3% by mass or more, and usually 20% by mass with respect to the total solid content of the photosensitive coloring composition. % or less, preferably 15% by mass or less, more preferably 10% by mass or less, and still more preferably 7% by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 1 mass % - 20 mass % are preferable, 2 mass % - 15 mass % are more preferable, 3 mass % - 10 mass % are still more preferable, 3 mass % - 7 mass % are especially preferable . There exists a tendency for sufficient dispersibility to be easily obtained by setting it as more than the said lower limit. There exists a tendency that the surface roughness of the electrode surface can be suppressed by setting it below the said upper limit.

The content of the dispersant (f1) is not particularly limited, but is usually 20% by mass or more in the dispersant (f), preferably 40% by mass or more, more preferably 60% by mass or more, and still more preferably 80% by mass or more. , and usually 100% by mass or less. There exists a tendency that the surface roughness of the electrode surface can be suppressed by setting it as more than the said lower limit.

The content ratio of (f) dispersant to 100 parts by mass of (a) colorant is not particularly limited, but is usually 5 parts by mass or more, more preferably 10 parts by mass or more, still more preferably 15 parts by mass or more, and usually 50 parts by mass It is preferably less than or equal to 30 parts by mass or less. The above upper and lower limits can be arbitrarily combined. For example, 5 parts by mass to 50 parts by mass are preferable, 10 parts by mass to 50 parts by mass are more preferable, and 15 parts by mass to 30 parts by mass are still more preferable. There exists a tendency for sufficient dispersibility to be easily obtained by setting it as more than the said lower limit. There exists a tendency that the surface roughness of the electrode surface can be suppressed by setting it below the said upper limit.

(d) The content ratio of the alkali-soluble resin (b) to 100 parts by mass of the ethylenically unsaturated compound is not particularly limited, but is usually 100 parts by mass or more, preferably 200 parts by mass or more, and more preferably 250 parts by mass or more, 300 parts by mass or more is more preferable, 350 parts by mass or more is particularly preferable, and usually 700 parts by mass or less and 500 parts by mass or less are preferable, 450 parts by mass or less are more preferable, and 400 parts by mass or less are still more preferable. . The above upper and lower limits can be arbitrarily combined. For example, preferably 100 parts by mass to 700 parts by mass, more preferably 200 parts by mass to 700 parts by mass, still more preferably 250 parts by mass to 500 parts by mass, still more preferably 250 parts by mass to 450 parts by mass, and even more preferably 250 parts by mass Part to 400 parts by mass is particularly preferred. By setting the above lower limit or more, it tends to be in an appropriate dissolution state without peeling or the like. There exists a tendency that an appropriate dissolution time can be obtained with respect to a developing solution by setting it below the said upper limit.

When an adhesion improver is used, the content thereof is not particularly limited, but 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 of the photosensitive coloring composition. am. There exists a tendency for the adhesive improvement effect to fully be acquired by setting it as more than the said lower limit. By setting it below the above upper limit, it tends to be able to suppress the decrease in sensitivity or the occurrence of defects due to residues remaining after development.

When a surfactant is used, the content thereof is not particularly limited, but is usually 0.001 to 10% by mass, preferably 0.005 to 1% by mass, and more preferably 0.01 to 0.5% by mass relative to the total solid content of the photosensitive coloring composition. , most preferably 0.03 to 0.3% by mass. There exists a tendency for the smoothness and uniformity of a coating film to be easily expressed by setting it as more than the said lower limit. By setting it below the said upper limit, the smoothness and uniformity of a coating film tend to be expressed easily, and deterioration of other characteristics also tends to be suppressed.

<Content of Chlorine Atoms in Photosensitive Coloring Composition>

In the photosensitive coloring composition of the present invention, the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.

In producing a partition, the process of hardening a photosensitive coloring composition by performing heat processing as mentioned later is accompanied. At that time, surface roughness may occur on the surface of the electrode. Surface roughness can be observed with an optical microscope, and surface roughness also increases. When surface roughness occurs on the electrode surface, a light emitting layer cannot be uniformly formed on that portion, and display defects due to a short circuit or the like may occur when an organic electroluminescent device is manufactured. This is presumed to be because chlorine atoms in the photosensitive coloring composition decompose, volatilize, or sublimate during heat treatment, particularly during firing, and act on a metal electrode such as silver to cause corrosion or etching. Surface roughness can be suppressed by making content into a fixed value or less.

Chlorine atoms in the photosensitive coloring composition are mainly contained in constituent materials such as (a) colorant, (b) alkali-soluble resin, and (f) dispersant, but may also be contained in other materials. In order to make the chlorine atom content fall within the numerical range stipulated by the present invention, the chlorine content of one constituent material may be reduced, or the chlorine content in each material may be reduced and designed to fall within the stipulated numerical range. You can do it.

The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is 0.05% by mass or less, preferably 0.04% by mass or less, more preferably 0.03% by mass or less, and 0.01% by mass with respect to the total solid content of the photosensitive coloring composition. The following is more preferable. By setting it below the said upper limit, there exists a tendency for the surface roughness of an electrode to be suppressed.

Although content of the chlorine atom in the photosensitive coloring composition is not specifically limited, It is 0.0005 mass % or more normally, 0.001 mass % or more is preferable, and 0.002 mass % is more preferable. It is effective at the point where refining can be alleviated at the time of manufacture of each constituent material by setting it as more than the said lower limit.

The above upper and lower limits can be arbitrarily combined. For example, 0.0005-0.05 mass % is preferable, 0.0005-0.04 mass % is more preferable, 0.001-0.03 mass % is still more preferable, and 0.002-0.01 mass % is especially preferable.

The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 100 µg/g or less, more preferably 80 µg/g or less, and 50 µg/g or less based on the total mass of the photosensitive coloring composition containing the solvent. g or less is more preferable, 30 μg/g or less is even more preferable, and 10 μg/g or less is particularly preferable. By setting it below the said upper limit, there exists a tendency for the surface roughness of an electrode to be suppressed.

The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is usually 0.5 μg/g or more, preferably 1.0 μg/g or more, and more preferably 2.0 μg/g or more. By setting it to the lower limit or more, it is effective at the point where refining can be relieved at the time of manufacturing each constituent material.

The above upper and lower limits can be arbitrarily combined. For example, 0.5 to 100 μg/g is preferable, 0.5 to 80 μg/g is more preferable, 1.0 to 50 μg/g is still more preferable, 1.0 to 30 μg/g is even more preferable, and 2.0 to 2.0 μg/g is more preferable. 10 μg/g is particularly preferred.

The content of chlorine atoms in the photosensitive coloring composition is not particularly limited, but is preferably 0.20% by mass or less, more preferably 0.15% by mass or less, and 0.10% by mass relative to 100% by mass of the colorant (a) of the photosensitive coloring composition. % or less is more preferable, 0.05 mass % or less is still more preferable, and 0.03 mass % or less is especially preferable. By setting it below the said upper limit, there exists a tendency for the surface roughness of an electrode to be suppressed.

Although content of the chlorine atom in the photosensitive coloring composition is not specifically limited, It is 0.001 mass % or more normally, 0.005 mass % or more is preferable, and 0.010 mass % is more preferable. By setting it to the lower limit or more, it is effective at the point where refining can be relieved at the time of manufacturing each constituent material.

The above upper and lower limits can be arbitrarily combined. For example, with respect to 100 mass% of content of the (a) coloring agent of the photosensitive coloring composition, 0.001-0.20 mass% is preferable, 0.001-0.15 mass% is more preferable, 0.005-0.10 mass% is still more preferable, and 0.005 - 0.05 mass % is more preferable, and 0.010 - 0.03 mass % is especially preferable.

The content of chlorine atoms in the photosensitive coloring composition can be measured, for example, by combustion ion chromatography or the like.

<Physical properties of photosensitive coloring composition>

In the photosensitive coloring composition of the present invention, the optical density (OD) per 1 μm of film thickness of the coating film is not particularly limited in the first aspect, but is preferably 0.5 or more. In the second aspect, it is 0.5 or more. 0.7 or more is more preferable, 1.0 or more is more preferable, 1.3 or more is still more preferable, 1.5 or more is particularly preferable, and it is usually 4.0 or less, 3.0 or less is preferable, and 2.0 or less is more preferable. The above upper and lower limits can be arbitrarily combined. Also in any of the 1st aspect and the 2nd aspect, 0.5-4.0 are preferable, 0.7-4.0 are more preferable, 1.0-3.0 are still more preferable, 1.3-3.0 are still more preferable, and 1.5-4.0 are still more preferable, for example. 2.0 is particularly preferred. There exists a tendency for sufficient light-shielding property to be obtained by setting it as more than the said lower limit. The surface roughness of an electrode tends to become favorable by setting it below the said upper limit.

The optical density (OD) per 1 μm of film thickness of the coating film may be measured using a coating film cured with the photosensitive coloring composition of the present invention, and can be measured using a coating film cured by heating at 230 ° C. for 20 minutes.

The optical density refers to the transmission optical density in which the spectral sensitivity characteristics of the light receiving section are expressed by ISO visual density in the ISO 5-3 standard. Usually, as a light source, the A light source prescribed|regulated by CIE (International Commission on Illumination) is used. An example of a measuring device that can be used for measuring the transmission optical density is X-Rite 361T(V) from Sakata Inks Engineering Co., Ltd.

<Method for producing photosensitive coloring composition>

The photosensitive coloring composition of the present invention is prepared according to a conventional method.

Usually, it is preferable that the colorant (a) be subjected to dispersion treatment in advance using a paint conditioner, sand grinder, ball mill, roll mill, stone mill, jet mill, homogenizer or the like. By the dispersion treatment (a), since the colorant is finely divided, the coating properties of the resist are improved.

Dispersion treatment is usually preferably carried out in a system in which a part or all of (a) colorant, (e) solvent, (f) dispersant, and (b) alkali-soluble resin are used in combination (hereinafter used for dispersion treatment). The resulting mixture and the composition obtained by the dispersion treatment may be referred to as "pigment dispersion"). Particularly, when a polymeric dispersant is used as the dispersant (f), the obtained pigment dispersion and the photosensitive colored resin composition are prevented from thickening over time, that is, the dispersion stability is excellent, so it is preferable.

Thus, in the process of producing a photosensitive coloring composition, it is preferable to prepare a pigment dispersion liquid containing at least (a) a colorant, (e) a solvent, and (f) a dispersing agent.

As the colorant (a), the solvent (e), and the dispersant (f) that can be used for the pigment dispersion, those described as those that can be used for the photosensitive colored resin composition can be preferably employed. Moreover, also as the content rate of each colorant of the (a) colorant in the pigment dispersion, what was described as the content rate in the photosensitive colored resin composition can be preferably employed.

When a dispersion treatment is performed on a liquid containing all components to be blended in the photosensitive coloring composition, highly reactive components may be denatured due to heat generated during the dispersion treatment. Therefore, it is preferable to carry out the dispersion treatment in a system containing a polymeric dispersant.

When dispersing (a) the coloring agent with a sand grinder, glass beads or zirconia beads having a particle diameter of about 0.1 to 8 mm are preferably used. As for the dispersion treatment conditions, the temperature is usually in the range of 0°C to 100°C, preferably room temperature to 80°C. The dispersing time is appropriately adjusted because the appropriate time differs depending on the composition of the liquid and the size of the dispersing treatment device. Controlling the gloss of the pigment dispersion so that the 20 degree specular gloss (JIS Z8741) of the photosensitive coloring composition is in the range of 50 to 300 is a standard for dispersion. When the glossiness of the photosensitive coloring composition is low, dispersion treatment is not sufficient and coarse pigment (coloring material) particles often remain, which may result in insufficient developability, adhesion, resolution, and the like. If the dispersion treatment is performed until the gloss value exceeds the above range, the pigment is crushed and a large number of ultrafine particles are generated, so the dispersion stability tends to deteriorate.

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

Next, the pigment dispersion obtained by the dispersion treatment and the other components contained in the photosensitive coloring composition are mixed to form a uniform solution or dispersion. In the manufacturing process of the photosensitive colored resin composition, since fine dust may be mixed in a liquid, it is preferable to filter the obtained photosensitive colored resin composition with a filter etc.

[cured material]

The cured product of the present invention can be obtained by curing the photosensitive coloring composition of the present invention. A cured product formed by curing the photosensitive coloring composition of the present invention can be suitably used as a barrier rib.

[septum]

The photosensitive coloring composition of the present invention can be suitably used to form barrier ribs, particularly barrier ribs for partitioning an organic layer of an organic electroluminescent device. As an organic layer used for an organic electroluminescent element, the organic layer used for the hole injection layer, the hole transport layer, or the hole transport layer on the hole injection layer described in Unexamined-Japanese-Patent No. 2016-165396 is mentioned, for example.

Next, the barrier rib using the photosensitive coloring composition of the present invention will be described according to its manufacturing method.

(1) support

As the support for forming the barrier rib, the material is not particularly limited as long as it has appropriate strength. A substrate is mainly used, but as a material, for example, polyester resins such as polyethylene terephthalate, polyolefin resins such as polypropylene and polyethylene, and thermoplastic resins such as polycarbonate, polymethyl methacrylate, and polysulfone. Sheets, thermosetting resin sheets such as epoxy resins, unsaturated polyester resins, and poly(meth)acrylic resins, and various types of glass are exemplified. Especially, from a viewpoint of heat resistance, glass and heat-resistant resin are preferable. In some cases, a transparent electrode such as ITO or IZO or a metal electrode such as silver, gold, platinum, aluminum or magnesium is formed on the surface of the substrate. It is also possible to form on a TFT array other than the above-mentioned substrate.

The support may be subjected to, for example, corona discharge treatment, ozone treatment, thin film formation treatment of various resins such as silane coupling agents and urethane-based resins, as necessary, in order to improve surface properties such as adhesiveness.

The thickness of the substrate is usually in the range of 0.05 to 10 mm, preferably 0.1 to 7 mm. In the case of performing thin film formation treatment of various resins, the film thickness is usually in the range of 0.01 to 10 µm, preferably 0.05 to 5 µm.

(2) Bulkhead

Although the photosensitive coloring composition of the present invention is used for the same purpose as the known photosensitive coloring composition for color filters, hereinafter, according to a specific example of a method for forming a partition using the photosensitive coloring composition of the present invention, for the case of being used as a partition wall. Explain.

Usually, a photosensitive coloring composition is supplied in the form of a film or pattern by a method such as coating on a substrate on which a barrier rib is to be formed, and the solvent is dried. Subsequently, pattern formation is performed by a method such as a photolithography method in which exposure-development is performed. Thereafter, barrier ribs are formed on the substrate by performing additional exposure or thermal curing treatment as necessary.

(3) Formation of bulkheads

[1] Supply method to the board

The photosensitive coloring composition of the present invention is usually supplied onto a substrate in a state of being dissolved or dispersed in a solvent. As the supply method, it can be carried out by a conventionally known method, for example, a spinner method, a wire bar method, a flow coating method, a die coating method, a roll coating method, or a spray coating method. Moreover, you may supply in pattern shape by the inkjet method or the printing method, for example. Among them, the die coating method is preferable from a comprehensive point of view, in that the amount of the coating liquid used is significantly reduced, and the influence of mist or the like adhered when the spin coating method is used is completely eliminated and the generation of foreign substances is suppressed.

The application amount varies depending on the application, but, for example, in the case of a barrier rib, the dry film thickness is usually 0.5 μm to 10 μm, preferably 1 μm to 9 μm, and particularly preferably 1 μm to 7 μm. It is important that the dry film thickness or the height of the finally formed barrier rib be uniform over the entire substrate. By making the variation small, the light emitting layer can be produced uniformly, and display defects at the time of light emission can be suppressed.

In the case of collectively forming barrier ribs having different heights by the photolithography method using the photosensitive coloring composition of the present invention, the finally formed barrier ribs become different in height.

As the substrate, known substrates such as glass substrates and array substrates can be used. Suitably, the substrate surface is planar.

[2] Drying method

Drying after supplying the photosensitive coloring composition onto the substrate is preferably performed by a drying method using a hot plate, IR oven, or convection oven. A reduced pressure drying method may be combined in which drying is performed in a reduced pressure chamber without raising the temperature.

Drying conditions can be appropriately selected according to the type of solvent component, the performance of the dryer to be used, and the like. The drying time is usually selected from the range of 15 seconds to 5 minutes at a temperature of 40 ° C. to 130 ° C., preferably at a temperature of 50 ° C. to 110 ° C. It is selected from the range of 30 second - 3 minutes.

[3] Exposure method

Exposure is performed by superimposing a negative mask pattern on the coating film of the photosensitive coloring composition, and irradiating a light source of ultraviolet rays or visible rays through this mask pattern. In the case of exposure using an exposure mask, a method of bringing the exposure mask close to the coating film of the photosensitive coloring composition, or arranging the exposure mask at a position away from the coating film of the photosensitive coloring composition, and exposure light passing through the exposure mask It may also depend on how to project . A scanning exposure method using a laser beam without using a mask pattern may be employed. If necessary, in order to prevent a decrease in the sensitivity of the photopolymerizable layer due to oxygen, exposure may be carried out in a deoxidized atmosphere or after forming an oxygen barrier layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

As a preferred aspect of the present invention, when barrier ribs having different heights are formed simultaneously by a photolithography method, for example, a light-shielding portion (light transmittance: 0%) and a plurality of openings, the opening having the highest average light transmittance (perfect An exposure mask having an opening having a small average light transmittance (intermediate transmission opening) with respect to the transmission opening) is used. With this method, a difference in remaining film rate is generated by the difference in average light transmittance between the intermediate transmission opening and the full transmission opening, that is, the difference in exposure amount.

There is known a method for producing the intermediate transmission opening by, for example, a matrix-like light-shielding pattern having minute polygonal light-shielding units. Further, as an absorber, a method of producing a film of, for example, a chromium-based, molybdenum-based, tungsten-based, or silicon-based material by controlling the light transmittance is known.

A light source used for the exposure is not particularly limited. As the light source, for example, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, an argon ion laser, a YAG laser , laser light sources such as excimer lasers, nitrogen lasers, helium cadmium lasers, blue-violet semiconductor lasers, and near-infrared semiconductor lasers. In the case of irradiating and using light of a specific wavelength, an optical filter may be used.

The optical filter may be, for example, a thin film and of a type capable of controlling light transmittance at an exposure wavelength. As a material in that case, for example, a Cr compound (oxide, nitride, oxynitride, fluoride, etc. of Cr) , MoSi, Si, W, and Al.

The exposure amount is not particularly limited, but is usually 1 mJ/cm ² or more, preferably 5 mJ/cm ² or more, more preferably 10 mJ/cm ² or more, and usually 300 mJ/cm ² or less, preferably 200 mJ/cm ² or less, more preferably 150 mJ/cm ² or less.

In the case of the proximity exposure method, the distance between the exposure target and the mask pattern is not particularly limited, but is usually 10 μm or more, preferably 50 μm or more, more preferably 75 μm or more, and usually 500 μm or less, preferably 400 μm or less, more preferably 300 μm or less.

[4] Development method

After performing the exposure, an image pattern can be formed on the substrate by development using an aqueous solution of an alkaline compound or an organic solvent. The aqueous solution of the alkaline compound may further contain, for example, a surfactant, an organic solvent, a buffer, a complexing agent, a dye or a pigment.

As the alkaline compound, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium silicate, potassium silicate, sodium metasilicate, sodium phosphate, potassium phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate , inorganic alkali compounds such as sodium dihydrogen phosphate, potassium dihydrogen phosphate, ammonium hydroxide, mono-, di- or triethanolamine, mono-, di- or trimethylamine, mono-, di- or triethylamine, mono- or and organic alkaline compounds such as diisopropylamine, n-butylamine, mono-, di- or triisopropanolamine, ethyleneimine, ethylenediimine, tetramethylammonium hydroxide (TMAH), and choline. 2 or more types of mixtures may be sufficient as these alkaline compounds.

Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, and monoglyceride alkyl esters. ; anionic surfactants such as alkylbenzenesulfonic acid salts, alkylnaphthalenesulfonic acid salts, alkyl sulfates, alkylsulfonic acid salts, and sulfosuccinic acid ester salts; Amphoteric surfactants, such as alkyl betaines and amino acids, are mentioned.

Examples of the organic solvent include isopropyl alcohol, benzyl alcohol, ethyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol, and diacetone alcohol. These organic solvents may use 2 or more types together. In addition, the organic solvent may be used alone or in combination with water or an aqueous solution of an alkaline compound.

The conditions for the development treatment are not particularly limited, and the development temperature is usually 10 to 50°C, preferably 15 to 45°C, and more preferably 20 to 40°C. The developing method may follow, for example, an immersion developing method, a spray developing method, a brush developing method, or an ultrasonic developing method.

[5] Additional exposure and heat curing treatment

The board|substrate after development may be additionally exposed by the same method as the said exposure method as needed. After development or additional exposure, a thermal curing treatment (also referred to as baking) may be performed. Regarding the thermal curing treatment conditions, the temperature is preferably 100°C to 280°C, more preferably 150°C to 250°C, and the time is 5 minutes to 60 minutes.

When the photosensitive coloring composition of the present invention is used as a barrier rib, the size, shape, etc. are appropriately adjusted depending on the specifications of the organic electroluminescent device to which it is applied, but the height of the barrier rib formed by the photosensitive coloring composition of the present invention is usually 0.5 to 0.5. It is about 10 μm.

In addition, the optical density (OD) per 1 μm of the barrier rib of the present invention is preferably 0.7 or more, more preferably 1.2 or more, still more preferably 1.5 or more, and particularly preferably 1.8 or more from the viewpoint of light-shielding properties. Moreover, it is preferable that it is 4.0 or less, and it is more preferable that it is 3.0 or less. The above upper and lower limits can be arbitrarily combined. For example, 0.7 to 4.0 are preferable, 1.2 to 4.0 are more preferable, 1.5 to 3.0 are still more preferable, and 1.8 to 3.0 are particularly preferable. Here, the optical density (OD) is a value measured by the method described below.

[Organic electroluminescence device]

The organic electroluminescent device of the present invention includes the cured product of the present invention, for example, a barrier rib.

For example, various organic electroluminescent elements are manufactured using a substrate having a barrier rib pattern manufactured by the method described above. The method of forming the organic electroluminescent element is not particularly limited, but preferably, after forming a pattern of barrier ribs on the substrate by the method described above, the functional material is sublimated in a vacuum state, and surrounded by the barrier ribs on the substrate. An organic electroluminescent device is manufactured by forming an organic layer such as a pixel by a deposition method in which a film is deposited in a region and a wet process such as a cast method, a spin coat method, or an inkjet printing method.

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

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

Moreover, as a light emitting layer, the organic electroluminescent layer described in Unexamined-Japanese-Patent No. 2009-146691 or Japanese Patent Publication No. 5734681 is mentioned. Moreover, you may use the quantum dot described in Japanese Patent Publication No. 5653387 or Japanese Patent Publication No. 5653101.

The layer configuration is not limited to this, and for example, each layer of the hole transport layer and the electron transport layer may have a laminate configuration composed of two or more layers from the viewpoint of luminous efficiency. The thickness of each layer is not particularly limited, but is usually 1 to 500 nm from the viewpoint of luminous efficiency and luminance.

The organic electroluminescent element may be formed by dividing each RGB color for each opening, or two or more colors may be laminated in one opening. The organic electroluminescent element may be provided with a sealing layer from the viewpoint of improving reliability. The encapsulation layer has a function of preventing moisture in the air from adsorbing to the organic electroluminescent device and reducing luminous efficiency. The organic electroluminescent element may have a low reflection film at the interface with air from the viewpoint of improving the light extraction efficiency. By arranging the low-reflection film at the interface between the air and the element, it is expected to reduce the refractive index gap and suppress reflection at the interface. For such a low-reflection film, for example, a moth-eye structure or super-multilayer film technology can be applied.

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

Further, in the organic electroluminescent element, since it is necessary to provide electrodes to the upper and lower surfaces of the barrier rib, it is preferable that the barrier rib has high resistance and low permittivity from the viewpoint of insulating property. Therefore, when using a coloring agent in order to provide light-shielding property to a partition, it is preferable to use the said organic pigment with high resistance and low dielectric constant.

[Image display device]

Examples of the image display device of the present invention include barrier ribs containing the cured product of the present invention and organic EL display devices having the organic electroluminescent element of the present invention.

As long as the organic EL display device includes the organic electroluminescent element described above, there is no particular limitation on the format or structure of the image display device, and for example, an active drive type organic electroluminescent element is used according to a conventional method. can be assembled For example, it can be formed by the method described in "Organic EL Display" (Oum Corporation, published on August 20, 2004, by Shizuo Tokito, Chihaya Adachi, and Hideyuki Murata). For example, image display may be performed by combining an organic electroluminescent element that emits white light and a color filter, or image display may be performed by combining organic electroluminescent elements of different emission colors such as RGB.

[light]

An organic electroluminescent device containing the cured product of the present invention can be used for lighting. There is no particular limitation on the form or structure of the lighting, and it can be assembled according to a conventional method using the organic electroluminescent device containing the cured product of the present invention. The organic electroluminescent element may be a simple matrix driving method or an active matrix driving method.

In order for illumination to emit white light, an organic electroluminescent element emitting white light may be used. Further, organic electroluminescent elements having different luminous colors may be combined, and each color may be mixed to become white, or a color mixing function may be provided by a configuration such that the mixing ratio can be adjusted.

Example

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded.

The constituent components of the photosensitive coloring composition used in the following Examples and Comparative Examples and their evaluation methods are as follows.

<Alkali Soluble Resin-I>

"XD1000" manufactured by Nippon Kayaku Co., Ltd. (Polyglycidyl ether of dicyclopentadiene/phenol polymer, epoxy equivalent 252) 300 parts by mass, 87 parts by mass of acrylic acid, 0.2 parts by mass of p-methoxyphenol, 5 parts by mass of triphenylphosphine part, and 255 parts by mass of propylene glycol monomethyl ether acetate were charged into the reaction vessel, and stirred at 100°C until the acid value became 3.0 mgKOH/g. Subsequently, 145 mass parts of tetrahydrophthalic anhydride was further added, and it was made to react at 120 degreeC for 4 hours. The weight average molecular weight (Mw) of alkali-soluble resin-I obtained in this way measured by GPC was 2600, and the acid value was 106 mgKOH/g.

<Alkali Soluble Resin-II>

[Formula 47]

50.0 parts by mass of the epoxy compound (epoxy equivalent 248) of the above structure, 14.2 parts by mass of acrylic acid, 52.6 parts by mass of methoxybutyl acetate, 1.29 parts by mass of triphenylphosphine, and 0.044 parts by mass of paramethoxyphenol, thermometer, stirrer, cooling tube into a flask equipped with, and reacted at 90°C with stirring until the acid value became 5 mgKOH/g or less. The reaction required 12 hours to obtain an epoxy acrylate solution.

To the epoxy acrylate solution, 42.9 parts by mass of methoxybutyl acetate, 1.98 parts by mass of trimethylolpropane (TMP), 24.9 parts by mass of biphenyltetracarboxylic dianhydride (BPDA), and 5.39 parts by mass of tetrahydrophthalic anhydride (THPA) , put into a flask equipped with a thermometer, stirrer, and cooling tube, and reacted by slowly raising the temperature to 105 ° C. while stirring.

When the resin solution became transparent, it was diluted with methoxybutyl acetate, and it prepared so that it might become 50 mass % of solid content, and obtained alkali-soluble resin (II) of acid value 100 mgKOH/g and weight average molecular weight (Mw) 12000.

<Alkali-soluble resin-III>

Nippon Kayaku Co., Ltd. "ZCR-8035H" (weight average molecular weight Mw = 7000, acid value = 82 mgKOH/g). It has a partial structure represented by the following formula (C-1).

[Formula 48]

<Pigment-I>

Irgaphor (registered trademark) Black S 0100 CF manufactured by BASF (has a chemical structure represented by the following formula (2))

[Formula 49]

<Pigment-II>

C.I. Pigment Orange 64

<Pigment-III>

C.I. Pigment Violet 29

<Pigment-IV>

C.I. Pigment Blue 60

<Dispersant-I>

A methacrylic A-B diblock copolymer composed of an A block containing a repeating unit having a solvophilic group and a B block containing a repeating unit having a pigment adsorbing group. It has repeating units of the following formulas (a) to (f). The amine value is 120 mgKOH/g. The weight average molecular weight is 9000. The dispersant does not substantially contain chlorine atoms.

The content ratio of the repeating units of the following formulas (a) to (f) in all the repeating units is (a) 33.3 mol%, (b) 13.3 mol%, (c) 6.7 mol%, and (d) 6.7 mol%, respectively. , (e) 6.7 mol%, and (f) 33.3 mol%.

[Formula 50]

[Formula 51]

<Dispersant-II>

A methacrylic A-B diblock copolymer composed of an A block containing a repeating unit having a solvophilic group and a B block containing a repeating unit having a pigment adsorbing group. It has repeating units of the following formulas (h) to (n). The amine value is 70 mgKOH/g. The weight average molecular weight before quaternizing the amino group is 9000. Content of the chlorine atom in a dispersing agent is 2.1 mass %.

The content ratio of the repeating units of the following formulas (h) to (n) in all the repeating units is (h) 33.3 mol%, (i) 13.3 mol%, (j) 6.7 mol%, and (k) 6.7 mol%, respectively. , (l) 6.7 mol%, (m) 24.0 mol%, and (n) 9.3 mol%.

[Formula 52]

[Formula 53]

<Solvent-I>

PGMEA: Propylene glycol monomethyl ether acetate

<Solvent-II>

MB: 3-methoxy-1-butanol

<Solvent-III>

MBA: 3-methoxybutyl acetate

<Photoinitiator-I>

Oxime ester-based photopolymerization initiator having the following chemical structure

[Formula 54]

<ethylenically unsaturated compounds>

DPHA-40H: Urethane acrylate manufactured by Nippon Chemical Co., Ltd.

<Surfactant>

Megafac F-559 manufactured by DIC

<Evaluation of viscosity>

The viscosity of the prepared pigment dispersion was measured with a RE-85L viscometer manufactured by Toki Sangyo (measurement conditions: 23°C, 20 rpm).

<Measurement of chlorine atom content>

The measurement was performed by combustion ion chromatography. The chlorine atom content in the photosensitive coloring composition was quantified by a calibration curve method using a combustion absorption ion chromatograph (CIC) apparatus AQF2100H manufactured by Mitsubishi Chemical Analytec (currently Nitto Seiko Analytec).

<Measurement of optical density per unit film thickness (unit OD value)>

The optical density per unit film thickness was measured in the following procedure.

First, the prepared photosensitive coloring composition was applied to a glass substrate with a spin coater so that the film thickness after firing was 1.5 µm, dried under reduced pressure for 1 minute, and then dried at 100°C for 120 seconds on a hot plate. The obtained coating film was exposed without using an exposure mask. A high-pressure mercury lamp having an intensity of 40 mW/cm ² at a wavelength of 365 nm was used as an irradiation light source, and an exposure amount was 50 mJ/cm ² . Subsequently, the resist coated substrate 1 was obtained by heat-curing at 230°C in an oven for 30 minutes.

The optical density (OD value) of the obtained resist-coated substrate 1 was measured using a 361T (V) transmission densitometer manufactured by X-Rite (color temperature of illumination light source: about 2850 K (equivalent to CIE standard light source A), spectral sensitivity characteristics of light receiving section: ISO 5 ISO visual density in the -3 standard), and the film thickness was measured by VertScan(R) 2.0, a non-contact surface/layer cross-section shape measurement system manufactured by Ryoka Systems, and from the optical density (OD value) and film thickness , the optical density (unit OD value) per unit film thickness (1 μm) was calculated. In addition, the OD value is a numerical value representing the light-shielding ability, and the higher the numerical value, the higher the light-shielding property.

<Evaluation of electrode surface roughness>

On an electrode substrate on which a silver thin film having a film thickness of 60 nm was deposited on the entire surface of a glass substrate, each photosensitive coloring composition was applied by a spin coater so that the film thickness after firing was 1.5 μm, dried under reduced pressure for 1 minute, and then dried on a hot plate was dried at 100 °C for 120 seconds. Next, using a photomask capable of forming a square opening pattern with a side of 50 μm on the obtained coating film substrate, a wavelength of 330 nm or less is cut with a high-pressure mercury lamp, and exposure gap is 5 μm, and 50 mJ/cm ² ultraviolet light exposure was carried out. The intensity at a wavelength of 365 nm at this time was 40 mW/cm ² . Then, using a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution as a developer, shower development at 25°C at a developer water pressure of 0.05 MPa was performed for 60 seconds, then the developer was flowed with pure water to stop the development, and a water washing spray washed for 60 seconds.

By these operations, the opening portion was removed from development to obtain an electrode substrate having partition walls patterned thereon. The board|substrate on which the said pattern was formed was heated (baked) for 30 minutes at 230 degreeC in oven, and the pattern was hardened.

The obtained electrode substrate on which the 50 μm opening pattern was formed was observed under an optical microscope at 200 times, and the presence or absence of a shape change (surface roughness) of the electrode surface in the opening pattern was confirmed. Surface roughness is good in the order of A, B, and C, and A shows that it is the best.

A: No surface roughness occurred on the surface of the electrode after heat curing.

B: After curing by heating, some surface roughness occurs on the surface of the electrode, but there is no practical problem and this is acceptable.

C: After heat curing, irregularities are seen on the surface of the electrode and surface roughness is generated, which is a problem in practical use and is difficult to accept.

<Evaluation of luminescence characteristics>

On a substrate on which an anode was formed by using a conventional photolithography technique and hydrochloric acid etching to deposit an indium tin oxide (ITO) transparent conductive film having a thickness of 70 nm on glass, each photosensitive coloring composition was applied to the film thickness after firing. was applied with a spin coater to a thickness of 1.5 μm, dried under reduced pressure for 1 minute, and dried at 100° C. for 120 seconds with a hot plate. Next, an exposure mask (one having a plurality of rectangular coating portions (40 μm long × 80 μm wide) at a pitch of 60 μm long and 100 μm wide) was used on the obtained coating film substrate, and a wavelength of 330 nm or less was subjected to ultraviolet light exposure at 50 mJ/cm ² with an exposure gap of 5 μm by a high-pressure mercury lamp that had cut . The light intensity at a wavelength of 365 nm at this time was 40 mW/cm ² . Then, using a 2.38 mass% TMAH (tetramethylammonium hydroxide) aqueous solution as a developing solution, shower development at 25 ° C. at a developer water pressure of 0.05 MPa was performed for 60 to 120 seconds, and then the developing solution was poured into pure water to stop development, It was washed for 60 seconds with a water washing spray. The shower developing time was set to be 1.2 times or more of the time for dissolving and removing the unexposed portion of the coating film.

By these operations, the opening portion was removed from development, and an electrode substrate having partition walls patterned was obtained. The board|substrate on which the said pattern was formed was heated (baked) for 30 minutes at 230 degreeC in oven, and the pattern was hardened.

<Production of organic electroluminescent device>

On the entire surface of the electrode substrate on which the prepared barrier rib is patterned, molybdenum oxide is applied as a hole injection layer with a film thickness of 10 nm and N-([1,1'-biphenyl]-4-yl)-9,9- as a hole transport layer. Dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine with a film thickness of 60 nm and tris(8-hydroxyquinolinate) as the light emitting layer An organic electroluminescent device was produced by sequentially laminating aluminum with a film thickness of 60 nm, 8-hydroxyquinolinolate-lithium as an electron injection layer with a film thickness of 1 nm, and aluminum as a cathode with a film thickness of 80 nm by vacuum evaporation. did

Next, a drying agent was applied to the concave portion of the sealing glass having a concave portion in the center, and a UV curable resin was applied to the frame portion around the concave portion. Organic electroluminescence by arranging the concave portion of the sealing glass so as to cover all the organic electroluminescent elements on the electrode substrate, attaching the sealing glass to the electrode substrate, curing the UV curable resin by irradiating UV, and encapsulating the hollow structure A device for element evaluation was fabricated.

<Evaluation of light emitting characteristics of organic electroluminescent device>

A voltage value (drive voltage) when a direct current having a current density of 10 mA/cm ² was passed through the fabricated element was measured.

Voltage value (drive voltage) when 10 mA/cm ² is energized at the current density when creating the cell

A: voltage 6.5 V or less

B: Voltage higher than 6.5 V

Next, when the manufactured element was driven with a direct current having a current density of 50 mA/cm ² at a constant current in a 60°C environment, the time (h) from the initial luminance to a value of 90% was measured as a drive life.

Time from initial luminance to 90% luminance (lifetime)

A: longer than 25 hours

B: 25 hours or less

<Preparation of Pigment Dispersions 1 to 3>

The pigments, dispersants, alkali-soluble resins, and solvents shown in Table 1 were mixed in a mass ratio shown in Table 1. This liquid mixture was subjected to dispersion treatment in the range of 25 to 45°C for 3 hours with a paint shaker. As beads, 0.5 mmφ zirconia beads were used, and 2.5 times the mass of the dispersion liquid was added. After completion of the dispersion, the beads and the dispersion were separated by a filter to prepare pigment dispersions 1 to 3.

In addition, the quantity of the solvent in Table 1 includes the quantity of the solvent derived from a dispersing agent and alkali-soluble resin. In addition, Table 1 shows the evaluation result of the viscosity of the pigment dispersion liquid measured by the method mentioned above.

[Examples 1 and 2, Comparative Example 1]

Each component was added so that the solid content ratio of each component in the total solid content was the value shown in Table 2, and PGMEA / MB / MBA = 72/20/8, the content ratio of the total solid content was 17% by mass A solvent was added as much as possible, and the mixture was stirred and dissolved to prepare photosensitive coloring compositions of Examples 1 and 2 and Comparative Example 1. In addition, Table 2 and Table 3 show the evaluation results of the chlorine atom content, unit OD value, and surface roughness of the electrode measured by the method described above.

In the substrate using the photosensitive coloring composition of Comparative Example 1, it was confirmed that irregularities were formed on the surface of the silver (electrode) and that it was rough. Since this is a large amount of chlorine atoms contained in the dispersant-II, it is also contained in a large amount in the photosensitive coloring composition, and a gas containing chlorine is generated during firing, and reacts with the silver (electrode) surface to form irregularities on the surface. I think.

On the other hand, in the substrate using the photosensitive coloring composition of Example 1, no irregularities were observed on the surface of the silver (electrode). This is considered to be that since there is no chlorine atomic weight in the dispersant-I and, as a result, the content in the photosensitive coloring composition is also small, a normal electrode substrate was obtained without causing surface roughness to the silver (electrode).

In terms of light emitting characteristics of the organic electroluminescent device, Example 1 has a longer lifetime than Comparative Example 1. This is considered to be because deterioration with time of the light emitting element was suppressed because the amount of chlorine was small.

Even in the substrate using the photosensitive coloring composition of Example 2, the unevenness of the surface of the silver (electrode) was at a substantially satisfactory level. The reason why the surface roughness of the silver (electrode) of Example 1 was better than that of Example 2 is that even a small amount of chlorine atoms were not released out of the film due to the rigid skeleton of Pigment-I composed of aromatic rings.

Regarding the emission characteristics of the organic electroluminescent device, Example 2 had a low initial driving voltage and was good. It was also better than Example 1.

Claims (11)

A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant,
The (a) colorant contains at least one selected from the group consisting of a compound represented by the following general formula (I), a geometric isomer of the compound, a salt of the compound, and a salt of the geometric isomer of the compound,
The (f) dispersant contains at least repeating units represented by the following general formulas (1), (2) and (3) and contains an acrylic copolymer (f1) having no repeating units containing a quaternary ammonium group, ,
Further, the photosensitive coloring composition characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.

(In formula (I), R ¹ and R ⁶ are each independently a hydrogen atom, CH ₃ , CF ₃ , a fluorine atom or a chlorine atom;
R ² , R ³ , R ⁴ , R ⁵ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are, independently of each other, a hydrogen atom, a halogen atom, R ¹¹ , COOH, COOR ¹¹ , COO ^- , CONH ₂ , CONHR ¹¹ , CONR ¹¹ R ¹² , CN, OH, OR ¹¹ , COCR ¹¹ , OOCNH ₂ , OOCNHR ¹¹ , OOCNR ¹¹ R ¹² , NO ₂ , NH ₂ , NHR ¹¹ , NR ¹¹ R ¹² , NHCOR ¹² , NR ¹¹ COR ¹² , N=CH ₂ , N=CHR ¹¹ , N=CR ¹¹ R ¹² , SH, SR ¹¹ , SOR ¹¹ , SO ₂ R ^{11 , SO 3 R 11} _, ^SO ₃ H, SO ₃ ^- , SO ₂ NH ₂ , SO ₂ NHR ¹¹ or SO ₂ NR ¹¹ R ¹² ;
At least one combination selected from the group consisting of R ² and R ³ , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁷ and R ⁸ , R ⁸ and R ⁹ , and R ⁹ and R ¹⁰ is directly related to each other. or may be bonded to each other by an oxygen atom, a sulfur atom, NH or NR ¹¹ bridge;
R ¹¹ and R ¹² are each independently an alkyl group of 1 to 12 carbon atoms, a cycloalkyl group of 3 to 12 carbon atoms, an alkenyl group of 2 to 12 carbon atoms, a cycloalkenyl group of 3 to 12 carbon atoms, or an alkynyl group of 2 to 12 carbon atoms. .)

(In Formula (1), R ³¹ 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 ³² is a hydrogen atom or a methyl group.
* indicates a binding hand.)

(In Formula (2), R ³³ is a methylene group, ethylene group or propylene group, R ³⁴ is an alkyl group which may have a substituent, and R ³⁵ is a hydrogen atom or a methyl group.
n is an integer of 1-20.
* indicates a binding hand.)

(In Formula (3), R ³⁶ and R ³⁷ 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, R ³⁶ and R ³⁷ These may combine with each other to form a cyclic structure.
R ³⁸ is a hydrogen atom or a methyl group.
Z is a divalent linking group.
* indicates a binding hand.) According to claim 1,
The photosensitive coloring composition in which the coloring agent (a) contains an organic color pigment. A photosensitive coloring composition containing (a) a colorant, (b) an alkali-soluble resin, (c) a photopolymerization initiator, (d) an ethylenically unsaturated compound, (e) a solvent, and (f) a dispersant,
The optical density per 1 μm of film thickness of the cured coating film is 0.5 or more,
The (f) dispersant contains at least repeating units represented by the following general formulas (1), (2) and (3) and contains an acrylic copolymer (f1) having no repeating units containing a quaternary ammonium group, ,
Further, the photosensitive coloring composition characterized in that the content of chlorine atoms in the photosensitive coloring composition is 0.05% by mass or less with respect to the total solid content of the photosensitive coloring composition.

(In Formula (1), R ³¹ 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 ³² is a hydrogen atom or a methyl group.
* indicates a bonding hand.)

(In Formula (2), R ³³ is a methylene group, ethylene group or propylene group, R ³⁴ is an alkyl group which may have a substituent, and R ³⁵ is a hydrogen atom or a methyl group.
n is an integer from 1 to 20;
* indicates a bonding hand.)

(In Formula (3), R ³⁶ and R ³⁷ 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, R ³⁶ and R ³⁷ These may combine with each other to form a cyclic structure.
R ³⁸ is a hydrogen atom or a methyl group.
Z is a divalent linking group.
* indicates a bonding hand.) According to claim 3,
The photosensitive coloring composition in which the said (a) coloring agent contains at least 1 sort(s) selected from the group which consists of a red pigment and an orange pigment, and at least 1 sort(s) selected from the group which consists of a blue pigment and a purple pigment. According to any one of claims 1 to 4,
The photosensitive coloring composition in which the said acrylic copolymer (f1) is a block copolymer. According to any one of claims 1 to 5,
The photosensitive coloring composition in which the amine value of the said acrylic copolymer (f1) is 90 mgKOH/g or more. According to any one of claims 1 to 6,
The photosensitive coloring composition in which the said (a) coloring agent is contained 10 mass % or more with respect to the total solid amount of the photosensitive coloring composition. According to any one of claims 1 to 7,
The photosensitive coloring composition used in order to form the partition of an organic electroluminescent element. A cured product obtained by curing the photosensitive colored resin composition according to any one of claims 1 to 8. An organic electroluminescent device comprising the cured product according to claim 9. An image display device comprising the organic electroluminescent device according to claim 10.