WO2022044972A1

WO2022044972A1 - Coloring composition, cured film, color filter, and display device

Info

Publication number: WO2022044972A1
Application number: PCT/JP2021/030474
Authority: WO
Inventors: 寛晃小川; 大助柏木; 啓之山本
Original assignee: 富士フイルム株式会社
Priority date: 2020-08-31
Filing date: 2021-08-19
Publication date: 2022-03-03
Also published as: CN115803682A; JPWO2022044972A1; TW202210527A

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, A^max1/A^min1, which is the ratio of the maximum value A^max1 of absorbance with respect to light having a wavelength of 400-500 nm and a minimum value A^min1 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 compositions, cured films, color filters and display devices

The present invention relates to a coloring composition. More specifically, the present invention relates to a coloring composition used for forming red pixels of a color filter and the like. The present invention also relates to a cured film, a color filter and a display device using a coloring composition.

In various display devices, color filters are generally used for colorizing displayed images. The color filter is manufactured by using a coloring composition containing a coloring agent, a resin, a polymerizable compound, and a photopolymerization initiator (for example, Patent Document 1 and the like).

Japanese Unexamined Patent Publication No. 2018-087956

When manufacturing a color filter or the like using a coloring composition, a color filter may be manufactured using the coloring composition immediately after production. Therefore, the coloring composition is required to have excellent storage stability.

Generally, a color filter has pixels of a plurality of colors. Such a color filter having pixels of a plurality of colors is manufactured by sequentially forming a pattern of coloring compositions for forming pixels of each color to form pixels of each color.

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

However, when pixels are formed by a low temperature process, the degree of curing of the pixels may be insufficient, and when forming pixels of other colors, color mixing with a coloring composition of another color occurs and the spectral characteristics fluctuate. It tended to be easy.

Further, according to the study of the present inventor, it was found that there is room for further improvement in the color mixing with other colors even in the coloring composition described in Patent Document 1.

Therefore, an object of the present invention is to provide a coloring composition, a cured film, a color filter and a display device capable of forming a cured film having excellent storage stability and suppressing color mixing with other colors. be.

According to the study of the present inventor, it has been found that the above object can be achieved by using the coloring composition described later, and the present invention has been completed. The present invention provides:
<1> A coloring composition containing a colorant containing a red colorant, a resin, a polymerizable compound, and a photopolymerization initiator.
The resin comprises a repeating unit A having at least one cyclic ether group A selected from a group represented by the formula (e-1) and a group represented by the formula (e-2).
It comprises a resin EP comprising 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 the acid group is protected by a protecting group.
The coloring composition has a ratio of A ^max1 / A ^min1 of the maximum value A ^max1 of the absorbance for light having a wavelength of 400 to 500 nm and the minimum value A ^min1 of the absorbance for light having a wavelength of 550 to 700 nm of 25 or more.
A coloring composition in which a wavelength having an absorbance of 0.3 exists in the range of 570 to 620 nm when the absorbance with respect to light having a wavelength of 500 nm is 1.

In formula (e-1), ^RE1 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, and * represents a bond.
<2> The resin EP has the content of the cyclic ether group A of 2.0 to 6.5 mmol / g, and the content of the acid group and the content of the group in which the acid group is protected by a protecting group. The coloring composition according to <1>, wherein the total amount of the above is 0.45 to 2.35 mmol / g.
<3> The content of the cyclic ether group A of the resin EP, the content of the acid group, and the content of the group in which the acid group is protected by a protecting group satisfy the condition of the following formula (1). , <1> or <2>.
1.0 ≦ (Content of the cyclic ether group A of the resin EP (unit: mmol / g) / (Content of the acid group of the resin EP (unit: mmol / g) + (The acid group of the resin EP is Content of groups protected by protecting groups (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 hydroxy group or a carboxy group.
<5> The coloring composition according to any one of <1> to <4>, wherein the protecting group is a group represented by any of the formulas (Y1) to (Y5);
Equation ( ^Y1 ): -C (RY1) ( ^RY2 ) ( ^RY3 )
Equation (Y2): -C (= O) OC ( ^RY4 ) ( ^RY5 ) ( ^RY6 )
Equation (Y3): -C ( ^RY7 ) ( ^RY8 ) (OR ^Y9 )
Equation (Y4): -C ( ^RY10 ) (H) (Ar ^Y1 )
Equation (Y5): -C (= O) ( ^RY11 )
In formula ( ^Y1 ), RY1 to ^RY3 each independently represent an alkyl group, and two of ^RY1 to ^RY3 may be bonded to form a ring;
In formula (Y2), ^RY4 to ^RY6 each independently represent an alkyl group, and two of ^RY4 to ^RY6 may be bonded to form a ring;
In formula (Y3), ^RY7 and ^RY8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of ^RY7 and ^RY8 is an alkyl group or an aryl group, and ^RY9 is an alkyl. Representing a group or aryl group, ^RY7 or ^RY8 and ^RY9 may be combined to form a ring;
In formula (Y4), Ar ^Y1 represents an aryl group and ^RY10 represents an alkyl or aryl group;
In formula (Y5), ^RY11 represents an alkyl or aryl group.
<6> The coloring composition according to any one of <1> to <5>, wherein the coloring agent further contains a yellow coloring agent.
<7> The coloring composition according to any one of <1> to <6>, wherein the content of the red colorant in the colorant is 70% by mass or more.
<8> The coloring composition according to any one of <1> to <7>, which is used for forming a cured film at a temperature of 150 ° C. or lower throughout the entire process.
<9> The coloring composition according to any one of <1> to <8>, which is for a color filter.
<10> The coloring composition according to any one of <1> to <9>, which is for a display device.
<11> A cured film obtained by curing the coloring composition according to any one of <1> to <10>.
<12> The color filter having the cured film according to <11>.
<13> A display device having the cured film according to <11>.

According to the present invention, a coloring composition capable of forming a cured film having good storage stability and suppressed color mixing with other colors, a cured film using this coloring composition, a color filter and a display. Equipment can be provided.

Hereinafter, the contents of the present invention will be described in detail.
In the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group). Is. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
As used herein, the term "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Further, as the light used for exposure, generally, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation can be mentioned.
The numerical range represented by using "-" in the present specification means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
As used herein, the total solid content means the total mass of all the components of the composition excluding the solvent.
As used herein, "(meth) acrylate" represents both acrylate and methacrylate, or either, and "(meth) acrylic" represents both acrylic and methacrylic, or either. ) Allyl ”represents both allyl and / or methacrylic, and“ (meth) acryloyl ”represents both / or either acryloyl and methacrylic acid.
In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values measured by gel permeation chromatography (GPC).

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

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

The detailed reason why such an effect is obtained is unknown, but it is presumed to be due to the following. It is presumed that the coloring composition having the above spectral characteristics does not easily release heat when the coloring composition is heated and cured, and the resin EP or the like can be cured by effectively utilizing the heat. Further, it is presumed that this resin EP is a highly reactive resin. Therefore, by containing the resin EP in the coloring composition having the above spectral characteristics, the curing of the coloring composition proceeds rapidly when the coloring composition is heated and cured, and as a result, comparison is made. It is presumed that a sufficiently cured cured film can be formed even by heating at a low temperature. Therefore, according to the coloring composition of the present invention, it is presumed that a cured film in which color mixing with other colors is suppressed can be formed.
Further, since the coloring composition has the above-mentioned specific spectral characteristics, it is possible to suppress the reaction of curable components such as resins and polymerizable compounds by external light during storage, and as a result, excellent storage stability is achieved. Presumed to have.

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

In the present invention, the absorbance value of the coloring composition may be a value measured in a solution state or a value of a cured film formed by using the coloring composition. When measuring the absorbance in the state of a cured film, a coloring composition is applied onto a glass substrate by a method such as spin coating, dried at 100 ° C. for 2 minutes using a hot plate or the like, and then the light illuminance is 20 mW / cm ² . It is possible to perform i-line exposure under the condition of an exposure amount of 1 J / cm ² , and then measure using a film (cured film) obtained by heating on a hot plate at 100 ° C. for 20 minutes and allowing to cool to room temperature. preferable. 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 to light having a wavelength of 400 to 500 nm and the minimum value A ^min1 of the absorbance to light having a wavelength of 550 to 700 nm is 25 or more, and 50. It is preferably 100 or more, and more preferably 100 or more. The higher the value of the ratio A ^max1 / A ^min1 , the more remarkable the effect of the present invention described above can be obtained, and further, it is easy to obtain a red pixel having excellent color separation from other colors. Therefore, the upper limit of the value of the ratio A ^max1 / A ^min1 is not particularly limited, but may be, for example, 10000 or less, 5000 or less, or 1000 or less.

When the absorbance of the coloring composition of the present invention with respect to light having a wavelength of 500 nm is 1, the wavelength having an absorbance of 0.3 is preferably in the range of 570 to 620 nm and preferably in the range of 575 to 615 nm. It is more preferably present in the range of ~ 610 nm, and even more preferably in the range of 585 to 605 nm.

When the absorbance of the coloring composition of the present invention with respect to light having a wavelength of 500 nm is 1, the wavelength at which the absorbance is 0.5 is preferably in the range of 565 to 605 nm, and preferably in the range of 570 to 600 nm. More preferably, it is more preferably present in the range of 575 to 595 nm.

In the coloring composition of the present invention, the ratio A ^max1 / A ⁵⁵⁰ of the maximum value A ^max1 of the absorbance to light having a wavelength of 400 to 500 nm and the absorbance A ⁵⁵⁰ to light having a wavelength of 550 nm is preferably 2.75 or less. It is more preferably less than or equal to, and even more preferably 1.5 or less.

In the coloring composition of the present invention, the ratio A ^max1 / A ⁶⁰⁰ of the maximum value A ^max1 of the absorbance to light having a wavelength of 400 to 500 nm and the absorbance A ⁶⁰⁰ to light having a wavelength of 600 nm is preferably 5 to 15. It is more preferably 5 to 13.5, and even more preferably 8 to 12.

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

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

The colored composition of the present invention preferably has a transmittance of 1% or less, preferably 0.75% or less, for light having a wavelength of 500 nm when a cured film having a film thickness of 0.5 to 3.0 μm is formed. It is more preferably present, and further preferably 0.5% or less. Further, the maximum value of the transmittance for light having a wavelength of 400 to 500 nm is preferably 1% or less, more preferably 0.75% or less, still 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% by mass or less, more preferably 20% by mass or less, still more preferably 18% by mass or less. As long as the solid content concentration is within the above range, the cured film (pixels) having excellent flatness is excellent even when the cured film (pixels) is formed at a temperature of 150 ° C. or lower (preferably a temperature of 120 ° C. or lower) throughout the entire process. Pixels) can be formed.

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

The coloring composition of the present invention can be preferably used as a coloring composition for a display device. More specifically, it can be preferably used as a coloring composition for forming pixels of a color filter for a display device, and more preferably as a coloring composition for forming red pixels of a color filter for a display device. The type of the display device is not particularly limited, and examples thereof include a display device having an organic semiconductor element as a light source such as an organic electroluminescence display device.

Further, the coloring composition of the present invention can also be used as a coloring composition for a solid-state image sensor. More specifically, it can be preferably used as a coloring composition for forming pixels of a color filter for a solid-state image sensor, and more preferably as a coloring composition for forming red pixels of a color filter for a solid-state image sensor.

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) throughout the entire process. In the present specification, the whole step includes, for example, a step of forming a cured film using a colorant composition. In the present specification, forming a cured film at a temperature of 150 ° C. or lower throughout the entire process is not limited, but all steps of forming a cured film using a coloring composition are performed at a temperature of 150 ° C. or lower. means.

The thickness of the cured film and pixels formed by the coloring composition of the present invention is preferably 0.5 to 3.0 μm. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, still more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, still more preferably 1.8 μm or less.

Further, the line width (pattern size) of the pixels formed by the coloring composition of the present invention 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, still more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, still 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 the present invention contains a coloring agent. Examples of the colorant include chromatic colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant. In the present invention, the colorant may be a pigment or a dye. As the colorant, a pigment and a dye may be used in combination. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or a material in which a part of the organic-inorganic pigment is replaced with an organic chromophore can also be used. By substituting inorganic pigments and organic-inorganic pigments with organic chromophores, hue design can be facilitated. When a colorant containing a pigment is used, it is easy to form a cured film having excellent durability such as heat resistance and light resistance. When a colorant containing a dye is used, it is easy to form a cured film having a higher red color reproduction range. Further, in general, a cured film obtained by using a dye tends to cause color mixing more easily than a cured film obtained by using a pigment, but according to the present invention, when a dye is used as a colorant, Even if it is present, it is possible to form a cured film in which color transfer is suppressed, so that it is particularly effective when a colorant containing a dye is used.

The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, still more preferably 100 nm or less. When the average primary particle size of the pigment is in the above range, the dispersion stability of the pigment in the coloring composition is good. In the present invention, the primary particle size of the pigment can be obtained from an image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment. Further, the average primary particle size in the present invention is an arithmetic average value of the primary particle size for the primary particles of 400 pigments. Further, the primary particles of the pigment refer to independent particles without aggregation.

A pigment multimer can also be used as the colorant. The dye multimer is preferably a dye that is used by dissolving it in a solvent. Further, the dye multimer may 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 the particle state can be obtained, for example, by emulsion polymerization, and the compounds and production methods described in JP-A-2015-214682 are specific examples. 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 may be 100 or less. The plurality of dye structures contained in one molecule may have the same dye structure or may have different dye structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, International Publication No. 2016/031442 and the like. Compounds 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 may be used in combination. The red colorant is preferably a pigment (red pigment) because it is easy to form a film having excellent solvent resistance.

The red colorant is preferably at least one selected from a xanthene compound, an anthraquinone compound, a monoazo compound, a diazo compound, an azomethine compound, an aminoketone compound, a quinacridone compound, a perylene compound and a diketopyrrolopyrrole compound, and an anthraquinone compound, It is more preferably at least one selected from the quinacridone compound, the perylene compound and the diketopyrrolopyrrole compound, further preferably at least one selected from the anthraquinone compound, the perylene compound and the diketopyrrolopyrrole compound, and the anthraquinone compound. And at least one selected from the diketopyrrolopyrrole compound is even more preferred. Among them, an anthraquinone compound is particularly preferable because it is a compound having absorption on the longer wave side and the effect of the present invention can be obtained more remarkably.

As the red pigment, the color index (CI) 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 and the like.

As a red dye, C.I. 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 and the like can be mentioned.

As a red colorant, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Patent No. 6248838. , The diketopyrrolopyrrole compound described in International Publication No. 2012/10239, the diketopyrrolopyrrole compound described in International Publication No. 2012/117956, the naphthol azo compound described in JP-A-2012-229344, Patent No. 6516119. The red colorant described in Japanese Patent No. 6525101, the red colorant described in Japanese Patent Application Laid-Open No. 2020-090632, the brominated diketopyrrolopyrrole compound described in paragraph No. 0229 of JP-A-2020-090632, Korean Publication No. 10-2019. It is also possible to use the anthraquinone compound described in Japanese Patent Application Laid-Open No. 0147741, the anthraquinone compound described in Japanese Patent Application Laid-Open No. 10-2019-0140744, the perylene compound described in JP-A-2020-079396, and the like. Further, as the red colorant, a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. You can also.

As a red colorant, C.I. I. Pigment Red 122,177,179,202,254,264,269,272 is preferable, and C.I. I. Pigment Red 177,179,202,254,264,269 is more preferable, and C.I. I. Pigment Red 177,254,264,269 is more preferable, and C.I. I. It is particularly preferable that it is Pigment Red 264.

(Other colorants)
The coloring composition of the present invention preferably further contains a coloring agent other than the red coloring agent. Examples of other colorants used in combination include a yellow colorant, a green colorant, a purple colorant, a blue colorant, an orange colorant, and the like, because it is easy to form a cured film having spectral characteristics more suitable for red color. It is preferably a yellow colorant. Further, the yellow colorant is preferably a pigment (yellow pigment) because it is easy to form a film having excellent solvent resistance.

Examples of the yellow colorant include azo compounds, azomethine compounds, quinophthalone compounds, isoindolinone compounds, isoindrin compounds, pteridine compounds and anthraquinone compounds, and azo compounds, azomethine compounds, isoindrin compounds and quinophthalone compounds are preferable. Indoline compounds and azo compounds are more preferred, and isoindolin compounds are particularly preferred.

As a yellow colorant, C.I. 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, Yellow pigments such as 180,181,182,185,187,188,193,194,199,213,214,215,228,231,232,233,234,235,236 can be mentioned.

Further, as the yellow colorant, a nickel azobarbituric acid complex (azo compound) having the following structure can also be used.

Further, as the yellow colorant, the compounds described in JP-A-2017-201003, the compounds described in JP-A-2017-197719, and paragraph numbers 0011 to 0062 and 0137-0276 of JP-A-2017-171912 are described. , The compounds described in paragraphs 0010 to 0062, 0138 to 0295 of JP-A-2017-171913, the compounds described in paragraphs 0011 to 0062, 0139-0190 of JP-A-2017-171914, JP-A-2017. -The compounds described in paragraphs 0010 to 0065 and 0142 to 0222 of JP-A-171915, the quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP2013-054339, paragraph numbers 0013 to JP-A-2014-0226228. The quinophthalone compound described in 0058, the isoindolin compound described in JP-A-2018-062644, the quinophthalone compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A-2018-062578, Patent No. 6432076. The quinophthalone compound described in JP-A-2018-155881, the quinophthalone compound described in JP-A-2018-11175, the quinophthalone compound described in JP-A-2018-040835, the quinophthalone compound described in JP-A-2018-040835, JP-A-2017. -Kinophthalone compound described in JP-A-197640, quinophthalone compound described in JP-A-2016-145282, quinophthalone compound described in JP-A-2014-0856565, quinophthalone compound described in JP-A-2014-021139, special The quinophthalone compound described in JP2013-209614, the quinophthalone compound described in JP2013-209435, the quinophthalone compound described in JP2013-181015, and the quinophthalone compound described in JP2013-061622. , A quinophthalone compound described in JP2013-032486, a quinophthalone compound described in JP2012-226110A, a quinophthalone compound described in JP-A-2008-074987, and a quinophthalone compound described in JP-A-2008-081565. Kinophthalone compound, quinophthalone compound described in JP-A-2008-074986, quinophthalone compound described in JP-A-2008-074985, quinophthalone compound described in JP-A-2008-054020, JP-A. The quinophthalone compound described in JP-A-2008-031281, the quinophthalone compound described in JP-A-48-032765, the quinophthalone compound described in JP-A-2019-008014, the quinophthalone compound described in JP-A-6607427, JP-A-B. Metin dyes described in JP-A-2019-073695, Metin dyes described in JP-A-2019-073696, Metin dyes described in JP-A-2019-073697, Metin dyes described in JP-A-2019-073698, Compounds described in Korean Publication No. 10-2014-0034963, compounds described in JP-A-2017-095076, compounds described in Taiwan Patent Application Publication No. 201920495, compounds described in Patent No. 6607427. , The quinophthalone dimer described in JP-A-2020-033521 can also be used. Further, a multimerized version of these compounds is also preferably used from the viewpoint of improving the color value. Further, as the yellow colorant, a compound represented by the following formula (QP1) and a compound represented by the following formula (QP2) can also be used.

In the formula (QP1), X ¹ to X ¹⁶ 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 compound described in paragraph No. 0016 of Japanese Patent No. 6443711.

^In the formula (QP2), Y1 to ^Y3 independently represent halogen atoms. n and m represent integers 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 the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.

As a yellow colorant, C.I. I. Pigment Yellow 129, 138, 139, 150, 185, 215 is preferable, and C.I. I. Pigment Yellow 139,150 is more preferable, and C.I. I. Pigment Yellow 139 is even more preferable.

As a green colorant, C.I. I. Examples thereof include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, 66. Further, as a green colorant, halogenated zinc phthalocyanine having an average number of halogen atoms in one molecule of 10 to 14, a bromine atom of 8 to 12, and a chlorine atom of 2 to 5 on average. Pigments can also be used. Specific examples include the compounds described in International Publication No. 2015/118720. Further, as a green colorant, the compound described in Chinese Patent Application No. 1069090227, the phthalocyanine compound having a phosphate ester as a ligand according to International Publication No. 2012/102395, and Japanese Patent Application Laid-Open No. 2019-008014. The phthalocyanine compound and the phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, the core-shell type dye described in JP-A-2020-076955, and the like can also be used.

As a green colorant, C.I. I. Pigment Green 7,36,37,58,59,65 is preferable, and C.I. I. Pigment Green 7,36,58,65 is more preferable, and C.I. I. Pigment Green 7,36 is more preferable.

As a blue colorant, C.I. 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 etc. Pigments can be mentioned. Further, as the blue colorant, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include the compounds described in paragraph numbers 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.

As a blue colorant, C.I. I. Pigment Blue 15,15: 4,15: 6,16,60,64,79 is preferable, and C.I. I. Pigment Blue 15: 4,15: 6,16,60,64 is more preferable, and C.I. I. Pigment Blue 15: 4, 15: 6 is more preferable.

As a purple colorant, C.I. I. Examples thereof include purple pigments such as Pigment Violet 1,19,23,27,32,37,42,60,61.

As an orange colorant, C.I. I. 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, etc. The orange pigment of.

The content of the colorant is preferably 5 to 70% by mass in the total solid content of the coloring composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, still more preferably 20% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by 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 further 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.

The colorant contained in the coloring composition preferably contains a red colorant and a yellow colorant. The content of the yellow colorant is preferably 3 to 45 parts by mass with respect to 100 parts by mass of the red colorant. 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, and more preferably 15 parts by mass or less. 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 further preferably 90% by mass or more. preferable.

<< Resin >>
The coloring composition of the present invention contains a resin. The resin is blended, for example, for the purpose of dispersing a pigment or the like in a coloring composition or for the purpose of a binder. A resin mainly used for dispersing a pigment or the like in a coloring composition is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for purposes other than such an application.

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

The weight average molecular weight of the resin EP is preferably 2000 to 70000. The upper limit is preferably 60,000 or less, and more preferably 50,000 or less. The lower limit is preferably 3000 or more, and more preferably 5000 or more. If the weight average molecular weight of the resin EP is in the above range, it is easy to achieve both color mixing and storage stability at a higher level.

The content of the specific cyclic ether group in the resin EP is preferably 2.0 to 6.5 mmol / g. If the content of the specific cyclic ether group in the resin EP is 2.0 to 6.5 mmol / g, a cured film that is sufficiently cured can be formed even by heating at a relatively low temperature, and the storage stability of the colored composition is also good. Is. The upper limit is preferably 6.3 mmol / g or less, more preferably 6.0 mmol / g or less, from the viewpoint of storage stability of the coloring composition. The lower limit is preferably 2.5 mmol / g or more, more preferably 3.0 mmol / g or more, still more preferably 3.2 mmol / g or more, from the viewpoint of film curability. It is particularly preferable that it is 4 mmol / g or more.

The total content of the acid group of the resin EP and the content of the group whose acid group is protected by the protecting group is preferably 0.45 to 2.35 mmol / g. When the total of the resin EP is 0.45 to 2.35 mmol / g, a sufficiently cured cured film can be formed even by heating at a relatively low temperature, and the storage stability of the colored composition is also good. The upper limit is preferably 2.25 mmol / g or less, more preferably 2.15 mmol / g or less, from the viewpoint of storage stability of the coloring composition. The lower limit is preferably 0.7 mmol / g or more, and more preferably 0.9 mmol / g or more from the viewpoint of film curability.

The resin EP preferably contains a repeating unit having an acid group. According to this aspect, it is possible to form a cured film that is sufficiently cured even by heating at a relatively low temperature, and it is possible to form a cured film in which color mixing with other colors is more suppressed. Further, when the unexposed portion is exposed in a pattern using the coloring composition, the unexposed portion can be easily developed and removed with a developing solution, the developability is excellent, and the generation of the residue in the unexposed portion can be further suppressed. The acid group content of the resin EP is preferably 0.45 to 2.35 mmol / g. The upper limit is preferably 2.25 mmol / g or less, and 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 specific cyclic ether group, the content of the acid group, and the content of the group in which the acid group is protected by the protecting group preferably satisfy the condition of the following formula (1), and the following formula is preferable. It is more preferable that the condition of (2) is satisfied, and it is further preferable that the condition of the following formula (3) is satisfied.
1.0 ≦ (Content of specific cyclic ether group of resin EP (unit: mmol / g) / (Content of acid group of resin EP (unit: mmol / g)) + (acid group of resin EP is a protecting group) Content of protected group (unit: mmol / g)) ≤14.0 ... (1)
2.5 ≦ (Content of specific cyclic ether group of resin EP (unit: mmol / g) / (Content of acid group of resin EP (unit: mmol / g)) + (acid group of resin EP is a protecting group Content of protected group (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)) + (acid group of resin EP is a protecting group Content of protected group (unit: mmol / g)) ≤ 10.0 ... (3)

When the resin EP contains an acid group content and a group in which the acid group is protected by a protecting group, respectively, the content of the acid group in the resin EP and the content of the group in which the acid group is protected by the protecting group are , The condition of the following formula (11) is preferable, the condition of the following formula (12) is more preferable, and the condition of the following formula (13) is further preferable. According to this aspect, the storage stability of the coloring composition is good, and when the coloring composition is exposed in a pattern, the unexposed portion can be easily developed and removed with a developing solution, and the developability is also excellent. , The generation of residue in the unexposed area can be further suppressed.
0.1 ≤ (content of group in which the acid group of the resin EP is protected by a protecting group (unit: mmol / g) / content of the acid group of the resin EP (unit: mmol / g)) ≤ 2.0.・・ (11)
0.2 ≤ (content of group in which the acid group of the resin EP is protected by a protecting group (unit: mmol / g) / content of the acid group of the resin EP (unit: mmol / g)) ≤ 1.9.・・ (12)
0.3 ≤ (content of group in which the acid group of the resin EP is protected by a protecting group (unit: mmol / g) / content of the acid group of the resin EP (unit: mmol / g)) ≤ 1.8.・・ (13)

[Repeating unit A]
The resin EP has 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). Includes unit A. The specific cyclic ether group is preferably a group represented by the formula (e-1) because a film having a high crosslink density can be formed.

In formula (e-1), ^RE1 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, and * represents a bond.

The number of carbon atoms of the alkyl group represented by ^RE1 is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 5, and particularly preferably 1 to 3. The alkyl group represented by ^RE1 is preferably linear or branched, and more preferably linear.

When n is 0, it is preferable that ^RE1 is a hydrogen atom. When n is 1, ^RE1 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).

The monocyclic aliphatic hydrocarbon ring represented by the ring ^AE1 of the formula (e-2) is preferably a 5- to 7-membered aliphatic hydrocarbon ring, and is preferably a 5-membered or 6-membered aliphatic ring. It is more preferably a hydrocarbon ring, and even more preferably a 6-membered aliphatic hydrocarbon ring. Specific examples include a cyclopentane ring, a cyclohexane ring, and a cycloheptane ring, preferably a cyclopentane ring or a cyclohexane ring, and more preferably a cyclohexane ring. Specific examples of the group represented by the formula (e-2) include the groups shown below.

Examples of the repeating unit A include a repeating unit represented by the following formula (A-1).

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

Examples of the trivalent linking group represented by ^Xa1 of the formula (A-1) include a poly (meth) acrylic linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, and a polyurea-based linking group. Examples thereof include polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, bisphenol-based linking groups, novolak-based linking groups, poly (meth) acrylic-based linking groups, polyether-based linking groups, polyester-based linking groups, Bisphenol-based linking groups and novolak-based linking groups are preferable, and poly (meth) acrylic-based linking groups are more preferable.

Examples of the divalent linking group represented by ^La1 of the formula (A-1) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), and-. NH-, -SO-, -SO _2- , -CO-, -O-, -COO-, -OCO-, -S- and groups consisting of a combination of two or more of these can be mentioned. The alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.

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.

[Repeating unit B]
From the repeating unit B-1 having an acid group (hereinafter, also referred to as repeating unit B-1) and the repeating unit B-2 having a group in which the acid group is protected by a protecting group (hereinafter, also referred to as repeating unit B-2). Includes at least one repeating unit B chosen. The resin EP may contain only one of the repeating unit B-1 and the repeating unit B-2, or may contain the repeating unit B-1 and the repeating unit B-2, respectively. The resin EP preferably contains at least the repeating unit B-1.

When the resin EP has the repeating unit B-1, it is possible to form a cured film that is sufficiently cured even by heating at a relatively low temperature, and it is possible to form a cured film in which color mixing with other colors is further suppressed. Further, when the unexposed portion is exposed in a pattern using the coloring composition, the unexposed portion can be easily developed and removed with a developing solution, the developability is excellent, and the generation of the residue in the unexposed portion can be further suppressed.
Further, when the resin EP contains the repeating unit B-2, it is possible to suppress the progress of the reaction of the specific cyclic ether group of the resin EP during storage of the coloring composition, and the storage stability of the coloring composition can be suppressed. Can be further improved.
Further, when the resin EP contains the repeating unit B-1 and the repeating unit B-2, the storage stability of the coloring composition, the developability, and the suppression of the color mixing of the obtained cured film are arranged at a higher level. be able to.

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 hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group. , A phenolic hydroxy group or a carboxy group is preferable, and a carboxy group is more preferable.

Examples of the protecting group that protects the acid group in the repeating unit B-2 include a group that decomposes and is eliminated by the action of an acid or a base. The protecting group is preferably a group represented by any of the formulas (Y1) to (Y5), and is a group represented by the formula (Y3) or the formula (Y5) because it is easy to deprotect. Is more preferable.

Equation ( ^Y1 ): -C (RY1) ( ^RY2 ) ( ^RY3 )
Equation (Y2): -C (= O) OC ( ^RY4 ) ( ^RY5 ) ( ^RY6 )
Equation (Y3): -C ( ^RY7 ) ( ^RY8 ) (OR ^Y9 )
Equation (Y4): -C ( ^RY10 ) (H) (Ar ^Y1 )
Equation (Y5): -C (= O) ( ^RY11 )

In formula ( ^Y1 ), RY1 to ^RY3 each independently represent an alkyl group, and two of ^RY1 to ^RY3 may be bonded to form a ring;
In formula (Y2), ^RY4 to ^RY6 each independently represent an alkyl group, and two of ^RY4 to ^RY6 may be bonded to form a ring;
In formula (Y3), ^RY7 and ^RY8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of ^RY7 and ^RY8 is an alkyl group or an aryl group, and ^RY9 is an alkyl. Representing a group or aryl group, ^RY7 or ^RY8 and ^RY9 may be combined to form a ring;
In formula (Y4), Ar ^Y1 represents an aryl group and ^RY10 represents an alkyl or aryl group;
In formula (Y5), ^RY11 represents an alkyl or aryl group.

The number of carbon atoms of the alkyl group represented by RY1 to ^RY3 in 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 is preferably linear or branched. In the formula ( ^Y1 ), two of RY1 to ^RY3 may be combined to form a ring. The ring formed by the bond of ^RY1 to ^RY3 includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl. Examples thereof include a polycyclic cycloalkyl group such as a group, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferable. Further, in the above cycloalkyl group, one of the methylene groups constituting the ring may be replaced with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

The number of carbon atoms of the alkyl group represented by ^RY4 to ^RY6 in 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 is preferably linear or branched. It is preferable that at least two of ^RY4 to ^RY6 of the formula (Y2) are methyl groups. In the formula (Y2), two of ^RY4 to ^RY6 may be combined to form a ring. Examples of the ring formed include the ring described by the formula (Y1).

In formula (Y3), ^RY7 and ^RY8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of ^RY7 and ^RY8 is an alkyl group or an aryl group, and ^RY9 is an alkyl. It represents a group or an aryl group, and ^RY7 or ^RY8 may be bonded to ^RY9 to form a ring.
The alkyl group may be linear, branched or cyclic. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. Examples of the ring formed by binding ^RY7 or ^RY8 and ^RY9 include a tetrahydrofuranyl group and a tetrahydropyranyl group. In the formula (Y3), it is preferable that ^RY7 or ^RY8 and ^RY9 are bonded to form a ring. Further, it is preferable that one of ^RY7 and ^RY8 is a hydrogen atom.

In formula (Y4), Ar ^Y1 represents an aryl group, ^RY10 represents an alkyl group or an aryl group, and Ar ^Y1 and ^RY10 may be bonded to each other to form a ring. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. In the formula (Y4), ^RY10 is preferably an alkyl group.

In the formula (Y5), ^RY11 represents an alkyl group or an aryl group, and is preferably an alkyl group. The number of carbon atoms of the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 4. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.

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

Specific examples of the protective group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-t-butoxyethyl group and 1-cyclopentyloxyethyl group. , 1-cyclohexyloxyethyl group, cyclohexyl (methoxy) methyl group, α-methoxybenzyl group, α-ethoxybenzyl group, α-n-propoxybenzyl group, 2-phenyl-1-methoxyethyl group, 2-phenyl-1 -Ethyl group, 2-phenyl-1-isopropoxyethyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 2-tetrahydrofuranyl group , 2-Tetrahydropyranyl group is preferable, 1-ethoxyethyl group and 1-cyclohexyloxyethyl group are more preferable.

Examples of the repeating unit B-1 include a repeating unit represented by the following formula (B1). Further, as the repeating unit B-2, a repeating unit represented by the following formula (B2) can be 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 the acid group is protected by a protecting group.

The trivalent linking group represented by X ^b1 of the formula (B1) and the trivalent linking group represented by X ^b2 of the formula (B2) are not particularly limited. For example, poly (meth) acrylic linking group, polyalkyleneimine-based linking group, polyester-based linking group, polyurethane-based linking group, polyurea-based linking group, polyamide-based linking group, polyether-based linking group, polystyrene-based linking group, bisphenol. Examples thereof include a system-based linking group and a novolak-based linking group, and poly (meth) acrylic-based linking groups, polyether-based linking groups, polyester-based linking groups, bisphenol-based linking groups and novolac-based linking groups are preferable, and poly (meth) acrylic is preferable. System linking groups are more preferred.

The divalent linking group represented by L ^b1 of the formula (B1) and the divalent linking group represented by L ^b3 of the formula (B2) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an arylene group (preferably an alkylene group having 1 to 12 carbon atoms). (Preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO _2- , -CO-, -O-, -COO-, -OCO-, -S- and two or more of these. Examples are combined groups. The alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.

Z ^b1 in the formula (B1) represents an acid group. Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group, and a phenolic hydroxy group or a carboxy group is preferable, and a carboxy group is more preferable.

Z ^b2 of the formula (B2) represents a group in which the acid group is protected by a protecting group. Examples of the group in which the acid group is protected by the protecting group include a group in which the acid group is protected by a group represented by any of the above-mentioned formulas (Y1) to (Y5), and the acid group is the formula (Y3). Alternatively, it is preferably a group protected by a group represented by the formula (Y5). Examples of the acid group include a phenolic hydroxy group, a carboxy group, a sulfo group and a phosphoric acid group, and a phenolic hydroxy group or a carboxy group is preferable, and a carboxy group is more preferable.

As one aspect of the repeating unit B2, a repeating unit represented by the following formula (B2-1) can be mentioned.

In the formula (B2-1), R ^b11 to R ^b13 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 the formula (Z). Represents a group represented by -1) or formula (Z-2);

In the formula (Z-1) and the formula (Z-2), Y ^b11 represents a protecting group, and * represents a portion to be bonded to L ^b11 .

Examples of the halogen atom represented by R ^b11 to R ^b13 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
The number of carbon atoms 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 is preferably linear or branched.
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 arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, and -SO-. Examples thereof include -SO _2- , -CO-, -O-, -COO-, -OCO-, -S-, and a group consisting of a combination of two or more of these. The alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.

Examples of the protecting group represented by Y ^b11 of the formula (Z-1) and the formula (Z-2) include a group represented by any of the above-mentioned formulas (Y1) to (Y5). When 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). When Z ^b11 of the formula (B2-1) is a group represented by the formula (Z-2), it is preferable that Y ^b11 is the formula (Y3).

When Z ^b11 of the formula (B2-1) is a group represented by the formula (Z-1), the storage stability of the colored composition can be further improved. When Z ^b11 of the formula (B2-1) is a group represented by the formula (Z-2), a coloring composition having excellent curability at a 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, 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 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, 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 to 65 mol% in all the 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 the resin EP contains the repeating unit B-1 and the repeating unit B-2, respectively, the resin EP contains 0.4 to 3.2 mol of the repeating unit B-2 for 1 mol of the repeating unit B-1. It is preferably contained, more preferably 0.8 to 2.8 mol, still more preferably 1.2 to 2.4 mol. According to this aspect, the storage stability of the coloring composition, the developability, and the suppression of the color mixing of the obtained cured film can be made parallel at a higher level.

[Repeating unit C]
The resin EP may contain a repeating unit containing a hydrocarbon ring group (hereinafter, also referred to as another repeating unit) as a repeating unit other than the repeating unit A and the repeating unit B. The hydrocarbon ring group may be an aliphatic hydrocarbon ring group or an aromatic hydrocarbon ring group. Further, the hydrocarbon ring group may be a monocyclic hydrocarbon ring group or a polycyclic hydrocarbon ring group such as a fused ring or a crosslinked ring. Further, the aromatic hydrocarbon ring group may be a monocyclic aromatic hydrocarbon ring group or an aromatic hydrocarbon ring group of a fused ring. Specific examples of the hydrocarbon ring group include a dicyclopentanyl group, an adamantyl group, a tert-butylcyclohexyl group, an isobornyl group and the like. Examples of the aromatic hydrocarbon ring group include a phenyl group and a naphthyl group.

The resin EP preferably contains a repeating unit containing an aliphatic hydrocarbon ring group and a repeating unit containing an aromatic hydrocarbon ring group, respectively. According to this aspect, the bulkiness of the side chain makes the resin rigid, the solvent resistance of the cured film is improved, and it is possible to form a cured film in which color mixing with other colors is further suppressed.

When the resin EP contains the repeating unit C, the content of the repeating unit C is preferably 0.1 to 40 mol% in all the 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.
When the resin EP contains a repeating unit containing an aliphatic hydrocarbon ring group as the repeating unit C and a repeating unit containing an aromatic hydrocarbon ring group, the resin EP contains a repeating unit containing an aliphatic hydrocarbon ring group. It is preferable that 1 mol of the unit contains 5 to 30 mol of the repeating unit containing an aromatic hydrocarbon ring group, more preferably 8 to 25 mol, and further preferably 10 to 20 mol. According to this aspect, the resin becomes rigid, the solvent resistance of the cured film is improved, and it is possible to form a cured film in which color mixing with other colors is further suppressed.

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

(Other resins)
The coloring composition of the present invention can further contain a resin other than the above resin EP (hereinafter, also referred to as another resin). The weight average molecular weight (Mw) of the other resin is preferably 2000 to 2000000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and even more preferably 5000 or more.

Examples of other resins include (meth) acrylic resin, (meth) acrylamide resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene ether. Examples thereof include phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and siloxane resin. Further, an epoxy resin other than the resin EP described above can also be used.

It is also preferable that the other resin is a resin having an acid group. Examples of the acid group include a carboxy group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like. The resin having an acid group can also be used as an alkali-soluble resin or a dispersant. 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 further preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, further 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. Examples of the maleimide compound include N-alkylmaleimide and N-arylmaleimide. Examples of the repeating unit derived from the maleimide compound include a repeating unit represented by the formula (C-mi).

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

The other resin is a repeating unit derived from a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferable that the resin is contained.

In formula (ED1), R ¹ and R ² each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or 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 the formula (ED2), the description in JP-A-2010-168539 can be referred to.

For a specific example of the ether dimer, paragraph number 0317 of JP2013-209760A can be referred to, and this content is incorporated in the present specification.

It is also preferable that the other resin is a resin containing a repeating unit having a polymerizable group. Examples of the polymerizable group include an ethylenically unsaturated bond-containing group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The other resin preferably contains a resin containing a repeating unit derived from the compound represented by the formula (III).

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 alkylene group represented by R ²¹ and R ²² preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms. preferable. 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.

Examples of the compound represented by the formula (III) include ethylene oxide of paracumylphenol or propylene oxide-modified (meth) acrylate. Examples of commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).

It is also preferable that the other resin is a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups. As the acidic dispersant (acidic resin), a resin in which the amount of acid groups accounts for 70 mol% or more is preferable, and substantially, when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. A resin consisting only of an acid group is more preferable. The acid group of the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Further, the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups. As the basic dispersant (basic resin), a resin in which the amount of basic groups exceeds 50 mol% is preferable when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%. The basic group contained in the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. Since the resin used as the dispersant contains a repeating unit having an acid group, it is possible to further suppress the generation of development residue when forming a pattern by a photolithography method.

It is also preferable that the resin used as the dispersant is a graft resin. For details of the graft resin, the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the contents thereof are incorporated in the present specification.

It is also preferable that the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. The resin to have is preferable. The basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity. Regarding the polyimine-based dispersant, the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and the content thereof is incorporated in the present specification.

It is also preferable that the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to the core portion. Specific examples of such resins include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.

The resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, and 20 to 70 in all the repeating units of the resin. It is more preferably mol%.

Further, as the dispersant, polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, and JP-A-2020-06667. Block polymers having an acrylamide structural unit, block polymers having an acrylamide structural unit described in JP-A-2020-066688, and the like can also be used.

Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by Big Chemie (for example, Disperbyk-111, 2001, etc.) and the Solsparse series manufactured by Japan Lubrizol Co., Ltd. (for example, Disperserbyk series). For example, Solsparse 20000, 76500, etc.), Ajinomoto Fine Techno Co., Ltd.'s Ajispar series and the like can be mentioned. Further, the product described in paragraph number 0129 of JP2012-137564A and the product described in paragraph number 0235 of JP2017-194662 can also be used as a dispersant. Further, as the dispersant, the resin described in paragraphs 0041 to 0060 of JP-A-2017-206689 and the resin containing the hindered amine quaternary salt described in JP-A-2019-095548 can also be preferably used.

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

<< Polymerizable compound >>
The coloring composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound used in the present invention is preferably a radically polymerizable compound.

The polymerizable compound may be in any chemical form such as a monomer, a prepolymer or an oligomer, but a monomer is preferable. The molecular weight of the polymerizable compound is preferably 100 to 3000. The upper limit is more preferably 2000 or less, and even more preferably 1500 or less. The lower limit is more preferably 150 or more, and even more preferably 250 or more.

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 from the viewpoint of the stability over time of the coloring composition. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and further 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 ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and more preferably an ethylenically unsaturated bond. It is more preferable that the compound contains 3 to 6 containing groups. Further, the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities. Specific examples of the polymerizable compound include paragraph numbers 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-029760, paragraphs 0254 to 0257 of JP2008-292970, and JP-A. 2013-253224, Paragraph Nos. 0034 to 0038, Japanese Patent Application Laid-Open No. 2012-208494, Paragraph Nos. 0477, Japanese Patent Laid-Open No. 2017-048637, Japanese Patent No. 6057891, Japanese Patent No. 6031807, Japanese Patent Application Laid-Open No. 2017-194662. Examples include the compounds described in the publication, the contents of which are incorporated herein.

Examples of the polymerizable compound include dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nihon Kayaku Co., Ltd.). ), Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; Nippon Kayaku) NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and the structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. Compounds (eg, SR454, SR499, commercially available from Sartmer) are preferred. As the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A) -TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nihon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toa Synthetic Co., Ltd.) , NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. You can also.

Examples of the polymerizable compound include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy-modified tri (meth) acrylate. It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toa Synthetic 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 Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.

As the polymerizable compound, a polymerizable compound having an acid group can also be used. By using a polymerizable compound having an acid group, the colored composition in the unexposed portion can be easily removed during development, and the generation of development residue can be suppressed. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group and the like, and a carboxy group is preferable. Examples of commercially available products of the polymerizable compound having an acid group include Aronix M-305, M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.). The preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.

As the polymerizable compound, a polymerizable compound having a caprolactone structure can also be used. The polymerizable compound having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.

As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. As the polymerizable compound having an alkyleneoxy group, a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group is preferable, a polymerizable compound having an ethyleneoxy group is more preferable, and 3 to 3 having 4 to 20 ethyleneoxy groups. A hexafunctional (meth) acrylate compound is more preferred. Examples of commercially available products of the polymerizable compound having an alkyleneoxy group include KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. Examples of commercially available products of the polymerizable compound having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth) acrylate monomer having a fluorene skeleton).

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

Examples of the polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-0322293, and Japanese Patent Laid-Open No. 02-016765. 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 suitable. Further, it is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A No. 01-105238. The polymerizable compounds are UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, and LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

The content of the polymerizable compound is preferably 5.0 to 35% by mass in the total solid content of the coloring composition. The upper limit is preferably 30% by mass or less, and more preferably 25% by 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 of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and may 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 triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, hydroxyalkylphenone compounds, aminoalkylphenone compounds and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, a hydroxyalkylphenone compound, an aminoalkylphenone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole dimer. , Onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound and 3-aryl substituted coumarin compound, preferably oxime compound, hydroxyalkylphenone compound, amino. A compound selected from an alkylphenone compound and an acylphosphine compound is more preferable, and an oxime compound is further preferable. Further, as the photopolymerization initiator, the compound described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019 Peroxide-based Photopolymerization Initiator, International Publication No. 2018/221177, Photopolymerization Initiator, International Publication No. 2018/110179, Photopolymerization Initiator, JP-A-2019-043864. Examples thereof include the photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the contents thereof are described in the present invention. Incorporated in the specification.

Examples of the aminoalkylphenone compound include the aminoalkylphenone compound described in JP-A No. 10-291969. Commercially available products of aminoalkylphenone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgure 369, Ir. BASF) and the like.

Examples of the acylphosphine compound include the acylphosphine compound described in Japanese Patent No. 4225898. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).

Examples of the hydroxyalkylphenone compound include compounds represented by the following formula (V).
Equation (V)

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent, and Rv ² and Rv ³ may be bonded to each other to form a ring. m represents an integer from 0 to 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, and more preferably linear. The alkyl group and alkoxy group represented by Rv ¹ may be unsubstituted or may have a substituent. Examples of the substituent include a hydroxy group and a group having a hydroxyalkylphenone structure. Examples of the group having a hydroxyalkylphenone structure include a benzene ring to which Rv ¹ is bonded in the formula (V) or a group having a structure in which one hydrogen atom is removed from Rv ¹ .

As the substituent in Rv ² and Rv ³ , an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferable. Further, 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 linear or branched, more preferably linear.

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 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 1173, Irgar Made) and so on.

Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015/152153, International Publication No. 2017. The compound described in / 051680, the compound described in JP-A-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, etc. Can be mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like. 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxy Examples thereof include imino-1-phenylpropane-1-one. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Powerful Electronics New Materials Co., Ltd.), and ADEKA Corporation. , The photopolymerization initiator 2) described in JP-A-2012-014052. Further, as the oxime compound, it is also preferable to use a compound having no coloring property or a compound having high transparency and hardly discoloring. Examples of commercially available products include ADEKA ARKULS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA).

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466, the compound described in Japanese Patent No. 6636081, and the compound described in Korean Patent Publication No. 10-2016-0109444. Will be.

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

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

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

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 , and -COOR ^X1 . , -OCOR ^X1 , -NR ^X1 R ^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 etc. Can be mentioned. ^RX1 and ^RX2 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is preferable. The number of carbon atoms of the alkyl group as a substituent and the alkyl group represented by ^RX1 and ^RX2 is preferably 1 to 30. The alkyl group may be linear, branched or cyclic, but linear or branched is preferred. The alkyl group may be partially or wholly substituted with a halogen atom (preferably a fluorine atom). Further, in the alkyl group, a part or all of hydrogen atoms may be substituted with the above-mentioned substituent. The aryl group as a substituent and the aryl group represented by ^RX1 and ^RX2 preferably have 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, still more preferably 6 to 10 carbon atoms. The aryl group may be a monocyclic ring or a fused ring. Further, the aryl group may have a part or all of hydrogen atoms substituted with the above-mentioned substituents. The heterocyclic group as a substituent and the heterocyclic group represented by ^RX1 and ^RX2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a fused 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 of 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. Further, in the heterocyclic group, a part or all of hydrogen atoms may be substituted with the above-mentioned substituent.

The aromatic hydrocarbon ring represented by Ar ¹ is preferably an unsubstituted aromatic hydrocarbon ring. The aromatic hydrocarbon ring represented by Ar ² preferably has a substituent. As the substituent, -COR ^X1 is preferable. ^RX1 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. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.

R ¹ of the formula (OX-1) represents an aryl group having a group containing a fluorine atom. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. 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). The fluorine-containing groups include -OR ^F1 , -SR ^F1 , -COR ^F1 , -COOR ^F1 , -OCOR ^F1 , -NR ^F1 R ^F2 , -NHCOR ^F1 , -CONR ^F1 R ^F2 , -NHCONR ^F1 R ^F2 , and -NHCOOR. At least one group selected from ^F1 , -SO ₂ R ^F1 , -SO ₂ OR ^F1 and -NHSO ₂ R ^F1 is preferred. ^RF1 represents a fluorine-containing alkyl group, and ^RF2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group or a heterocyclic group. The fluorine-containing group is preferably -OR ^F1 .

The fluorine-containing alkyl group represented by ^RF1 and ^RF2 and the alkyl group represented by ^RF2 preferably have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms. .. The fluorine-containing alkyl group and the alkyl group may be linear, branched or cyclic, but linear or branched is preferable. In the fluorine-containing alkyl group, the substitution rate of the fluorine atom is preferably 40 to 100%, more preferably 50 to 100%, still more preferably 60 to 100%. The substitution rate of fluorine atoms means the ratio (%) of the number of substitutions to fluorine atoms to the number of total hydrogen atoms of the alkyl group.

The aryl group represented by ^RF2 preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.

The heterocyclic group represented by ^RF2 is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a fused ring. The number of condensations 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 of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the hetero ring group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.

The group containing a fluorine atom preferably has a terminal structure represented by the formula (1) or (2). * In the formula represents a connecting hand.
* -CHF ₂ (1) * -CF ₃ (2)

R ² of the formula (OX-1) represents an alkyl group or an aryl group, and an alkyl group is preferable. The alkyl group and the aryl group may be unsubstituted or may have a substituent.
Examples of the substituent include the substituents described in the above-mentioned substituents that Ar ¹ and Ar ² may have. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched or cyclic, but linear or branched is preferred. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.

R ³ of the formula (OX-1) represents an alkyl group or an aryl group, and an alkyl group is preferable. The alkyl group and the aryl group may be unsubstituted or may have a substituent.
Examples of the substituent include the substituents described in the above-mentioned substituents that Ar ¹ and Ar ² may have. The number of carbon atoms of the alkyl group represented by R ³ is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The alkyl group may be linear, branched or cyclic, but linear or branched is preferred. The aryl group represented by R ³ preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms.

Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like can be mentioned.

As the photopolymerization initiator, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKULS NCI-831 (manufactured by ADEKA).

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 hydroxy group is bonded to the carbazole skeleton can also be used. Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.

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

In the present invention, as the photopolymerization initiator, the photopolymerization initiator A1 having an extinction coefficient of 1.0 × 10 ³ mL / g cm or more in methanol and the extinction coefficient of 365 nm in methanol are 1. It is preferable to use in combination with the photopolymerization initiator A2 having an extinction coefficient of 0 × 10 ² mL / g cm or less and a wavelength of 254 nm of 1.0 × 10 ³ mL / g cm or more. According to this aspect, the coloring composition is easily cured sufficiently by exposure, has good flatness in a low temperature process (for example, a temperature of 150 ° C. or lower, preferably a temperature of 120 ° C. or lower throughout the whole process), and has good flatness. It is possible to form a cured film having excellent 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 extinction coefficient from the above-mentioned compounds.

In the present invention, the absorption coefficient of the photopolymerization initiator at the above wavelength is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution and measuring the absorbance of the above-mentioned measurement solution. Specifically, the above-mentioned measurement solution was placed in a glass cell having a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrum meter (Cary5000) manufactured by Agilent Technologies. The absorbance coefficient (mL / gcm) at 254 nm was calculated.

In the above formula, ε represents the extinction 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 / g cm or more, preferably 1.0 × 10 ⁴ mL / g cm or more, preferably 1.1 ×. It is more preferably 10 ⁴ mL / g cm or more, further preferably 1.2 × 10 ⁴ to 1.0 × 10 ⁵ mL / g cm, and 1.3 × 10 ⁴ to 5.0 × 10 ⁴ mL. It is even more preferably / gcm, and particularly preferably 1.5 × 10 ⁴ to 3.0 × 10 ⁴ mL / gcm.
The absorption coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 254 nm is preferably 1.0 × 10 ⁴ to 1.0 × 10 ⁵ mL / g cm, preferably 1.5 × 10 ⁴ to. It is more preferably 9.5 × 10 ⁴ mL / gcm, and even more preferably 3.0 × 10 ⁴ to 8.0 × 10 ⁴ mL / gcm.

As the photopolymerization initiator A1, an oxime compound, an aminoalkylphenone compound, and an acylphosphine compound are preferable, an oxime compound and an acylphosphine compound are more preferable, an oxime compound is further preferable, and compatibility with other components contained in the composition. From the viewpoint of the above, it is particularly preferable that the oxime compound contains a fluorine atom. Specific examples of the photopolymerization initiator A1 include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (commercially available products include, for example, Irgure OXE01, BASF). , Etanon, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (commercially available products include, for example, Irgacure OXE02, BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercially available products include, for example, Omnirad 819 (IGM Resins BV), Irgacure 819 (BASF)), Examples thereof include (C-13) and (C-14) shown in the above-mentioned specific examples of the oxime compound.

The extinction coefficient of the light having a wavelength of 365 nm in methanol of the photopolymerization initiator A2 is 1.0 × 10 ² mL / gcm or less, preferably 10 to 1.0 × 10 ² mL / gcm, 20 More preferably, it is ~ 1.0 × 10 ² mL / g cm. The difference between the absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator A1 and the absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator A2 is 9.0 × 10 ² mL. It is / gcm or more, preferably 1.0 × 10 ³ mL / gcm or more, more preferably 5.0 × 10 ³ to 3.0 × 10 ⁴ mL / gcm, and more preferably 1.0 × 10 It is more preferably ⁴ to 2.0 × 10 ⁴ mL / g cm. The absorption coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 254 nm is 1.0 × 10 ³ mL / gcm or more, and 1.0 × 10 ³ to 1.0 × 10 ⁶ mL / gcm. It is preferably 5.0 × 10 ³ to 1.0 × 10 ⁵ mL / g cm.

As the photopolymerization initiator A2, a hydroxyalkylphenone compound, a phenylglioxylate compound, an aminoalkylphenone compound and an acylphosphine compound are preferable, a hydroxyalkylphenone compound and a phenylglycilate compound are more preferable, and a hydroxyalkylphenone compound is further preferable. preferable. Further, as the 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-ketone (commercially available products include, for example, Omnirad 184 (IGM Resins BV), Irgure 184 (BASF)). 1- [4- (2-Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one (As a commercial product, for example, Omnirad 2959 (manufactured by IGM Resins BV). , Irgacure 2959 (manufactured by BASF) and the like.

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

The content of the photopolymerization initiator is preferably 0.1 to 17.5% by mass based on the total solid content of the coloring composition. The lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and further preferably 1.5% by mass or more. The upper limit is preferably 15.0% by mass or less, more preferably 12.5% by mass or less, and further preferably 10.0% by mass or less.
Further, the coloring composition of the present invention preferably contains 1.0 to 50 parts by mass of the photopolymerization initiator with respect to 100 parts by mass of the polymerizable compound. The upper limit is preferably 40 parts by mass or less, and 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 good.

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

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

When the above-mentioned photopolymerization initiator A1 and photopolymerization initiator A2 are used as the photopolymerization initiator in the coloring composition of the present invention, the coloring composition of the present invention comprises 100 parts by mass of the photopolymerization initiator A1. On the other hand, it is preferable to contain 50 to 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 having excellent properties such as solvent resistance can be formed in a low temperature process (for example, a temperature of 150 ° C. or lower, preferably a temperature of 120 ° C. or lower throughout the entire process).

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

<< Frill group-containing compound >>
The coloring composition of the present invention can contain a compound containing a frill group (hereinafter, also referred to as a frill group-containing compound). According to this aspect, a coloring composition excellent in low temperature curing can be obtained.

The structure of the frill group-containing compound is not particularly limited as long as it contains a frill group (a group obtained by removing one hydrogen atom from furan). As the frill group-containing compound, the compounds described in paragraphs 0049 to 0089 of JP-A-2017-194662 can be used. Further, JP-A-2000-233581, JP-A-1994-271558, JP-A-1994-293830, JP-A-1996-239421, JP-A-1998-508655, JP-A-2000-001529, Compounds described in JP-A-2003-183348, JP-A-2006-193628, JP-A-2007-186648, JP-A-2010-265377, JP-A-2011-170069, etc. may also be used. can.

The frill group-containing compound may be a monomer or a polymer. A polymer is preferable because it is easy to improve the durability of the obtained film. In the case of a polymer, the weight average molecular weight is preferably 2000 to 70000. The upper limit is preferably 60,000 or less, more preferably 50,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and even more preferably 5000 or more. The polymer-type frill group-containing compound is also a component corresponding to the resin in the coloring composition of the present invention.

The content of the frill group-containing compound is preferably 0.1 to 70% by mass in the total solid content of the coloring composition. The lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and further preferably 7.5% by mass or more. The upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less. The frill group-containing compound may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range.

<< Solvent >>
The coloring composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. 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 these details, paragraph 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein. Further, an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbi Tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methylethylketone, Gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane diacetate-1,3-diyl, dipropylene glycol methyl ether acetate, diacetone alcohol and the like can be mentioned. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) or less, 10 mass ppm or less, or 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, further preferably 130 ° C. or lower. The lower limit of the boiling point is not particularly limited, but is preferably 100 ° C. or higher, for example. Examples of such an organic solvent include butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate and the like, and butyl acetate, propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate are preferable.

In the present invention, it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, a solvent at the mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).

Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter. 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 filter material is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.

In the present invention, the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.

The content of the solvent in the coloring composition is preferably 60 to 95% by mass. Further, the upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and further preferably 85% by mass or less. Further, the lower limit is preferably 65% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more. The solvent may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total amount thereof is within the above range.

Further, it is preferable that the coloring composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations. In the present invention, substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the coloring composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These are REACH (Registration Evolution Analysis and Restriction of Chemicals) rules, PRTR (Pollutant Release and Transfer Register) method, VOC (Volatile and Transfer Registor) method, VOC (Volatile Organic Compounds), and VOC (Volatile Organic Compounds). The method is strictly regulated. These compounds may be used as a solvent in producing each component used in the coloring composition of the present invention, and may be mixed in the coloring composition as a residual solvent. From the viewpoint of human safety and consideration for the environment, it is preferable to reduce these substances as much as possible. As a method for reducing the environmentally regulated substance, there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to improve efficiency. When a compound having radical polymerization property is contained, a polymerization inhibitor or the like is added and the mixture is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be. These distillation methods are either a raw material step, a product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a colored composition step prepared by mixing these compounds. It is also possible at the stage of.

<< Pigment derivative >>
The coloring composition of the present invention can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is replaced with an acid group, a basic group or a phthalimide methyl group. The chromogens constituting the pigment derivative include quinoline skeleton, benzoimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthracinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone skeleton, perylene skeleton, thioindigo skeleton, and iso. Examples thereof include indolin skeleton, isoindolinone skeleton, quinophthalone skeleton, slene skeleton, metal complex skeleton, etc. , Azo skeleton and benzoimidazolone skeleton are more preferred. As the acid group of the pigment derivative, a sulfo group and a carboxy group are preferable, and a sulfo group is more preferable. As the basic group of the pigment derivative, an amino group is preferable, and a tertiary amino group is more preferable.

Specific examples of the pigment derivative 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. Japanese Patent Application Laid-Open No. 03-153780, Japanese Patent Application Laid-Open No. 03-405662, Japanese Patent Application Laid-Open No. 04-285646, Japanese Patent Application Laid-Open No. 06-145546, Japanese Patent Application Laid-Open No. 06-212088, Japanese Patent Application Laid-Open No. 06-240158, Japanese Patent Application Laid-Open No. 10-030063, Japanese Patent Laid-Open No. 10-195326, paragraph numbers 0086 to 0998 of International Publication No. 2011/024896, paragraph numbers 0063 to 0094 of International Publication No. 2012/102399, International Publication No. 2017/038252. Paragraph No. 0087, Paragraph No. 0171 of JP-A-2015-151530, Paragraph Nos. 0162 to 0183 of JP-A-2011-52065, JP-A-2003-081972, JP-A No. 5299151, JP-A-2015-172732 In JP-A-2014-199308, JP-A-2014-085562, JP-A-2014-035351, JP-A-2008-081565, JP-A-2019-109512, JP-A-2019-133154 The described compounds are mentioned.

The content of the pigment derivative is preferably 0.1 to 30 parts by mass with respect to 100 parts by mass of the pigment. The lower limit of this range is more preferably 0.25 parts by mass or more, further preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and 1 part by mass or more. It is more preferable to have. Further, the upper limit of this range is more preferably 25 parts by mass or less, further 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 with time is further improved. As the pigment derivative, only one kind may be used, or two or more kinds may be used in combination. When two or more types are used in combination, it is preferable that the total amount thereof is within the above range.

<< Curing Accelerator >>
In the coloring composition of the present invention, a curing accelerator may be added for the purpose of accelerating the reaction of the polymerizable compound or lowering the curing temperature. Examples of the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the molecule. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like. The polyfunctional thiol compound is preferably a secondary alkanethiol compound, and more preferably a compound represented by the formula (T1).
Equation (T1)

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

Further, the curing accelerator is a methylol-based compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2015-034963), amines, phosphonium salt, amidin salt, amide compound (for example, above, for example. A curing agent described in paragraph No. 0186 of JP2013-041165A, a base generator (eg, an ionic compound described in JP2014-0551114), a cyanate compound (eg, JP2012-150180). A compound described in paragraph No. 0071 of JP-A), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-253504), and an onium salt compound (eg, JP-A-2015-034963). A compound exemplified as an acid generator in paragraph No. 0216, a compound described in JP-A-2009-180949) and the like can also be used.

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

<< Silane Coupling Agent >>
The coloring composition of the present invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two kinds of functional groups having different reactivity in one molecule is preferable. The silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacrylic group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. A silane compound having a above is preferable. Specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (KBM-602, manufactured by Shin-Etsu Chemical Co., Ltd.), 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 (Shin-Etsu Chemical Co., Ltd.) KBE-903) manufactured by Kagaku Kogyo Co., Ltd., 3-methacryloxypropyltrimethoxysilane (KBM-503 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) , KBM-403) and the like. For details of the silane coupling agent, the description in paragraphs 0155 to 0158 of JP2013-254047A can be referred to, and the contents thereof are incorporated in the present specification. When the coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass, preferably 0.01 to 10% by mass, based on the total solid content of the coloring composition. Is more preferable, and 0.1% by mass to 5% by mass is particularly preferable. The coloring composition of the present invention may contain only one kind of silane coupling agent, or may contain two or more kinds of silane coupling agents. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.

<< Polymerization inhibitor >>
The coloring composition of the present invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, first cerium salt, etc.). When the coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the coloring composition. The coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types of the polymerization inhibitor. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.

<< UV absorber >>
The coloring composition of the present invention can contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound and the like can be used. For details thereof, refer to paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-066814, and paragraph numbers 0061 to 0080 of JP2016-162946. It can be taken into consideration and these contents are incorporated in the present specification. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016). Further, 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 is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, based on the total solid content of the coloring composition. It is preferable, and 0.1 to 3% by mass is particularly preferable. Further, as the ultraviolet absorber, only one kind may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

<< Surfactant >>
The coloring composition of the present 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 surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.

The surfactant is preferably a fluorine-based surfactant. By containing a fluorine-based surfactant in the coloring composition, the liquid characteristics (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. It is also possible to form a film having a small thickness unevenness.

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. A fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in a coloring composition.

Examples of the fluorine-based surfactant include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-. The surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification. Commercially available products of fluorine-based surfactants include, for example, Megafax 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 -141-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, manufactured by DIC Co., Ltd.), Fluorard FC430, FC431, FC171 (above, Sumitomo) 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, AGC Co., Ltd.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA), Surfactant 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710F , (Above, manufactured by NEOS Co., Ltd.) and the like.

Further, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied. Can be suitably used. Examples of such a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.

Further, 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. Examples of such a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.

As the fluorine-based surfactant, a block polymer can also be used. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. Further, the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.

The weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000. Among the above compounds,% indicating the ratio of the repeating unit is mol%.

Further, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K, manufactured by DIC Corporation. RS-72-K and the like can be mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.

It is also preferable from the viewpoint of environmental regulation to use the surfactant described in International Publication No. 2020/088454 as a substitute for the surfactant having a perfluoroalkyl group having 6 or more carbon atoms.

It is also preferable to use a fluorine-containing imide salt compound represented by the formula (fi-1) as a surfactant.

In the 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, a primary ammonium ion, and a first. Represents a secondary ammonium ion, a tertiary ammonium ^ion , a quaternary ammonium ion or NH ₄₊ .

Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc. Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF) , Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsparse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.) (Manufactured by Kogyo Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (manufactured by Takemoto Yushi Co., Ltd.), Orfin E1010, Surfinol 104, 400, 440 (manufactured by Nissin Chemical Industry Co., Ltd.) And so on.

Examples of the silicone-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all, Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Chemical Industry Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (all manufactured by Big Chemie), FZ-2122 (Dow Toray Co., Ltd.) Made) and the like.

Further, a compound having the following structure can also be used as the silicone-based surfactant.

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001 to 5.0% by mass, more preferably 0.005 to 3.0% by mass. The surfactant may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount thereof is within the above range.

<< Other additives >>
Various additives such as fillers, adhesion promoters, antioxidants, antiaggregating agents and the like can be added to the coloring composition of the present invention, if necessary. Examples of these additives include the additives described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated in the present specification. Further, as the antioxidant, for example, a phenol compound, a phosphorus-based compound (for example, the compound described in paragraph No. 0042 of JP-A-2011-090147), a thioether compound and the like can be used. Examples of commercially available products include ADEKA's ADEKA stub series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330, etc. ). Further, as the antioxidant, the polyfunctional hindered amine antioxidant described in International Publication No. 2017/006600, the antioxidant described in International Publication No. 2017/1604024, paragraph Nos. 0023 to Patent No. 6268967. The antioxidant described in 0048 can also be used. Only one kind of antioxidant may be used, or two or more kinds may be used. In addition, the coloring composition of the present invention may contain a latent antioxidant, if necessary. The latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Specific examples of the latent antioxidant include the compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219. Examples of commercially available products include ADEKA ARKULS GPA-5001 (manufactured by ADEKA). Further, the coloring composition of the present invention includes a sensitizer and a photostabilizer described in paragraph 0078 of JP-A-2004-295116, a thermal polymerization inhibitor described in paragraph 1981 of JP-A-2004-091940, and JP-A-2018-091940. The storage stabilizer described in paragraph No. 0242 of the publication can be contained.

From the viewpoint of environmental regulation, the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be restricted. In the coloring composition of the present invention, when the content of the above-mentioned compound is reduced, the perfluoroalkyl sulfonic acid (particularly the perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group), a salt thereof, and a par The content of the fluoroalkylcarboxylic acid (particularly the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01 ppb to 1,000 ppb with respect to the total solid content of the coloring composition. It is preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb. The coloring composition of the present invention may be substantially free of perfluoroalkyl sulfonic acid and salts thereof, as well as perfluoroalkyl carboxylic acid and salts thereof. For example, by using a compound that can substitute for perfluoroalkyl sulfonic acid and its salt, and a compound that can substitute for perfluoroalkyl carboxylic acid and its salt, perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid can be used. And a coloring composition that is substantially free of salts thereof may be selected. Examples of compounds that can substitute for the regulated compound include compounds excluded from the regulation due to the difference in the number of carbon atoms of the perfluoroalkyl group. However, the above-mentioned contents do not prevent the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The coloring composition of the present invention may contain a perfluoroalkyl sulfonic acid and a salt thereof, and a perfluoroalkyl carboxylic acid and a salt thereof within the maximum allowable range.

<Accommodation container>
The container for containing the coloring composition of the present invention is not particularly limited, and a known container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and coloring compositions, a multi-layer bottle having a container inner wall made of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure. It is also preferable to use. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351. Further, the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, improving the storage stability of the composition, and suppressing the deterioration of the components.

<Manufacturing method of coloring composition>
The coloring composition of the present invention can be produced by mixing the above-mentioned components. In the production of the coloring composition, all the components may be simultaneously dissolved and / or dispersed in a solvent to produce the coloring composition, or each component may be appropriately used as two or more solutions or dispersions, if necessary. Then, these may be mixed at the time of use (at the time of application) to produce a colored composition.

Further, the process of dispersing the pigment may be included in the production of the coloring composition. In the process of dispersing the pigment, the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to perform the treatment under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove the coarse particles by filtration, centrifugation or the like after the pulverization treatment. In addition, the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial". Practical application The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the pigment, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.

In the production of the coloring composition, it is preferable to filter the coloring composition with a filter for the purpose of removing foreign substances and reducing defects. As the filter, any filter that has been conventionally used for filtration or the like can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP). Examples thereof include filters using materials such as (including high-density, ultra-high molecular weight polyethylene resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

The pore diameter 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. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. For the hole diameter value of the filter, the nominal value of the filter manufacturer can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitts Microfilter Co., Ltd., etc. can be used. ..

It is also preferable to use a fiber-like filter medium as the filter. Examples of the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Examples of 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, different filters (eg, first filter and second filter, etc.) may be combined. At that time, the filtration with each filter may be performed only once or twice or more. Further, filters having different pore diameters may be combined within the above-mentioned range. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.

<Hardened film>
The cured film of the present invention is a film obtained by curing the above-mentioned coloring composition of the present 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 colored layer (pixel) of a color filter, and more preferably used as a red pixel. The film thickness of the cured film of the present invention can be appropriately adjusted depending on the intended purpose, but is preferably 0.5 to 3.0 μm. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, still more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, still more preferably 1.8 μm or less.

<Method of forming a cured film>
Next, a method for forming the cured film will be described.
The method for forming the cured film includes a step of applying the coloring composition of the present invention on a support to form a coloring composition layer, a step of exposing the coloring composition layer (exposure step), and coloring after exposure. It is preferable to include a step of heat-treating the composition layer (post-baking step). Further, when forming a patterned cured film (pixels), the colored composition layer is exposed in a pattern in the above exposure step, and the colored composition layer after exposure is formed between the exposure step and the post-baking step. It is preferable to further include a step of developing (development step).

In forming the cured film, in the present invention, it is preferable to carry out at a temperature of 150 ° C. or lower throughout the entire process. In the present invention, "performing at a temperature of 150 ° C. or lower throughout the entire process" means that all the steps of forming a cured film using the coloring composition are performed at a temperature of 150 ° C. or lower. When a step of further heating after developing the colored composition layer after exposure is provided, it means that this heating step is also performed at a temperature of 150 ° C. or lower. Hereinafter, each step will be described in detail.

In the step of forming the coloring composition layer, the coloring composition of the present invention is applied onto the support to form the coloring composition layer. Examples of the support include a glass substrate and a resin substrate. Examples of the resin substrate include a polycarbonate substrate, a polyester substrate, an aromatic polyamide substrate, a polyamide-imide substrate, a polyimide substrate and the like. An organic light emitting layer may be formed on these substrates. Further, a silicon substrate can also be used as the support. A charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, the support may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the coating property of the coloring composition is good. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant. The underlayer may be formed by using a composition obtained by removing the coloring agent from the coloring composition described in the present specification, a composition containing the resin, the polymerizable compound, the surfactant and the like described in the present specification, and the like. good.

As a method for applying the coloring composition, a known method can be used. For example, a drop method (drop cast); a slit coat method; a spray method; a roll coat method; a rotary coating method (spin coating); a cast coating method; a slit and spin method; a pre-wet method (for example, JP-A-2009-145395). Methods described in the publication); Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned. The method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the coloring 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 the present specification.

The colored composition layer formed on the support may be dried (prebaked). When prebaking is performed, the prebake 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 prebake time is preferably 10 to 3600 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.

Next, the coloring composition layer is exposed (exposure step). For example, the coloring composition layer can be subjected to a stepper exposure machine, a scanner exposure machine, or the like. When forming a patterned cured film (pixels), the colored 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. As a result, the exposed portion can be cured.

Examples of the light that can be used for exposure include ultraviolet rays such as g-line (wavelength 436 nm) and i-line (wavelength 365 nm). The exposure using the i-line may be performed while cutting light having a wavelength shorter than that of the i-line, as described in Japanese Patent Application Laid-Open No. 10201701122130. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm) and the like, and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.

Further, at the time of exposure, light may be continuously irradiated for exposure, or pulsed irradiation may be performed for exposure (pulse exposure). The pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a cycle of a short time (for example, a millisecond level or less).

The irradiation amount (exposure amount) 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 the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment), or may be exposed in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. The exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m ² to 100,000 W / m ² (for example, 5000 W / m ² , 15,000 W / m ² , or 35,000 W / m ² ). Can be done. The oxygen concentration and the exposure illuminance may be appropriately combined with each other, and for example, the illuminance may be 10,000 W / m ² when the oxygen concentration is 10% by volume, the illuminance may be 20000 W / m ² when the oxygen concentration is 35% by volume, and the like.

In the method for forming the cured film, it is also preferable to develop the colored composition layer after exposure. In particular, when the colored composition layer is exposed in a pattern in the exposure step, the unexposed portion of the colored composition layer is developed and removed by developing the exposed colored composition layer to pattern the cured film. It can be formed into a shape to form a pixel. The development and removal of the unexposed portion of the coloring composition layer can be performed using a developing solution. As a result, the colored composition layer of the unexposed portion in the exposure step is eluted in the developing solution, and only the photocured portion remains. The temperature of the developer is preferably, for example, 20 to 30 ° C. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.

Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferable. As the alkaline developer, an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable. Examples of the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. , Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, etc. Examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. As the alkaline agent, a compound having a large molecular weight is preferable in terms of environment and safety. 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. Further, the developer may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed colored composition layer while rotating the support on which the developed colored composition layer is formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support. At this time, when moving the nozzle from the central portion of the support to the peripheral portion, the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion of the support to the peripheral portion.

It is also preferable to perform additional exposure treatment or heat treatment (post-baking) after development and drying. Additional exposure processing and post-baking are post-development curing treatments to complete the curing.

When performing 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, further preferably 100 ° C. or lower. The lower limit of the heating temperature is not particularly limited as long as it can promote the curing of the composition, but is more preferably 50 ° C. or higher, further preferably 75 ° C. or higher. The heating time is preferably 1 minute or longer, more preferably 5 minutes or longer, and even more preferably 10 minutes or longer. The upper limit is not particularly limited, but 20 minutes or less is preferable from the viewpoint of productivity. Post-baking is also preferably carried out in an atmosphere of an inert gas. According to this aspect, thermal polymerization can proceed with very high efficiency without being hindered by oxygen, and even when pixels are manufactured at a temperature of 120 ° C. or lower throughout the entire process, flatness is achieved. It is possible to manufacture pixels having excellent properties such as solvent resistance. Examples of the inert gas include nitrogen gas, argon gas, helium gas and the like, and nitrogen gas is preferable. The oxygen concentration at the time of post-baking is preferably 100 ppm or less.

When performing the additional exposure processing, it is preferable to irradiate with light having a wavelength of 254 to 350 nm for exposure. In a more preferred embodiment, the step of exposing the colored composition layer in a pattern (exposure before development) involves light having a wavelength of more than 350 nm and 380 nm or less (preferably having a wavelength of 355 to 370 nm) with respect to the colored composition layer. The exposure is performed by irradiating with light, more preferably i-line), and the additional exposure treatment (exposure after development) is performed with respect to the developed colored composition layer with light having a wavelength of 254 to 350 nm (preferably a wavelength of 254 nm). It is preferable to irradiate and expose the light. According to this aspect, the coloring composition layer can be appropriately cured by the first exposure (exposure before development), and the entire coloring composition layer is cured almost completely by the next exposure (exposure after development). As a result, the colored composition layer can be sufficiently cured even under low temperature conditions to form pixels having excellent properties such as solvent resistance, adhesion, and rectangularity of the pattern. When the exposure is carried out in two steps as described above, the coloring composition contains, as a photopolymerization initiator, a photopolymerization initiator having an extinction coefficient of 1.0 × 10 ³ mL / g cm or more in a wavelength of 365 nm in methanol. Those containing a photopolymerization initiator having an extinction coefficient of 1.0 × 10 ² mL / g cm or less at a wavelength of 365 nm in methanol and an extinction coefficient of 1.0 × 10 ³ mL / g cm or more at a wavelength of 254 nm. It is preferable to use it.

Exposure after development can be performed using, for example, an ultraviolet photoresist curing device. The ultraviolet photoresist curing apparatus may irradiate light having a wavelength of 254 to 350 nm and other light (for example, i-line).

The exposure amount (irradiation amount) in the exposure after development is preferably 30 to 4000 mJ / cm ² , more preferably 50 to 3500 mJ / cm ² . The difference between the wavelength of the light used in the exposure before development and the wavelength of the light used in the 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 the present invention has the above-mentioned cured film of the present invention. The cured film of the present invention is preferably provided as a colored pixel of a color filter, more preferably as a red pixel.

It is preferable that the color filter of the present invention has colored pixels of other hues in addition to the pixels of the cured film of the present invention. Examples of the colored pixels of other hues include blue pixels, green pixels, yellow pixels, magenta pixels, cyan pixels, and the like. A preferred embodiment of the color filter of the present invention includes an embodiment having a red pixel, a green pixel, and a blue pixel composed of the cured film of the present invention.

The coloring composition for forming green pixels, which is preferably used in combination with the pixels of the cured film of the present invention, has a maximum absorbance A ^max11 for light having a wavelength of 400 to 450 nm and a minimum absorbance A for light having a wavelength 475 to 575 nm. The ratio A ^max11 / A ^min11 with ^min12 is preferably 15 or more, more preferably 20 or more, and further preferably 25 or more.

Further, when the absorbance for light having a wavelength of 450 nm indicated by the coloring composition for forming green pixels is 1, the wavelength at which the absorbance is 0.3 is preferably in the range of 455 to 505 nm, preferably 460 to 500 nm. It is more preferably present in the range, further preferably in the range of 465 to 495 nm, and particularly preferably in the range of 470 to 490 nm.

The coloring composition for forming blue pixels, which is preferably used in combination with the pixels of the cured film of the present invention, has a maximum absorbance A ^max21 for light having a wavelength of 550 to 650 nm and a minimum absorbance Amin21 for light having a wavelength of 400 to 500 nm. The ratio of A max21 / A min21 to and A ^max21 / A ^min21 is preferably 10 or more, more preferably 12.5 or more, and further preferably 15 or more.

Further, when the absorbance for light having a wavelength of 600 nm indicated by the coloring composition for forming blue pixels is 1, the wavelength at which the absorbance is 0.3 is preferably in the range of 475 to 555 nm, preferably 480 to 540 nm. It is more preferably present in the range, more preferably in the range of 485 to 525 nm, and particularly preferably in the range of 490 to 510 nm.

The color filter of the present invention can be used for a display device, a solid-state image pickup device such as a CCD (charge-coupled device) or CMOS (complementary metal oxide semiconductor).

In the color filter of the present invention, the film thickness of the cured film of the present invention can be appropriately adjusted depending on the intended purpose, but is preferably 0.5 to 3.0 μm. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, still more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, still 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, still more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, still more preferably 2.75 μm or more.

The color filter of the present invention may be provided with a protective layer on the surface of the cured film of the present invention. By providing the protective layer, various functions such as oxygen blocking, low reflection, prohydrophobicization, and shielding of light of a specific wavelength (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. Examples of the method for forming the protective layer include a method of applying a resin composition dissolved in an organic solvent to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. The components constituting the protective layer include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide. Resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples thereof include resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ , and the like, and two or more of these components may be contained. For example, in the case of a protective layer for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO ₂ , and Si ₂ N ₄ . Further, in the case of a protective layer for the purpose of reducing reflection, it is preferable that the protective layer contains a (meth) acrylic resin and a fluororesin.

When the resin composition is applied to form the protective layer, a known method such as a spin coating method, a casting method, a screen printing method, or an inkjet method can be used as the application method of 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 the chemical vapor deposition method, the known chemical vapor deposition method (thermochemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) is used as the chemical vapor deposition method. Can be used.

As necessary, the protective layer is added with organic fine particles, inorganic fine particles, an absorbent for light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an antioxidant, an adhesive, a surfactant, and the like. It may contain an agent. Examples of organic fine particles include polymer fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), and examples of inorganic fine particles include titanium oxide, zinc oxide, zirconium oxide, indium oxide, and aluminum oxide. Examples thereof include titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like. A known absorber can be used as the absorber of light having a specific wavelength. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer.

Further, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of JP-A-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. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the coating property of the coloring composition is good. The surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.

The color filter may have a structure in which each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.

<Display device>
The display device of the present invention has the above-mentioned cured film of the present invention. Examples of the display device include a liquid crystal display device and an organic electroluminescence display device. For details on the definition of display devices and the details of each display device, see, for example, "Electronic Display Devices (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", "Display Devices (Junaki Ibuki, Sangyo Tosho Co., Ltd.)" (Published in 1989) ”and so on. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".

The organic electroluminescence display device may have a light source composed of a white organic electroluminescence element. The white organic electroluminescence device preferably has a tandem structure. Regarding the tandem structure of organic electroluminescence elements, Japanese Patent Application Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association It is described on pages 326-328, 2008 and the like. The spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 nm-700 nm) are more preferable.

The present invention will be specifically described below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate 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) according to the following conditions.
Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000 linked. Developing solvent: tetrahydrofuran Column temperature: 40 ° C.
Flow rate (sample injection amount): 1.0 μL (sample concentration 0.1% by mass)
Device name: HLC-8220GPC manufactured by Tosoh Corporation
Detector: RI (refractive index) detector Calibration curve base resin: Polystyrene resin

<Preparation of colorant solution>
The raw materials listed in the table below were uniformly stirred and mixed, and then dispersed with an Eiger motor mill (“Mini Model M-250MKII” manufactured by Eiger Japan) for 5 hours 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 size of 5 μm. The table below shows the blending amount of each raw material by mass. Blank indicates that it is not included.

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

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

(Dispersant)
Dispersant 1: Solsparse 20000 (manufactured by Japan Lubrizol)
Dispersant 2: Resin solution D2 prepared by the following method
Put 90.0 parts by mass of cyclohexanone in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux cooler, and gas introduction tube, heat to 60 ° C while injecting nitrogen gas into the vessel, and polymerize at the same temperature. A mixture of 20.0 parts by mass of 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. The polymerization reaction was carried out by dropping over 2 hours. After completion of the dropping, the mixture was further reacted at 60 ° C. for 1 hour, and then 0.5 parts by mass of 2,2'-azobisisobutyronitrile was dissolved in 10.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). Was added, and then stirring was continued at the same temperature for 3 hours to obtain a resin (copolymer). After cooling to room temperature, the mixture was diluted with cyclohexanone to obtain a resin solution D2 having a solid content concentration of 20%. The weight average molecular weight of the obtained resin (copolymer) was 30,000.

(Pigment derivative)
Pigment derivative 1: A compound having the following structure

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

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 produced above.

(Photopolymerization initiator)
I-1: Irgure OXE02 (manufactured by BASF, a compound having the following structure)
I-2: Omnirad 2959 (manufactured by IGM Resins B.V., compound having the following structure)
I-3: Compound with the following structure

(Resin solution)
A-1 to A-9: 40% by mass PGMEA solution of resin having the following structure Resin solution A-1 was prepared by the following method. That is, 207 parts by mass of PGMEA was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-necked flask, the temperature was raised to 80 ° C., and the inside of the reaction vessel was replaced with nitrogen. Then, from the dropping tube, 16 parts by mass of styrene, 75 parts by mass of glycidyl methacrylate, 2 parts by mass of dicyclopentanyl methacrylate, 10 parts by mass of methyl methacrylate, and 2,2'-azobisisobutyronitrile 1. 33 parts by weight of the mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a resin having the following structure. 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.
The resin solutions A-2 to A-9 were prepared in the same manner as the resin solution A-1.

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

A-111: A 40% by mass PGMEA solution of a resin having the following structure.

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

D-1: A 40% by mass PGMEA solution of a resin having 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 whose acid group is protected by the protecting group are shown in the table below. For the resins A-1 to A-10, A-12, and D-1, the value of the ratio of the content of the cyclic ether group to the content of the acid group is described in the column of content ratio. Further, for the 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 the protecting group is described in the column of content ratio.

(Polymerizable compound)
M-1: Aronix M-402 (Made by Toagosei Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
M-2: Compound with the following structure (a + b + c = 3)

M-3: NK Ester A-TMMT (manufactured by Shin Nakamura Chemical Industry 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 onto 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. Then, 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 was heated on a hot plate at 100 ° C. for 20 minutes and allowed to cool to form a cured film. In the preparation of the cured film, the temperature of the substrate is in the range of 20 to 100 ° C. throughout the entire process. The obtained cured film was measured for the absorbance of light in the wavelength range of 300 to 800 nm using an ultraviolet-visible near-infrared spectrophotometer (UV3600, manufactured by Shimadzu Corporation) using a reference as a glass substrate, and the wavelength was 400. The ratio of the maximum absorbance A ^max1 for light of up to 500 nm and the minimum absorbance A ^min1 for light with a wavelength of 550 to 700 nm A ^max1 / A ^min1 (hereinafter referred to as the absorbance ratio 1), the absorbance for light with a wavelength of 500 nm is 1. Then, the wavelengths at which the absorbance was 0.3 (hereinafter referred to as wavelength 1) were measured.

<Evaluation of color mixing>
Using a spin coater, each coloring composition was applied onto 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. Then, 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 . Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Then, it was heated on a hot plate at 100 ° C. for 20 minutes and allowed to cool to form a cured film. Using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.), the transmittance (T1) of the obtained cured film having a wavelength of 450 nm was measured.
Next, a coloring composition for color mixing evaluation is applied onto this cured film using a spin coater so that the film thickness after drying is 2 μm, and the mixture is dried on a hot plate at 100 ° C. for 2 minutes to evaluate the color mixing. A coating film of the coloring composition for use was formed, and a laminated film was formed. As the coloring composition for color mixing evaluation, the blue coloring composition used for forming the blue pixels of Example 1001 described later was used.
Next, the glass substrate on which this laminated film was formed was placed on a horizontal rotary table of a spin shower processor (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fujifilm Electronics Materials Co., Ltd.) Paddle development was performed at 23 ° C. for 60 seconds using a 60% diluted solution (manufactured by Co., Ltd.), and the coating film of the coloring composition for color mixing evaluation formed on the cured film was developed and removed. Next, the above-mentioned glass substrate is fixed to a horizontal rotary table by a vacuum chuck method, and while the glass substrate is rotated at a rotation speed of 50 rpm by a rotating device, pure water is supplied from above the center of rotation in a shower shape from above the center of rotation. It was rinsed and then spray dried.
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 the coating film of the coloring composition for color mixing evaluation was developed and removed was measured.
The rate of change in transmittance was calculated from the following formula, and the color mixing was evaluated according to the following evaluation criteria.
Change rate of transmittance (%) = {| Transmittance (T1) -Transmittance (T2) | / Transmittance (T1)} x 100
S: The change rate of the transmittance is less than 0.1% A: The change rate of the transmittance is 0.1% or more and less than 0.25% B: The change rate of the transmittance is 0.25% or more and 1% Less than C: Transmittance change rate is 1% or more and less than 2.5% D: Transmittance change rate is 2.5% or more and less than 5% E: Transmittance change rate is 5% or more Is

<Evaluation of storage stability>
The viscosity (V ₁ ) of the coloring composition immediately after production obtained above was measured with "RE-85L" manufactured by Toki Sangyo Co., Ltd. The coloring composition was allowed to stand for 3 days under a temperature condition of 40 ° C., and then the viscosity (V ₂ ) was measured. The thickening rate was calculated from 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 shown in the table below.
Thickness increase rate (%) = {(viscosity (V ₂ ) -viscosity (V ₁ )) / viscosity (V ₁ )} × 100
S: The thickening rate is less than 0.1% A: The thickening rate is 0.1% or more and less than 0.25% B: The thickening rate is 0.25% or more and less than 1% C: Increased The viscosity is 1% or more and less than 2.5%. D: The viscosity is 2.5% or more and less than 5%. E: The viscosity is 5% or more.

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

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

<Example 1001>
The green coloring composition was applied onto the silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 μm. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at an exposure amount of 1000 mJ / cm ² through a mask with a dot pattern of 12 μm square. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water. Then, it was heated on a hot plate at 100 ° C. for 20 minutes and allowed to cool to form a green coloring pattern (green pixel). Similarly, the red coloring composition and the blue coloring composition were sequentially patterned to form a red coloring pattern (red pixel) and a blue coloring pattern (blue pixel), respectively, to produce a color filter.
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 was incorporated into an organic electroluminescence display device according to a known method. This organic electroluminescence display device had suitable image recognition ability.

[Green coloring composition]
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a green coloring composition.
Green pigment dispersion: 85 parts by mass Photopolymerization initiator (Irgacure OXE02, manufactured by BASF) ... 1.04 parts by mass Photopolymerization initiator (Omnirad 2959, manufactured by IGM Resins B.V.)
・・・ 0.77 parts by mass Resin solution 1 ・・・ 0.9 parts by mass Frill group-containing compound solution 1 ・・・ 1.4 parts by mass Polymerizable compound (compound with the following structure) ・・・ 2.04 parts by mass

Surfactant (compound having the following structure, Mw = 14000, the numerical value of% indicating the ratio of the repeating unit is mol%, fluorine-based surfactant) ... 0.008 parts by mass

Propylene glycol monomethyl ether acetate: 8.8 parts by mass

[Blue coloring composition]
The following components were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a blue coloring composition.
Blue pigment dispersion: 51.0 parts by mass Photopolymerization initiator (Irgacure OXE01, manufactured by BASF) ... 2.17 parts by mass Photopolymerization initiator (Omnirad 2959, manufactured by IGM Resins B.V.).・・ 0.83 parts by mass Resin solution 1 ・・・ 4.1 parts by mass Frill group-containing compound solution 1 ・・・ 6.2 parts by mass Polymerizable compound (compound with 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, the Blue pigment dispersion, the resin solution 1, and the frill group-containing compound solution 1 used for preparing the green coloring composition and the blue coloring composition are as follows.

(Green pigment dispersion)
C. I. 7.4 parts by mass of Pigment Green 36, C.I. I. A mixed solution consisting of 5.2 parts by mass of Pigment Yellow 185, 1.4 parts by mass of pigment derivative 1, 4.86 parts by mass of dispersant 1, and 81.14 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm). The pigment dispersion was prepared by mixing and dispersing according to the diameter) for 3 hours. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a pressure of 2000 kg / cm ³ at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

Pigment derivative 1: A compound having the following structure

Dispersant 1: A resin having the following structure. The numbers in parentheses in the main chain represent the molar ratio of each repeating unit, and the numbers in parentheses in the side chain represent the number of repetitions in the repeating unit. The weight average molecular weight is 24000.

(Blue pigment dispersion)
C. I. Pigment Blue 15: 6, 9.5 parts by mass, C.I. I. A mixture consisting of 5.0 parts by mass of Pigment Violet 23, 5.5 parts by mass of dispersant 1, and 80.0 parts by mass of PGMEA was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.3 mm diameter). , A pigment dispersion was prepared. After that, a high-pressure disperser with a decompression mechanism NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) was used to perform a dispersion treatment at a pressure of 2000 kg / cm ³ at a flow rate of 500 g / min. This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion liquid.

(Resin solution 1)
30% by mass PGMEA solution of resin A synthesized by the following method Put 70.0 parts by mass of cyclohexanone in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and raise the temperature to 80 ° C. After warming and replacing the inside of the flask with nitrogen, 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, and paracumylphenol ethylene oxide modification from the dropping tube. A mixture of 7.4 parts by mass of acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.) and 0.4 parts by mass of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to synthesize resin A (Mw = 26000) and diluted with PGMEA to obtain a 30% by mass PGMEA solution of resin A.

(Frill group-containing compound solution 1)
20% by mass PGMEA solution of frill group-containing compound F1 synthesized by the following method Put 90.0 parts by mass of PGMEA in a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, and nitrogen gas in the container. Heat to 60 ° C. while injecting, and at the same temperature, 50.0 parts by mass of flufuryl methacrylate, 26.7 parts by mass of 2-methacryloyloxyethyl succinic acid, 23.3 parts by mass of 2-hydroxyethyl methacrylate, 2,2. A mixture of 2.5 parts by mass of'-azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropping, the mixture was further reacted at 60 ° C. for 1 hour, and then 0.5 part by mass of 2,2'-azobis (2,4-dimethylvaleronitrile) dissolved in 10.0 parts by mass of PGMEA was added. After that, stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, the mixture was diluted with PGMEA to obtain a 20% by mass PGMEA solution of the frill group-containing compound F1 (Mw = 52000).

Claims

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

In formula (e-1), RE1 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, and * represents a bond.
The resin EP has the content of the cyclic ether group A of 2.0 to 6.5 mmol / g, and is the sum of the content of the acid group and the content of the group in which the acid group is protected by a protecting group. The coloring composition according to claim 1, wherein the amount is 0.45 to 2.35 mmol / g.
The claim that the content of the cyclic ether group A of the resin EP, the content of the acid group, and the content of the group in which the acid group is protected by a protecting group satisfy the condition of the following formula (1). The coloring composition according to 1 or 2.
1.0 ≦ (Content of the cyclic ether group A of the resin EP (unit: mmol / g) / (Content of the acid group of the resin EP (unit: mmol / g) + (The acid group of the resin EP is Content of groups protected by protecting groups (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 hydroxy group or a carboxy group.
The coloring composition according to any one of claims 1 to 4, wherein the protecting group is a group represented by any of the formulas (Y1) to (Y5);
Equation ( Y1 ): -C (RY1) ( RY2 ) ( RY3 )
Equation (Y2): -C (= O) OC ( RY4 ) ( RY5 ) ( RY6 )
Equation (Y3): -C ( RY7 ) ( RY8 ) (OR Y9 )
Equation (Y4): -C ( RY10 ) (H) (Ar Y1 )
Equation (Y5): -C (= O) ( RY11 )
In formula ( Y1 ), RY1 to RY3 each independently represent an alkyl group, and two of RY1 to RY3 may be bonded to form a ring;
In formula (Y2), RY4 to RY6 each independently represent an alkyl group, and two of RY4 to RY6 may be bonded to form a ring;
In formula (Y3), RY7 and RY8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of RY7 and RY8 is an alkyl group or an aryl group, and RY9 is an alkyl. Representing a group or aryl group, RY7 or RY8 and RY9 may be combined to form a ring;
In formula (Y4), Ar Y1 represents an aryl group and RY10 represents an alkyl or aryl group;
In formula (Y5), RY11 represents an alkyl or aryl group.
The coloring composition according to any one of claims 1 to 5, wherein the coloring agent further contains a yellow coloring agent.
The coloring composition according to any one of claims 1 to 6, 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 7, which is used for forming a cured film at a temperature of 150 ° C. or lower throughout the entire process.
The coloring composition according to any one of claims 1 to 8, which is for a color filter.
The coloring composition according to any one of claims 1 to 9, which is for a display device.
A cured film obtained by curing the coloring composition according to any one of claims 1 to 10.
The color filter having the cured film according to claim 11.
A display device having the cured film according to claim 11.