TW202210527A - Coloring composition, cured film, color filter, and display device - Google Patents

Abstract

Provided are: a coloring composition from which it is possible to form a cured film which has superior storage stability and in which mixing of color with other colors is suppressed; a coloring composition; a cured film; a color filter; and a display device. This coloring composition contains a coloring agent including a red coloring agent, a resin, a polymerizable compound, and a photoinitiator. The resin includes a resin EP including a repeating unit A having at least one cyclic ether group A selected from groups represented by formula (e-1) and groups represented by formula (e-2), and at least one repeating unit B selected from a repeating unit B-1 having an acid group and a repeating unit B-2 having a group in which an acid group is protected by a protecting group. In the coloring composition, Amax1/Amin1, which is the ratio of the maximum value Amax1 of absorbance with respect to light having a wavelength of 400-500 nm and a minimum value Amin1 of absorbance with respect to light having a wavelength of 550-700 nm, is 25 or more. When the absorbance with respect to light having a wavelength of 500 nm is defined as 1, a wavelength at which the absorbance becomes 0.3 exists in a range of 570-620 nm.

Description

Coloring composition, cured film, color filter, and display device

The present invention relates to a coloring composition. More specifically, it relates to a coloring composition used for red pixel formation of a color filter and the like. Moreover, this invention relates to the cured film using a coloring composition, a color filter, and a display apparatus.

In various display devices, color filters are generally used to colorize a displayed image. The color filter is manufactured using a coloring composition containing a colorant, a resin, a polymerizable compound, and a photopolymerization initiator (for example, Patent Document 1, etc.).

[Patent Document 1] Japanese Patent Application Laid-Open No. 2018-087956

When manufacturing a color filter etc. using a coloring composition, a color filter can also be manufactured using the coloring composition just produced. Therefore, the storage stability of the coloring composition is required to be excellent.

Typically, color filters have pixels of multiple colors. A color filter having such a plurality of colors of pixels is manufactured by sequentially patterning the coloring composition for forming a pixel of each color into a pattern to form pixels of each color.

On the other hand, in recent years, color filters may be formed on members with low heat resistance (eg, organic semiconductor elements such as organic electroluminescence display elements). Since such a member has low heat resistance, it is desirable to suppress thermal damage to the support by forming the pixels of the color filter in a low-temperature process of 150° C. or lower, for example.

However, in the case of forming pixels in a low temperature process, the degree of hardening of the pixels may be insufficient, and when forming pixels of other colors, the coloring compositions of other colors tend to be mixed and the spectral characteristics tend to change.

Moreover, according to the research of the present inventors, it is known that the coloring composition described in Patent Document 1 has room for further improvement regarding color mixing with other colors.

Accordingly, the object of the present invention is to provide a coloring composition, a cured film, a color filter, and a display device that can form a cured film that is excellent in storage stability and suppresses color mixing with other colors.

式(e-1)中，R^E1 表示氫原子或烷基，n表示0或1，*表示鍵結鍵； 式(e-2)中，環A^E1 表示單環的脂肪族烴環，*表示鍵結鍵。 ＜2＞如＜1＞所述之著色組成物，其中 上述樹脂EP中，上述環狀醚基A的含量為2.0～6.5mmol/g，上述酸基的含量與上述酸基被保護基保護之基團的含量的合計為0.45～2.35mmol/g。 ＜3＞如＜1＞或＜2＞所述之著色組成物，其中 上述樹脂EP的上述環狀醚基A的含量、上述酸基的含量及上述酸基被保護基保護之基團的含量滿足下述式(1)的條件。 1.0≤（樹脂EP的上述環狀醚基A的含量（單位：mmol/g）/（樹脂EP的上述酸基的含量（單位：mmol/g）+（樹脂EP的上述酸基被保護基保護之基團的含量（單位：mmol/g））≤14.0    ……(1) ＜4＞如＜1＞至＜3＞之任一項所述之著色組成物，其中 上述酸基為酚性羥基或羧基。 ＜5＞如＜1＞至＜4＞之任一項所述之著色組成物，其中 上述保護基為由式(Y1)～(Y5)中的任一個表示之基團， 式(Y1)：-C(R^Y1 )(R^Y2 )(R^Y3 ) 式(Y2)：-C(=O)OC(R^Y4 )(R^Y5 )(R^Y6 ) 式(Y3)：-C(R^Y7 )(R^Y8 )(OR^Y9 ) 式(Y4)：-C(R^Y10 )(H)(Ar^Y1 ) 式(Y5)：-C(=O)(R^Y11 ) 式(Y1)中，R^Y1 ～R^Y3 分別獨立地表示烷基，R^Y1 ～R^Y3 中的2個可以鍵結而形成環； 式(Y2)中，R^Y4 ～R^Y6 分別獨立地表示烷基，R^Y4 ～R^Y6 中的2個可以鍵結而形成環； 式(Y3)中，R^Y7 及R^Y8 分別獨立地表示氫原子、烷基或芳基，R^Y7 及R^Y8 中的至少一個為烷基或芳基，R^Y9 表示烷基或芳基，R^Y7 或R^Y8 與R^Y9 可以鍵結而形成環； 式(Y4)中，Ar^Y1 表示芳基，R^Y10 表示烷基或芳基， 式(Y5)中，R^Y11 表示烷基或芳基。 ＜6＞如＜1＞至＜5＞之任一項所述之著色組成物，其中 上述著色劑進一步包含黃色著色劑。 ＜7＞如＜1＞至＜6＞之任一項所述之著色組成物，其中 上述著色劑中的上述紅色著色劑的含量為70質量%以上。 ＜8＞如＜1＞至＜7＞之任一項所述之著色組成物，其係用於在整個製程中在150℃以下的溫度下形成硬化膜。 ＜9＞如＜1＞至＜8＞之任一項所述之著色組成物，其係用於彩色濾光片。 ＜10＞如＜1＞至＜9＞之任一項所述之著色組成物，其係用於顯示裝置。 ＜11＞一種硬化膜，其係藉由將＜1＞至＜10＞之任一項所述之著色組成物硬化而獲得。 ＜12＞一種彩色濾光片，其係具有＜11＞所述之硬化膜。 ＜13＞一種顯示裝置，其係具有＜11＞所述之硬化膜。 [發明效果]Based on the research of the present inventors, it was found that the above-mentioned object can be achieved by using a coloring composition described later, and the present invention was completed. The present invention provides the following. <1> A coloring composition comprising a colorant containing a red colorant, a resin, a polymerizable compound, and a photopolymerization initiator, wherein the resin comprises a resin EP containing a repeating unit A and a repeating unit B, the repeating unit A has at least one cyclic ether group A selected from the group represented by the formula (e-1) and the group represented by the formula (e-2), and the aforementioned repeating unit B is selected from the repeating unit B- having an acid group 1 and at least one of the repeating units B-2 having a group in which an acid group is protected by a protecting group, the maximum value ^Amax1 of the absorbance of the above-mentioned coloring composition for light with a wavelength of 400 to 500 nm, and the light with a wavelength of 550 to 700 nm. When the ratio A ^max1 /A ^min1 of the minimum value A ^min1 of the absorbance is 25 or more, and the absorbance for light having a wavelength of 500 nm is set to 1, the wavelength at which the absorbance becomes 0.3 exists in the range of 570 to 620 nm.

In formula (e-1), R ^E1 represents a hydrogen atom or an alkyl group, n represents 0 or 1, and * represents a bond; In formula (e-2), ring A ^E1 represents a monocyclic aliphatic hydrocarbon ring, * Represents a bond key. <2> The coloring composition according to <1>, wherein in the resin EP, the content of the cyclic ether group A is 2.0 to 6.5 mmol/g, and the content of the acid group and the acid group protected by the protecting group are combined. The total content of the groups is 0.45 to 2.35 mmol/g. <3> The coloring composition according to <1> or <2>, wherein the content of the above-mentioned cyclic ether group A, the content of the above-mentioned acid group, and the content of the above-mentioned acid group protected by a protective group of the above-mentioned resin EP The condition of the following formula (1) is satisfied. 1.0≤(The content of the above-mentioned cyclic ether group A of the resin EP (unit: mmol/g)/(the content of the above-mentioned acid group of the resin EP (unit: mmol/g) + (the above-mentioned acid group of the resin EP is protected by a protective group) (unit: mmol/g))≤14.0 ... (1) <4> The coloring composition according to any one of <1> to <3>, wherein the acid group is a phenolic hydroxyl group or a carboxyl group. <5> The coloring composition according to any one of <1> to <4>, wherein the protecting group is a group represented by any one of the formulae (Y1) to (Y5), and the formula ( Y1): -C(R ^Y1 )(R ^Y2 )(R ^Y3 ) Formula (Y2): -C(=O)OC(R ^Y4 )(R ^Y5 )(R ^Y6 ) Formula (Y3): -C(R ^Y7 )(R ^Y8 )(OR ^Y9 ) Formula (Y4): -C(R ^Y10 )(H)(Ar ^Y1 ) Formula (Y5): -C(=O)(R ^Y11 ) In formula (Y1), R ^Y1 to R ^Y3 each independently represent an alkyl group, and two of R ^Y1 to R ^Y3 may be bonded to form a ring; in formula (Y2), R ^Y4 to R ^Y6 each independently represent an alkyl group, and R ^Y4 to R ^Y6 Two of them can be bonded to form a ring; In formula (Y3), R ^Y7 and R ^Y8 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at least one of R ^Y7 and R ^Y8 is an alkyl group or an aryl group , R ^Y9 represents an alkyl group or an aryl group, and R ^Y7 or R ^Y8 and R ^Y9 can be bonded to form a ring; In formula (Y4), Ar ^Y1 represents an aryl group, R ^Y10 represents an alkyl group or an aryl group, formula (Y5) wherein, R ^Y11 represents an alkyl group or an aryl group. <6> The coloring composition according to any one of <1> to <5>, wherein the coloring agent further comprises a yellow coloring agent. <7> As in <1> The coloring composition according to any one of <6>, wherein the content of the red coloring agent in the coloring agent is 70% by mass or more. <8> The coloring composition according to any one of <1> to <7> The coloring composition is used for forming a cured film at a temperature below 150° C. in the whole process. <9> The coloring composition according to any one of <1> to <8>, which is used for A color filter. <10> The coloring composition according to any one of <1> to <9>, which is used in a display device. <11> A cured film obtained by adding <1> to The coloring composition described in any one of <10> is obtained by curing. <12> A color filter having the cured film described in <11>. <13> A display device having <11 >The above-mentioned cured film. [Effect of the invention]

ADVANTAGE OF THE INVENTION According to this invention, the coloring composition which can form the cured film which is favorable in storage stability and the color mixing with other colors is suppressed, the cured film using this coloring composition, a color filter, and a display device can be provided.

Hereinafter, the content of the present invention will be described in detail. In the notation of groups (atomic groups) in this specification, the notation of substituted and unsubstituted includes groups (atomic groups) without substituents and groups (atomic groups) with substituents. For example, the term "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, the term "exposure" includes exposure using particle beams such as electron beams and ion beams in addition to exposure using light. In addition, the light used for exposure generally includes actinic rays such as bright-line spectrum of mercury lamps, and excimer lasers, extreme ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams, and radiation. In this specification, the numerical range shown using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition. In this specification, "(meth)acrylate" means both or either of acrylate and methyl acrylate, "(meth)acrylic acid" means both or either of acrylic acid and methacrylic acid, "((meth)acrylic acid)" "Meth)allyl" means both or either of allyl and methallyl, and "(meth)acryloyl" means both or either of acrylyl and methacryloyl By. In this specification, the term "process" is included in this term as long as the intended function of the process is exerted, except for an independent process, even if it cannot be clearly distinguished from other processes. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Coloring composition> The coloring composition of the present invention includes a colorant containing a red colorant, a resin, a polymerizable compound, and a photopolymerization initiator, and the coloring composition is characterized in that the resin contains a repeating unit A and a repeating unit. Resin EP of B, the aforementioned repeating unit A has at least one cyclic ether group A selected from the group represented by the formula (e-1) and the group represented by the formula (e-2), and the aforementioned repeating unit B is selected from At least one of the repeating unit B-1 having an acid group and the repeating unit B-2 having a group in which the acid group is protected by a protecting group, the maximum value A ^max1 of the absorbance of the above-mentioned coloring composition for light having a wavelength of 400 to 500 nm The ratio A ^max1 /A ^min1 to the minimum value A ^min1 of the absorbance for light with a wavelength of 550 to 700 nm is 25 or more, and when the absorbance for light with a wavelength of 500 nm is set to 1, the wavelength at which the absorbance becomes 0.3 exists in 570 to 620 nm. within the range.

According to the coloring composition of the present invention, it is possible to form a cured film which is excellent in storage stability and has suppressed color mixing with other colors. In particular, even when a cured film is formed at a low temperature of 150° C. or lower (preferably 120° C. or lower, more preferably 100° C. or lower), a cured film in which color mixing with other colors is suppressed can be formed.

The detailed reason why such an effect can be obtained is not clear, but it is presumed to be based on the following. It is presumed that the coloring composition having the above-mentioned spectroscopic properties is difficult to release heat when the coloring composition is heated and hardened, and the resin EP and the like can be hardened effectively by the heat. Moreover, this resin EP is presumed to be a resin with high reactivity. Therefore, it is presumed that by including the above-mentioned resin EP in the coloring composition having the above-mentioned spectroscopic properties, when the coloring composition is heated and hardened, the hardening of the coloring composition proceeds rapidly, and as a result, it is possible to form the coloring composition even when heated at a relatively low temperature. Fully hardened hardened film. Therefore, according to the coloring composition of this invention, it can be estimated that the cured film which suppresses color mixing with other colors can be formed. Moreover, since the coloring composition has the above-mentioned specific spectral characteristics, it is presumed that the reaction of the resin and the curable components such as the polymerizable compound caused by external light during storage can be suppressed, and as a result, it has excellent storage stability.

The absorbance Aλ at a certain wavelength λ is defined by the following formula (Ab1). Aλ=-log(Tλ/100)…(Ab1) Aλ is the absorbance at wavelength λ, and Tλ is the transmittance (%) of light at wavelength λ.

In this invention, the value of the absorbance of a coloring composition may be the value measured in the state of a solution, and may be the value of the cured film formed into a film using the coloring composition. In the case of measuring the absorbance in the state of the cured film, the coloring composition is applied on a glass substrate by a method such as spin coating, and dried at 100° C. for 2 minutes using a hot plate or the like, and then, the light intensity is 20 mW. It is preferable to perform i-ray exposure under the conditions of an exposure dose of 1 J/cm ² /cm ² , and then heat it on a hot plate at 100° C. for 20 minutes, and use a film (cured film) obtained by natural cooling to room temperature for measurement. . The absorbance can be measured using a conventionally known spectrophotometer.

In the coloring composition of the present invention, the ratio A ^max1 /A ^min1 of the maximum value A ^max1 of the absorbance for light with a wavelength of 400 to 500 nm and the minimum value A ^min1 of the absorbance for light with a wavelength of 550 to 700 nm is 25 or more, and 50 or more is Preferably, more than 100 is more preferable. The higher the value of the ratio A ^max1 /A ^min1 , the more remarkably the effect of the present invention described above can be obtained, and further, it is easy to obtain a red pixel excellent in color separation from other colors. Therefore, the upper limit of the value of the above-mentioned ratio A ^max1 /A ^min1 is not particularly limited.

When the absorbance to light having a wavelength of 500 nm shown by the coloring composition of the present invention is set to 1, a wavelength having an absorbance of 0.3 exists in the range of 570 to 620 nm, preferably in the range of 575 to 615 nm. It is more preferable to exist in the range of 580-610nm, and it is more preferable to exist in the range of 585-605nm.

When the absorbance to light with a wavelength of 500 nm shown by the coloring composition of the present invention is set to 1, it is preferable that the wavelength with absorbance of 0.5 exists in the range of 565 to 605 nm, and even more preferably exists in the range of 570 to 600 nm. It is preferable that it exists in the range of 575-595 nm.

In the coloring composition of the present invention, the ratio of the maximum value A max1 of the absorbance to light with a wavelength of 400 to 500 nm, ^Amax1 , and the absorbance of light with a wavelength of 550 nm, A550, A ^max1 /A ⁵⁵⁰ is preferably 2 or less, ^more preferably 1.75 or less. , 1.5 or less is further better.

The coloring composition of the present invention has a ratio A ^max1 /A ⁶⁰⁰ of the maximum value A ^max1 of absorbance to light with a wavelength of 400 to 500 nm and an absorbance A ⁶⁰⁰ of light with a wavelength of 600 nm, preferably 5 to 15, and 6.5 to 13.5 is More preferably, 8-12 are more preferable.

The coloring composition of the present invention has a ratio A max1 /A ⁶⁵⁰ of the maximum value A ^max1 of the absorbance to light with a wavelength of 400 to 500 nm and the ratio A ^max1 /A ⁶⁵⁰ of the absorbance to light with a wavelength of 650 nm, preferably 25 or more, more preferably 50 or more. , 100 or more is further preferred.

In the coloring composition of the present invention, when a cured film having a film thickness of 0.5 to 3.0 μm is formed, the maximum value of the transmittance to light having a wavelength of 550 to 700 nm in the thickness direction of the film is 85% or more, and the average transmittance is 50% or more is preferable, and the maximum value of the transmittance to light having a wavelength of 550 to 700 nm in the thickness direction of the film is more preferably 90% or more and the average transmittance is 55% or more.

When the coloring composition of the present invention forms a cured film with a thickness of 0.5 to 3.0 μm, the transmittance to light with a wavelength of 500 nm is preferably 1% or less, more preferably 0.75% or less, and even more preferably 0.5% or less. . Furthermore, the maximum value of the transmittance to light having a wavelength of 400 to 500 nm is preferably 1% or less, more preferably 0.75% or less, and even more preferably 0.5% or less.

The solid content concentration of the coloring composition of the present invention is preferably 5 to 25% by mass. The upper limit is preferably 22.5 mass % or less, more preferably 20 mass % or less, and even more preferably 18 mass % or less. If the solid content concentration is within the above-mentioned range, even when a cured film (pixel) is formed at a temperature of 150° C. or lower (preferably a temperature of 120° C. or lower) in the entire process, curing with excellent flatness can be formed. film (pixels).

The coloring composition of the present invention can be preferably used as a coloring composition for pixel formation of a color filter, and can be more preferably used as a coloring composition for forming a red pixel of a color filter.

The coloring composition of the present invention can be preferably used as a coloring composition for display devices. More specifically, it can be preferably used as a coloring composition for forming a pixel of a color filter for a display device, and can be more preferably used as a coloring composition for forming a red pixel of a color filter for a display device. Although it does not specifically limit as a kind of display apparatus, The display apparatus etc. which have organic semiconductor elements, such as an organic electroluminescent display apparatus, as a light source are mentioned.

In addition, the coloring composition of the present invention can also be used as a coloring composition for solid-state imaging elements. More specifically, it can be preferably used as a coloring composition for forming a pixel of a color filter for a solid-state imaging element, and can be preferably used as a coloring composition for forming a red pixel of a color filter for a solid-state imaging element.

It is also preferable that the coloring composition of the present invention is used for forming a cured film at a temperature of 150° C. or lower (preferably a temperature of 120° C. or lower) in the entire process. In addition, in this specification, the whole process includes, for example, a process of forming a cured film using a colorant composition. In this specification, forming a cured film at a temperature of 150° C. or lower in the entire process refers to all processes of forming a cured film using a coloring composition at a temperature of 150° C. or lower, but is not limited.

It is preferable that the thickness of the cured film and pixel formed from the coloring composition of this invention is 0.5-3.0 micrometers. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and even more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.8 μm or less.

Moreover, it is preferable that the line width (pattern size) of the pixel formed from the coloring composition of this invention is 2.0-10.0 micrometers. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and even more preferably 2.75 μm or more.

Hereinafter, the coloring composition of the present invention will be described in detail.

＜＜Colorant＞＞ The coloring composition of this invention contains a coloring agent. Examples of the colorant include color colorants such as red colorants, green colorants, blue colorants, yellow colorants, purple colorants, and orange colorants. In the present invention, the colorant may be a pigment or a dye. A colorant may use a pigment and a dye together. In addition, the pigment may be either an inorganic pigment or an organic pigment. Moreover, as a pigment, the thing obtained by replacing a part of an inorganic pigment or an organic-inorganic pigment with an organic chromophore can also be used. Hue design can be easily performed by replacing inorganic pigments or organic-inorganic pigments with organic chromophores. When using what contains a pigment as a coloring agent, it becomes easy to form a cured film which is excellent in durability, such as heat resistance and light resistance. In the case of using those containing a dye as a colorant, it is easy to form a cured film with a higher red color reproduction area. Moreover, in general, the cured film obtained by using dyes tends to be more prone to color mixing than the cured films obtained by using pigments. According to the present invention, even when a dye is used as a colorant, color shift can be suppressed. Therefore, it is particularly effective in the case of using those containing dyes as colorants.

The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. When the average primary particle size of the pigment is within the above-mentioned range, the dispersion stability of the pigment in the coloring composition will be favorable. In addition, in this invention, the primary particle diameter of a pigment can be calculated|required from the obtained image photograph by observing the primary particle of a pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the equivalent circle diameter corresponding thereto is calculated as the primary particle diameter of the pigment. In addition, the average primary particle diameter in this invention is made into the arithmetic mean value of the primary particle diameter of the primary particle of 400 pigments. In addition, the primary particles of the pigment refer to unagglomerated independent particles.

Pigment polymers can also be used in colorants. The dyestuffs used in the dyestuff polymer system dissolved in the solvent are preferred. In addition, the dye multimer can form particles. When the dye multimer is a particle, it is usually used in a state of being dispersed in a solvent. The dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples thereof include the compounds and production methods described in JP-A No. 2015-214682. The dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but can also be set to 100 or less. The plurality of pigment structures in one molecule may be the same pigment structure or may be different pigment structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and more preferably 20,000 or less. As the dye multimer, compounds described in JP 2011-213925 A, JP 2013-041097 A, JP 2015-028144 A, JP 2015-030742 A, and WO 2016/031442 A can also be used .

(red colorant) The coloring composition of the present invention contains a red colorant. The red colorant may be a pigment or a dye. Pigments and dyes can also be used in combination. A red colorant-based pigment (red pigment) is preferable because it is easy to form a film having excellent solvent resistance.

As a red colorant, selected from the group consisting of Kouyama-guchi compound, anthraquinone compound, monoazo compound, diazo compound, azomethine compound, aminoketone compound, quinacridone compound, perylene compound and diketopyrrolopyrrole At least one compound is preferred, at least one selected from anthraquinone compounds, quinacridone compounds, perylene compounds and diketopyrrolopyrrole compounds is more preferred, selected from anthraquinone compounds, perylene compounds and diketones At least one kind of pyrrolopyrrole compounds is further preferred, and at least one kind selected from anthraquinone compounds and diketopyrrolopyrrole compounds is still more preferred. Among them, an anthraquinone compound is particularly preferable because it is a compound having absorption on the longer wavelength side, and the effect of the present invention is obtained more remarkably.

As the red pigment, the color index (C.I.) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, 291, 294, 295, 296, 297, etc.

As the red dye, C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183, 198, 211, 215, 216, 217, 249, 252, 257, 260, 266, 274, etc.

As the red colorant, diketopyrrolopyrrole compounds substituted with at least one bromine atom in the structure described in JP 2017-201384 A and those described in paragraphs 0016 to 0022 of JP 6248838 can also be used Diketopyrrolopyrrole compounds, diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, JP 2012-229344 A The naphthol azo compound described in, the red colorant described in Japanese Patent No. 6516119, the red colorant described in Japanese Patent No. 6525101, the paragraph 0229 of Japanese Patent Laid-Open No. 2020-090632 Brominated diketopyrrolopyrrole compounds, anthraquinone compounds described in Korean Laid-open Patent No. 10-2019-0140741, anthraquinone compounds described in Korean Laid-open Patent No. 10-2019-0140744, Japanese Laid-Open Patent Publication No. 2020- The perylene compound and the like described in No. 079396. In addition, as the red colorant, a structure in which an aromatic ring group having a group in which an oxygen atom, a sulfur atom or a nitrogen atom is introduced and bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used the compound.

As the red colorant, C.I. Pigment Red 122, 177, 179, 202, 254, 264, 269, 272 is preferable, and C.I. Pigment Red 177, 179, 202, 254, 264, 269 are more preferred, C.I. Pigment Red 177, 254, 264, 269 are further preferred, and C.I. Pigment Red 264 is particularly preferred.

(other colorants) It is preferable that the coloring composition of this invention further contains other coloring agent other than a red coloring agent. As other colorants used in combination, a yellow colorant, a green colorant, a purple colorant, a blue colorant, an orange colorant, etc. are exemplified, and it is easy to form a cured film having spectral characteristics more suitable for red. Yellow colorants are preferred. Moreover, since it is easy to form a film excellent in solvent resistance, a yellow colorant-type pigment (yellow pigment) is preferable.

As the yellow colorant, azo compounds, azomethine compounds, quinoline yellow compounds, isoindolinone compounds, isoindoline compounds, pteridine compounds, anthraquinone compounds, etc., azo compounds, Azomethine compounds, isoindoline compounds and quinoline yellow compounds are preferred, isoindoline compounds and azo compounds are more preferred, and isoindoline compounds are particularly preferred.

Examples of yellow colorants include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and other yellow pigments.

Moreover, as a yellow coloring agent, the azobarbiturate nickel complex (azo compound) of the following structure can also be used.

In addition, as the yellow coloring agent, the compounds described in JP 2017-201003 A, the compounds described in JP 2017-197719 A, and 0011-0062 and 0137-1 in JP 2017-171912 A can also be used. Compounds described in paragraph 0276, compounds described in paragraphs 0010-0062 and 0138-0295 of JP-A No. 2017-171913, compounds described in paragraphs 0011-0062 and 0139-0190 of JP-A No. 2017-171914 Compounds, compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of JP 2017-171915 A, quinoline yellow compounds described in paragraphs 0011 to 0034 of JP 2013-054339 A, JP 2014- The quinoline yellow compound described in paragraphs 0013 to 0058 of No. 026228, the isoindoline compound described in Japanese Patent Laid-Open No. 2018-062644, the quinoline yellow compound described in Japanese Patent Laid-Open No. 2018-203798, The quinoline yellow compound described in Japanese Patent Laid-Open No. 2018-062578, the quinoline yellow compound described in Japanese Patent Laid-Open No. 6432076, the quinoline yellow compound described in Japanese Patent Laid-Open No. 2018-155881, Japanese Patent Laid-Open No. 2018- Quinoline yellow compound described in No. 111757, Quinoline yellow compound described in Japanese Patent Laid-Open No. 2018-040835, Quinoline yellow compound described in Japanese Patent Laid-Open No. 2017-197640, Japanese Patent Laid-Open No. 2016-145282 The quinoline yellow compound described in Japanese Patent Laid-Open No. 2014-085565, the quinoline yellow compound described in Japanese Patent Laid-Open No. 2014-021139, the quinoline yellow compound described in Japanese Patent Laid-Open No. 2013-209614 The quinoline yellow compound described, the quinoline yellow compound described in JP 2013-209435 A, the quinoline yellow compound described in JP 2013-181015 A, the quinoline yellow compound described in JP 2013-061622 A Quinoline yellow compound, the quinoline yellow compound described in Japanese Patent Laid-Open No. 2013-032486, the quinoline yellow compound described in Japanese Patent Laid-Open No. 2012-226110, the quinoline yellow compound described in Japanese Patent Laid-Open No. 2008-074987 Yellow compounds, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2008-081565, quinoline yellow compounds described in Japanese Patent Laid-Open No. 2008-074986, and quinoline yellow compounds described in Japanese Patent Laid-Open No. 2008-074985 , the quinoline yellow compound described in Japanese Patent Laid-Open No. 2008-050420, the quinoline yellow compound described in Japanese Patent Laid-Open No. 2008-031281, the quinoline yellow compound described in Japanese Patent Publication No. 48-032765, Japan special open The quinoline yellow compound described in No. 2019-008014, the quinoline yellow compound described in Japanese Patent No. 6607427, the methine dye described in Japanese Patent Laid-Open No. 2019-073695, Japanese Patent Laid-Open No. 2019-073696 The methine dyes described in Japanese Patent Laid-Open No. 2019-073697, the methine dyes described in Japanese Patent Laid-Open No. 2019-073698, Korean Laid-Open Patent Publication No. 10-2014-0034963 The compound described in No., the compound described in Japanese Patent Laid-Open No. 2017-095706, the compound described in Taiwan Patent Application Publication No. 201920495, the compound described in Japanese Patent No. 6607427, the compound described in Japanese Patent Laid-Open No. 2020-033521 The quinoline yellow dimer described in No. In addition, from the viewpoint of increasing the color value, it is also preferable to use those compounds which are polymerized. Moreover, the compound represented by following formula (QP1) and the compound represented by following formula (QP2) can also be used for a yellow coloring agent.

In formula (QP1), X ¹ to X ¹⁶ each independently represent a hydrogen atom or a halogen atom, and Z ¹ represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP1) include the compounds described in paragraph 0016 of Japanese Patent No. 6443711.

In formula (QP2), Y ¹ to Y ³ each independently represent a halogen atom. n and m represent an integer of 0 to 6, and p represents an integer of 0 to 5. (n+m) is 1 or more. Specific examples of the compound represented by the formula (QP2) include compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

As the yellow colorant, C.I. Pigment Yellow 129, 138, 139, 150, 185, 215 are preferable, C.I. Pigment Yellow 139, 150 are more preferable, and C.I. Further preferred.

Green pigments, such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66, are mentioned as a green coloring agent. Moreover, as a green coloring agent, the halogenated zinc phthalocyanine pigment whose average number of halogen atoms in one molecule is 10 to 14, the average number of bromine atoms is 8 to 12, and the average number of chlorine atoms is 2 to 5 can also be used. Specific examples include the compounds described in International Publication No. 2015/118720. In addition, as green colorants, compounds described in Chinese Patent Application No. 106909027, phthalocyanine compounds having phosphoric acid esters described in International Publication No. 2012/102395 as ligands, Japanese Patent Laid-Open No. 2019 can also be used - The phthalocyanine compound described in No. 008014, the phthalocyanine compound described in Japanese Patent Laid-Open No. 2018-180023, the compound described in Japanese Patent Laid-Open No. 2019-038958, the compound described in Japanese Patent Laid-Open No. 2020-076995 Core-shell pigments, etc.

As the green colorant, C.I. Pigment Green 7, 36, 37, 58, 59, 65 are preferable, C.I. Pigment Green 7, 36, 58, 65 are more preferable, and C.I. Pigment Green 7, 36 is further preferred.

Examples of the blue colorant include C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79 , 80, 87, 88 and other blue pigments. Moreover, as a blue coloring agent, the aluminum phthalocyanine compound which has a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP 2012-247591 A and paragraph 0047 of JP 2011-157478 A.

As the blue colorant, C.I. Pigment Blue 15, 15:4, 15:6, 16, 60, 64, 79 is preferable, and C.I. Pigment Blue 15:4, 15 is preferable from the viewpoint of spectroscopic properties, durability, etc. : 6, 16, 60, 64 are more preferred, C.I. Pigment Blue 15: 4, 15: 6 are further preferred.

Examples of the purple colorant include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

As the orange colorant, C.I.Pigment Orange (Pigment Orange) 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 and other orange pigments.

It is preferable that content of a coloring agent is 5-70 mass % in the total solid content of a coloring composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is preferably 60 mass % or less, more preferably 55 mass % or less, and still more preferably 50 mass % or less.

The content of the red colorant in the colorant is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more. The upper limit of the content of the red colorant in the colorant is preferably 100% by mass or less, and more preferably 95% by mass or less.

It is preferable that the coloring agent contained in a coloring composition contains a red coloring agent and a yellow coloring agent. Moreover, it is preferable that content of a yellow coloring agent is 3-45 mass parts with respect to 100 mass parts of red coloring agents. The lower limit is preferably 5 parts by mass or more, and more preferably 8 parts by mass or more. The upper limit is preferably 30 parts by mass or less, more preferably 15 parts by mass or less. Moreover, the total content of the red colorant and the yellow colorant in the colorant is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

＜＜Resin＞＞ The coloring composition of this invention contains resin. The resin is blended, for example, for the purpose of dispersing pigments and the like in a coloring composition, and for the purpose of a binder. Moreover, resin mainly used for dispersing a pigment etc. in a coloring composition is also called a dispersing agent. However, this use of the resin is an example, and the resin can be used for purposes other than this use.

(Resin EP) The coloring composition of the present invention comprises a resin EP (hereinafter, also referred to as a numerical value EP) containing a repeating unit A and a repeating unit B, wherein the repeating unit A has a group selected from the group represented by the formula (e-1) and the group represented by the formula (e). -2) In the group represented by at least one cyclic ether group A (hereinafter, also referred to as a specific cyclic ether group), the aforementioned repeating unit B is selected from the repeating unit B-1 having an acid group and having an acid group protected at least one of the repeating units B-2 of the group protected by the group.

The weight average molecular weight of resin EP is preferably 2,000 to 70,000. The upper limit is preferably 60,000 or less, and more preferably 50,000 or less. The lower limit is preferably 3,000 or more, and more preferably 5,000 or more. If the weight-average molecular weight of the resin EP is within the above-mentioned range, color mixing and storage stability can be more easily achieved at a higher level.

The content of the above-mentioned specific cyclic ether group in the resin EP is preferably 2.0 to 6.5 mmol/g. When content of the said specific cyclic ether group of resin EP is 2.0-6.5 mmol/g, even if it heats at a relatively low temperature, the cured film which hardens fully can be formed, and the storage stability of a coloring composition is also favorable. From the viewpoint of the storage stability of the coloring composition, the upper limit is preferably 6.3 mmol/g or less, and more preferably 6.0 mmol/g or less. From the viewpoint of the curability of the film, the lower limit is preferably 2.5 mmol/g or more, more preferably 3.0 mmol/g or more, further more preferably 3.2 mmol/g or more, and particularly preferably 3.4 mmol/g or more.

It is preferable that the total of the content of the acid group of the resin EP and the content of the group protected by the protecting group of the acid group is 0.45 to 2.35 mmol/g. Even if the said sum total of resin EP is 0.45-2.35 mmol/g, even if it heats at a relatively low temperature, a fully hardened cured film can be formed, and the storage stability of a coloring composition is also favorable. From the viewpoint of the storage stability of the coloring composition, the upper limit is preferably 2.25 mmol/g or less, and more preferably 2.15 mmol/g or less. From the viewpoint of the curability of the film, the lower limit is preferably 0.7 mmol/g or more, and more preferably 0.9 mmol/g or more.

The resin EP preferably contains a repeating unit having an acid group. According to this aspect, even if heated at a relatively low temperature, a cured film which is sufficiently cured can be formed, and a cured film in which color mixing with other colors is further suppressed can be formed. In addition, when exposed in a pattern using a coloring composition, the unexposed portion can be easily developed and removed with a developing solution, the developability is also excellent, and the generation of residues in the unexposed portion can be more suppressed. The content of the acid group of the resin EP is preferably 0.45 to 2.35 mmol/g. The upper limit is preferably 2.25 mmol/g or less, more preferably 2.15 mmol/g or less. The lower limit is preferably 0.55 mmol/g or more, and more preferably 0.65 mmol/g or more.

The content of the above-mentioned specific cyclic ether group, the content of the acid group and the content of the group protected by the acid group of the resin EP satisfy the conditions of the following formula (1), and it is better to satisfy the conditions of the following formula (2) More preferably, it is more preferable to satisfy the condition of the following formula (3). 1.0≤(content of specific cyclic ether groups of resin EP (unit: mmol/g)/(content of acid groups of resin EP (unit: mmol/g) + (groups protected by protecting groups of acid groups of resin EP) content (unit: mmol/g))≤14.0  …(1) 2.5≤(content of specific cyclic ether groups of resin EP (unit: mmol/g)/(content of acid groups of resin EP (unit: mmol/g) + (groups protected by protecting groups of acid groups of resin EP) content (unit: mmol/g))≤12.0  …(2) 4.0≤(content of specific cyclic ether group of resin EP (unit: mmol/g)/(content of acid group of resin EP (unit: mmol/g) + (group protected by protecting group of acid group of resin EP) content (unit: mmol/g))≤10.0  …(3)

When the resin EP contains the content of the acid group and the group protected by the protecting group, the content of the acid group and the content of the group protected by the protecting group of the resin EP satisfy the condition of the following formula (11): Preferably, it is more preferable to satisfy the condition of the following formula (12), and it is still more preferable to satisfy the condition of the following formula (13). According to this aspect, the storage stability of the coloring composition is good, and when the coloring composition is used for pattern exposure, the unexposed portion can be easily developed and removed with a developing solution, the developability is also excellent, and the unexposed portion can be more suppressed. generation of residues. 0.1≤(content of the acid group of resin EP protected by protective group (unit: mmol/g)/content of acid group of resin EP (unit: mmol/g))≤2.0  …(11) 0.2≤(The content of the acid group of the resin EP protected by the protecting group (unit: mmol/g)/the content of the acid group of the resin EP (unit: mmol/g))≤1.9  …(12) 0.3≤(content of the acid group of resin EP protected by protective group (unit: mmol/g)/content of acid group of resin EP (unit: mmol/g))≤1.8  …(13)

[Repeat Unit A] The resin EP contains at least one cyclic ether group (hereinafter, also referred to as a specific cyclic ether group) selected from the group represented by the formula (e-1) and the group represented by the formula (e-2). ether group.) repeating unit A. The specific cyclic ether group is preferably a group represented by the formula (e-1) because it can form a film with a high crosslinking density.

In formula (e-1), R ^E1 represents a hydrogen atom or an alkyl group, n represents 0 or 1, and * represents a bond; In formula (e-2), ring A ^E1 represents a monocyclic aliphatic hydrocarbon ring, * Represents a bond key.

The carbon number of the alkyl group represented by R ^E1 is preferably 1-20, more preferably 1-10, further preferably 1-5, and particularly preferably 1-3. The alkyl group represented by R ^E1 is preferably a straight chain or branched chain, more preferably a straight chain.

When n is 0, R ^E1 -based hydrogen atoms are preferred. When n is 1, R ^E1 is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

Here, when n in the formula (e-1) is 0, the formula (e-1) is a group represented by the following formula (e-1a).

As the monocyclic aliphatic hydrocarbon ring represented by ring A ^E1 of the formula (e-2), a 5- to 7-membered aliphatic hydrocarbon ring is preferable, and a 5- or 6-membered aliphatic hydrocarbon ring is more preferable. Preferably, a 6-membered aliphatic hydrocarbon ring is more preferable. As a specific example, a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring are mentioned, a cyclopentane ring or a cyclohexane ring is preferable, and a cyclohexane ring is more preferable. As a specific example of the group represented by formula (e-2), the group shown below is mentioned.

As repeating unit A, the repeating unit represented by following formula (A-1) is mentioned.

In formula (A-1), X ^a1 represents a trivalent linking group, L ^a1 represents a single bond or a divalent linking group, and Z ^a1 represents the aforementioned cyclic ether group.

Examples of the trivalent linking group represented by X ^a1 in the formula (A-1) include a poly(meth)acrylic linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, and a polyurethane-based linking group. base, polyurea-based linking group, polyamide-based linking group, polyether-based linking group, polystyrene-based linking group, bisphenol-based linking group, novolak-based linking group, etc., poly(meth)acrylic-based linking group , Polyether-based linking group, polyester-based linking group, bisphenol-based linking group and novolak-based linking group are preferred, and poly(meth)acrylic-based linking group is more preferred.

Examples of the divalent linking group represented by L ^a1 of the formula (A-1) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylidene group (preferably an alkylene group having 6 to 12 carbon atoms). 20 aryl group), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, and a combination of two or more of these the group. The alkylene group may be any of linear, branched and cyclic, and linear or branched is preferred. Moreover, an alkylene group may have a substituent, and may be unsubstituted. As a substituent, a hydroxyl group, an alkoxy group, etc. are mentioned.

In the resin EP, the content of the repeating unit A is preferably 15 to 95 mol % in all the repeating units of the resin EP. The upper limit is preferably 85 mol % or less, more preferably 75 mol % or less. The lower limit is preferably 20 mol % or more, more preferably 30 mol % or more.

[Repeat unit B] It includes a repeating unit B-1 (hereinafter, also referred to as repeating unit B-1) with an acid group and a repeating unit B-2 (hereinafter, also referred to as repeating unit B) having an acid group protected by a protecting group -2) at least one repeating unit B. Resin EP may contain only any one of repeating unit B-1 and repeating unit B-2, or may contain repeating unit B-1 and repeating unit B-2, respectively. It is preferable that the resin EP contains at least the repeating unit B-1.

When the resin EP has the repeating unit B-1, a sufficiently hardened cured film can be formed even when heated at a relatively low temperature, and a cured film with more suppressed color mixing with other colors can be formed. In addition, when exposed in a pattern using a coloring composition, the unexposed portion can be easily developed and removed with a developing solution, the developability is also excellent, and the generation of residues in the unexposed portion can be more suppressed. Moreover, when resin EP contains repeating unit B-2, the progress of the reaction of the said specific cyclic ether group etc. of resin EP can be suppressed at the time of storage of a coloring composition, and the storage stability of a coloring composition can be improved further. Moreover, when resin EP contains repeating unit B-1 and repeating unit B-2, respectively, the storage stability of a coloring composition, developability, and suppression of color mixing of the cured film obtained can coexist at a higher level.

Examples of the acid group contained in the repeating unit B-1 and the acid group protected by the protecting group in the repeating unit B-2 include a phenolic hydroxyl group, a carboxyl group, a sulfo group, a phosphoric acid group, a phenolic hydroxyl group or a carboxyl group. More preferred, carboxyl group is more preferred.

As a protective group which protects the said acid group in the said repeating unit B-2, the group which decompose|disassembles and leaves|separates by the action of an acid or a base is mentioned. The protecting group is preferably a group represented by any one of the formulae (Y1) to (Y5), and the group represented by the formula (Y3) or the formula (Y5)) is preferably for the reason of easy deprotection. better.

Formula (Y1): -C(R ^Y1 )(R ^Y2 )(R ^Y3 ) Formula (Y2): -C(=O)OC(R ^Y4 )(R ^Y5 )(R ^Y6 ) Formula (Y3): -C (R ^Y7 )(R ^Y8 )(OR ^Y9 ) Formula (Y4): -C(R ^Y10 )(H)(Ar ^Y1 ) Formula (Y5): -C(=O)(R ^Y11 )

In formula (Y1), R ^Y1 to R ^Y3 each independently represent an alkyl group, and two of R ^Y1 to R ^Y3 may be bonded to form a ring; in formula (Y2), R ^Y4 to R ^Y6 each independently represent an alkane In formula (Y3), R ^Y7 and R ^Y8 each independently represent a hydrogen atom, an alkyl group or an aryl group, and at ^{least one of R Y7 and} R ^Y8 One is an alkyl group or an aryl group, R ^Y9 represents an alkyl group or an aryl group, and R ^Y7 or R ^Y8 and R ^Y9 can be bonded to form a ring; In formula (Y4), Ar ^Y1 represents an aryl group, and R ^Y10 represents an alkyl group or Aryl, In formula (Y5), R ^Y11 represents an alkyl group or an aryl group.

The carbon number of the alkyl group represented by R ^Y1 to R ^Y3 of the formula (Y1) is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred. In formula (Y1), two of R ^Y1 to R ^Y3 may be bonded to form a ring. Examples of the ring formed by the bonding of two of R ^Y1 to R ^Y3 include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantine. Polycyclic cycloalkyl groups such as alkyl groups, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. In the above-mentioned cycloalkyl group, one methylene group constituting the ring may be substituted with a heteroatom such as an oxygen atom or a group having a heteroatom such as a carbonyl group.

The carbon number of the alkyl group represented by R ^Y4 to R ^Y6 of the formula (Y2) is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred. At least two of R ^Y4 to R ^Y6 in the formula (Y2) are preferably methyl groups. In formula (Y2), two of R ^Y4 to R ^Y6 may be bonded to form a ring. The ring to be formed includes the ring described in the formula (Y1).

In formula (Y3), R ^Y7 and R ^Y8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^Y7 and R ^Y8 is an alkyl group or an aryl group, R ^Y9 represents an alkyl group or an aryl group, and R ^Y7 or R ^Y8 and R ^Y9 may be bonded to form a ring. The alkyl group may be linear, branched, or cyclic. The carbon number of the alkyl group is preferably 1-12, more preferably 1-6, and even more preferably 1-4. The carbon number of the aryl group is preferably 6-20, more preferably 6-12. A tetrahydrofuranyl group, a tetrahydropyranyl group, etc. are mentioned as a ring formed by bonding R ^Y7 or R ^Y8 and R ^Y9 . In formula (Y3), it is preferable that R ^Y7 or R ^Y8 and R ^Y9 are bonded to form a ring. In addition, one of R ^Y7 and R ^Y8 is preferably a hydrogen atom.

In formula (Y4), Ar ^Y1 represents an aryl group, R ^Y10 represents an alkyl group or an aryl group, and Ar ^Y1 and R ^Y10 may be bonded to each other to form a ring. The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The carbon number of the aryl group is preferably 6-20, more preferably 6-12. In formula (Y4), R ^Y10 is preferably an alkyl group.

In formula (Y5), R ^Y11 represents an alkyl group or an aryl group, preferably an alkyl group. The carbon number of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The carbon number of the aryl group is preferably 6-20, more preferably 6-12.

The molecular weight of the protecting group is preferably 40-200, more preferably 40-150, and even more preferably 40-120. When the molecular weight of the protective group is within the above-mentioned range, a coloring composition having excellent storage stability and excellent curability at low temperature can be obtained.

Specific examples of the protecting group include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, and 1-tertiary butoxy Ethyl, 1-cyclopentyloxyethyl, 1-cyclohexyloxyethyl, cyclohexyl(methoxy)methyl, α-methoxybenzyl, α-ethoxybenzyl, α-n-normal Propoxybenzyl, 2-phenyl-1-methoxyethyl, 2-phenyl-1-ethoxyethyl, 2-phenyl-1-isopropoxyethyl, 2-tetrahydrofuranyl , 2-tetrahydropyranyl, 1-ethoxyethyl, 1-cyclohexyloxyethyl, 2-tetrahydrofuranyl, 2-tetrahydropyranyl are preferred, 1-ethoxyethyl, 1-cyclohexyloxyethyl is more preferred.

As repeating unit B-1, the repeating unit represented by following formula (B1) is mentioned. Moreover, as repeating unit B-2, the repeating unit represented by following formula (B2) is mentioned.

In formula (B1), X ^b1 represents a trivalent linking group, L ^b1 represents a single bond or a divalent linking group, and Z ^b1 represents an acid group. In formula (B2), X ^b2 represents a trivalent linking group, L ^b2 represents a single bond or a divalent linking group, and Z ^b2 represents a group in which an acid group is protected by a protecting group.

The trivalent linking group represented by X ^b1 in the formula (B1) and the trivalent linking group represented by X ^b2 in the formula (B2) are not particularly limited. For example, a poly(meth)acrylic-based linking group, a polyalkyleneimide-based linking group, a polyester-based linking group, a polyurethane-based linking group, a polyurea-based linking group, a polyamide-based linking group, a polyether Linking group, polystyrene linking group, bisphenol linking group, novolak linking group, etc., poly(meth)acrylic linking group, polyether linking group, polyester linking group, bisphenol linking A base and a novolac-based linking group are preferred, and a poly(meth)acrylic-based linking group is more preferred.

Examples of the divalent linking group represented by L ^b1 in the formula (B1) and the divalent linking group represented by L ^b3 in the formula (B2) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms). group), aryl group (preferably aryl group with 6-20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S- and a group formed by combining two or more of these. The alkylene group may be any of linear, branched and cyclic, and linear or branched is preferred. Moreover, an alkylene group may have a substituent, and may be unsubstituted. As a substituent, a hydroxyl group, an alkoxy group, etc. are mentioned.

Z ^b1 of formula (B1) represents an acid group. The acid group includes a phenolic hydroxyl group, a carboxyl group, a sulfo group, and a phosphoric acid group, and a phenolic hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.

Z ^b2 of formula (B2) represents a group in which an acid group is protected by a protecting group. Examples of the group in which the acid group is protected by a protecting group include groups in which the acid group is protected by a group represented by any one of the above formulae (Y1) to (Y5), and the acid group is protected by the formula (Y3) or the formula The group protected by the group represented by (Y5) is preferred. As said acid group, a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group are mentioned, A phenolic hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.

式(B2-1)中，R^b11 ～R^b13 分別獨立地表示氫原子、鹵素原子或烷基，L^b11 表示單鍵或2價的連結基，Z^b11 表示由式(Z-1)或式(Z-2)表示之基團；

式(Z-1)及(Z-2)中，Y^b11 表示保護基，*表示與L^b11 鍵結之部分。As an aspect of the repeating unit B2, the repeating unit represented by the following formula (B2-1) can be mentioned.

In the formula (B2-1), R ^b11 to R ^b13 each independently represent a hydrogen atom, a halogen atom or an alkyl group, L ^b11 represents a single bond or a divalent linking group, and Z ^b11 represents a compound represented by the formula (Z-1) or the formula The group represented by (Z-2);

In formulas (Z-1) and (Z-2), Y ^b11 represents a protecting group, and * represents a moiety bonded to L ^b11 .

As a halogen atom represented by R ^b11 to R ^b13 , a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned. The carbon number of the alkyl group represented by R ^b11 to R ^b13 is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. The alkyl group may be linear, branched, or cyclic, but linear or branched is preferred. Examples of the divalent linking group represented by L ^b11 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylidene group (preferably an arylidene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, and a group combining two or more of these. The alkylene group may be any of linear, branched and cyclic, and linear or branched is preferred. Moreover, an alkylene group may have a substituent, and may be unsubstituted. As a substituent, a hydroxyl group, an alkoxy group, etc. are mentioned.

As the protecting group represented by Y ^b11 of the formula (Z-1) and the formula (Z-2), the group represented by any one of the above-mentioned formulas (Y1) to (Y5) can be exemplified. In the case where Z ^b11 of the formula (B2-1) is a group represented by the formula (Z-1), it is preferable that Y ^b11 is the formula (Y5). In the case where Z ^b11 of formula (B2-1) is a group represented by formula (Z-2), Y ^b11 is preferably the formula (Y3).

When Z ^b11 of formula (B2-1) is a group represented by formula (Z-1), the storage stability of the coloring composition can be further improved. When Z ^b11 of formula (B2-1) is a group represented by formula (Z-2), a colored composition excellent in curability at low temperature can be obtained.

In the resin EP, the content of the repeating unit B is preferably 5 to 85 mol % in all the repeating units of the resin EP. The upper limit is preferably 60 mol % or less, more preferably 40 mol % or less. The lower limit is preferably 8 mol % or more, and more preferably 10 mol % or more.

When the resin EP contains the repeating unit B-1, the content of the unit B-1 in the resin EP is preferably 5-85 mol % in all repeating units of the resin EP. The upper limit is preferably 60 mol % or less, more preferably 40 mol % or less. The lower limit is preferably 8 mol % or more, and more preferably 10 mol % or more.

When the resin EP contains the repeating unit B-2, the content of the unit B-2 in the resin EP is preferably 1-65 mol % in all repeating units of the resin EP. The upper limit is preferably 45 mol % or less, more preferably 30 mol % or less. The lower limit is preferably 2 mol % or more, more preferably 3 mol % or more.

When resin EP contains repeating unit B-1 and repeating unit B-2 respectively, resin EP preferably contains 0.4-3.2 mol of repeating unit B-2 with respect to 1 mol of repeating unit B-1, including 0.8-3.2 mol of repeating unit B-2. 2.8 mol is more preferable, and 1.2-2.4 mol is more preferable. According to this aspect, the storage stability of the coloring composition, the developability, and the suppression of color mixing of the obtained cured film can be simultaneously achieved at a higher level.

[Repeat unit C] Resin EP may contain a repeating unit containing a hydrocarbon ring group (hereinafter, also referred to as another repeating unit) as repeating units other than the repeating unit A and repeating unit B described above. The hydrocarbon ring group may be an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group. In addition, the hydrocarbon ring group may be a monocyclic hydrocarbon ring group, or may be a polycyclic hydrocarbon ring group such as a condensed ring or a cross-linked ring. In addition, the aromatic hydrocarbon ring group may be a monocyclic aromatic hydrocarbon ring group or a condensed ring aromatic hydrocarbon ring group. Specific examples of the hydrocarbon ring group include a dicyclopentyl group, an adamantyl group, a t-butylcyclohexyl group, an isocamphenyl group, and the like. As an aromatic hydrocarbon ring group, a phenyl group, a naphthyl group, etc. are mentioned.

Resin EP preferably contains repeating units containing an aliphatic hydrocarbon ring group and repeating units containing an aromatic hydrocarbon ring group, respectively. According to this aspect, the resin becomes rigid due to the increase of the side chain, the solvent resistance of the cured film is improved, and the cured film that further suppresses color mixing with other colors can be formed.

When the resin EP contains the repeating unit C, the content of the repeating unit C is preferably 0.1-40 mol % in all repeating units of the resin EP. The upper limit is preferably 35 mol % or less, more preferably 30 mol % or less. The lower limit is preferably 1 mol % or more, more preferably 5 mol % or more. Also, when the resin EP contains a repeating unit containing an aliphatic hydrocarbon ring group and a repeating unit containing an aromatic hydrocarbon ring group as the repeating unit C, the resin EP contains 5 with respect to 1 of the repeating unit containing an aliphatic hydrocarbon ring group. A repeating unit containing an aromatic hydrocarbon ring group of about 30 moles is preferable, more preferably 8 to 25 moles, and even more preferably 10 to 20 moles. In this state, the resin becomes rigid, the solvent resistance of the cured film is improved, and the cured film that further suppresses color mixing with other colors can be formed.

[Other repeating units] Resin EP may contain repeating units (hereinafter, also referred to as other repeating units) other than the repeating unit A, repeating unit B, and repeating unit C described above. The content of other repeating units in all repeating units of the resin EP is preferably 30 mol % or less, more preferably 20 mol % or less, and even more preferably 10 mol % or less.

(other resins) The coloring composition of the present invention can further contain resins other than the above-mentioned resin EP (hereinafter, also referred to as other resins). The weight average molecular weight (Mw) of other resins is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more.

Examples of other resins include (meth)acrylic resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysiloxane resins, and polyether resins. Resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, etc. Moreover, epoxy resins other than the said resin EP can also be used.

Other resins are also preferably resins with acid groups. As an acid group, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group, etc. are mentioned, for example. Resins with acid groups can also be used as alkali-soluble resins and dispersants. The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and particularly preferably 120 mgKOH/g or less.

The resin having an acid group may have a repeating unit derived from a maleimide compound. As a maleimide compound, N-alkylmaleimide, N-arylmaleimide, etc. are mentioned. As a repeating unit derived from a maleimide compound, the repeating unit represented by formula (C-mi) is mentioned.

In formula (C-mi), Rmi represents an alkyl group or an aryl group. The carbon number of the alkyl group is preferably 1-20. The alkyl group may be linear, branched, or cyclic. The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and further preferably 6-10. Rmi is preferably an aryl group.

Other resins contain repetitions derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers".) The resin of the unit is also preferred.

式（ED2）中，R表示氫原子或碳數1～30的有機基。作為式（ED2）的具體例，能夠參閱日本特開2010-168539號的記載。In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of Formula (ED2), the description of Unexamined-Japanese-Patent No. 2010-168539 can be referred to.

For a specific example of the ether dimer, reference can be made to paragraph 0317 of JP 2013-029760 A, and the content is incorporated in the present specification.

Other resins are also preferably resins containing repeating units having a polymerizable group. As a polymerizable group, the group containing an ethylenically unsaturated bond, such as a vinyl group, a (meth)allyl group, and a (meth)acryloyl group, is mentioned.

式中，R¹ 表示氫原子或甲基，R²¹ 及R²² 分別獨立地表示伸烷基，n表示0～15的整數。R²¹ 及R²² 表示之伸烷基的碳數係1～10為較佳，1～5更佳，1～3為進一步較佳，2或3特佳。n係0～5的整數為較佳，0～4的整數更佳，0～3的整數為進一步較佳。Other resins containing repeating units derived from the compound represented by the formula (III) are also preferred.

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0 to 15. The carbon number of the alkylene group represented by R ²¹ and R ²² is preferably 1-10, more preferably 1-5, further preferably 1-3, and particularly preferably 2 or 3. n is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.

As a compound represented by formula (III), ethylene oxide or propylene oxide modified (meth)acrylate of p-cumylphenol, etc. are mentioned. As a commercial item, ARONIX M-110 (made by TOAGOSEI CO., LTD.) etc. are mentioned.

Other resin-based dispersants are also preferred. As a dispersing agent, an acidic dispersing agent (acidic resin) and a basic dispersing agent (basic resin) are mentioned. Here, the acidic dispersant (acidic resin) means a resin in which the amount of acid groups is larger than the amount of bases. As an acidic dispersant (acidic resin), when the total amount of the acid group and the base is 100 mol%, a resin in which the acid group accounts for 70 mol% or more is preferable, and substantially only contains Acid-based resins are more preferred. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. In addition, the basic dispersant (basic resin) refers to a resin in which the amount of bases is larger than the amount of acid groups. As a basic dispersant (basic resin), when the total amount of the amount of acid groups and the amount of bases is set to 100 mol%, a resin in which the amount of bases exceeds 50 mol% is preferable. The base-based amine group possessed by the alkaline dispersant is preferred.

It is preferable that the resin used as a dispersant contains a repeating unit having an acid group. Since the resin used as a dispersant contains a repeating unit having an acid group, it is possible to further suppress the generation of development residues when a pattern is formed by a photolithography method.

Resin-based graft resins used as dispersants are also preferred. For details of the graft resin, the descriptions in paragraphs 0025 to 0094 of JP 2012-255128 A can be referred to, and the contents are incorporated in this specification.

The resin used as the dispersant is also preferably a polyimide-based dispersant in which at least one of the main chain and the side chain contains a nitrogen atom. As the polyimine-based dispersant, resins having a main chain and a side chain, and having a basic nitrogen atom on at least one of the main chain and the side chain are preferred, and the main chain includes a resin having a functional group of pKa14 or less. Part of the structure, the number of atoms in the side chain is 40 to 10,000. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. Regarding the polyimide-based dispersant, reference can be made to the descriptions in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated in the present specification.

The resin used as the dispersant is preferably a resin having a structure in which a plurality of polymer chains are bonded to the core. Specific examples of such resins include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP 2013-043962 A, and the like.

It is also preferable that the resin used as the dispersing agent is a resin containing a repeating unit having a group containing an ethylenically unsaturated bond in the side chain. Among all the repeating units of the resin, the content of repeating units having groups containing ethylenically unsaturated bonds on the side chain is preferably 10 mol% or more, more preferably 10-80 mol%, 20-70 mol% Ear% is further preferred.

In addition, as the dispersant, polyethyleneimine having polyester side chains described in International Publication No. 2016/104803, block copolymers described in International Publication No. 2019/125940, Japanese Patent Laid-Open No. 2020- The block polymer having an acrylic acid amide structural unit described in No. 066687, the block polymer having an acrylic acid amide structural unit described in Japanese Patent Laid-Open No. 2020-066688, and the like.

The dispersant can also be obtained as a commercial product, and specific examples of this include Disperbyk series (for example, Disperbyk-111, 2001, etc.) manufactured by BYK Chemie GmbH, Solsperse series (for example, Solsperse20000, etc.) manufactured by Lubrizol Japan Ltd. 76500, etc.), Azisper series manufactured by Ajinomoto Fine-Techno Co., Inc., etc. Moreover, the product described in the paragraph 0129 of Japanese Patent Laid-Open No. 2012-137564 and the product described in the paragraph 0235 of Japanese Patent Laid-Open No. 2017-194662 can also be used as a dispersant. In addition, the resins described in paragraphs 0041 to 0060 of Japanese Patent Laid-Open No. 2017-206689 and the resins described in Japanese Patent Laid-Open No. 2019-095548 containing the quaternary hindered amine salt can also be preferably used as the dispersant.

It is preferable that content of resin is 5-50 mass % in the total solid content of a coloring composition. The upper limit is preferably 40 mass % or less, more preferably 30 mass % or less. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. Moreover, it is preferable that content of the resin EP mentioned above is 5-50 mass % in the total solid content of a coloring composition. The upper limit is preferably 40 mass % or less, more preferably 30 mass % or less. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. Moreover, it is preferable that content of the resin EP mentioned above in the resin contained in a coloring composition is 80-100 mass %. The upper limit is preferably 97.5 mass % or less, more preferably 95 mass % or less. The lower limit is preferably 82.5 mass % or more, and more preferably 85 mass % or more.

＜＜Polymerizable compound＞＞ The coloring composition of the present invention contains a polymerizable compound. As a polymerizable compound, the compound etc. which have a group containing an ethylenically unsaturated bond are mentioned. As a group containing an ethylenically unsaturated bond, a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.

As the polymerizable compound, any of chemical forms such as monomers, prepolymers, and oligomers may be used, and monomers are preferred. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and further more preferably 1500 or less. The lower limit is more preferably 150 or more, and more preferably 250 or more.

From the viewpoint of the temporal stability of the coloring composition, the content of the ethylenically unsaturated bond-containing group (hereinafter, referred to as C=C value) of the polymerizable compound is preferably 2 to 14 mmol/g. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more. The upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less. The C=C value of the polymerizable compound is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.

The polymerizable compound is preferably a compound containing 3 or more groups containing an ethylenically unsaturated bond, more preferably a compound containing 3 to 15 groups containing an ethylenically unsaturated bond, and 3 to 6 groups containing an ethylenically unsaturated bond. The compound of the group of an ethylenically unsaturated bond is more preferable. Moreover, the polymerizable compound is preferably a 3- to 15-functional (meth)acrylate compound, and more preferably a 3- to 6-functional (meth)acrylate compound. Specific examples of the polymerizable compound include paragraphs 0095 to 0108 of JP 2009-288705 A, paragraph 0227 of JP 2013-029760 A, paragraphs 0254 to 0257 of JP 2008-292970 A, and JP 2013-029760 A. Paragraphs 0034 to 0038 of No. 2013-253224, Paragraph 0477 of Japanese Patent Laid-Open No. 2012-208494, Japanese Patent Laid-Open No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and Japanese Patent Laid-Open No. 2017-194662 Compounds described, and these contents are incorporated into this specification.

As the polymerizable compound, dipentaerythritol triacrylate (a commercial product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (a commercial product: KAYARAD D-320; Nippon Kayaku Co., Ltd.) ., Ltd.), dipentaerythritol penta(meth)acrylate (available as KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (available as a commercial product) products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) and these ( Compounds of the structure of meth)acryloyl group (for example, commercially available SR454 and SR499 manufactured by SARTOMER Company, Inc.) are preferred. Further, as the polymerizable compound, diglycerol EO (ethylene oxide) modified (meth)acrylate (as a commercial item, M-460; manufactured by TOAGOSEI CO., Ltd.), pentaerythritol tetraacrylate can also be used (manufactured by Shin Nakamura Chemical Co., Ltd., NK Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co. , Ltd.), ARONIX TO-2349 (manufactured by TOAGOSEI CO., Ltd.), NK Oligo UA-7200 (manufactured by Shin Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (Taisei Fine Chemical Co. , Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL Co., LTD.), etc.

As the polymerizable compound, trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, and trimethylolpropane ethylene oxide modified tri(meth)acrylate were used. Trifunctional (meth)acrylate compounds such as meth)acrylate, isocyanurate-modified ethylene oxide tri(meth)acrylate, and pentaerythritol tri(meth)acrylate are also preferred. As a commercial item of a trifunctional (meth)acrylate compound, ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 are mentioned , M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A- TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (Nippon Manufactured by Kayaku Co., Ltd.) etc.

As the polymerizable compound, a polymerizable compound having an acid group can also be used. By using the polymerizable compound having an acid group, the coloring composition of the unexposed portion can be easily removed during development, and the generation of development residues can be suppressed. As an acid group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, A carboxyl group is preferable. As a commercial item of the polymerizable compound which has an acid group, ARONIX M-305, M-510, M-520, ARONIX TO-2349 (made by TOAGOSEI CO., LTD.) etc. are mentioned. As a preferable acid value of the polymerizable compound which has an acid group, it is 0.1-40 mgKOH/g, More preferably, it is 5-30 mgKOH/g. When the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the solubility with respect to the developing solution is good, and when it is 40 mgKOH/g or less, it is advantageous for production and handling.

As the polymerizable compound, a polymerizable compound having a caprolactone structure can also be used. As a polymerizable compound which has a caprolactone structure, it is marketed by Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120 etc. are mentioned.

As the polymerizable compound, a polymerizable compound having an alkaneoxy group can also be used. The polymerizable compound with an alkeneoxy group is preferably a polymerizable compound with an ethyleneoxy group and/or a propylideneoxy group, and the polymerizable compound with an ethylideneoxy group is more preferably, and has 4-20 A 3- to 6-functional (meth)acrylate compound having an ethylideneoxy group is further preferred. As a commercial item of the polymerizable compound which has an alkaneoxy group, KAYARAD RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

As the polymerizable compound, a polymerizable compound having a perylene skeleton can also be used. As a commercial item of the polymerizable compound which has a perylene skeleton, OGSOL EA-0200, EA-0300 (Osaka Gas Chemicals Co., Ltd. make, the (meth)acrylate monomer which has a perylene skeleton) etc. are mentioned.

As the polymerizable compound, it is also preferable to use a compound that does not substantially contain environmental control substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable compound, there are acrylates such as those described in Japanese Patent Publication No. Sho 48-041708, Japanese Patent Publication No. Sho 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765; Japanese Patent Publication No. 02-016765 The urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. Moreover, it is also preferable to use the polymerizable compound which has an amine group structure and a sulfide structure in a molecule|numerator as described in Unexamined-Japanese-Patent No. 63-277653, Unexamined-Japanese-Patent No. 63-260909, and Unexamined-Japanese-Patent No. 01-105238. As the polymerizable compound, UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH -600, T-600, AI-600, LINC-202UA (produced by Kyoeisha Chemical Co., Ltd.) and other commercial products.

It is preferable that content of a polymerizable compound is 5.0-35 mass % in the total solid content of a coloring composition. The upper limit is preferably 30 mass % or less, and more preferably 25 mass % or less. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.

＜＜Photopolymerization initiator＞＞ The coloring composition concerning this invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and can be appropriately selected from known photopolymerization initiators. The photopolymerization initiator is preferably a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a trisium skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbisimidazoles, oxime compounds, and organic peroxides. compounds, sulfur compounds, ketone compounds, aromatic onium salts, hydroxyalkylphenone compounds, aminoalkylphenone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiators are trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, hydroxyalkylphenone compounds, and aminoalkylphenone compounds. , Acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene- Iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds are preferred, selected from oxime compounds, hydroxyalkylphenone compounds, aminoalkylphenone compounds and acylphosphine The compound among the compounds is more preferable, and the oxime compound is further preferable. Moreover, as a photopolymerization initiator, the compound described in Japanese Patent Laid-Open No. 2014-130173, paragraphs 0065 to 0111, Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No. 3, 2019 can be mentioned. Peroxide-based photopolymerization initiators described in, Photopolymerization initiators described in International Publication No. 2018/221177, Photopolymerization initiators described in International Publication No. 2018/110179, Japanese Patent Publication No. 2018/110179 The photopolymerization initiator described in Kokai No. 2019-043864, the photopolymerization initiator described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiator described in Japanese Kokai Publication No. 2019-167313 , and these contents are incorporated into this specification.

As an aminoalkylphenone compound, the aminoalkylphenone compound described in Unexamined-Japanese-Patent No. 10-291969 is mentioned, for example. In addition, examples of commercially available aminoalkylphenone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (the above are manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG ( The above are manufactured by BASF Corporation) and so on.

As an acylphosphine compound, the acylphosphine compound described in Japanese Patent No. 4225898, etc. are mentioned. As a specific example, bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide etc. are mentioned. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (the above are manufactured by IGM Resins B.V.), Irgacure 819, and Irgacure TPO (the above are manufactured by BASF Corporation).

式中Rv¹ 表示取代基，Rv² 及Rv³ 分別獨立地表示氫原子或取代基，Rv² 和Rv³ 亦可以彼此鍵結而形成環，m表示0～5的整數。The hydroxyalkylphenone compound may, for example, be a compound represented by the following formula (V). Formula (V)

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent, Rv ² and Rv ³ may be bonded to each other to form a ring, and m represents an integer of 0-5.

Examples of the substituent represented by Rv ¹ include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms). The alkyl group and the alkoxy group are preferably linear or branched, more preferably linear. The alkyl group and alkoxy group represented by Rv ¹ may be unsubstituted or may have a substituent. As a substituent, a hydroxyl group, a group which has a hydroxyalkylphenone structure, etc. are mentioned. Examples of the group having a hydroxyalkylphenone structure include a benzene ring to which Rv ¹ in formula (V) is bonded, or a group having a structure in which one hydrogen atom is removed from Rv ¹ .

As a substituent in Rv ² and Rv ³ , an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferable. In addition, Rv ² and Rv ³ may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms). The alkyl group is preferably straight chain or branched chain, more preferably straight chain.

Specific examples of the compound represented by the formula (V) include the following compounds.

Commercially available hydroxyalkylphenone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (the above are manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (the above are BASF company) etc.

As the oxime compound, the compound described in JP 2001-233842, the compound described in JP 2000-080068, the compound described in JP 2006-342166, J.C.S. Perkin II (1979, pp.1653-1660) Compounds described, compounds described in J.C.S. Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), described in Japanese Patent Laid-Open No. 2000-066385 The compound described in Japanese Patent Publication No. 2004-534797, the compound described in Japanese Patent Publication No. 2017-019766, the compound described in Japanese Patent No. 6065596, the compound described in International Publication No. 2015/152153, the compound described in International Publication No. 2017/ The compound described in No. 051680, the compound described in JP-A No. 2017-198865, the compound described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, the compound described in International Publication No. 2013/167515, and the like. Specific examples of the oxime compound include 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-acetoxyiminobutan-2-one. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxy Imino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one and 2-ethoxycarbonyloxyimino-1-benzene propan-1-one, etc. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (the above are manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Trolly New Electronic Materials CO., LTD.), Adeka Optomer N-1919 (The photopolymerization initiator 2 described in Japanese Patent Laid-Open No. 2012-014052, manufactured by ADEKA CORPORATION). Moreover, as an oxime compound, it is also preferable to use a non-colorable compound or a compound with high transparency and hardly discoloration. As a commercial item, ADEKA ARKLS NCI-730, NCI-831, NCI-930 (the above are manufactured by ADEKA CORPORATION) etc. are mentioned.

As the photopolymerization initiator, an oxime compound having a perylene ring can also be used, and specific examples include the compound described in Japanese Patent Laid-Open No. 2014-137466, the compound described in Japanese Patent No. 6636081, and the compound described in Korean Patent Laid-Open No. 10-2016-0109444 .

As the photopolymerization initiator, an oxime compound having at least one benzene ring of a carbazole ring serving as a skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

(OX-1) 式(OX-1)中，Ar¹ 及Ar² 分別獨立地表示可以具有取代基之芳香族烴環，R¹ 表示具有包含氟原子之基團之芳基，R² 及R³ 分別獨立地表示烷基或芳基。As the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. The oxime compound containing a fluorine atom is preferably a compound represented by the formula (OX-1).

(OX-1) In formula (OX-1), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent, R ¹ represents an aryl group having a group containing a fluorine atom, R ² and R ³ each independently represents an alkyl group or an aryl group.

The aromatic hydrocarbon ring represented by Ar ¹ and Ar ² in formula (OX-1) may be a monocyclic ring or a condensed ring. The number of carbon atoms of the ring constituting the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10. The aromatic hydrocarbon rings are preferably a benzene ring and a naphthalene ring. Among them, an Ar ¹ -series benzene ring is preferable. Ar ² is preferably a benzene ring or a naphthalene ring, more preferably a naphthalene ring.

Examples of substituents that Ar ¹ and Ar ² may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , - OCOR ^X1 , -NRX1R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 , -NHSO ₂ R ^X1 and the like. R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. The alkyl group as a substituent and the alkyl group represented by R ^X1 and R ^X2 preferably have 1 to 30 carbon atoms. The alkyl group may be any of straight chain, branched chain and cyclic chain, but straight chain or branched chain is preferred. In the alkyl group, a part or all of hydrogen atoms may be substituted with halogen atoms (preferably fluorine atoms). In addition, in the alkyl group, a part or all of the hydrogen atoms may be substituted with the above-mentioned substituents. The number of carbon atoms of the aryl group as a substituent and the aryl group represented by R ^X1 and R ^X2 is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a single ring or a condensed ring. In addition, in the aryl group, a part or all of the hydrogen atoms may be substituted with the above-mentioned substituents. The heterocyclic group as a substituent and the heterocyclic group represented by R ^X1 and R ^X2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12. The number system of the heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In addition, in the heterocyclic group, a part or all of the hydrogen atoms may be substituted with the above-mentioned substituents.

The aromatic hydrocarbon ring represented by Ar ¹ is preferably an unsubstituted aromatic hydrocarbon ring. It is preferable that the aromatic hydrocarbon ring represented by Ar ² has a substituent. As a substituent, -COR ^X1 is preferable. R ^X1 is preferably an alkyl group, an aryl group or a heterocyclic group, more preferably an aryl group. The aryl group may have a substituent or may be unsubstituted. The substituent may, for example, be an alkyl group having 1 to 10 carbon atoms.

R ¹ of formula (OX-1) represents an aryl group having a group containing a fluorine atom. The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and further preferably 6-10. The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing group). As the fluorine-containing group, selected from -OR ^F1 , -SR ^F1 , -COR ^F1 , -COOR ^F1 , -OCOR ^F1 , -NR ^F1 R ^F2 , -NHCOR ^F1 , -CONR ^F1 R ^F2 , -NHCONR ^F1 R ^F2 , At least one of -NHCOOR ^F1 , -SO ₂ R ^F1 , -SO ₂ OR ^F1 and -NHSO ₂ R ^F1 is preferred. R ^F1 represents a fluorine-containing alkyl group, and R ^F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group or a heterocyclic group. Preferably, the fluorine-containing group is -OR ^F1 .

The carbon number of the fluorine-containing alkyl group represented by R ^F1 and R ^F2 and the alkyl group represented by R ^F2 is preferably 1-20, more preferably 1-15, more preferably 1-10, and 1-4 is Excellent. The fluorine-containing alkyl group and the alkyl group may be linear, branched, or cyclic, but linear or branched chains are preferred. In the fluorine-containing alkyl group, the substitution rate of fluorine atoms is preferably 40 to 100%, more preferably 50 to 100%, and even more preferably 60 to 100%. In addition, the substitution rate of a fluorine atom means the ratio (%) of the number substituted by a fluorine atom with respect to the number of all hydrogen atoms which an alkyl group has.

The carbon number of the aryl group represented by R ^F2 is preferably 6-20, more preferably 6-15, and even more preferably 6-10.

The heterocyclic group represented by R ^F2 is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The condensation number coefficient is preferably 2 to 8, more preferably 2 to 6, further preferably 3 to 5, and particularly preferably 3 to 4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and even more preferably 3 to 20. The number system of the heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heteroatom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.

It is preferable that the group containing a fluorine atom has a terminal structure represented by formula (1) or (2). The * in the formula represents the connection bond. *-CHF ₂ (1) *-CF ₃ (2)

R ² in formula (OX-1) represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or may have a substituent. As a substituent, the substituent demonstrated in the said substituent which Ar ¹ and Ar ² may have can be mentioned. The carbon number of the alkyl group is preferably 1-20, more preferably 1-15, still more preferably 1-10, and particularly preferably 1-4. The alkyl group may be any of straight chain, branched chain and cyclic chain, but straight chain or branched chain is preferred. The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and further preferably 6-10.

R ³ in formula (OX-1) represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or may have a substituent. As a substituent, the substituent demonstrated in the said substituent which Ar ¹ and Ar ² may have can be mentioned. The carbon number of the alkyl group represented by R ³ is preferably 1-20, more preferably 1-15, and even more preferably 1-10. The alkyl group may be any of straight chain, branched chain and cyclic chain, but straight chain or branched chain is preferred. The carbon number of the aryl group represented by R ³ is preferably 6-20, more preferably 6-15, and even more preferably 6-10.

Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24, 36 to 40 described in JP 2014-500852, and JP 2013-164471 Compound (C-3) and the like described in No.

As a photopolymerization initiator, an oxime compound having a nitro group can also be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466 A, and Japanese Patent Application Laid-Open No. 2013-114249. The compound described in paragraphs 0007 to 0025 of No. 4223071, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

As the photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. As such a photopolymerization initiator, the compound described in International Publication No. 2019/088055, etc. are mentioned.

Specific examples of the oxime compound preferably used in the present invention are shown below, but the present invention is not limited to these.

In the present invention, as a photopolymerization initiator, a photopolymerization initiator A1 having an absorption coefficient at a wavelength of 365 nm in methanol of 1.0×10 ³ mL/gcm or more and an absorption coefficient at a wavelength of 365 nm in methanol of The photopolymerization initiator A2 having an absorption coefficient of 1.0×10 ² mL/gcm or less and an absorption coefficient at a wavelength of 254 nm of 1.0×10 ³ mL/gcm or more is preferable. According to this aspect, it is easy to sufficiently harden the coloring composition by exposure, and a low-temperature process (for example, a temperature of 150° C. or lower in the whole process, preferably a temperature of 120° C. or lower) can be used to form a flat and smooth material. A cured film that is also excellent in properties such as solvent resistance. As the photopolymerization initiator A1 and the photopolymerization initiator A2, it is preferable to select and use a compound having the above-mentioned light absorption coefficient from the above-mentioned compounds.

上述式中，ε表示吸光係數（mL/gcm），A表示吸光度，c表示光聚合起始劑的濃度（g/mL），l表示光徑長度（cm）。In addition, in this invention, the light absorption coefficient in the said wavelength of a photopolymerization initiator is the value measured in the following way. That is, a measurement solution was prepared by dissolving the photopolymerization initiator in methanol, and the calculation was performed by measuring the absorbance of the aforementioned measurement solution. Specifically, the aforementioned measurement solution was placed in a glass tank with a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies, Inc., and applied to the following formula to calculate the wavelength of 365 nm. and the absorption coefficient (mL/gcm) at a wavelength of 254 nm.

In the above formula, ε represents the absorption coefficient (mL/gcm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g/mL), and l represents the optical path length (cm).

The absorption coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm is 1.0×10 ³ mL/gcm or more, preferably 1.0×10 ⁴ mL/gcm or more, more preferably 1.1×10 ⁴ mL/gcm or more, 1.2×10 ⁴ to 1.0×10 ⁵ mL/gcm is further preferable, 1.3×10 ⁴ to 5.0×10 ⁴ mL/gcm is further preferable, and 1.5×10 ⁴ to 3.0×10 ⁴ mL/gcm is particularly preferable . In addition, the absorption coefficient of the light with a wavelength of 254 nm in methanol of the photopolymerization initiator A1 is preferably 1.0×10 ⁴ to 1.0×10 ⁵ mL/gcm, more preferably 1.5×10 ⁴ to 9.5×10 ⁴ mL/gcm Preferably, 3.0×10 ⁴ to 8.0×10 ⁴ mL/gcm is further preferable.

As the photopolymerization initiator A1, oxime compounds, aminoalkylphenone compounds, and acylphosphine compounds are preferred, oxime compounds and acylphosphine compounds are more preferred, and oxime compounds are further preferred, which are combined with the composition. From the viewpoint of compatibility with other components contained, an oxime compound containing a fluorine atom is particularly preferred. Specific examples of the photopolymerization initiator A1 include 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzyl oxime)] (as a commercial item, For example, Irgacure OXE01, manufactured by BASF Corporation), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O- Acetoxime) (as a commercial item, for example, Irgacure OXE02, manufactured by BASF Corporation), bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (as a commercial item, for example, Omnirad 819 (manufactured by IGM Resins B.V. Co., Ltd.), Irgacure 819 (manufactured by BASF Co., Ltd.), (C-13), (C-14) and the like shown in the specific examples of the above-mentioned oxime compounds.

The light absorption coefficient of the photopolymerization initiator A2 in methanol with a wavelength of 365 nm is below 1.0×10 ² mL/gcm, preferably 10～1.0×10 ² mL/gcm, and 20～1.0×10 ² mL/gcm is better. In addition, the difference between the absorption coefficient of light with a wavelength of 365 nm in methanol of the photopolymerization initiator A1 and the absorption coefficient of light with a wavelength of 365 nm in methanol of the photopolymerization initiator A2 is 9.0×10 ² mL/gcm or more, 1.0 ×10 ³ mL/gcm or more is preferable, 5.0×10 ³ to 3.0×10 ⁴ mL/gcm is more preferable, and 1.0×10 ⁴ to 2.0×10 ⁴ mL/gcm is further preferable. In addition, the light absorption coefficient of the photopolymerization initiator A2 in methanol with a wavelength of 254 nm is 1.0×10 ³ mL/gcm or more, preferably 1.0×10 ³ to 1.0×10 ⁶ mL/gcm, and 5.0×10 3 to 5.0×10 ³ to 1.0×10 ⁵ mL/gcm is better.

As the photopolymerization initiator A2, hydroxyalkylphenone compounds, phenyl glyoxylate compounds, aminoalkylphenone compounds, and acylphosphine compounds are preferred, and hydroxyalkylphenone compounds and A phenylglyoxylate compound is more preferable, and a hydroxyalkylphenone compound is further preferable. Moreover, as a hydroxyalkylphenone compound, the compound represented by the above-mentioned formula (V) is preferable. Specific examples of the photopolymerization initiator A2 include 1-hydroxy-cyclohexyl-phenyl-one (commercially available, for example, Omnirad 184 (manufactured by IGM Resins B.V.) and Irgacure 184 (manufactured by BASF)) , 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (as a commercial item, for example, Omnirad 2959 (IGM Resins B.V. manufactured), Irgacure 2959 (manufactured by BASF)), etc.

As a combination of the photopolymerization initiator A1 and the photopolymerization initiator A2, the photopolymerization initiator A1 is a combination of an oxime compound, and the photopolymerization initiator A2 is a combination of a hydroxyalkylphenone compound. The initiator A1 is an oxime compound, and the photopolymerization initiator A2 is a combination of compounds represented by the above-mentioned formula (V), and the photopolymerization initiator A1 is an oxime compound containing a fluorine atom, and the photopolymerization initiator The agent A2 is a combination of compounds represented by the above formula (V) which is particularly preferred.

It is preferable that content of a photoinitiator is 0.1-17.5 mass % in the total solid content of a coloring composition. The lower limit is preferably 0.5 mass % or more, more preferably 1.0 mass % or more, and even more preferably 1.5 mass % or more. The upper limit is preferably 15.0 mass % or less, more preferably 12.5 mass % or less, and even more preferably 10.0 mass % or less. Moreover, it is preferable that the coloring composition of this invention contains 1.0-50 mass parts of photoinitiators with respect to 100 mass parts of polymerizable compounds. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less. The lower limit is preferably 2.5 parts by mass or more, and more preferably 5.0 parts by mass or more. According to this aspect, the pattern shape after development is favorable.

In the coloring composition of the present invention, when the above-mentioned photopolymerization initiator A1 is used as the photopolymerization initiator, the content of the photopolymerization initiator A1 in the total solid content of the coloring composition is 0.1 to 17.5 Mass % is better. The lower limit is preferably 0.5 mass % or more, more preferably 1.0 mass % or more, and even more preferably 1.5 mass % or more. The upper limit is preferably 15.0 mass % or less, more preferably 12.5 mass % or less, and even more preferably 10.0 mass % or less.

In the coloring composition of the present invention, when the above-mentioned photopolymerization initiator A2 is used as a photopolymerization initiator, the content of the photopolymerization initiator A2 in the total solid content of the coloring composition is 0.1 to 10.0 Mass % is better. The lower limit is preferably 0.5 mass % or more, more preferably 1.0 mass % or more, and even more preferably 1.5 mass % or more. The upper limit is preferably 9.0 mass % or less, more preferably 8.0 mass % or less, and even more preferably 7.0 mass % or less.

In the coloring composition of the present invention, when the above-mentioned photopolymerization initiator A1 and photopolymerization initiator A2 are used as photopolymerization initiators, the present invention is The coloring composition preferably contains 50-200 parts by mass of the photopolymerization initiator A2. The upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less. The lower limit is preferably 60 parts by mass or more, and more preferably 70 parts by mass or more. According to this aspect, a cured film excellent in properties such as solvent resistance can be formed by a low temperature process (for example, a temperature of 150° C. or lower in the entire process, preferably a temperature of 120° C. or lower).

In the coloring composition of the present invention, when the above-mentioned photopolymerization initiator A1 and photopolymerization initiator A2 are used as photopolymerization initiators, the photopolymerization initiator A1 in the total solid content of the coloring composition The total content with the photopolymerization initiator A2 is preferably 0.1 to 20.0 mass %. The lower limit is preferably 1.0 mass % or more, more preferably 2.0 mass % or more, and even more preferably 2.5 mass % or more. The upper limit is preferably 17.5 mass % or less, more preferably 15.0 mass % or less, and even more preferably 12.5 mass % or less.

＜＜Compounds containing furanyl＞＞ The coloring composition of the present invention can contain a furan group-containing compound (hereinafter, also referred to as a furan group-containing compound). According to this aspect, it can be set as a coloring composition excellent in low temperature hardening.

The structure of the furan group-containing compound is not particularly limited as long as it contains a furan group (a group obtained by removing one hydrogen atom from furan). As the furan group-containing compound, the compounds described in paragraphs 0049 to 0089 of JP-A No. 2017-194662 can be used. Furthermore, Japanese Patent Application Laid-Open No. 2000-233581, Japanese Patent Application Laid-Open No. 1994-271558, Japanese Patent Application Laid-Open No. 1994-293830, Japanese Patent Application Laid-Open No. 1996-239421, Japanese Patent Application Laid-Open No. 1998-508655, Compounds described in JP 2003-183348 A, JP 2006-193628 A, JP 2007-186684 A, JP 2010-265377 A, JP 2011-170069 A, and the like.

The furan group-containing compound may be a monomer or a polymer. The polymer is preferable for the reason of easily improving the durability of the obtained film. In the case of a polymer, the weight average molecular weight is preferably 2,000 to 70,000. The upper limit is preferably 60,000 or less, and more preferably 50,000 or less. The lower limit is preferably 3,000 or more, more preferably 4,000 or more, and even more preferably 5,000 or more. In addition, the polymer-type furan group-containing compound is a component also corresponding to the resin in the coloring composition of the present invention.

The content of the furan group-containing compound in the total solid content of the coloring composition is preferably 0.1 to 70% by mass. The lower limit is preferably 2.5 mass % or more, more preferably 5.0 mass % or more, and even more preferably 7.5 mass % or more. The upper limit is preferably 65 mass % or less, more preferably 60 mass % or less, and even more preferably 50 mass % or less. The furan group-containing compound may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that the total amount is in the said range.

＜＜Solvent＞＞ It is preferable that the coloring composition of this invention contains a solvent. As a solvent, an organic solvent is mentioned. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring composition. Examples of the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents, and the like. For details of these, reference can be made to paragraph 0223 of International Publication No. WO 2015/166779, and the content is incorporated into the present specification. In addition, a cyclic alkyl-substituted ester-based solvent and a cyclic alkyl-substituted ketone-based solvent can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl celsuyl acetate. , ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methyl Cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carb Bristol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropane Amide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, cyclobutane, anisole, 1,4-diacetoxybutane, ethyl acetate Glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol, etc. However, for environmental reasons, it may be preferable to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents (for example, it can be set to 50 with respect to the total amount of organic solvents). Mass ppm (parts per million: parts per million) or less, can also be set to 10 mass ppm or less, and can also be set to 1 mass ppm or less).

In the present invention, from the viewpoint of efficiently volatilizing the solvent, the solvent is preferably an organic solvent having a boiling point of 160° C. or lower. The boiling point of the organic solvent is more preferably 140°C or lower, and further preferably 130°C or lower. The lower limit of the boiling point is not particularly limited, but is preferably, for example, 100°C or higher. Examples of such organic solvents include butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, etc. Butyl acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate are better.

In the present invention, it is preferable to use a solvent with less metal content, and the metal content of the solvent is preferably 10 parts per billion (parts per billion) or less, for example. As needed, a solvent of quality ppt (parts per trillion: parts per trillion) grade, such as a high-purity solvent provided by Toyo Gosei Co., Ltd, for example (Chemical Industry Daily, November 13, 2015) can be used.

As a method of removing impurities such as metals from the solvent, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter can be mentioned. The filter pore diameter of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

Solvents may contain isomers (compounds with the same number of atoms but different structures). In addition, only one type of isomer may be contained, or a plurality of types may be contained.

In the present invention, the content of the peroxide in the organic solvent is preferably 0.8 mmol/L or less, and it is more preferably that the peroxide is not substantially contained.

The content of the solvent in the coloring composition is preferably 60 to 95% by mass. Furthermore, the upper limit is preferably 90 mass % or less, more preferably 87.5 mass % or less, and even more preferably 85 mass % or less. Furthermore, the lower limit is preferably 65 mass % or more, more preferably 70 mass % or more, and even more preferably 75 mass % or more. A solvent may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that these total amounts fall into the said range.

Moreover, from the viewpoint of environmental regulation, it is preferable that the coloring composition of the present invention does not substantially contain an environmental regulation substance. In addition, in the present invention, substantially free of environmental control substances means that the content of the environmental control substances in the coloring composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and 1 mass ppm or less Excellent. Examples of environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like. These are registered as environmentally controlled substances under REACH (Registration Evaluation Authorization and Restriction of CHemicals) control, PRTR (Pollutant Release and Transfer Register) law, VOC (Volatile Organic Compounds) control, etc., and their usage and disposal methods are strictly controlled. These compounds may be used as a solvent when producing each component of the coloring composition used in the present invention, etc., and may be mixed into the coloring composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. As a method of reducing the environmentally regulated substances, there is a method of heating and depressurizing the inside of the system to make it more than the boiling point of the environmentally regulated substances, and distilling off the environmentally regulated substances from the inside of the system to reduce them. In addition, in the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having the same boiling point as the solvent in order to improve efficiency. In addition, when a compound having radical polymerizability is contained, a polymerization inhibitor or the like may be added and removed by distillation under reduced pressure in order to suppress the progress of radical polymerization reaction and intermolecular crosslinking during the removal by distillation under reduced pressure. Such distillation removal methods can be performed at any of the stage of the raw materials, the stage of the products (such as the polymerized resin solution and the polyfunctional monomer solution) that react the raw materials, or the stage of the coloring composition produced by mixing these compounds. carried out in one stage.

＜＜Pigment Derivative＞＞ The coloring composition of the present invention can contain a pigment derivative. As the pigment derivative, a compound having a structure in which a part of a chromophore group is substituted with an acid group, a base group, or a phthalimidomethyl group is exemplified. Examples of the chromophore constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, and a dioxin skeleton. , perylene skeleton, perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinoline yellow skeleton, Shilin skeleton, metal complex skeleton, etc., quinoline skeleton, benzimidazolone The skeleton, the diketopyrrolopyrrole skeleton, the azo skeleton, the quinoline yellow skeleton, the isoindoline skeleton and the phthalocyanine skeleton are preferred, and the azo skeleton and the benzimidazolone skeleton are more preferred. As the acid group possessed by the pigment derivative, a sulfonic acid group and a carboxyl group are preferable, and a sulfonic acid group is more preferable. As the base of the pigment derivative, an amine group is preferable, and a tertiary amine group is more preferable.

Specific examples of pigment derivatives include Japanese Patent Application Laid-Open No. 56-118462, Japanese Patent Application Laid-Open No. 63-264674, Japanese Patent Application Laid-Open No. 01-217077, Japanese Patent Application Laid-Open No. 03-009961, and Japanese Patent Application Laid-Open No. 03-026767 No. 03-153780, Japanese No. 03-045662, No. 04-285669, No. 06-145546, No. 06-212088, No. 06-240158, Japanese Patent Laid-Open No. 10-030063, Japanese Patent Laid-Open No. 10-195326, Paragraphs 0086 to 0098 of International Publication No. 2011/024896, Paragraphs 0063 to 0094 of International Publication No. 2012/102399, and International Publication No. 2017/038252 Paragraph 0082, Paragraph 0171 of Japanese Patent Application Laid-Open No. 2015-151530, Paragraphs 0162 to 0183 of Japanese Patent Application Laid-Open No. 2011-252065, Japanese Patent Application Laid-Open No. 2003-081972, Japanese Patent Application No. 5299151, Japanese Patent Application Laid-Open No. 2015-172732, Japan JP 2014-199308, JP 2014-085562, JP 2014-035351, JP 2008-081565, JP 2019-109512, JP 2019-133154 compound.

The content of the pigment derivative is preferably 0.1 to 30 parts by mass relative to 100 parts by mass of the pigment. The lower limit of the range is more preferably 0.25 parts by mass or more, more preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and still more preferably 1 part by mass or more. Moreover, the upper limit of this range is more preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content of the pigment derivative is within the above range, there is an effect that the stability over time is further improved. Only one type of pigment derivatives may be used, or two or more types may be used in combination. When using 2 or more types together, it is preferable that these total amounts fall into the said range.

<<hardening accelerator>> In the coloring composition of the present invention, in order to accelerate the reaction of the polymerizable compound or lower the hardening temperature, a hardening accelerator may be added. As a hardening accelerator, the polyfunctional thiol compound etc. which have two or more mercapto groups in a molecule|numerator are mentioned. The polyfunctional thiol compound can be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably the compound represented by the formula (T1). Formula (T1)

In formula (T1), n represents an integer of 2 to 4, and L represents a 2- to tetravalent linking group. In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and the L series alkylene group having 2 to 12 carbon atoms is particularly preferred.

Further, as the curing accelerator, methylol-based compounds (for example, compounds exemplified as cross-linking agents in paragraph 0246 of JP-A-2015-034963), amines, phosphonium salts, amidine salts, amide compounds ( As mentioned above, for example, the curing agent described in paragraph 0186 of JP 2013-041165 A), alkali generator (eg, the ionic compound described in JP 2014-055114 A), cyanate ester compound (eg, Compounds described in paragraph 0071 of Japanese Patent Laid-Open No. 2012-150180), alkoxysilane compounds (for example, alkoxysilane compounds having an epoxy group described in Japanese Patent Laid-Open No. 2011-253054), onium salts Compounds (for example, compounds exemplified as acid generators in paragraph 0216 of JP 2015-034963 A, compounds described in JP 2009-180949 A) and the like.

When the coloring composition of the present invention contains a hardening accelerator, the content of the hardening accelerator is preferably 0.3 to 8.9 mass %, more preferably 0.8 to 6.4 mass % in the total solid content of the coloring composition.

＜＜Silane coupling agent＞＞ The coloring composition of this invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two functional groups having different reactivity in one molecule is preferable. The silane coupling agent has at least one group selected from the group consisting of vinyl group, epoxy group, styryl group, methacrylic group, amine group, triisocyanate group, urea group, mercapto group, thioether group and isocyanate group Silane compounds of radicals and alkoxy groups are preferred. Specific examples of the silane coupling agent include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., KBM-602) , N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., KBM-603), 3-aminopropyltrimethoxysilane ( manufactured by Shin-Etsu Chemical Co., LTD., KBM-903), 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., KBE-903), 3-methacrylonitrile Oxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., KBM-503), 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., KBM-403) etc. For details of the silane coupling agent, the descriptions in paragraphs 0155 to 0158 of JP-A No. 2013-254047 can be referred to, and the contents are incorporated in this specification. When the coloring composition of the present invention contains a silane coupling agent, in the total solid content of the coloring composition, the content of the silane coupling agent is preferably 0.001 to 20 mass %, more preferably 0.01 to 10 mass %, and 0.1 mass % % to 5% by mass is particularly preferred. The coloring composition of this invention may contain only 1 type of silane coupling agent, and may contain 2 or more types. When two or more types are included, it is preferable that these total amounts fall into the said range.

＜＜Polymerization inhibitor＞＞ The coloring composition of this invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4' - Thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), N-nitrosophenyl Hydroxylamine salts (ammonium salts, cerous salts, etc.), etc. When the coloring composition of this invention contains a polymerization inhibitor, it is preferable that content of a polymerization inhibitor is 0.0001-5 mass % in the total solid content of a coloring composition. The coloring composition of this invention may contain only 1 type of polymerization inhibitor, and may contain 2 or more types. When two or more types are included, it is preferable that these total amounts fall into the said range.

＜＜UV Absorber＞＞ The coloring composition of this invention can contain an ultraviolet absorber. As the ultraviolet absorber, conjugated diene compounds, aminodiene compounds, salicylic acid compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazole compounds, indole compounds, and triazole compounds can be used. 𠯤 Compounds, etc. For such details, reference can be made to the descriptions in paragraphs 0052 to 0072 of JP 2012-208374 A, paragraphs 0317 to 0334 of JP 2013-068814 A, and paragraphs 0061 to 0080 of JP 2016-162946 A. And these contents are incorporated into this specification. As a commercial item of an ultraviolet absorber, UV-503 (made by DAITO CHEMICAL CO., LTD.) etc. are mentioned, for example. Moreover, as a benzotriazole compound, the MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by MIYOSHI OIL & FAT CO., LTD. can be mentioned. In addition, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used. When the coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and 0.1 to 5% by mass. 3 mass % is particularly preferred. Moreover, only 1 type may be used for an ultraviolet absorber, and 2 or more types may be used for it. When using 2 or more types, it is preferable that these total amounts fall into the said range.

＜＜Surfactant＞＞ The coloring composition of this invention can contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used. As for the surfactant, the surfactants described in paragraphs 0238 to 0245 of International Publication No. WO 2015/166779 can be mentioned, and the contents are incorporated in the present specification.

The surfactant is preferably a fluorine-based surfactant. By containing the fluorine-based surfactant in the coloring composition, the liquid properties (especially the fluidity) are further improved, and the liquid saving property can be further improved. In addition, a film with less uneven thickness can be formed.

The fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. The fluorine-based surfactant having the fluorine content in this range is effective from the viewpoints of the thickness uniformity of the coating film and the liquid saving property, and also has good solubility in the coloring composition.

As the fluorine-based surfactant, the surfactants described in paragraphs 0060 to 0064 of JP 2014-041318 A (corresponding to paragraphs 0060 to 0064 of WO 2014/017669 A), and paragraphs of JP 2011-132503 The surfactants described in 0117 to 0132 and the surfactants described in Japanese Patent Laid-Open No. 2020-008634 are incorporated into this specification. Commercially available fluorine-based surfactants include Megaface F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F -437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F -561, F-563, F-565, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40, R-40-LM, R-41, R-41 -LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited) , Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Inc.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA Solutions Inc.), Ftergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, FTX-218, (above, Neos Corporation system) etc.

In addition, as the fluorine-based surfactant, an acrylic compound can also be preferably used. The acrylic compound has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cleaved and the fluorine atom is removed. volatilize. Examples of such fluorine-based surfactants include MEGAFACE DS series manufactured by DIC Corporation (Chemical Industry Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, MEGAFACE DS-21 .

In addition, as the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. Such a fluorine-based surfactant may, for example, be the fluorine-based surfactant described in JP 2016-216602 A, the contents of which are incorporated in this specification.

上述化合物的重量平均分子量較佳為3000～50000，例如為14000。上述化合物中，表示重複單元的比例之%為莫耳%。As the fluorine-based surfactant, a block polymer can also be used. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound, the fluorine-containing polymer compound comprising: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; The repeating unit of the (meth)acrylate compound of preferably 5 or more) alkeneoxy group (preferably etheneoxy group and propoxy group). In addition, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of Japanese Patent Laid-Open No. 2010-032698 and the following compounds are also exemplified as fluorine-based surfactants used in the present invention.

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, for example, 14,000. In the above-mentioned compounds, the % indicating the ratio of repeating units is mol%.

Moreover, the fluorine-containing polymer which has a group containing an ethylenically unsaturated bond in a side chain can also be used for a fluorine-type surfactant. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A, MEGAFACE RS-101, RS-102, RS-718K, and RS-72- manufactured by DIC Corporation. K et al. Moreover, the compound described in the paragraphs 0015-0158 of Unexamined-Japanese-Patent No. 2015-117327 can also be used as a fluorine-type surfactant.

Moreover, from the viewpoint of environmental management, it is also preferable to use the surfactant described in International Publication No. WO 2020/084854 in place of the surfactant having a perfluoroalkyl group having 6 or more carbon atoms.

在式(fi-1)中，m表示1或2，n表示1～4的整數，α表示1或2，X^α+ 表示α價的金屬離子、第1級銨離子、第2級銨離子、第3級銨離子、第4級銨離子或NH₄ ⁺ 。Moreover, it is also preferable to use the fluorine-containing imide salt compound represented by formula (fi-1) as a surfactant.

In formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, α represents 1 or 2, and X ^α+ represents an α-valent metal ion, first-order ammonium ion, and second-order ammonium ion , 3rd order ammonium ion, 4th order ammonium ion or NH ₄ ⁺ .

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate). bases, glycerol ethoxylates, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylbenzene base ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF Corporation), Solsperse 20000 (manufactured by Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.) and the like.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co. , Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, made by Momentive Performance Materials Inc.), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Chemical Co., LTD. manufactured), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (above, manufactured by BYK-Chemie Corporation), FZ-2122 (Dow manufactured by Toray Co., Ltd.) etc.

Moreover, the compound of the following structure can also be used for a silicone type surfactant.

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001 to 5.0 mass %, more preferably 0.005 to 3.0 mass %. Only one type of surfactant may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount of these be in the above-mentioned range.

＜＜Other additives＞＞ In the coloring composition of the present invention, various additives such as fillers, adhesion promoters, antioxidants, anti-agglomeration agents, and the like can be blended as necessary. As such additives, the additives described in paragraphs 0155 to 0156 of JP-A No. 2004-295116 can be mentioned, and the contents are incorporated in this specification. Moreover, as an antioxidant, a phenol compound, a phosphorus compound (for example, the compound described in the paragraph 0042 of Unexamined-Japanese-Patent No. 2011-090147), a thioether compound, etc. can be used, for example. Examples of commercially available products include Adekastab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330 manufactured by ADEKA CORPORATION) Wait). In addition, as antioxidants, the polyfunctional hindered amine antioxidants described in International Publication No. 2017/006600, the antioxidants described in International Publication No. 2017/164024, and paragraphs 0023 to 0023 of Japanese Patent No. 6268967 can also be used. Antioxidants described in 0048. Only one type of antioxidant may be used, or two or more types may be used. Moreover, the coloring composition of this invention may contain a latent antioxidant as needed. As potential antioxidants, compounds in which the sites functioning as antioxidants are protected by protective groups, and the protective groups are protected by heating at 100 to 250°C or in the presence of acid/base catalysts at 80 to 200°C can be exemplified. Compounds that dissociate upon heating and function as antioxidants. Specific examples of potential antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A No. 2017-008219. As a commercial item, ADEKA ARKLS GPA-5001 (made by ADEKA CORPORATION) etc. are mentioned. Furthermore, the coloring composition of the present invention can contain the sensitizers and light stabilizers described in paragraph 0078 of JP-A No. 2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of JP-A No. 2004-295116 , the storage stabilizer described in paragraph 0242 of Japanese Patent Laid-Open No. 2018-091940.

From the viewpoint of environmental regulations, the use of perfluoroalkylsulfonic acid and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof is restricted. In the coloring composition of the present invention, when the content of the above-mentioned compound is reduced, perfluoroalkanesulfonic acid (especially perfluoroalkanesulfonic acid having a perfluoroalkyl group of 6 to 8 carbon atoms) and salts thereof, And the content ratio of perfluoroalkyl carboxylic acid (especially perfluoroalkyl carboxylic acid having 6 to 8 carbon atoms in perfluoroalkyl group) and its salt is 0.01 ppb to 1 with respect to the total solid content of the coloring composition, The range of 000 ppb is preferable, the range of 0.05 ppb to 500 ppb is more preferable, and the range of 0.1 ppb to 300 ppb is further preferable. The coloring composition of the present invention may not substantially contain perfluoroalkyl sulfonic acid and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof. For example, by using compounds that can replace perfluoroalkanesulfonic acid and salts thereof, and compounds that can replace perfluoroalkanecarboxylic acid and salts thereof, it is possible to select substantially no perfluoroalkanesulfonic acid and salts thereof, and coloring compositions of perfluoroalkyl carboxylic acids and their salts. Examples of compounds that can be substituted for the regulated compounds include compounds excluded from regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and salts thereof, and perfluoroalkylcarboxylic acids and salts thereof. The coloring composition of the present invention may contain perfluoroalkyl sulfonic acid and its salts, and perfluoroalkyl carboxylic acids and its salts within the maximum allowable range.

<Accommodating container> There is no restriction|limiting in particular as a container of the coloring composition of this invention, A well-known container can be used. In addition, as the container, in order to suppress the contamination of impurities into the raw material and the coloring composition, it is also preferable to use a multi-layer bottle in which the inner wall of the container is composed of six kinds of resins with six layers, or a bottle with six kinds of resins in a seven-layer structure. As such a container, the container described in Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example. In addition, in order to prevent elution of metal from the inner wall of the container, improve the storage stability of the composition, or suppress the deterioration of components, it is also preferable that the inner wall of the container is made of glass or stainless steel.

<Manufacturing method of coloring composition> The coloring composition of this invention can be manufactured by mixing the said components. When producing the coloring composition, all the components may be dissolved and/or dispersed in a solvent at the same time to produce the coloring composition, and if necessary, each component may be appropriately used as two or more solutions or dispersions, and when used (At the time of coating) These are mixed to manufacture a colored composition.

Moreover, when manufacturing a coloring composition, the process of dispersing a pigment may be included. In the process of dispersing the pigment, the mechanical force for dispersing the pigment includes compression, extrusion, impact, shearing, pitting, and the like. Specific examples of such procedures include bead milling, sand milling, roll milling, ball milling, paint stirring, microjet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, and the like. Further, in the grinding of the pigment by sand grinding (bead grinding), it is preferable to carry out the treatment under the conditions that the grinding efficiency can be improved by using microbeads with a small diameter and increasing the filling rate of the microbeads. In addition, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Also, regarding the procedure and dispersing machine for dispersing the pigment, "Complete Collection of Dispersion Technology, Published by JOHOKIKO CO., LTD., July 15, 2005" or "To surround the suspension (solid/liquid dispersion system) can be preferably used. ) is the center's comprehensive collection of dispersion technology and industrial applications, issued by the Publishing Department of the Management Development Center, "October 10, 1978", the program and dispersion machine described in paragraph 0022 of Japanese Patent Laid-Open No. 2015-157893. In addition, in the process of dispersing the pigment, the micronization of the particles can be performed by a salt milling process. The raw materials, equipment, processing conditions, etc. used in the salt milling process can be referred to, for example, the descriptions of Japanese Patent Laid-Open No. 2015-194521 and Japanese Patent Laid-Open No. 2012-046629.

When producing a coloring composition, it is preferable to filter the coloring composition with a filter in order to remove foreign matter, reduce defects, and the like. As a filter, it can be used without a restriction|limiting in particular, as long as it is a filter conventionally used for filtration applications, etc. For example, fluorine resins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (for example, nylon-6, nylon-6,6), polyethylene, polypropylene ( PP) and other polyolefin resins (including high-density, ultra-high molecular weight polyolefin resins) and other materials. Among these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. As long as the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. The pore size value of the filter can be referred to the nominal value of the filter manufacturer. As filters, various filters provided by NIHON PALL LTD. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantec Toyo Kaisha, Ltd., Japan Entegris Inc. (formerly Japan Microlis Co., Ltd.), and KITZ MICRO FILTER CORPORATION, etc., can be used .

Moreover, it is also preferable to use a fibrous filter medium as a filter. As a fibrous filter medium, polypropylene fiber, nylon fiber, glass fiber, etc. are mentioned, for example. Commercially available products include SBP-type series (SBP008, etc.), TPR-type series (TPR002, TPR005, etc.), and SHPX-type series (SHPX003, etc.) manufactured by ROKI TECHNO CO., LTD. When using filters, you can combine different filters (eg, 1st filter, 2nd filter, etc.). At this time, the filtration with each filter may be performed only once, or may be performed twice or more. Also, filters of different pore sizes may be combined within the above-mentioned range. In addition, only the dispersion liquid may be filtered using the first filter, and other components may be mixed and then filtered using the second filter.

＜Curing film＞ The cured film of this invention is a film obtained by hardening the above-mentioned coloring composition of this invention. The cured film of the present invention can be used for a color filter or the like. Specifically, it can be preferably used as a coloring layer (pixel) of a color filter, and can be preferably used as a red pixel. Although the film thickness of the cured film of this invention can be adjusted suitably according to the objective, 0.5-3.0 micrometers is preferable. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and even more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.8 μm or less.

<Method for forming a cured film> Next, the formation method of a cured film is demonstrated. The method for forming the cured film preferably includes the following processes: a process of coating the coloring composition of the present invention on a support to form a coloring composition layer; a process of exposing the coloring composition layer (exposure process); and A process of heat-treating the exposed coloring composition layer (post-baking process). Moreover, in the case of forming a patterned cured film (pixel), in the above-mentioned exposure process, the coloring composition layer is exposed in a pattern, and between the exposure process and the post-baking process, the coloring after exposure is further included. A process (development process) in which the composition layer is developed is preferred.

When forming a cured film, in this invention, it is preferable to carry out at the temperature below 150 degreeC in the whole process. In addition, in the present invention, "performing at a temperature of 150° C. or lower throughout the entire process" means that all the processes of forming a cured film using the coloring composition are performed at a temperature of 150° C. or lower. It means that in the case of setting a heating process after developing the exposed coloring composition layer, the heating process is also performed at a temperature below 150°C. The details of each process are described below.

In the process of forming the coloring composition layer, the coloring composition of the present invention is coated on the support to form the coloring composition layer. As a support body, a glass substrate, a resin substrate, etc. are mentioned. As the resin substrate, a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamide imide substrate, a polyimide substrate, and the like can be mentioned. An organic light-emitting layer may be formed on these substrates. In addition, a silicon substrate can also be used on the support. A charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, and the like can be formed on the silicon substrate. Also, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the surface of the substrate, a base layer may be provided on the support. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. Moreover, when measuring with water, 30-80 degrees are preferable. When the surface contact angle of the base layer is within the above-mentioned range, the coating properties of the coloring composition are favorable. The adjustment of the surface contact angle of the base layer can be performed, for example, by adding a surfactant or the like. The base layer can be formed using a composition obtained by removing a colorant from the coloring composition described in this specification, a composition containing a resin, a polymerizable compound, a surfactant and the like described in this specification, and the like.

A known method can be used for the coating method of the coloring composition. A drop coating method (drop casting); a slot coating method; a spray method; a roll coating method; a spin coating method (spin coating); a casting coating method; a slit spin coating method; The method described in Japanese Patent Laid-Open No. 2009-145395); inkjet (for example, on-demand method, piezoelectric method, thermal method), ejection system printing such as nozzle jetting, flexographic printing, screen printing, gravure printing, reverse offset Various printing methods such as printing and metal mask printing; transfer printing using molds, etc.; nanoimprinting, etc. The applicable method in inkjet is not particularly limited, for example, "Inkjet that can be promoted and used - Infinite Possibilities Seen in Patent-, Issued in February 2005, Sumitbe Techon Research Co., Ltd." methods (especially pages 115 to 133) or Japanese Patent Laid-Open No. 2003-262716, Japanese Patent Laid-Open No. 2003-185831, Japanese Patent Laid-Open No. 2003-261827, The method described in No. 169325 et al. In addition, regarding the coating method of a colored composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in this specification.

The coloring composition layer formed on the support may be dried (pre-baked). In the case of pre-baking, the pre-baking temperature is preferably 80°C or lower, more preferably 70°C or lower, further preferably 60°C or lower, and particularly preferably 50°C or lower. The lower limit can be, for example, 40°C or higher. The pre-baking time is preferably 10 to 3600 seconds. The prebaking can be performed with a hot plate, an oven, or the like.

Next, the coloring composition layer is exposed to light (exposure process). For example, a coloring composition layer can be exposed using a stepper, a scanning exposure machine, or the like. When forming a patterned cured film (pixel), the coloring composition layer is exposed in a pattern. For example, the colored composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern. Thereby, the exposed part can be hardened.

Examples of light that can be used during exposure include ultraviolet rays such as g-rays (wavelength: 436 nm) and i-rays (wavelength: 365 nm). As described in Korean Laid-Open Patent Publication No. 1020170122130, exposure using i-rays can be performed while cutting off light having a wavelength shorter than that of i-rays. In addition, light with a wavelength of 300 nm or less (preferably, light with a wavelength of 180 to 300 nm) may be used. As light with a wavelength of 300 nm or less, KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), etc. are exemplified, and KrF rays (wavelength 248 nm) are preferred. In addition, a long-wavelength light source of 300 nm or more can also be used.

In addition, at the time of exposure, light may be continuously irradiated for exposure, or pulsed exposure may be performed (pulse exposure). In addition, the pulse exposure refers to an exposure method in which exposure is performed by repeating light irradiation and pausing in a cycle of a short time (eg, milliseconds or less).

The irradiation dose (exposure dose) is, for example, preferably 0.03 to 2.5 J/cm ² , more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed in the atmosphere, for example, a hypoxic environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially no oxygen) can be used. Exposure may be performed under a high oxygen environment with an oxygen concentration exceeding 21 vol % (eg, 22 vol %, 30 vol %, or 50 vol %). In addition, the exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m ² to 100000 W/m ² (for example, 5000 W/m ² , 15000 W/m ² or 35000 W/m ² ). The oxygen concentration and the exposure illuminance can be appropriately combined conditions, for example, oxygen concentration of 10 vol % and illuminance of 10000 W/m ² , oxygen concentration of 35 vol % and illuminance of 20000 W/m ² , and the like.

In the formation method of a cured film, it is also preferable to develop the coloring composition layer after exposure. In particular, in the exposure process, when the coloring composition layer is exposed in a pattern, the exposed coloring composition layer is developed, thereby developing and removing the unexposed portion of the coloring composition layer and forming a cured film. Pixels are formed in a pattern. The development and removal of the unexposed portion of the colored composition layer can be performed using a developing solution. Thereby, the coloring composition layer of the unexposed part in the exposure process is dissolved in the developing solution, and only the photohardened part remains. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal property, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

As a developing solution, an organic solvent, an alkali developing solution, etc. are mentioned, An alkali developing solution is preferable. As the alkali developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkali agent with pure water is preferable. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethylhydroxide Ammonium, Tetrapropylammonium Hydroxide, Tetrabutylammonium Hydroxide, Ethyltrimethylammonium Hydroxide, Benzyltrimethylammonium Hydroxide, Dimethylbis(2-hydroxyethyl)ammonium Hydroxide, Cholesterol Base, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene and other organic basic compounds, or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, Inorganic basic compounds such as sodium silicate and sodium metasilicate. In terms of environment and safety, the alkaline agent is preferably a compound with a large molecular weight. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. In addition, the developer may contain a surfactant. As a surfactant, the above-mentioned surfactant is mentioned, and a nonionic surfactant is preferable. From the viewpoint of convenient transportation and storage, the developer can be temporarily prepared as a concentrated solution, and can be diluted to a desired concentration at the time of use. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. Moreover, it is also preferable to wash (rinse) with pure water after image development. Moreover, it is preferable to perform rinsing by supplying a rinse liquid to the coloring composition layer after development, rotating the support body in which the coloring composition layer after development was formed. Moreover, it is also preferable to carry out by moving the nozzle which discharges a rinse liquid from the center part of a support body to the peripheral part of a support body. At this time, when moving from the center portion of the support body of the nozzle to the peripheral portion, the nozzle can be moved while gradually reducing the moving speed. By performing rinsing in this manner, in-plane variation in rinsing can be suppressed. Also, the same effect can be obtained by gradually reducing the rotational speed of the support body while moving the nozzle from the center portion of the support body to the peripheral portion.

After image development, it is also preferable to perform additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure processing and post-baking are hardening processing after development for making a fully hardened one.

In the case of post-baking, the heating temperature is preferably 150° C. or lower. The upper limit of the heating temperature is more preferably 120°C or lower, and even more preferably 100°C or lower. The lower limit of the heating temperature is not particularly limited as long as the hardening of the composition can be accelerated, but it is more preferably 50°C or higher, and even more preferably 75°C or higher. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, and even more preferably 10 minutes or more. The upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 20 minutes or less. It is also preferable to carry out the post-baking in an atmosphere of an inert gas. According to this aspect, thermal polymerization can be carried out with very high efficiency without being hindered by oxygen, and even when a pixel is produced at a temperature of 120° C. or lower in the entire process, characteristics such as good flatness and solvent resistance can be produced. Excellent pixels. As an inert gas, nitrogen gas, argon gas, helium gas, etc. are mentioned, nitrogen gas is preferable. The oxygen concentration at the time of post-baking is preferably 100 ppm or less.

When performing an additional exposure process, it is preferable to irradiate the light of wavelength 254-350nm, and perform exposure. As a more preferable aspect, in the process of exposing the coloring composition layer in a pattern (exposure before development), the coloring composition layer is irradiated with light having a wavelength exceeding 350 nm and 380 nm or less (preferably a wavelength of 355 to 370 nm). light, more preferably i-ray), is exposed, and in the additional exposure treatment (exposure after development), the developed coloring composition layer is irradiated with light with a wavelength of 254 to 350 nm (preferably with light with a wavelength of 254 nm). Exposure is better. According to this aspect, the coloring composition layer can be appropriately hardened by the first exposure (exposure before development), and the entire coloring composition layer can be hardened almost completely by the next exposure (exposure after development), As a result, even under low temperature conditions, the colored composition layer can be sufficiently cured, and a pixel excellent in characteristics such as solvent resistance, adhesion, and pattern squareness can be formed. As described above, when exposure is performed in two steps, in the coloring composition, as a photopolymerization initiator, a photopolymerization initiator containing an absorption coefficient of 1.0×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol is used. A photopolymerization initiator having an absorption coefficient at a wavelength of 365 nm in methanol of 1.0×10 ² mL/gcm or less and an absorption coefficient at a wavelength of 254 nm of 1.0×10 ³ mL/gcm or more is preferable.

The exposure after image development can be performed, for example, using an ultraviolet photoresist curing apparatus. For example, light having a wavelength of 254 to 350 nm and other light (for example, i-rays) can be irradiated from an ultraviolet photoresist curing device.

The exposure amount (irradiation amount) under exposure after development is preferably 30 to 4000 mJ/cm ² , and more preferably 50 to 3500 mJ/cm ² . The difference between the wavelength of light used for exposure before development and the wavelength of light used for exposure after development is preferably 200 nm or less, and more preferably 100 to 150 nm.

＜Color filter＞ Next, the color filter of the present invention will be described. The color filter of this invention has the said cured film of this invention. It is preferable that it is a colored pixel as a color filter, and it is more preferable that it has the cured film of this invention as a red pixel.

In addition to the pixel of the cured film of the present invention, the color filter of the present invention is preferably a colored pixel having another hue. Examples of colored pixels of other hues include blue pixels, green pixels, yellow pixels, magenta pixels, cyan pixels, and the like. As a preferable aspect of the color filter of this invention, the aspect which has the red pixel which consists of the cured film of this invention, a green pixel, and a blue pixel is mentioned.

The coloring composition for blue pixel formation preferably used in combination with the pixel of the cured film of the present invention is the maximum value A ^max11 of the absorbance for light with a wavelength of 400 to 450 nm and the minimum value of the absorbance for light with a wavelength of 475 to 575 nm. The ratio of A ^min12 A ^max11 /A ^min11 is preferably 15 or more, more preferably 20 or more, and even more preferably 25 or more.

Moreover, when the absorbance to light having a wavelength of 450 nm shown by the coloring composition for forming a green pixel is set to 1, the wavelength at which the absorbance becomes 0.3 preferably exists in the range of 455 to 505 nm, and preferably exists in the range of 460 to 500 nm It is more preferable to exist in the range of 465-495 nm, and it is especially preferable to exist in the range of 470-490 nm.

The coloring composition for blue pixel formation preferably used in combination with the pixel of the cured film of the present invention is the maximum value A ^max21 of the absorbance for light with a wavelength of 550 to 650 nm and the minimum value of the absorbance for light with a wavelength of 400 to 500 nm. The ratio of A ^{min21 to A max21 /} A ^min21 is preferably 10 or more, more preferably 12.5 or more, and even more preferably 15 or more.

Furthermore, when the absorbance to light having a wavelength of 600 nm shown by the coloring composition for forming a blue pixel is set to 1, the wavelength having absorbance of 0.3 preferably exists in the range of 475 to 555 nm, and preferably exists in the range of 480 to 540 nm. It is more preferable to exist in the range of 485-525 nm, and it is especially preferable to exist in the range of 490-510 nm.

The color filter of the present invention can be used for a display device, a solid-state imaging element such as a CCD (Charge Coupled Device), a CMOS (Complementary Metal Oxide Semiconductor), or the like.

In the color filter of this invention, although the film thickness of the cured film of this invention can be adjusted suitably according to the objective, 0.5-3.0 micrometers is preferable. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and even more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.8 μm or less.

In the color filter of the present invention, the line width (pattern size) of the pixels is preferably 2.0 to 10.0 μm. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and even more preferably 2.75 μm or more.

In the color filter of the present invention, a protective layer may be provided on the surface of the cured film of the present invention. By providing the protective layer, various functions such as oxidation resistance, low reflection, hydrophilicity and hydrophobicity, and shielding of specific wavelengths of light (ultraviolet rays, near-infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. As a method of forming the protective layer, a method of forming by coating a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of attaching the formed resin with an adhesive material, etc. are mentioned. Examples of components constituting the protective layer include (meth)acrylic resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polystyrene resins, polyether resins, polyphenylene resins, polyamide resins Arylene ether phosphine oxide resin, polyimide resin, polyimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, Melamine resin, urethane resin, aromatic polyamide resin, polyamide resin, alkyd resin, epoxy resin, modified polysiloxane resin, fluorine resin, polycarbonate resin, polyacrylonitrile resin, cellulose resin , Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ , etc., and may contain two or more of these components. For example, in the case of the protective layer for the purpose of blocking oxygen, the protective layer preferably contains polyol resin, SiO ₂ and Si ₂ N ₄ . Moreover, in the case of the protective layer used for low reflection, it is preferable that the protective layer contains a (meth)acrylic resin and a fluororesin.

When a resin composition is applied to form a protective layer, known methods such as spin coating, casting, screen printing, and inkjet method can be used as a method for applying the resin composition. As the organic solvent contained in the resin composition, a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by chemical vapor deposition, known chemical vapor deposition methods (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition, etc.) can be used as the chemical vapor deposition method. phase deposition method).

The protective layer may also contain additives such as organic fine particles, inorganic fine particles, light absorbers of specific wavelengths (eg, ultraviolet, near-infrared, etc.), refractive index modifiers, antioxidants, adhesives, and surfactants, as required. Examples of organic fine particles include polymer fine particles (for example, polysiloxane fine particles, polystyrene fine particles, melamine resin fine particles), and examples of inorganic fine particles include titanium oxide, zinc oxide, zirconium oxide, indium oxide, Alumina, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silicon dioxide, silicon dioxide, calcium carbonate, barium sulfate, etc. As the absorber of light of a specific wavelength, a known absorber can be used. Although content of these additives can be adjusted suitably, 0.1-70 mass % is preferable with respect to the total mass of a protective layer, and 1-60 mass % is more preferable.

Moreover, as a protective layer, the protective layer described in the paragraphs 0073-0092 of Unexamined-Japanese-Patent No. 2017-151176 can also be used.

The color filter may have a base layer. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. Moreover, when measuring with water, 30-80 degrees are preferable. When the surface contact angle of the base layer is within the above-mentioned range, the coating properties of the coloring composition are favorable. The adjustment of the surface contact angle of the base layer can be performed, for example, by adding a surfactant or the like.

The color filter may have a structure in which each coloring pixel is embedded in a space partitioned by a partition wall, for example, in a lattice shape.

<Display device> The image display device of this invention has the above-mentioned cured film of this invention. As a display device, a liquid crystal display device, an organic electroluminescence display device, etc. are mentioned. The definition of a display device or the details of each display device are described in, for example, "Electronic Display Devices (Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)", "Display Devices (Ibuki Junsho, Sangyo Tosho Publishing Co., Ltd., issued in 1989)" etc. In addition, the liquid crystal display device is described in, for example, "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., published in 1994)." The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, it can be applied to liquid crystal display devices of various types described in the above-mentioned "Next Generation Liquid Crystal Display Technology".

The organic electroluminescence display device may be one having a light source composed of white organic electroluminescence elements. As a white organic electroluminescence element, a tandem structure is preferable. Regarding the tandem structure of organic electroluminescence elements, it is described in Japanese Patent Application Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Frontline of Organic EL Technology Development - High Brightness, High Precision, Long Life, and Collection of Techniques-", Technical Information Institute Co., Ltd., pp. 326-328, 2008, etc. The spectrum of the white light emitted by the organic EL element has strong maximum emission peaks in the blue region (430 nm to 485 nm), the green region (530 nm to 580 nm), and the yellow region (580 nm to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm to 700 nm) are more preferable. [Example]

Hereinafter, an Example is given and this invention is demonstrated concretely. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

<Measurement of weight average molecular weight (Mw)> The weight average molecular weight (Mw) of the measurement sample was measured by gel permeation chromatography (GPC) under the following conditions. Type of column: A column formed by connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000 Developing solvent: tetrahydrofuran Column temperature: 40℃ Flow rate (sample injection amount): 1.0 μL (sample concentration: 0.1 mass %) Device name: HLC-8220GPC manufactured by TOSOH CORPORATION Detector: RI (Refractive Index) detector Calibration Curve Base Resin: Polystyrene Resin

<Preparation of colorant solution> After uniformly stirring and mixing the raw materials described in the following table, dispersion was carried out for 5 hours with an EIGER mill (“Mini Model M-250MKII” manufactured by EIGER Japan) using zirconia beads having a diameter of 1 mm. Then, the colorant solutions P-R1, P-R2, P-R3, P-R4, P-R5, and P-RC1 were prepared by filtering with a filter having a pore diameter of 5 μm. In the following table, the blending amount of each raw material is shown in parts by mass. An empty column means not included.

Table 1 colorant solution P-R1 P-R2 P-R3 P-R4 P-R5 P-Rc1 red colorant PR177 10.5 8.41 5.25 PR264 10.5 PR269 10.5 PR254 5.25 PR7 5.95 yellow colorant PY139 1.04 3.13 1.04 1.04 1.04 5.59 Dispersant 1 2.29 2.29 2.29 2.29 2.29 2.29 Dispersant 2 7.66 7.66 7.66 7.66 7.66 7.66 Pigment Derivative 1 2.69 2.69 2.69 2.69 2.69 2.69 Cyclohexanone 75.82 75.82 75.82 75.82 75.82 75.82

The raw materials indicated by the abbreviations in the table are as follows. (red colorant) PR177: C.I.Pigment Red 177 (red pigment) PR264: C.I.Pigment Red 264 (red pigment) PR269: C.I.Pigment Red 269 (red pigment) PR254: C.I.Pigment Red 254 (red pigment) PR7: C.I.Pigment Red 7 (red pigment)

(yellow colorant) PY139: C.I.Pigment Yellow 139 (yellow pigment)

(Dispersant) Dispersant 1: Solsperse 20000 (manufactured by The Lubrizol Corporation) Dispersant 2: Resin solution D2 prepared by the following method 90.0 parts by mass of cyclohexanone was placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux cooler, and a gas introduction tube, and the vessel was heated to 60° C. while injecting nitrogen gas, and was added dropwise at the same temperature over 2 hours. 20.0 parts by mass of methacrylic acid, 10.0 parts by mass of methyl methacrylate, 55.0 parts by mass of n-butyl methacrylate, 15 parts by mass of benzyl methacrylate, and 2.5 parts by mass of 2,2'-azobisisobutyronitrile mixture and polymerized. After the dropwise addition was completed, and further reacted at 60° C. for 1 hour, 0.5 parts by mass of 2,2′-azobisisobutyronitrile was dissolved in 10.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) to be added. Then, stirring was continued at the same temperature for 3 hours to obtain a resin (copolymer). After cooling to room temperature, it diluted with cyclohexanone, and obtained the resin solution D2 of 20% of solid content concentration. The weight average molecular weight of the obtained resin (copolymer) was 30,000.

(Pigment Derivative) Pigment Derivative 1: Compound of the following structure

<Preparation of coloring composition> The raw materials shown below were mixed and stirred, and then filtered using a nylon filter (manufactured by Nihon Pall Ltd.) having a pore diameter of 0.45 μm to prepare a colored composition.

Table 2 colorant solution photopolymerization initiator resin solution polymeric compound solvent type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) type Content (mass parts) Example 1 P-R1 65 I-1 2 A-1 5.5 M-1 2.6 S-1 19.4 Example 2 P-R2 65 I-1 2 A-1 5.5 M-1 2.6 S-1 19.4 Example 3 P-R3 65 I-1 2 A-1 5.5 M-1 2.6 S-1 19.4 Example 4 P-R4 65 I-1 2 A-1 5.5 M-1 2.6 S-1 19.4 Example 5 P-R5 65 I-1 2 A-1 5.5 M-1 2.6 S-1 19.4 Example 6 P-R1 65 I-1 2 A-2 5.5 M-1 2.6 S-1 19.4 Example 7 P-R1 65 I-1 2 A-3 5.5 M-1 2.6 S-1 19.4 Example 8 P-R1 65 I-1 2 A-4 5.5 M-1 2.6 S-1 19.4 Example 9 P-R1 65 I-1 2 A-5 5.5 M-1 2.6 S-1 19.4 Example 10 P-R1 65 I-1 2 A-6 5.5 M-1 2.6 S-1 19.4 Example 11 P-R1 65 I-1 2 A-7 5.5 M-1 2.6 S-1 19.4 Example 12 P-R1 65 I-1 2 A-8 5.5 M-1 2.6 S-1 19.4 Example 13 P-R1 65 I-1 2 A-9 5.5 M-1 2.6 S-1 19.4 Example 14 P-R1 65 I-1 2 A-10 5.5 M-1 2.6 S-1 19.4 Example 15 P-R1 65 I-1 2 A-11 5.5 M-1 2.6 S-1 19.4 Example 16 P-R1 65 I-1 2 A-1 5.5 M-1 2.6 S-1 S-2 9.7 9.7 Example 17 P-R1 65 I-1 2 A-1 5.5 M-1 M-2 1.3 1.3 S-1 19.4 Example 18 P-R1 65 I-1 2 A-1 5.5 M-3 2.6 S-1 19.4 Example 19 P-R1 65 I-1 I-2 1 1 A-1 5.5 M-1 2.6 S-1 19.4 Example 20 P-R1 65 I-3 2 A-1 5.5 M-1 2.6 S-1 19.4 Example 21 P-R1 65 I-1 2 A-12 5.5 M-1 2.6 S-1 19.4 Comparative Example 1 P-Rc1 65 I-1 2 A-1 5.5 M-1 2.6 S-1 19.4 Comparative Example 2 P-R1 65 I-1 2 D-1 5.5 M-1 2.6 S-1 19.4

The raw materials indicated by the abbreviations in the table are as follows. (colorant solution) P-R1 to P-R5, P-Rc1: colorant solutions P-R1 to P-R5, P-Rc1 prepared above

(Photopolymerization initiator) I-1: Irgacure OXE02 (manufactured by BASF, a compound of the following structure) I-2: Omnirad 2959 (manufactured by IGM Resins BV, a compound of the following structure) I-3: The following structure compound of.

(Resin solution) A-1 to A-9: 40 mass % PGMEA solution of resin of the following structure Resin solution A-1 was prepared by the following method. That is, 207 parts by mass of PGMEA was put into a reaction vessel in which a thermometer, a cooling tube, a nitrogen introduction tube, a drip tube, and a stirring device were attached to a separable 4-neck flask, the temperature was raised to 80° C., and the reaction vessel was built into the reaction vessel. After changing to nitrogen, 16 parts by mass of styrene, 75 parts by mass of glycidyl methacrylate, 2 parts by mass of dicyclopentyl methacrylate, and 10 parts by mass of methyl methacrylate were added dropwise from the dropping tube over 2 hours. and a mixture of 1.33 parts by mass of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for further 3 hours, whereby a resin having the following structure was obtained. After cooling to room temperature, the resin solution A-1 was prepared by diluting with PGMEA to adjust the solid content concentration to 40% by mass. Resin solutions A-2 to A-9 were prepared in the same manner as resin solution A-1, respectively.

A-10: 40 mass % PGMEA solution of resin of the following structure.

A-11: 40 mass % PGMEA solution of the resin of the following structure.

A-12: 40 mass % PGMEA solution of resin of the following structure.

D-1: 40 mass % PGMEA solution of resin of the following structure.

The weight-average molecular weight of each resin, the content of the cyclic ether group, the content of the acid group, and the content of the group in which the acid group is protected by a protecting group are recorded in the following tables, respectively. Moreover, about resin A-1-A-10, A-12, D-1, the value of the ratio of the content of a cyclic ether group with respect to the content of an acid group is described in the content ratio column. In addition, with respect to resin A-11, the value of the ratio of the content of the cyclic ether group to the total content of the acid group and the group in which the acid group is protected by a protective group is described in the content ratio column. table 3 weight average molecular weight Content of cyclic ether group (mmol/g) Content of acid group (mmol/g) The content of the acid group protected by the protecting group (mmol/g) Content ratio A-1 11000 5.33 1.05 0 5.08 A-2 11500 6.33 0.70 0 9.04 A-3 11300 6.33 0.46 0 13.76 A-4 10800 6.33 1.16 0 5.46 A-5 11800 6.68 0.40 0 16.70 A-6 10500 3.50 1.16 0 3.02 A-7 10800 2.52 1.16 0 2.17 A-8 11000 2.52 2.32 0 1.09 A-9 11200 1.41 3.48 0 0.41 A-10 10000 3.95 0.95 0 4.16 A-11 10800 5.33 0.40 0.705 4.82 A-12 9800 3.83 1.25 0 3.06 D-1 10600 3.09 2.28 0 1.36

M-3：NK ESTER A-TMMT（Shin Nakamura Chemical Co., Ltd.製）(Polymerizable compound) M-1: ARONIX M-402 (manufactured by TOAGOSEI CO., LTD., a mixture of bis-pentaerythritol hexaacrylate and bis-pentaerythritol pentaacrylate) M-2: Compound of the following structure (a+b+ c=3)

M-3: NK ESTER A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd.)

(solvent) S-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA) S-2: Propylene Glycol Monomethyl Ether (PGME)

<Evaluation of Spectroscopy> Using a spin coater, each coloring composition was applied on a glass substrate so that the film thickness after drying was 2 μm, and dried on a hot plate at 100° C. for 2 minutes. Next, using an ultra-high pressure mercury lamp, exposure was performed under the conditions of an exposure illuminance of 20 mW/cm ² and an exposure amount of 1 J/cm ² . Then, it heated on the hotplate of 100 degreeC for 20 minutes, and it cooled naturally, and formed the cured film. In the production of the cured film, the temperature of the substrate is in the range of 20-100° C. in the whole process. About the obtained cured film, using an ultraviolet-visible-near-infrared spectrophotometer (UV3600, manufactured by Shimadzu Corporation), a reference source circuit (reference) was used as a glass substrate, and the absorbance of light in the range of wavelength 300 to 800 nm was measured. The ratio A ^max1 /A ^min1 (hereinafter referred to as absorbance ratio 1) of the maximum value A ^max1 of the absorbance of light with a wavelength of 550 to 700 nm and the minimum value A ^min1 of the absorbance of light with a wavelength of 550 to 700 nm, and the absorbance of light with a wavelength of 500 nm When set to 1, the wavelength at which the absorbance becomes 0.3 (hereinafter, referred to as wavelength 1) was measured, respectively.

<Evaluation of color mixing> Using a spin coater, each coloring composition was applied on a glass substrate so that the film thickness after drying was 2 μm, and dried on a hot plate at 100° C. for 2 minutes. Next, using an ultra-high pressure mercury lamp, exposure was performed under the conditions of an exposure illuminance of 20 mW/cm ² and an exposure amount of 100 mJ/cm ² . Next, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), spin-on immersion development was performed on the condition of 23° C. for 60 seconds. Then, it rinsed with a rotary shower, and also rinsed with pure water. Then, it heated on the hotplate of 100 degreeC for 20 minutes, and it cooled naturally, and formed the cured film. Using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.), the transmittance (T1) of light having a wavelength of 450 nm of the obtained cured film was measured. Next, using a spin coater, the cured film was coated with a coloring composition for color mixing evaluation so that the film thickness after drying was 2 μm, and dried on a hot plate at 100° C. for 2 minutes to form a coloring composition for color mixing evaluation. coating film to form a laminated film. As the coloring composition for color mixture evaluation, the blue coloring composition used for formation of the blue pixel of Example 1001 described later was used. Next, the glass substrate on which the laminated film was formed was placed on a horizontal turntable of a spin/shower developer (Model DW-30, manufactured by Chemitronics Co., Ltd.), and a CD-2000 (FUJIFILM Electronic Materials Co., Ltd.) was used. ., Ltd. product) was subjected to spin-on immersion development for 60 seconds at 23° C., and the coating film of the coloring composition for color mixing evaluation formed on the cured film was removed by development. Next, the above-mentioned glass substrate was fixed on a horizontal turntable by a vacuum chuck method, and the glass substrate was rotated at a rotational speed of 50 rpm by a rotating device while supplying pure water in a spray form from a nozzle from above the rotation center to perform the operation. Rinse treatment followed by spray drying. Using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.), the transmittance (T2) of light having a wavelength of 450 nm of the cured film after developing and removing the coating film of the coloring composition for color mixing evaluation was measured. The rate of change in transmittance was calculated according to the following formula, and color mixing was evaluated according to the following evaluation criteria. Change rate of transmittance (%)={|Transmittance(T1)-Transmittance(T2)|/Transmittance(T1)}×100 S: Change rate of transmittance is less than 0.1% A: Change rate of transmittance 0.1% or more and less than 0.25% B: The change rate of transmittance is 0.25% or more and less than 1% C: The change rate of transmittance is 1% or more and less than 2.5% D: The change rate of transmittance is 2.5% or more and less than 5% E: The change rate of transmittance is 5% or more

<Evaluation of Storage Stability> The viscosity (V ₁ ) of the coloring composition obtained immediately after production was measured using “RE-85L” manufactured by TOKI SANGYO CO., LTD. The viscosity (V ₂ ) was measured after the coloring composition was allowed to stand at a temperature of 40° C. for 3 days. The viscosity increase rate was calculated according to the following formula, and the storage stability was evaluated according to the following evaluation criteria. The viscosity of the coloring composition was measured in a state where the temperature was adjusted to 23°C. The evaluation criteria are as follows, and the evaluation results are described in the following table. Viscosity increase rate (%)={(viscosity (V ₂ )-viscosity (V ₁ ))/viscosity (V ₁ )}×100 S: viscosity increase rate is less than 0.1% A: viscosity increase rate is more than 0.1% and less than 0.25 % B: The viscosity increase rate is 0.25% or more and less than 1% C: The viscosity increase rate is 1% or more and less than 2.5% D: The viscosity increase rate is 2.5% or more and less than 5% E: The viscosity increase rate is 5% or more

Table 4 Absorbance ratio 1 Wavelength 1 (nm) mixed color storage stability Example 1 230 589 A A Example 2 195 576 A B Example 3 195 580 A A Example 4 180 577 A B Example 5 170 608 A A Example 6 230 589 A A Example 7 230 589 A B Example 8 230 589 S C Example 9 230 589 B D Example 10 230 589 A B Example 11 230 589 C A Example 12 230 589 B B Example 13 230 589 C B Example 14 230 589 B S Example 15 230 589 B S Example 16 230 589 A A Example 17 230 589 A A Example 18 230 589 A A Example 19 230 589 A A Example 20 230 589 A A Example 21 230 589 B A Comparative Example 1 twenty three 532 A E Comparative Example 2 230 589 E A

As shown in the above table, the examples can achieve both color mixing and storage stability at a high level.

Even when the fluorine-based surfactant or the silicone-based surfactant described in this specification is added to the coloring composition of each example, the same effect can be obtained.

<Example 1001> The green coloring composition was applied on a silicon wafer by spin coating so that the film thickness after film formation was 1.0 μm. Next, using a hotplate, it heated on the condition of 100 degreeC for 2 minutes. Next, using an i-ray stepper FPA-3000i5+ (manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ/cm ² through a mask of a 12 μm square dot pattern. Next, using a 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), spin-on immersion development was performed on the condition of 23° C. for 60 seconds. Then, it rinsed with a rotary shower, and also rinsed with pure water. Next, it heated for 20 minutes on a 100 degreeC hotplate, and it cooled naturally, and formed the green coloring pattern (green pixel). Similarly, the red coloring composition and the blue coloring composition were sequentially patterned, and a red coloring pattern (red pixel) and a blue coloring pattern (blue pixel) were formed, respectively, and a color filter was produced. As the red coloring composition, the coloring composition of Example 1 was used. The green coloring composition and the blue coloring composition will be described later. The obtained color filter is assembled into an organic electroluminescence display device according to a known method. The organic electroluminescence display device has better image recognition capability.

界面活性劑（下述結構的化合物，Mw=14000，表示重複單元的比例之%的數值為莫耳%，氟系界面活性劑）……0.008質量份

丙二醇單甲醚乙酸酯……8.8質量份[Green Coloring Composition] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nihon Pall Ltd.) having a pore diameter of 0.45 μm to prepare a green coloring composition. Green pigment dispersion liquid...85 parts by mass of a photopolymerization initiator (Irgacure OXE02, manufactured by BASF Corporation)...1.04 parts by mass of a photopolymerization initiator (Omnirad 2959, manufactured by IGM Resins BV Corporation)...0.77 parts by mass Resin solution 1...0.9 parts by mass Furan group-containing compound solution 1...1.4 parts by mass polymerizable compound (compound of the following structure)...2.04 parts by mass

Surfactant (compound of the following structure, Mw=14000, the value representing the percentage of repeating units is mol%, fluorine-based surfactant) ...... 0.008 parts by mass

Propylene glycol monomethyl ether acetate...8.8 parts by mass

界面活性劑（KF-6001，Shin-Etsu Chemical Co.,LTD.製造）……0.008質量份 乙酸丁酯……33.2質量份[Blue Colored Composition] The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nihon Pall Ltd.) having a pore diameter of 0.45 μm to prepare a blue colored composition. Blue (blue) pigment dispersion liquid...51.0 parts by mass of a photopolymerization initiator (Irgacure OXE01, manufactured by BASF Corporation)...2.17 parts by mass of a photopolymerization initiator (Omnirad 2959, manufactured by IGM Resins BV Corporation)...0.83 mass Parts of resin solution 1...4.1 parts by mass of furan group-containing compound solution 1...6.2 parts by mass of polymerizable compound (compound of the following structure)...2.5 parts by mass

Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., LTD.)...0.008 parts by mass Butyl acetate...33.2 parts by mass

The Green pigment dispersion liquid, the Blue pigment dispersion liquid, the resin solution 1, and the furan group-containing compound solution 1 used for the preparation of the green coloring composition and the blue coloring composition are as follows.

(Green Pigment Dispersion Liquid) By a bead mill (the diameter of zirconia beads is 0.3 mm), a mixture containing 7.4 parts by mass of CI Pigment Green 36, 5.2 parts by mass of CI Pigment Yellow 185, and 1.4 parts by mass was mixed and dispersed over 3 hours. Pigment dispersion liquid was prepared by a mixed liquid of pigment derivative 1, 4.86 parts by mass of dispersant 1, and 81.14 parts by mass of PGMEA. Then, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism, dispersion treatment was performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion liquid.

分散劑1：下述結構的樹脂。標註在主鏈的括號之數值表示各重複單元的莫耳比，標註在側鏈的括號之數值表示重複單元的重複數。重量平均分子量為24000。

Pigment Derivative 1: Compound of the following structure

Dispersant 1: Resin of the following structure. The numerical value in parentheses in the main chain indicates the molar ratio of each repeating unit, and the numerical value in parentheses in the side chain indicates the number of repetitions of the repeating unit. The weight average molecular weight was 24,000.

(Blue Pigment Dispersion) Mix and disperse 9.5 parts by mass of CIPigment Blue 15:6, 5.0 parts by mass of CIPigment Violet 23, 5.5 parts by mass by a bead mill (the diameter of zirconia beads is 0.3 mm) over 3 hours 1 part of dispersant and 80.0 parts by mass of PGMEA mixed solution to prepare a pigment dispersion. Then, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism, dispersion treatment was performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

(Resin solution 1) 30 mass % PGMEA solution of resin A synthesized by the following method 70.0 parts by mass of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dripping tube, and a stirring device, the temperature was raised to 80° C., and the inside of the flask was replaced with nitrogen, and then added dropwise. 13.3 parts by mass of n-butyl methacrylate, 4.6 parts by mass of 2-hydroxyethyl methacrylate, 4.3 parts by mass of methacrylic acid, p-cumylphenol ethylene oxide modified acrylate (TOAGOSEI CO., LTD. product, ARONIX M110) 7.4 parts by mass and a mixture of 0.4 parts by mass of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was continued for 3 hours to synthesize resin A (Mw=26000) and diluted with PGMEA to obtain a 30 mass % PGMEA solution of resin A.

(Furanyl-containing compound solution 1) 20 mass % PGMEA solution of furan group-containing compound F1 synthesized by the following method 90.0 parts by mass of PGMEA was put into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux cooler, and a gas introduction tube, and the vessel was heated to 60° C. while injecting nitrogen gas, and was added dropwise at the same temperature over 2 hours. 50.0 parts by mass of furfuryl methacrylate, 26.7 parts by mass of 2-methacryloyloxyethylsuccinic acid, 23.3 parts by mass of 2-hydroxyethyl methacrylate, 2,2'-azobis(2,4 - dimethylvaleronitrile) 2.5 parts by mass of the mixture and subjected to a polymerization reaction. After completion of the dropwise addition, and after further reacting on the condition of 60° C. for 1 hour, 0.5 parts by mass of 2,2′-azobis(2,4-dimethylvaleronitrile) was dissolved in 10.0 parts by mass of PGMEA to be added. Then, stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, it diluted with PGMEA, and obtained the 20 mass % PGMEA solution of furan group-containing compound F1 (Mw=52000).

Claims (13)

A coloring composition comprising a colorant containing a red colorant, a resin, a polymerizable compound and a photopolymerization initiator, wherein the resin comprises a resin EP containing a repeating unit A and a repeating unit B, and the repeating unit A has an optional At least one cyclic ether group A in the group represented by the formula (e-1) and the group represented by the formula (e-2), the repeating unit B is selected from the repeating unit B-1 having an acid group and at least one of the repeating units B-2 having an acid group protected by a protecting group, the maximum value Amax1 of the absorbance for light with a wavelength of 400 to 500 nm of the coloring composition and the maximum value ^Amax1 for light with a wavelength of 550 to 700 nm When the ratio A ^max1 /A ^min1 of the minimum value A ^min1 of the absorbance of the light is 25 or more, and when the absorbance of light with a wavelength of 500 nm is set to 1, the wavelength at which the absorbance becomes 0.3 exists in the range of 570 to 620 nm,

In formula (e-1), R ^E1 represents a hydrogen atom or an alkyl group, n represents 0 or 1, * represents a bond, in formula (e-2), ring A ^E1 represents a monocyclic aliphatic hydrocarbon ring, * Represents a bond key. The coloring composition according to claim 1, wherein In the resin EP, the content of the cyclic ether group A is 2.0-6.5 mmol/g, and the total content of the acid group and the content of the acid group protected by the protecting group is 0.45-2.35 mmol/g /g. The coloring composition according to claim 1, wherein The content of the cyclic ether group A, the content of the acid group and the content of the group protected by the protecting group of the resin EP satisfy the conditions of the following formula (1), 1.0≤(The content of the cyclic ether group A of the resin EP (unit: mmol/g)/(the content of the acid group of the resin EP (unit: mmol/g) + (the acid group of the resin EP is The content of the group protected by the protecting group (unit: mmol/g))≤14.0  …(1). The coloring composition according to any one of claims 1 to 3, wherein The acid group is a phenolic hydroxyl group or a carboxyl group. The coloring composition according to any one of claims 1 to 3, wherein the protecting group is a group represented by any one of formulae (Y1) to (Y5), formula (Y1): -C(R ^Y1 )(R ^Y2 )(R ^Y3 ) Formula (Y2): -C(=O)OC(R ^Y4 )(R ^Y5 )(R ^Y6 ) Formula (Y3): -C(R ^Y7 )(R ^Y8 )( OR ^Y9 ) Formula (Y4): -C(R ^Y10 )(H)(Ar ^Y1 ) Formula (Y5): -C(=O)(R ^Y11 ) In formula (Y1), R ^Y1 to R ^Y3 are independently Represents an alkyl group, and two of R ^Y1 to R ^Y3 may be bonded to form a ring. In formula (Y2), R ^Y4 to R ^Y6 each independently represent an alkyl group, and two of R ^Y4 to R ^Y6 may be bonded to each other. In formula (Y3), R ^Y7 and R ^Y8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^Y7 and R ^Y8 is an alkyl group or an aryl group, and R ^Y9 represents an alkyl group or Aryl, R ^Y7 or R ^Y8 and R ^Y9 can be bonded to form a ring, in formula (Y4), Ar ^Y1 represents an aryl group, R ^Y10 represents an alkyl group or an aryl group, in formula (Y5), R ^Y11 represents an alkyl group or aryl. The coloring composition according to any one of claims 1 to 3, wherein The colorant further includes a yellow colorant. The coloring composition according to any one of claims 1 to 3, wherein The content of the red colorant in the colorant is 70% by mass or more. The coloring composition according to any one of claims 1 to 3, which is used for forming a cured film at a temperature of 150° C. or lower in the entire process. The coloring composition according to any one of claims 1 to 3, which is used for a color filter. The coloring composition according to any one of claims 1 to 3, which is used in a display device. A cured film obtained by curing the coloring composition according to any one of claims 1 to 10. A color filter having the hardened film described in claim 11. A display device having the cured film of claim 11.