CN115803682A

CN115803682A - Coloring composition, hardening film, color filter and display device

Info

Publication number: CN115803682A
Application number: CN202180048015.3A
Authority: CN
Inventors: 小川宽晃; 柏木大助; 山本启之
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2020-08-31
Filing date: 2021-08-19
Publication date: 2023-03-14
Also published as: JPWO2022044972A1; WO2022044972A1; TW202210527A

Abstract

The invention provides a coloring composition, a cured film, a color filter and a display device, wherein the coloring composition can form the cured film which has excellent storage stability and can inhibit color mixing with other colors. The coloring composition comprises a colorant containing a red colorant, a resin, a polymerizable compound and a photopolymerization initiator, wherein the resin comprises a resin EP containing a repeating unit A and a repeating unit B, the repeating unit A has at least one cyclic ether group A selected from a group represented by a formula (e-1) and a group represented by a formula (e-2), and the repeating unit B is at least one 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 maximum value Ama of absorbance with respect to light having a wavelength of 400 to 500nm in the colored composition ^x1 Absorption of light having a wavelength of 550 to 700nmMinimum value of luminosity A ^min1 Ratio of A ^max1 /A ^min1 The absorbance of the light is 25 or more, and when the absorbance for light having a wavelength of 500nm is 1, the wavelength at which the absorbance becomes 0.3 is in the range of 570 to 620 nm.

Description

Coloring composition, hardening film, color filter and display device

Technical Field

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. The present invention also relates to a cured film, a color filter and a display device using the colored composition.

Background

In various display devices, a color filter is generally used to colorize a display image. A color filter is manufactured using a colored composition containing a colorant, a resin, a polymerizable compound, and a photopolymerization initiator (for example, patent document 1).

Prior art documents

Patent document

Patent document 1: japanese patent laid-open publication No. 2018-087956

Disclosure of Invention

Technical problem to be solved by the invention

When a color filter or the like is produced using the colored composition, a color filter can also be produced using the colored composition immediately after production. Therefore, the coloring composition is required to have excellent storage stability.

In general, a color filter has pixels of a plurality of colors. The color filter having such pixels of a plurality of colors is manufactured by sequentially patterning the color compositions for forming pixels of respective colors to form pixels of respective colors.

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 a low-temperature process at 150 ℃.

However, when pixels are formed in a low-temperature process, the degree of curing of the pixels may be insufficient, and when pixels of other colors are formed, color mixing with a coloring composition of another color tends to occur, and spectral characteristics tend to be easily changed.

Further, according to the study of the present inventors, it is known that the coloring composition described in patent document 1 has room for further improvement in color mixture with other colors.

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

Means for solving the technical problems

According to the studies of the present inventors, it was found that the above object can be achieved by using a coloring composition described later, and the present invention was completed. The present invention provides the following.

<1> a coloring composition comprising a colorant comprising a red colorant, a resin, a polymerizable compound and a photopolymerization initiator,

the above resin comprises a resin EP containing a repeating unit A having at least one cyclic ether group A selected from the group represented by the formula (e-1) and the group represented by the formula (e-2) and a repeating unit B selected from at least one 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 colored composition, the maximum value A of the absorbance with respect to light having a wavelength of 400 to 500nm ^max1 And the minimum value A of absorbance with respect to light having a wavelength of 550 to 700nm ^min1 Ratio of A ^max1 /A ^min1 The content of the organic acid is more than 25,

when the absorbance for light having a wavelength of 500nm is 1, the wavelength at which the absorbance becomes 0.3 is in the range of 570 to 620nm,

[ chemical formula 1]

In the formula (e-1), R ^E1 Represents a hydrogen atom or an alkyl group, n represents 0 or 1, represents a connecting bond,

in the formula (e-2), ring A ^E1 Fats representing a single ringA hydrocarbon ring, representing a bond.

<2> the coloring composition according to <1>, wherein,

in the resin EP, the content of the cyclic ether group A is 2.0 to 6.5mmol/g, and the total of the content of the acid group and the content of the group in which the acid group is protected by the protecting group is 0.45 to 2.35mmol/g.

<3> the coloring composition according to <1> or <2>, wherein,

the content of the cyclic ether group a, the content of the acid group, and the content of the group in which the acid group is protected by the protecting group in the resin EP satisfy the condition of the following formula (1).

1.0. Ltoreq. With respect to the total amount of the cyclic ether group A in the resin EP (unit: mmol/g)/(acid group in the resin EP (unit: mmol/g) + acid group in the resin EP (unit: mmol/g)) 14.0. Ltoreq.8230, (1)

<4> the coloring composition according to any one of <1> to <3>, wherein,

the acid group is a phenolic hydroxyl group or a carboxyl group.

<5> the coloring composition according to any one of <1> to <4>, wherein,

the protective group is a group represented by any one of formulae (Y1) to (Y5),

formula (Y1): -C (R) ^Y1 )(R ^Y2 )(R ^Y3 )

Formula (Y2): -C (= 0) OC (R) ^Y4 )(R ^Y5 )(R ^Y6 )

Formula (Y3): -C (R) ^Y7 )(R ^Y8 )(OR ^Y9 )

Formula (Y4): -C (R) ^Y10 )(H)(Ar ^Y1 )

Formula (Y5): -C (= O) (R) ^Y11 )

In the formula (Y1), R ^Y1 ～R ^Y3 Each independently represents an alkyl group, R ^Y1 ～R ^Y3 2 of which may be bonded to form a ring,

in the formula (Y2), R ^Y4 ～R ^Y6 Each independently represents an alkyl group, R ^Y4 ～R ^Y6 2 of which may be bonded to form a ring,

in the formula (Y3), R ^Y7 And R ^Y8 Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ^Y7 And R ^Y8 At least one of which is alkyl or aryl, R ^Y9 Represents alkyl or aryl, R ^Y7 Or R ^Y8 And R ^Y9 May be bonded to form a ring,

in the formula (Y4), ar ^Y1 Represents aryl, R ^Y10 Represents an alkyl group or an aryl group,

in the formula (Y5), R ^Y11 Represents an alkyl group or an aryl group.

<6> the coloring composition according to any one of <1> to <5>, wherein,

the colorant further comprises a yellow colorant.

<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 ℃ or less throughout the process.

<9> the colored composition according to any one of <1> to <8>, which is used for a color filter.

<10> the coloring composition according to any one of <1> to <9> for a display device.

<11> a cured film obtained by curing the coloring composition of any one of <1> to <10 >.

<12> a color filter having the cured film <11 >.

<13> a display device having the cured film of <11 >.

Effects of the invention

According to the present invention, it is possible to provide a coloring composition capable of forming a cured film having good storage stability and suppressed color mixing with other colors, a cured film using the coloring composition, a color filter, and a display device.

Detailed Description

The present invention will be described in detail below.

In labeling of a group (atomic group) in the present specification, a label not labeled with a substitution and a label not labeled with a substitution include a group (atomic group) having no substituent and also include a group (atomic group) having a substituent. For example, the term "alkyl group" encompasses not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, unless otherwise specified, "exposure" includes exposure using a particle beam such as an electron beam or an ion beam, in addition to exposure using light. The light used for exposure is usually an active light or radiation such as far ultraviolet light typified by a bright line spectrum of a mercury lamp or an excimer laser, extreme ultraviolet light (EUV light), X-ray, and electron beam.

In the present specification, the numerical range expressed by the term "to" refers to a range including numerical values before and after the term "to" as a lower limit value and an upper limit value.

In the present specification, the total solid content means the total mass of the components excluding the solvent from all the components of the composition.

In the present specification, "(meth) acrylate" represents both or either of acrylate and methyl acrylate, "(meth) acrylic acid" represents both or either of acrylic acid and methacrylic acid, "(meth) allyl" represents both or either of allyl and methallyl, and "(meth) acryloyl" represents both or either of acryloyl and methacryloyl.

In the present specification, the term "step" is included in the present term as long as the intended function of the step is exhibited, even when the step cannot be clearly distinguished from other steps other than the independent step.

In the present specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by Gel Permeation Chromatography (GPC).

< coloring composition >

The coloring composition of the present invention contains a resin.

A coloring composition comprising a coloring agent containing a red coloring agent, a resin, a polymerizable compound and a photopolymerization initiator, wherein,

in the colored composition, the maximum value A of the absorbance with respect to light having a wavelength of 400 to 500nm ^max1 And the minimum value A of absorbance with respect to light having a wavelength of 550 to 700nm ^min1 Ratio of A ^maxt /A ^min1 The content of the organic acid is more than 25,

when the absorbance for light having a wavelength of 500nm is 1, the wavelength at which the absorbance becomes 0.3 is in the range of 570 to 620 nm.

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

The detailed reason why such an effect can be obtained is not clear, but the reason is presumed as follows. It is presumed that the coloring composition having the spectral characteristics is difficult to emit heat when the coloring composition is heated and cured, and the resin EP and the like can be cured by effectively utilizing heat. The resin EP is assumed to be a highly reactive resin. Therefore, it is presumed that when the resin EP is contained in the coloring composition having the spectral characteristics, curing of the coloring composition rapidly proceeds when the coloring composition is heated and cured, and as a result, a sufficiently cured film can be formed even when the coloring composition is heated at a relatively low temperature. Therefore, it is presumed that the coloring composition of the present invention can form a cured film in which color mixing with other colors is suppressed.

Further, it is presumed that since the colored composition has the above-mentioned specific spectral characteristics, the reaction of the resin and the curable component such as the polymerizable compound caused by external light during storage can be suppressed, and as a result, the colored composition has excellent storage stability.

The absorbance a λ at a certain wavelength λ is defined by the following formula (Ab 1).

Aλ＝-log(Tλ/100)…… (Ab1)

A λ is an absorbance at the wavelength λ, and T λ is a transmittance (%) of light at the wavelength λ.

In the present invention, the value of the absorbance of the coloring composition may be a value measured in a state of a solution, or may be a value of a cured film formed using the coloring composition. When the absorbance is measured in a state where the film is cured, it is preferable that the coloring composition is applied to a glass substrate by a spin coating method or the like, dried at 100 ℃ for 2 minutes using a hot plate or the like, and then, the resultant is irradiated with 20mW/cm of illuminance ² The exposure amount was 1J/cm ² I-ray exposure was performed under the conditions of (1), followed by heating on a hot plate at 100 ℃ for 20 minutes, and measurement was performed using a film (cured film) obtained by naturally cooling to room temperature. The absorbance can be measured using a conventionally known spectrophotometer.

In the colored composition of the invention, the maximum value A of absorbance with respect to light having a wavelength of 400 to 500nm ^max1 And the minimum value A of absorbance with respect to light having a wavelength of 550 to 700nm ^min1 Ratio of A ^max1 /A ^min1 Is 25 or more, preferably 50 or more, and more preferably 100 or more. The above ratio A ^max1 /A ^min1 The higher the value of (b), the more remarkable the effects of the present invention described above can be obtained, and further, a red pixel excellent in color separation from other colors can be easily formed. Thus, with respect to the above ratio A ^max1 /A ^min1 The upper limit of the value of (b) is not particularly limited, but may be 10000 or less, 5000 or less, or 1000 or less, for example。

When the absorbance of the colored composition of the present invention with respect to light having a wavelength of 500nm is 1, the wavelength at which the absorbance becomes 0.3 is in the range of 570 to 620nm, preferably 575 to 615nm, more preferably 580 to 610nm, and still more preferably 585 to 605 nm.

When the absorbance for light having a wavelength of 500nm shown in the colored composition of the present invention is 1, the wavelength at which the absorbance becomes 0.5 is preferably in the range of 565 to 605nm, more preferably in the range of 570 to 600nm, and still more preferably in the range of 575 to 595 nm.

In the colored composition of the present invention, the maximum value A of absorbance with respect to light having a wavelength of 400 to 500nm ^max1 And absorbance A with respect to light having a wavelength of 550nm ⁵⁵⁰ Ratio of A to B ^max1 /A ⁵⁵⁰ Preferably 2 or less, more preferably 1.75 or less, and still more preferably 1.5 or less.

In the colored composition of the present invention, the maximum value A of absorbance with respect to light having a wavelength of 400 to 500nm ^max1 And absorbance A with respect to light having a wavelength of 600nm ⁶⁰⁰ Ratio of A to B ^max1 /A ⁶⁰⁰ Preferably 5 to 15, more preferably 6.5 to 13.5, and still more preferably 8 to 12.

In the colored composition of the present invention, the maximum value A of absorbance with respect to light having a wavelength of 400 to 500nm ^max1 And absorbance A with respect to light having a wavelength of 650nm ⁶⁵⁰ Ratio of A ^max1 /A ⁶⁵⁰ Preferably 25 or more, more preferably 50 or more, and still more preferably 100 or more.

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

The coloring composition of the present invention has a transmittance of preferably 1% or less, more preferably 0.75% or less, and even more preferably 0.5% or less, with respect to light having a wavelength of 500nm, when forming a cured film having a film thickness of 0.5 to 3.0. Mu.m. The maximum value of the transmittance with respect to light having a wavelength of 400 to 500nm is preferably 1% or less, more preferably 0.75% or less, and still more preferably 0.5% or less.

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

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

The coloring composition of the present invention can be preferably used as a coloring composition for a display device. More specifically, the coloring composition for forming pixels can be preferably used as a color filter for a display device, and more preferably used 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, but 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 imaging element. More specifically, the coloring composition for forming pixels can be preferably used as a color filter for a solid-state imaging element, and more preferably used as a coloring composition for forming red pixels of a color filter for a solid-state imaging element.

The coloring composition of the present invention is also preferably a coloring composition for forming a cured film at a temperature of 150 ℃ or lower (preferably 120 ℃ or lower) throughout the entire process. In the present specification, the entire process includes, for example, a process of forming a cured film using the colorant composition. In the present specification, the formation of a cured film at a temperature of 150 ℃ or lower throughout the entire process means that all processes for forming a cured film using a coloring composition are performed at a temperature of 150 ℃ or lower, but is not limited thereto.

The thickness of the cured film and the pixel formed from the colored composition of the present invention is preferably 0.5 to 3.0. Mu.m. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and further preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.8 μm or less.

Further, the line width (pattern size) of the pixel formed from 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, and 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, and further preferably 2.75 μm or more.

The coloring composition of the present invention will be described in detail below.

< coloring agent >

The coloring composition of the present invention contains a colorant. Examples of the colorant include color colorants such as a red colorant, a green colorant, a blue colorant, a yellow colorant, a violet colorant, and an orange colorant. In the present invention, the colorant may be a pigment or a dye. The colorant may be a combination of a pigment and a dye. The pigment may be any of an inorganic pigment and an organic pigment. As the pigment, a material in which an organic chromophore replaces a part of an inorganic pigment or an organic-inorganic pigment can also be used. By substituting an organic chromophore for an inorganic pigment or an organic-inorganic pigment, hue design can be easily performed. When a substance containing a pigment is used as a colorant, a cured film having excellent durability such as heat resistance and light resistance is easily formed. In the case of using a substance containing a dye as a colorant, a cured film having a higher color reproduction region of red color is easily formed. Further, in general, a cured film obtained using a dye tends to be more likely to cause color mixing than a cured film obtained using a pigment, and according to the present invention, a cured film in which color shift is suppressed can be formed even when a dye is used as a colorant, and therefore, the present invention is particularly effective when a substance containing a dye is used as a colorant.

The average primary particle diameter of the pigment is preferably 1 to 200nm. The lower limit is preferably 5nm or more, and more preferably 10nm or more. The upper limit is preferably 180nm or less, more preferably 150nm or less, and further preferably 100nm or less. When the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the coloring composition is good. In the present invention, the primary particle diameter of the pigment can be determined from a transmission electron microscope observation of the primary particles of the pigment and an obtained image photograph. Specifically, the projected area of the primary particles of the pigment is determined, and the equivalent circle diameter corresponding thereto is calculated as the primary particle diameter of the pigment. The average primary particle size in the present invention is an arithmetic average of the primary particle sizes of the primary particles of 400 pigments. And, the primary particles of the pigment mean individual particles that are not aggregated.

Pigment multimers can also be used in the colorants. The pigment multimer is preferably a dye used dissolved in a solvent. Also, the pigment multimer may form particles. When the pigment multimer is a particle, it is generally used in a state of being dispersed in a solvent. The pigment multimer in a particle state can be obtained by, for example, emulsion polymerization, and specific examples thereof include the compounds and the production methods described in Japanese patent laid-open No. 2015-214682. The dye multimer has 2 or more dye structures, preferably 3 or more dye structures, in one molecule. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures in one molecule may be the same dye structure or different dye structures. The weight average molecular weight (Mw) of the pigment multimer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and still more preferably 6000 or more. The upper limit is more preferably 30000 or less, and still more preferably 20000 or less. As the dye multimer, compounds described in Japanese patent application laid-open Nos. 2011-213925, 2013-041097, 2015-028144, 2015-030742, and International publication No. 2016/031442 can 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 also be used in combination. The red colorant is preferably a pigment (red pigment) because a film having excellent solvent resistance is easily formed.

The red colorant is preferably at least 1 selected from xanthene compounds, anthraquinone compounds, monoazo compounds, diazo compounds, azomethine compounds, aminoketone compounds, quinacridone compounds, perylene compounds and diketopyrrolopyrrole compounds, more preferably at least 1 selected from anthraquinone compounds, quinacridone compounds, perylene compounds and diketopyrrolopyrrole compounds, still more preferably at least 1 selected from anthraquinone compounds, perylene compounds and diketopyrrolopyrrole compounds, and still more preferably at least 1 selected from anthraquinone compounds and diketopyrrolopyrrole compounds. Among these, compounds having absorption on the longer wave side are particularly preferable from the viewpoint of more remarkably obtaining the effect of the present invention.

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

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

As the red colorant, a diketopyrrolopyrrole compound substituted with at least 1 bromine atom in the structure described in japanese patent application laid-open No. 2017-201384, a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of japanese patent No. 6248838, a diketopyrrolopyrrole compound described in international publication No. 2012/102399, a diketopyrrolopyrrole compound described in international publication No. 2012/117965, a naphthol azo compound described in japanese patent No. 2012-229344, a red colorant described in japanese patent No. 6516119, a red colorant described in japanese patent No. 6525101, a brominated diketopyrrolopyrrole compound described in paragraph 9 of japanese patent application laid-open No. 2020-090632, an anthraquinone compound described in korean patent No. 10-2019-0140741, an anthraquinone compound described in japanese patent No. 10-2019-01444, a perylene compound described in japanese patent laid-open No. 0220796, and the like can be used. As the red colorant, a compound having a structure in which an aromatic ring group into which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used.

The red colorant is preferably c.i. pigment red 122, 177, 179, 202, 254, 264, 269, 272, more preferably c.i. pigment red 177, 179, 202, 254, 264, 269, even more preferably c.i. pigment red 177, 254, 264, 269, and particularly preferably c.i. pigment red 264, from the viewpoint of spectral characteristics, durability, and the like.

(other coloring agents)

The coloring composition of the present invention preferably further contains a colorant other than the red colorant. Examples of the other colorants used in combination include a yellow colorant, a green colorant, a violet colorant, a blue colorant, and an orange colorant, and the yellow colorant is preferred because a cured film having spectral characteristics more suitable for red can be easily formed. Further, the yellow colorant is preferably a pigment (yellow pigment) because a film having excellent solvent resistance is easily formed.

The yellow colorant includes azo compounds, azomethine compounds, quinophthalone compounds, isoindolinone compounds, isoindoline compounds, pteridinyl compounds, anthraquinone compounds, and the like, preferably azo compounds, azomethine compounds, isoindoline compounds, and quinophthalone compounds, more preferably isoindoline compounds and azo compounds, and particularly preferably isoindoline compounds.

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

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

[ chemical formula 2]

Further, as the yellow colorant, a compound described in Japanese patent application laid-open Nos. 2017-201003, a compound described in Japanese patent application laid-open Nos. 2017-197719, 0011 to 0062 and 0137 to 0276, a compound described in Japanese patent application laid-open Nos. 0010 to 0062 and 0138 to 0295, a compound described in 0011 to 0062 and 0139 to 0190 of Japanese patent application laid-open No. 2017-171913, a compound described in 0010 to 0065 and 0140140140142 to 0222 of Japanese patent application laid-open No. 2017-171914, a quinophthalone compound described in 0011 to 0062 and 0139 to 2017,019 0 of Japanese patent laid-open No. 2017-171914, a quinophthalone compound described in 0013-171915, a quinophthalone compound described in 0013 to 0061 to 003228 of Japanese patent application laid-open No. 2017-20149, a quinophthalone compound described in 0013 to 0058, a quinophthalone compound described in 2018-06255578, a quinophthalone compound described in JP patent application laid-2018-062798, a quinophthalone compound described in 06255578, a 0621 to 2018, a quinophthalone compound described in JP patent application laid-2018-062-2014, a compound described in 2018, a compound described in JP patent publication No. 021-15507,699, a compound described in JP patent application laid-2018, a compound disclosed in jp-15507,699, a compound disclosed in a, quinophthalone compound described in Japanese patent laid-open publication No. 2013-209435, quinophthalone compound described in Japanese patent laid-open publication No. 2013-181015, quinophthalone compound described in Japanese patent laid-open publication No. 2013-061622, quinophthalone compound described in Japanese patent laid-open publication No. 2013-032486, quinophthalone compound described in Japanese patent laid-open publication No. 2012-226110, quinophthalone compound described in Japanese patent laid-open publication No. 2008-074987, quinophthalone compound described in Japanese patent laid-open publication No. 2008-081565, quinophthalone compound described in Japanese patent laid-open publication No. 2008-074986, quinophthalone compound described in Japanese patent laid-open publication No. 2008-074985, quinophthalone compound described in Japanese patent laid-open publication No. 2008-050420, quinophthalone compound described in Japanese patent laid-open publication No. 2008-031281 quinophthalone compound described in Japanese patent publication Sho-48-032765, quinophthalone compound described in Japanese patent publication Kokai No. 2019-008014, quinophthalone compound described in Japanese patent publication Kokai No. 6607427, methine dye described in Japanese patent publication Kokai No. 2019-073695, methine dye described in Japanese patent publication Kokai No. 2019-073696, methine dye described in Japanese patent publication Kokai No. 2019-073697, methine dye described in Japanese patent publication Kokai No. 2019-073698, methine dye described in Korean patent publication Kokai No. 10-2014-0034963, compound described in Japanese patent publication Kokai No. 2017-095706, compound described in Japanese patent publication Korea publication Kokai No. 201920495, compound described in Japanese patent publication Kokai No. 6607427, compound described in Japanese patent publication Korea, A quinophthalone dimer as described in Japanese patent laid-open No. 2020-033521. Further, from the viewpoint of increasing the color number, those obtained by polymerizing these compounds are also preferably used. Further, as the yellow colorant, a compound represented by the following formula (QP 1) or a compound represented by the following formula (QP 2) can be used.

[ chemical formula 3]

In formula (QP 1), X ¹ ～X ¹⁶ Each independently represents a hydrogen atom or a halogen atom, Z ¹ Represents an alkylene group having 1 to 3 carbon atoms. Specific examples of the compound represented by the formula (QP 1) include compounds described in paragraph 0016 of japanese patent No. 6443711.

[ chemical formula 4]

In formula (QP 2), Y ¹ ～Y ³ Each independently represents a halogen atom. n and m are integers of 0 to 6, and p is an integer of 0 to 5. (n + m) is 1 or more. Specific examples of the compound represented by the formula (QP 2) include compounds described in paragraphs 0047 to 0048 of japanese patent No. 6432077.

The yellow colorant is preferably c.i. pigment yellow 129, 138, 139, 150, 185, 215, more preferably c.i. pigment yellow 139, 150, and even more preferably c.i. pigment yellow 139, from the viewpoints of spectral characteristics, durability, and the like.

Examples of the green colorant include green pigments such as c.i. pigment green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Further, as the green colorant, a halogenated zinc phthalocyanine pigment having 10 to 14 halogen atoms, 8 to 12 bromine atoms and 2 to 5 chlorine atoms on average in one molecule can be used. Specific examples thereof include compounds described in International publication No. 2015/118720. Further, as the green colorant, a compound described in the specification of chinese patent application No. 106909027, a phthalocyanine compound having a phosphate ester described in international publication No. 2012/102395 as a ligand, a phthalocyanine compound described in japanese patent application laid-open No. 2019-008014, a phthalocyanine compound described in japanese patent application laid-open No. 2018-023, a compound described in japanese patent application laid-open No. 2019-038958, a core-shell type pigment described in japanese patent application laid-open No. 2020-076995, and the like can be used.

The green colorant is preferably c.1 pigment green 7, 36, 37, 58, 59, 65, more preferably c.i. pigment green 7, 36, 58, 65, and even more preferably c.i. pigment green 7, 36, from the viewpoints of spectral characteristics, durability, and the like.

As the blue colorant, c.i. pigment blue 1,2, 15, 15:1,15: 2,15: 3,15: 4,15: 6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc. Further, as the blue colorant, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples thereof include compounds described in paragraphs 0022 to 0030 of Japanese patent application laid-open No. 2012-247591 and paragraph 0047 of Japanese patent application laid-open No. 2011-157478.

The blue colorant is preferably c.i. pigment blue 15, 15:4,15: 6, 16, 60, 64, 79, more preferably c.i. pigment blue 15:4,15: 6, 16, 60, 64, and more preferably c.i. pigment blue 15:4,15: 6.

examples of the violet colorant include violet pigments such as c.i. pigment violet 1, 19, 23, 27, 32, 37, 42, 60, 61 and the like.

As the orange colorant, c.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 content of the colorant in the total solid content of the coloring composition is preferably 5 to 70% by mass. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and 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 still 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 mass% or less, and more preferably 95 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 still more preferably 90% by mass or more.

< resin > <

The coloring composition of the present invention comprises a resin. The resin is formulated, for example, for use in dispersing a pigment or the like in a coloring composition and for use in a binder. In addition, 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 may be used for purposes other than this application.

(resin EP)

The coloring composition of the present invention comprises a resin EP (hereinafter, also referred to as a numerical value EP) containing a repeating unit A having 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), and a repeating unit B selected from at least one of 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 with a protecting group.

The weight average molecular weight of the resin EP is preferably 2000 to 70000. The upper limit is preferably 60000 or less, more preferably 50000 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 within the above range, the color mixing and the preservation stability are more easily achieved at a higher level.

The content of the above-mentioned specific cyclic ether group in the resin EP is preferably 2.0 to 6.5mmol/g. When the content of the specific cyclic ether group in the resin EP is 2.0 to 6.5mmol/g, a cured film which is sufficiently cured can be formed even by heating at a relatively low temperature, and the storage stability of the coloring composition is also good. From the viewpoint of storage stability of the coloring composition, the upper limit is preferably 6.3mmol/g or less, and more preferably 6.Ommol/g or less. From the viewpoint of curability of the film, the lower limit is preferably 2.5mmol/g or more, more preferably 3.0mmol/g or more, still more preferably 3.2mmol/g or more, and particularly preferably 3.4mmol/g or more.

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

The resin EP preferably comprises repeating units having acid groups. According to this aspect, a sufficiently cured film can be formed even when heated at a relatively low temperature, and a cured film in which color mixing with other colors is more suppressed can be formed. In addition, when the coloring composition is used for pattern exposure, unexposed parts are easy to remove by developing with a developer, the developability is excellent, and the generation of residues in the unexposed parts can be more effectively inhibited. The content of acid groups in the resin EP is preferably from 0.45 to 2.35mmol/g. The upper limit is preferably 2.25mmol/g or less, and more preferably 2.15mmol/g or less. The lower limit is preferably 0.55mmol/g or more, more preferably 0.65mmol/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 in the resin EP preferably satisfy the condition of the following formula (1), more preferably satisfy the condition of the following formula (2), and further preferably satisfy the condition of the following formula (3).

1.0. Ltoreq. With respect to the content of a specific cyclic ether group of the resin EP (unit: mmol/g)/(content of an acid group of the resin EP (unit: mmol/g) + content of a group in which an acid group of the resin EP is protected with a protecting group (unit: mmol/g))) 14.0. Ltoreq.8230; (1)

2.5. Ltoreq. The content of a specific cyclic ether group of the resin EP (unit: mmol/g)/(content of an acid group of the resin EP (unit: mmol/g) + content of a group in which an acid group of the resin EP is protected with a protecting group (unit: mmol/g))). Ltoreq.12.0 \8230; (2)

4.0. Ltoreq. With respect to the content of a specific cyclic ether group of the resin EP (unit: mmol/g)/(content of an acid group of the resin EP (unit: mmol/g) + content of a group in which an acid group of the resin EP is protected with a protecting group (unit: mmol/g))) 10.0. Ltoreq.8230; (3)

When the resin EP contains the acid group content and the group in which the acid group is protected with a protecting group, respectively, the acid group content and the group in which the acid group is protected with a protecting group of the resin EP preferably satisfy the condition of the following formula (11), more preferably satisfy the condition of the following formula (12), and further preferably satisfy the condition of the following formula (13). According to this embodiment, the coloring composition has good storage stability, and when the coloring composition is used and exposed in a pattern, unexposed portions are easily removed by development with a developer, and the coloring composition is excellent in developability, and the generation of residue in the unexposed portions can be more favorably suppressed.

0.1. Ltoreq. The content of groups in which the acid groups of the resin EP are protected with a protecting group (unit: mmol/g)/the content of acid groups of the resin EP (unit: mmol/g). Ltoreq.2.0 \8230; (11)

0.2. Ltoreq. The content (unit: mmol/g) of a group whose acid group of the resin EP is protected with a protecting group/the content (unit: mmol/g) of an acid group of the resin EP) is not less than 1.9 \8230; (12)

0.3. Ltoreq. The content (unit: mmol/g) of a group whose acid group of the resin EP is protected with a protecting group/the content (unit: mmol/g) of an acid group of the resin EP) is not less than 1.8 \ 8230; \8230; (13)

[ repeating unit A ]

The resin EP contains a repeating unit A having 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). The specific cyclic ether group is preferably a group represented by the formula (e-1) from the viewpoint of being able to form a film having a high crosslinking density.

[ chemical formula 5]

in the formula (e-2), ring A ^E1 Represents a monocyclic aliphatic hydrocarbon ring and represents a connecting bond.

R ^E1 The alkyl group represented by the formula (i) preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, still more preferably 1 to 5 carbon atoms, and particularly preferably 1 to 3 carbon atoms. R ^E1 The alkyl group represented is preferably a straight chain or a branched chain, and more preferably a straight chain.

When n is 0, R ^E1 Preferably a hydrogen atom. When n is 1, R ^E1 Preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.

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

[ chemical formula 6]

As ring A of formula (e-2) ^E1 The monocyclic aliphatic hydrocarbon ring is preferably a 5-to 7-membered aliphatic hydrocarbon ring, more preferably a 5-membered ring orAnd 6-membered aliphatic hydrocarbon rings, more preferably 6-membered aliphatic hydrocarbon rings. Specific examples thereof include a cyclopentane ring, a cyclohexane ring and a cycloheptane ring, and a cyclopentane ring or a cyclohexane ring is preferable, and a cyclohexane ring is more preferable. Specific examples of the group represented by the formula (e-2) include the following groups.

[ chemical formula 7]

The repeating unit A may be a repeating unit represented by the following formula (A-1).

[ chemical formula 8]

In the formula (A-1), X ^a1 Represents a linking group having a valence of 3, L ^a1 Represents a single bond or a 2-valent linking group, Z ^a1 Represents the above cyclic ether group.

X as formula (A-1) ^a1 The 3-valent linking group may be a poly (meth) acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, a polystyrene linking group, a bisphenol linking group, a novolac linking group, or the like, and is preferably a poly (meth) acrylic linking group, a polyether linking group, a polyester linking group, a bisphenol linking group, and a novolac linking group, and more preferably a poly (meth) acrylic linking group.

L as formula (A-1) ^a1 The linking group having a valence of 2 may, for example, be 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-, -SO-, -SO ₂ -, -CO-, -O-, or-COO-, -OCO-) -S-and a group combining 2 or more of these. The alkylene group may be linear, branched or cyclic,the linear or branched chain is preferable. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxyl 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, and more preferably 75 mol% or less. The lower limit is preferably 20 mol% or more, and more preferably 30 mol% or more.

[ repeating unit B ]

Comprises at least one repeating unit B selected from the group consisting of a repeating unit B-1 having an acid group (hereinafter, also referred to as a repeating unit B-1) and a repeating unit B-2 having a group in which an acid group is protected with a protecting group (hereinafter, also referred to as a repeating unit B-2). The resin EP may contain only either 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 comprises at least the repeating unit B-1.

When the resin EP has the repeating unit B-1, a sufficiently cured film can be formed even by heating at a relatively low temperature, and a cured film in which color mixing with other colors is more suppressed can be formed. Further, when the colored composition is used for pattern-wise exposure, unexposed portions are easily removed by development with a developer, and the composition is excellent in developability and is capable of more effectively suppressing the generation of residue in the unexposed portions.

Further, when the resin EP contains the repeating unit B-2, the progress of the reaction of the above-mentioned specific cyclic ether group of the resin EP during storage of the coloring composition can be suppressed, and the storage stability of the coloring composition can be further improved.

Further, when the resin EP contains the repeating units B-1 and B-2, respectively, the storage stability and developability of the colored composition and the suppression of color mixing of the obtained cured film can be achieved at the same time.

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

Examples of the protecting group for protecting the acid group in the repeating unit B-2 include groups which are decomposed and released by the action of an acid or a base. The protecting group is preferably a group represented by any of formulae (Y1) to (Y5), and more preferably a group represented by formula (Y3) or formula (Y5)) for the reason of easy deprotection.

Formula (Y1): -C (R) ^Y1 )(R ^Y2 )(R ^Y3 )

Formula (Y2): -C (= O) OC (R) ^Y4 )(R ^Y5 )(R ^Y6 )

Formula (Y3): -C (R) ^Y7 )(R ^Y8 )(OR ^Y9 )

Formula (Y4): -C (R) ^Y10 )(H)(Ar ^Y1 )

Formula (Y5): -C (= O) (R) ^Y11 )

in the formula (Y5), R ^Y11 Represents an alkyl group or an aryl group.

R of the formula (Y1) ^Y1 ～R ^Y3 The alkyl group represented by the formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. In the formula (Y1), R ^Y1 ～R ^Y3 2 of which may be bonded to form a ring. As R ^Y1 ～R ^Y3 2 of the rings formed by bonding may beExamples thereof include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl and adamantyl, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferable. In the cycloalkyl group, 1 methylene group constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

R of formula (Y2) ^Y4 ～R ^Y6 The alkyl group represented by the formula (I) preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched. R of formula (Y2) ^Y4 ～R ^Y6 At least 2 of (a) are preferably methyl groups. In the formula (Y2), R ^Y4 ～R ^Y6 2 of which may be bonded to form a ring. Examples of the ring to be formed include the ring described in formula (Y1).

In the formula (Y3), R ^Y7 And R ^Y8 Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ^Y7 And R ^Y8 At least one of which is alkyl or aryl, R ^Y9 Represents alkyl or aryl, R ^Y7 Or R ^Y8 And R ^Y9 May be bonded to form a ring.

The alkyl group may be linear, branched, or cyclic. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 12. As R ^Y7 Or R ^Y8 And R ^Y9 Examples of the ring to be bonded include tetrahydrofuranyl group and tetrahydropyranyl group. In the formula (Y3), R is preferred ^Y7 Or R ^Y8 And R ^Y9 Bonded to form a ring. And, R ^Y7 And R ^Y8 One of them is preferably hydrogen.

In the formula (Y4), ar ^Y1 Represents aryl, R ^Y10 Represents an alkyl or aryl group, ar ^Y1 And R ^Y10 May be bonded to each other to form a ring. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 12. In the formula (Y4), R ^Y10 Preferably an alkyl group.

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

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

Specific examples of the protecting group include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-n-butoxyethyl, 1-tert-butoxyethyl, 1-cyclopentyloxyethyl, 1-cyclohexyloxyethyl, cyclohexyl (methoxy) methyl, α -methoxybenzyl, α -ethoxybenzyl, α -n-propoxybenzyl, 2-phenyl-1-methoxyethyl, 2-phenyl-1-ethoxyethyl, 2-phenyl-1-isopropoxyethyl, 2-tetrahydrofuryl, and 2-tetrahydropyranyl, with 1-ethoxyethyl, 1-cyclohexyloxyethyl, 2-tetrahydrofuranyl, and 2-tetrahydropyranyl being preferred, and 1-ethoxyethyl and 1-cyclohexyloxyethyl being more preferred.

The repeating unit B-1 may be a repeating unit represented by the following formula (B1). The repeating unit B-2 may be a repeating unit represented by the following formula (B2).

[ chemical formula 9]

In the formula (B1), X ^b1 Represents a linking group having a valence of 3, L ^b1 Represents a single bond or a 2-valent linking group, Z ^b1 Represents an acid group.

In the formula (B2), X ^b2 Represents a linking group having a valence of 3, L ^b2 Represents a single bond or a 2-valent linking group, Z ^b2 Represents a group in which an acid group is protected by a protecting group.

X as formula (B1) ^b1 A linking group having a valence of 3 and X of the formula (B2) ^b2 A linking group having a valence of 3The cluster is not particularly limited. For example, there may be mentioned a poly (meth) acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, a polystyrene linking group, a bisphenol linking group, a novolac linking group and the like, preferably a poly (meth) acrylic linking group, a polyether linking group, a polyester linking group, a bisphenol linking group and a novolac linking group, more preferably a poly (meth) acrylic linking group.

L as formula (B1) ^b1 A 2-valent linking group represented by the formula (B2) ^b3 The linking group having a valence of 2 may, for example, be 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-, -SO-, -SO ₂ <xnotran> -, -CO-, -O-, -COO-, -OCO-, -S- 2 . </xnotran> The alkylene group may be linear, branched or cyclic, and is preferably linear or branched. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxyl group and an alkoxy group.

Z of formula (B1) ^b1 Represents an acid group. Examples of the acid group include a phenolic hydroxyl group, a carboxyl group, a sulfo group and a phosphate group, and a phenolic hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.

Z of formula (B2) ^b2 Represents a group in which an acid group is protected by a protecting group. Examples of the group in which an acid group is protected with a protecting group include groups in which an acid group is protected with a group represented by any of the above formulas (Y1) to (Y5), and preferably groups in which an acid group is protected with a group represented by formula (Y3) or formula (Y5). Examples of the acid group include a phenolic hydroxyl group, a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and a phenolic hydroxyl group or a carboxyl group is preferable, and a carboxyl group is more preferable.

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

[ chemical formula 10]

In the formula (B2-1), R ^b11 ～R ^b13 Each independently represents a hydrogen atom, a halogen atom or an alkyl group, L ^b11 Represents a single bond or a 2-valent linking group, Z ^b11 Represents a group represented by the formula (Z-1) or the formula (Z-2);

[ chemical formula 11]

In the formulae (Z-1) and (Z-2), Y ^b11 Denotes a protecting group, denotes a group with L ^b11 A bonded portion.

As R ^b11 ～R ^b13 Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like.

R ^b11 ～R ^b13 The alkyl group represented by the formula (I) has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 5 carbon atoms. The alkyl group may be linear, branched or cyclic, but is preferably linear or branched.

As L ^b11 The linking group having a valence of 2 may be 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-, -SO-, -SO ₂ <xnotran> -, -CO-, -O-, -COO-, -OCO-, -S- 2 . </xnotran> The alkylene group may be linear, branched or cyclic, and is preferably linear or branched. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxyl group and an alkoxy group.

Y as formula (Z-1) and formula (Z-2) ^b11 Examples of the protective group include those represented by any of the above-mentioned formulae (Y1) to (Y5). At Z of formula (B2-1) ^b11 In the case of a group represented by the formula (Z-1), Y ^b11 Preferably, the formula (Y5). At Z of formula (B2-1) ^b11 In the case of a group represented by the formula (Z-2), Y ^b11 Preferably, formula (Y3).

At Z of formula (B2-1) ^b11 In the case of the group represented by the formula (Z-1), the storage stability of the coloring composition can be further improved. At Z of formula (B2-1) ^b11 In the case of the group represented by the formula (Z-2), a colored composition having excellent curability at low temperatures can be obtained.

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

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

When the resin EP comprises the repeating unit B-2, the content of the unit B-2 in the resin EP is preferably from 1 to 65 mol% in all the repeating units of the resin EP. The upper limit is preferably 45 mol% or less, and more preferably 30 mol% or less. The lower limit is preferably 2 mol% or more, and 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 preferably contains 0.4 to 3.2 moles of the repeating unit B-2, more preferably 0.8 to 2.8 moles, and further preferably 1.2 to 2.4 moles, based on 1 mole of the repeating unit B-1. According to this embodiment, the storage stability and developability of the coloring composition and the suppression of color mixture of the obtained cured film can be achieved at the same time at a higher level.

[ repeating unit C ]

The resin EP may contain a hydrocarbon ring group-containing repeating unit (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. The hydrocarbon ring group may be a monocyclic hydrocarbon ring group, or may be a polycyclic hydrocarbon ring group such as a fused ring or a crosslinked ring. The aromatic hydrocarbon ring group may be a monocyclic aromatic hydrocarbon ring group or a condensed ring aromatic hydrocarbon ring group. Specific examples of the hydrocarbon ring group include dicyclopentyl group, adamantyl group, t-butylcyclohexyl group, isoborneyl 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. According to this aspect, the resin becomes rigid due to the increase in the volume of the side chain, the solvent resistance of the cured film is improved, and a cured film in which color mixing with other colors is further suppressed can be formed.

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, and more preferably 30 mol% or less. The lower limit is preferably 1 mol% or more, and more preferably 5 mol% or more.

When the resin EP contains a repeating unit containing an aliphatic hydrocarbon ring group and a repeating unit containing an aromatic hydrocarbon ring group as the repeating unit C, the resin EP preferably contains 5 to 30 moles, more preferably 8 to 25 moles, and further preferably 10 to 20 moles of the repeating unit containing an aromatic hydrocarbon ring group with respect to 1 mole of the repeating unit containing an aliphatic hydrocarbon ring group. According to this embodiment, the resin becomes rigid, the solvent resistance of the cured film is improved, and a cured film in which color mixing with other colors is further suppressed can be formed.

[ other repeating units ]

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

(other resins)

The coloring composition of the present invention may further contain a resin (hereinafter, also referred to as another resin) other than the above-mentioned resin EP. The weight average molecular weight (Mw) of the other resin is preferably 2000 to 2000000. The upper limit is preferably 1000000 or less, more preferably 500000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more.

Examples of the other resin include (meth) acrylic resins, (meth) acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenyl resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and silicone resins. Epoxy resins other than the above-mentioned resin EP can also be used.

The other resin is also preferably a resin having an acid group. Examples of the acid group include a carboxyl group, a phosphoric group, a sulfonic group, and a phenolic hydroxyl group. Resins having acid groups can also be used as alkali soluble resins, dispersants. The acid value of the resin having an acid group is preferably 30 to 500mgKOH/g. The lower limit is more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more. The upper limit is more preferably 400mgKOH/g or less, still more preferably 200mgKOH/g or less, yet more preferably 150mgKOH/g or less, and particularly preferably 120mgKOH/g or less.

The resin having an acid group may have a repeating unit derived from a maleimide compound. As the maleimide compound, N-alkyl maleimide, N-aryl maleimide and the like can be mentioned. As the repeating unit derived from the maleimide compound, a repeating unit represented by the formula (C-mi) can be mentioned.

[ chemical formula 12]

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

The other resin is also preferably a resin containing a repeating unit derived from a compound represented by the following formula (ED 1) and/or a compound represented by the following formula (ED 2) (hereinafter, these compounds may be referred to as "ether dimer").

[ chemical formula 13]

In the formula (ED 1), R ¹ And R ² Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[ chemical formula 14]

In the formula (ED 2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. As a specific example of formula (ED 2), reference can be made to the description of japanese patent application laid-open No. 2010-168539.

As a specific example of the ether dimer, reference can be made to paragraph number 0317 of japanese patent laid-open No. 2013-029760, and the contents thereof are incorporated in the present specification.

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

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

[ chemical formula 15]

In the formula, R ¹ Represents a hydrogen atom or a methyl group, R ²¹ And R ²² Each independently represents an alkylene group, and n represents an integer of 0 to 15. R is ²¹ And R ²² The number of carbon atoms of the alkylene group represented by (a) is preferably 1 to 10, more preferably 1 to 5, furtherThe steps are preferably from 1 to 3, particularly preferably 2 or 3.n is preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and still more preferably an integer of 0 to 3.

Examples of the compound represented by the formula (III) include ethylene oxide-or propylene oxide-modified (meth) acrylates of p-cumylphenol. Examples of commercially available products include ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.).

Other resins are also preferred as dispersants. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin). Here, the acidic dispersant (acidic resin) means a resin having an acid group in an amount larger than that of a basic group. When the total amount of the acid groups and the base groups is 100 mol%, the acid dispersant (acidic resin) is preferably a resin in which the acid groups occupy 70 mol% or more, and more preferably a resin substantially containing only acid groups. The acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105mgKOH/g. The basic dispersant (basic resin) is a resin having a base group in an amount larger than that of an acid group. When the total amount of the acid groups and the base groups is 100 mol%, the basic dispersant (basic resin) is preferably a resin in which the amount of the base groups exceeds 50 mol%. The basic group of the basic dispersant is preferably an amino group.

The resin used as the dispersant preferably contains a repeating unit having an acid group. By the resin serving as the dispersant containing a repeating unit having an acid group, generation of development residue can be further suppressed at the time of forming a pattern by the photolithography.

The resin used as the dispersant is also preferably a graft resin. The details of the graft resin can be found in paragraphs 0025 to 0094 of jp 2012-255128 a, and are incorporated herein.

The resin used as the dispersant is also preferably a polyimide-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimide-based dispersant is preferably a resin having a main chain having a partial structure including a functional group having a pKa of 14 or less and a side chain having 40 to 10000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain. The basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. As for the polyimide-based dispersant, reference can be made to the descriptions of japanese patent application laid-open No. 2012-255128, paragraphs 0102 to 0166, the contents of which are incorporated in the present specification.

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

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

Further, as the dispersant, a polyethyleneimine having a polyester side chain as described in international publication No. 2016/104803, a block copolymer as described in international publication No. 2019/125940, a block polymer having an acrylic amide structural unit as described in japanese patent laid-open No. 2020-066687, a block polymer having an acrylic amide structural unit as described in japanese patent laid-open No. 2020-066688, or the like can be used.

The dispersant is also available as a commercially available product, and specific examples thereof include Disperbyk series (for example, disperbyk-111, 2001 and the like) manufactured by BYK Chemie GmbH, solsperse series (for example, solsperse20000, 76500 and the like) manufactured by Lubrizol Japan ltd, azisper series manufactured by Ajinomoto Eine-Techno co. Further, a product described in paragraph 0129 of jp 2012-137564 a and a product described in paragraph 0235 of jp 2017-194662 a can also be used as the dispersant. Further, as the dispersant, a resin described in paragraphs 0041 to 0060 of Japanese patent application laid-open No. 2017-206689, or a resin containing a hindered amine quaternary salt described in Japanese patent application laid-open No. 2019-095548 can be preferably used.

The content of the resin in the total solid content of the coloring composition is preferably 5 to 50% by mass. 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 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 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 a group having an ethylenically unsaturated bond. Examples of the group having an ethylenically unsaturated bond include a vinyl group, (meth) allyl group, and (meth) acryloyl group. The polymerizable compound used in the present invention is preferably a radical polymerizable compound.

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

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

The polymerizable compound is preferably a compound having 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound having 3 to 15 ethylenically unsaturated bond-containing groups, and still more preferably a compound having 3 to 6 ethylenically unsaturated bond-containing groups. The polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound. Specific examples of the polymerizable compound include those described in paragraphs 0095 to 0108 of Japanese patent application laid-open No. 2009-288705, 0227 of Japanese patent application laid-open No. 2013-029760, 0254 to 0257 of Japanese patent application laid-open No. 2008-292970, 0034 to 0038 of Japanese patent application laid-open No. 2013-253224, 0477 of Japanese patent application laid-open No. 2012-208494, 2017-048367, japanese patent application laid-open No. 6057891, japanese patent application laid-open No. 6031807, and Japanese patent application laid-open No. 2017-194662, and these are incorporated in the present specification.

As the polymerizable compound, dipentaerythritol triacrylate (KAYARAD D-330, manufactured by ltd., as a commercially available product), dipentaerythritol tetraacrylate (KAYARAD D-320, manufactured by ltd., as a commercially available product), dipentaerythritol penta (meth) acrylate (KAYARAD D-310, manufactured by ltd., as a commercially available product, nippon Kayaku Co., ltd., as a commercially available product), dipentaerythritol hexa (meth) acrylate (KAYARAD DPHA; nippon Kayaku Co., ltd., manufactured by NK ESTER a-DPH-12e, shin-Nakamura Chemicai Co., ltd., manufactured by ltd.), and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (for example, SR454, SR499 commercially available from SARTOMER Company, inc.). Further, as the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth) ACRYLATE (commercially available, M-460 TOAGOSEI CO., ltd. Manufactured), pentaerythritol tetraacrylate (Shin Nakamura Chemical CO., ltd. Manufactured, NK Ester a-TMMT), 1, 6-hexanediol diacrylate (Nippon Kayaku CO., ltd. Manufactured, KAYARAD hda), RP-1040 (Nippon Kayaku CO., ltd. Manufactured), aronium TO-2349 (TOAGOSEI CO., ltd. Manufactured), NK Oligo UA-7200 (Shin Nakamura Chemical CO., ltd. Manufactured, 8UH-1006, 8UH-1012 (Taisei e CO., ltd. Manufactured), lig yh ye b-A0 (poical isl, chemical), etc. can also be used.

Also, as the polymerizable compound, a 3-functional (meth) acrylate compound such as trimethylolpropane tri (meth) acrylate, trimethylolpropane-propylene oxide-modified tri (meth) acrylate, trimethylolpropane-ethylene oxide-modified tri (meth) acrylate, isocyanuric acid-ethylene oxide-modified tri (meth) acrylate, pentaerythritol tri (meth) acrylate, or the like is preferably used. Commercially available products of 3-functional (meth) acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (Shin-Nakamura Chemical Co., ltd., manufactured by Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (Nippon Kayaku Co., ltd., manufactured by Ltd.) and THE like.

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 coloring 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 carboxyl group, a sulfonic acid group, and a phosphoric acid group, and a carboxyl group is preferable. Commercially available products of polymerizable compounds having an acid group include ARONIX M-305, M-510, M-520, and ARONIX TO-2349 (TOAGOSEI CO., LTD.). The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40mgKOH/g, more preferably 5 to 30mgKOH/g. When the acid value of the polymerizable compound is 0.1mgKOH/g or more, the solubility in a developer is good, and when it is 40mgKOH/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 KAYARAD DPCA series, and includes DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

As the polymerizable compound, a polymerizable compound having an alkyleneoxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and still more preferably a 3 to 6-functional (meth) acrylate compound having 4 to 20 ethyleneoxy groups. Examples of commercially available polymerizable compounds 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 polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (a (meth) acrylate monomer having a fluorene skeleton, manufactured by Osaka Gas Chemicals Co., ltd.).

As the polymerizable compound, a compound substantially free of environmental control substances such as toluene is also preferably used. Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12LT (manufactured by Nippon Kayaku Co., ltd.).

As the polymerizable compound, acrylic acid amine esters such as those described in JP-B-48-041708, JP-B-51-037193, JP-B-02-032293 and JP-B-02-016765; amine ester compounds having an ethylene oxide skeleton as described in Japanese patent publication Sho-58-049860, japanese patent publication Sho-56-017654, japanese patent publication Sho-62-039417 and Japanese patent publication Sho-62-039418. It is also preferable to use polymerizable compounds having an amino group structure or a thioether structure in the molecule as described in Japanese patent application laid-open Nos. 63-277653, 63-260909 and 01-105238. Further, commercially available compounds such as UA-7200 (Shin-Nakamura Chemical Co., ltd.), DPHA-40H (Nippon Kayaku Co., ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, and LINC-202UA (Kyoeisha Chemical Co., ltd.) can be used as the polymerizable compound.

The content of the polymerizable compound in the total solid content of the coloring composition is preferably 5.0 to 35% by mass. 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 can be appropriately selected from known photopolymerization initiators. The photopolymerization initiator is preferably a photo radical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbisimidazoles, oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, hydroxyalkylphenone compounds, aminoalkylphenone compounds, and the like. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyl triazine (trihalomethyl triazine) compound, a benzyl dimethyl ketal compound, a hydroxyalkylphenone compound, an aminoalkylphenone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyl oxadiazole compound, and a 3-aryl-substituted coumarin compound, more preferably a compound selected from the group consisting of an oxime compound, a hydroxyalkylphenone compound, an aminoalkylphenone compound, and an acylphosphine compound, and even more preferably an oxime compound. Examples of the photopolymerization initiator include paragraph 0065 to 0111 of japanese patent application laid-open No. 2014-130173, a compound described in japanese patent No. 6301489, MATERIAL STAGE 37 to 60 pages vo1.19, no.3, a peroxide photopolymerization initiator described in 2019, a photopolymerization initiator described in international publication No. 2018/221177, a photopolymerization initiator described in international publication No. 2018/110179, a photopolymerization initiator described in japanese patent application laid-open No. 2019-043864, a photopolymerization initiator described in japanese patent application laid-open No. 2019-040, and a peroxide photopolymerization initiator described in japanese patent application laid-open No. 2019-167313, and these are incorporated in the present specification.

Examples of the aminoalkyl phenone compound include the aminoalkyl phenone compounds described in Japanese patent application laid-open No. 10-291969. Further, examples of commercially available aminoalkyl phenone compounds include Omnirad 907, omnirad 369E, omnirad 379EG (manufactured by IGM Resins B.V. Co., ltd.), irgacure 907, irgacure 369E, and Irgacure 379EG (manufactured by BASF Co., ltd.).

Examples of the acylphosphine compound include acylphosphine compounds described in japanese patent No. 4225898. Specific examples thereof include bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide and the like. Commercially available acylphosphine compounds include Omnirad 819, omnirad TPO (manufactured by IGM Resins b.v., inc.), irgacure 819, and Irgacure TPO (manufactured by BASF, inc.).

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

Formula (V)

[ chemical formula 16]

In the formula Rv ¹ Represents a substituent group, rv ² And Rv ³ Each independently represents a hydrogen atom or a substituent, rv ² And Rv ³ May be bonded to each other to form a ring, and m represents an integer of 0 to 5.

As Rv ¹ Examples of the substituent 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. Rv ¹ The alkyl and alkoxy groups may be unsubstituted or substitutedTo have a substituent. Examples of the substituent include a hydroxyl group and a group having a hydroxyalkylphenone structure. As the group having a hydroxyalkylphenone structure, there may be mentioned Rv in the formula (V) ¹ Bound benzene ring or from Rv ¹ A group having a structure in which 1 hydrogen atom is removed.

As Rv ² And Rv ³ The substituent(s) in (1) is preferably an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms). And, 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.

[ chemical formula 17]

Commercially available hydroxyalkylphenone compounds include Omnirad 184, omnirad 1173, omnirad 2959, omnirad 127 (described above, manufactured by IGM Resins b.v.), irgacure 184, irgacure 1173, irgacure 2959, and Irgacure 127 (described above, manufactured by BASF).

Examples of the oxime compound include a compound described in Japanese patent laid-open No. 2001-233842, a compound described in Japanese patent laid-open No. 2000-080068, a compound described in Japanese patent laid-open No. 2006-342166, a compound described in J.C.S.Perkin II (1979, pp.1653-1660), a compound described in J.C.S.Perkin II (1979, pp.156-162), a compound described in Journal of Photoploymer Science and Technology (1995, pp.202-232), a compound described in Japanese patent laid-open No. 2000-066385, a compound described in Japanese patent laid-open No. 2004-534797, a compound described in Japanese patent laid-open No. 2017-2015766, a compound described in Japanese patent laid-open No. 606565051, a compound described in Japanese patent laid-open No. 606565019, a compound described in Japanese patent laid-open No. 2017/865, a compound described in International publication No. 2017/051, a compound described in International publication No. 2017/2015, a compound described in Japanese patent laid-open No. 2017/019, a publication No. 2017/1678, a compound disclosed in Japanese patent laid-open No. 2017/167515, a/1678, a compound disclosed in paragraphs 2010038/1678, and a paragraph/1678, and a compound disclosed in paragraphs, and a compound laid-167515/167515, and so on. Specific examples of the oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products include Irgacure OXE01, irgacure OXE02, irgacure OXE03, irgacure OXE04 (BASF Co., ltd.), TR-PBG-304 (Changzhou Tronly New Electronic Materials CO., LTD. Co., ltd.), adeka Optomer N-1919 (ADEKA CORPORATION, JP 2012-052014A 2). Further, as the oxime compound, a compound having no coloring property or a compound having high transparency and being less likely to be discolored is also preferably used. Commercially available products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA CORPORATION, supra).

As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of oxime compounds having a fluorene ring include compounds described in Japanese patent laid-open No. 2014-137466, compounds described in Japanese patent No. 6636081, and compounds described in Korean patent laid-open No. 10-2016-0109444.

As the photopolymerization initiator, an oxime compound having a skeleton in which at least 1 benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such oxime compounds include those 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 (0X-1).

(OX-1)

[ chemical formula 18]

In the formula (OX-1), ar ¹ And Ar ² Each independently represents an optionally substituted aromatic hydrocarbon ring, R ¹ Represents an aryl group having a group containing a fluorine atom, R ² And R ³ Each independently represents an alkyl group or an aryl group.

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

As Ar ¹ And Ar ² Examples of the substituent which may be present include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR ^X1 、-SR ^X1 、-COR ^X1 、-COOR ^X1 、-OCOR ^X1 、-NR ^X1 R ^X2 、-NHCOR ^X1 、-CONR ^X1 R ^X2 、-NHCONR ^X1 R ^X2 、-NHCOOR ^X1 、-SO ₂ R ^X1 、-SO ₂ OR ^X1 and-NHSO ₂ R ^X1 And the like. R ^X1 And R ^X2 Each independently represents 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, an iodine atom and the like, and a fluorine atom is preferable. Alkyl as a substituent and R ^X1 And R ^X2 The number of carbon atoms of the alkyl group is preferably 1 to 30. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. In the alkyl group, a part or all of the hydrogen atoms may be substituted with a halogen atom (preferably, fluorine atom). In the alkyl group, a part or all of hydrogen atoms may be substituted by the above-mentioned substituent. Aryl as a substituent and R ^X1 And R ^X2 Carbon atom of aryl group represented byThe number is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The aryl group may be a single ring or a condensed ring. In the aryl group, a part or all of hydrogen atoms may be substituted by the above-mentioned substituents. Heterocyclic group as substituent and R ^X1 And R ^X2 The heterocyclic group represented is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and still more preferably 3 to 12. The number of hetero atoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, a part or all of the hydrogen atoms may be substituted by the above-mentioned substituents.

Ar ¹ The aromatic hydrocarbon ring represented is preferably an unsubstituted aromatic hydrocarbon ring. Ar (Ar) ² The aromatic hydrocarbon ring represented preferably has a substituent. As the substituent, preferred is-COR ^X1 。R ^X1 Preferably an alkyl, aryl or 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 of formula (OX-1) ¹ Represents an aryl group having a group containing a fluorine atom. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10. The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing alkyl group) or a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing group). As fluorine-containing group, it is preferably selected from the group consisting of-OR ^F1 、-SR ^F1 、-COR ^F1 、-COOR ^F1 、-OCOR ^F1 、-NR ^F1 R ^F2 、-NHCOR ^F1 、-CONR ^F1 R ^F2 、-NHCONR ^F1 R ^F2 、-NHCOOR ^F1 、-SO ₂ R ^F1 、-SO ₂ OR ^F1 and-NHSO ₂ R ^F1 At least 1 group. R ^F1 Represents a fluorine-containing alkyl group, R ^F2 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 。

R ^F1 And R ^F2 Fluorine-containing alkyl group represented by the formula and R ^F2 The alkyl group represented by the formula (I) has preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more 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 are preferably linear or branched. In the fluoroalkyl group, the substitution rate of fluorine atoms is preferably 40 to 100%, more preferably 50 to 100%, and still more preferably 60 to 100%. The substitution rate of fluorine atoms means the ratio (%) of the number of fluorine atoms substituted with fluorine atoms to the number of all hydrogen atoms in the alkyl group.

R ^F2 The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.

R ^F2 The heterocyclic group represented is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a single ring or a condensed ring. The number of condensation is preferably 2 to 8, more preferably 2 to 6, still more 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 still more preferably 3 to 20. The number of hetero atoms 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, and more preferably a nitrogen atom.

The group containing a fluorine atom preferably has a terminal structure represented by formula (1) or (2). Wherein denotes a bond.

*-CHF ₂ (1)

*-CF ₃ (2)

R of formula (OX-1) ² Represents an alkyl or aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or substituted.

As the substituent, the above-mentioned Ar ¹ And Ar ² The substituents illustrated in the substituents which may be present. The number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.

R of formula (OX-1) ³ Represents an alkyl or aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or substituted.

As the substituent, the above-mentioned Ar ¹ And Ar ² The substituents illustrated in the substituents which may be present. R ³ The alkyl group represented by the formula (I) preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched. R ³ The number of carbon atoms of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.

Specific examples of the oxime compound having a fluorine atom include a compound described in Japanese patent application laid-open No. 2010-262028, compounds 24 and 36 to 40 described in Japanese patent application laid-open No. 2014-500852, and a compound (C-3) described in Japanese patent application laid-open No. 2013-164471.

As the photopolymerization initiator, an oxime compound having a nitro group can also be used. The oxime compound having a nitro group is also preferably provided as a dimer. Specific examples of the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese patent application laid-open No. 2013-114249, paragraphs 0008 to 0012 and 0070 to 0079 of Japanese patent application laid-open No. 2014-137466, compounds described in paragraphs 0007 to 0025 of Japanese patent application laid-open No. 4223071, and ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

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

As the photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can be used. Examples of such a photopolymerization initiator include compounds described in international publication No. 2019/088055.

Specific examples of oxime compounds preferably used in the present invention will be described below, but the present invention is not limited to these.

[ chemical formula 19]

[ chemical formula 20]

In the present invention, it is preferable to use a photopolymerization initiator having an absorption coefficient of 1.0X 10 at 365nm in methanol ³ A photopolymerization initiator A1 having a concentration of mL/gcm or more and an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol ² mL/gcm or less and an absorption coefficient at a wavelength of 254nm of 1.0X 10 ³ A photopolymerization initiator A2 having a concentration of mL/gcm or more. According to this aspect, the coloring composition can be easily cured sufficiently by exposure to light, and a cured film having good flatness and excellent properties such as solvent resistance can be formed by a low-temperature process (for example, a temperature of 150 ℃ or lower, preferably 120 ℃ or lower throughout the entire process). The photopolymerization initiator A1 and the photopolymerization initiator A2 are preferably used by selecting a compound having the above-mentioned absorption coefficient from the above-mentioned compounds.

In the present invention, the absorption coefficient at the above wavelength of the photopolymerization initiator is a value measured in the following manner. That is, a measurement solution was prepared by dissolving the photopolymerization initiator in methanol, and the absorbance of the measurement solution was measured to calculate. Specifically, the measurement solution was put into a glass cell having a width of 1cm, and absorbance was measured using a UV-Vis-NIR spectrometer (Cary 5000) manufactured by Agilent technologies, inc., and applied to the following formula, and the absorption coefficients at a wavelength of 365nm and a wavelength of 254nm (mL/gcm) were calculated.

[ numerical formula 1]

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

The photopolymerization initiator A1 had an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol ³ mL/gcm or more, preferably 1.0X 10 ⁴ mL/gcm or more, more preferably 1.1X 10 ⁴ mL/gcm or more, and more preferably 1.2X 10 ⁴ ～1.0×10 ⁵ mL/gcm, more preferably 1.3X 10 ⁴ ～5.0×10 ⁴ mL/gcm, particularly preferably 1.5X 10 ⁴ ～3.0×10 ⁴ mL/gcm。

The photopolymerization initiator A1 preferably has an absorption coefficient of 1.0X 10 for light having a wavelength of 254nm in methanol ⁴ ～1.0×10 ⁵ mL/gcm, more preferably 1.5X 10 ⁴ ～9.5×10 ⁴ mL/gcm, more preferably 3.0X 10 ⁴ ～8.0×10 ⁴ mL/gcm。

The photopolymerization initiator A1 is preferably an oxime compound, an aminoalkylphenone compound, or an acylphosphine compound, more preferably an oxime compound or an acylphosphine compound, even more preferably an oxime compound, and particularly preferably an oxime compound containing a fluorine atom from the viewpoint of compatibility with other components contained in the composition. Specific examples of the photopolymerization initiator A1 include 1, 2-octanedione, 1- [4- (phenylthio) -,2- (O-benzoyloxime) ] (commercially available products such as Irgacure OXE01, manufactured by BASF corporation), ethanone, 1- [ 9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl ] -,1- (O-acetyloxime) (commercially available products such as Irgacure OXE02, manufactured by BASF corporation), bis (2, 4, 6-trimethylbenzoyl) -phenylphosphine oxide (commercially available products such as Omnirad 819 (manufactured by IGM Resins B.V. corporation) and Irgacure 819 (manufactured by BASF corporation)), and (C-13) and (C-14) shown in the specific examples of the oxime compounds.

The photopolymerization initiator A2 had an absorption coefficient of 1.0X 10 for 365nm wavelength light in methanol ² mL/gcm or less, preferably 10 to 1.0X 10 ² mL/gcm, more preferably 20 to 1.0X 10 ² mL/gcm. The absorbance coefficient of 365nm wavelength light in methanol of the photopolymerization initiator A1 and the absorbance of 365nm wavelength light in methanol of the photopolymerization initiator A2The difference of optical coefficients was 9.0X 10 ² mL/gcm or more, preferably 1.0X 10 ³ mL/gcm or more, more preferably 5.0X 10 ³ ～3.0×10 ⁴ mL/gcm, more preferably 1.0X 10 ⁴ ～2.0×10 ⁴ mL/gcm. The photopolymerization initiator A2 had an absorption coefficient of 1.0X 10 for light having a wavelength of 254nm in methanol ³ mL/gcm or more, preferably 1.0X 10 ³ ～1.0×10 ⁶ mL/gcm, more preferably 5.0X 10 ³ ～1.0×10 ⁵ mL/gcm。

The photopolymerization initiator A2 is preferably a hydroxyalkyl benzophenone compound, a phenylglyoxylate compound, an aminoalkyl benzophenone compound, or an acylphosphine compound, more preferably a hydroxyalkyl benzophenone compound and a phenylglyoxylate compound, and still more preferably a hydroxyalkyl benzophenone compound. The hydroxyalkyl phenone compound is preferably a compound represented by the above formula (V). Specific examples of the photopolymerization initiator A2 include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available products such as Omnirad 184 (IGM Resins b.v. co.), irgacure 184 (BASF co.), and 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (commercially available products such as Omnirad 2959 (IGM Resins b.v. co.), and Irgacure 2959 (BASF co)).

The combination of the photopolymerization initiator A1 and the photopolymerization initiator A2 is preferably a combination in which the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a hydroxyalkylphenone compound, more preferably a combination in which the photopolymerization initiator A1 is an oxime compound and the photopolymerization initiator A2 is a compound represented by the above formula (V), and particularly preferably a combination in which the photopolymerization initiator A1 is an oxime compound containing a fluorine atom and the photopolymerization initiator A2 is a compound represented by the above formula (V).

The content of the photopolymerization initiator in the total solid content of the coloring composition is preferably 0.1 to 17.5% 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.

The coloring composition of the present invention preferably contains 1.0 to 50 parts by mass of a photopolymerization initiator per 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 embodiment, the pattern shape after development is good.

In the colored composition of the present invention, when the above photopolymerization initiator A1 is used as a photopolymerization initiator, the content of the photopolymerization initiator A1 in the total solid content of the colored composition is preferably 0.1 to 17.5% 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 still more preferably 10.0% by mass or less.

In the colored composition of the present invention, when the above-mentioned photopolymerization initiator A2 is used as a photopolymerization initiator, the content of the photopolymerization initiator A2 in the total solid content of the colored composition is preferably 0.1 to 10.0% 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 still more preferably 7.0% by mass or less.

In the colored composition of the present invention, when the above-mentioned photopolymerization initiator A1 and photopolymerization initiator A2 are used as photopolymerization initiators, the colored composition of the present invention preferably contains 50 to 200 parts by mass of the photopolymerization initiator A2 per 100 parts by mass of the photopolymerization initiator A1. 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 embodiment, a cured film having excellent properties such as solvent resistance can be formed by a low-temperature process (for example, a temperature of 150 ℃ or lower, preferably 120 ℃ or lower throughout the entire process).

In the colored composition of the present invention, when the photopolymerization initiator A1 and the photopolymerization initiator A2 described above are used as photopolymerization initiators, the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the colored composition 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.

< Compound containing furyl group >)

The coloring composition of the present invention can contain a compound containing a furyl group (hereinafter, also referred to as a furyl group-containing compound). According to this embodiment, a coloring composition having excellent low-temperature curing properties can be provided.

The compound having a furyl group is not particularly limited in structure as long as it contains a furyl group (a group obtained by removing 1 hydrogen atom from furan). As the compound containing a furyl group, compounds described in paragraphs 0049 to 0089 of Japanese patent application laid-open No. 2017-194662 can be used. Further, compounds described in Japanese patent laid-open Nos. 2000-233581, 1994-271558, 1994-293830, 1996-239421, 1998-508655, 2000-001529, 2003-183348, 2006-193628, 2007-186684, 2010-265377, 2011-170069, and the like can be used.

The compound containing a furyl group may be a monomer or a polymer. From the viewpoint of easily improving the durability of the obtained film, a polymer is preferable. In the case of a polymer, the weight average molecular weight is preferably 2000 to 70000. The upper limit is preferably 60000 or less, more preferably 50000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and further preferably 5000 or more. The polymer type furyl group-containing compound is a component corresponding to the resin in the coloring composition of the present invention.

The content of the compound having a furyl group in the total solid content of the coloring composition is preferably 0.1 to 70% by mass. 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 still more preferably 50% by mass or less. The compound containing a furyl group may be used alone in 1 kind, or may be used in combination in2 or more kinds. When 2 or more kinds 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. The solvent may be an organic solvent. The solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the coloring composition. Examples of the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For details of these, reference can be made to paragraph 0223 of international publication No. 2015/166779, and this content is incorporated into the present specification. Also, a cyclic alkyl group-substituted ester solvent or a cyclic alkyl group-substituted ketone solvent can be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethylcetoacetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3v methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methylethylketone, γ -butyrolactone, sulfolane, anisole, 1, 4-diacetoxybutane, ethylene glycol monoethyl ether acetate, butane-1, 3-diyl diacetate, dipropylene glycol methyl ether acetate, and diacetone alcohol. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the organic solvent are preferably reduced from the environmental point of view (for example, the amount of aromatic hydrocarbons may be 50 mass ppm (parts per million) or less, may be 10 mass ppm or less, and may be 1 mass ppm or less with respect to the total amount of the organic solvent).

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

In the present invention, a solvent having a small metal content is preferably used, and the metal content of the solvent is preferably 10 ppb by mass (parts per billion) or less, for example. Solvents of quality ppt (parts per trillion: parts per million) grade, such as those provided by Toyo Gosei co., ltd (journal of chemical industry, 2015, 11/13/d), may be used as desired.

Examples of a method for removing impurities such as metals from a solvent include distillation (molecular distillation, thin film distillation, or the like) 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 still more preferably 3 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.

The solvent may contain isomers (compounds which differ in structure although having the same number of atoms). The isomer may include only 1 kind or a plurality of kinds.

In the present invention, the content of the peroxide in the organic solvent is preferably 0.8mmol/L or less, and more preferably substantially no 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 still more preferably 75% by mass or more. The solvent can be used alone in 1, can also be combined with more than 2. When 2 or more kinds are used in combination, the total amount of these is preferably in the above range.

In view of environmental control, the coloring composition of the present invention preferably contains substantially no environmental control substance. In the present invention, the substantial absence of the environmental control substance means that the content of the environmental control substance in the coloring composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of the environment-controlling substance include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like. These are registered as environmental control substances under the regulation of REACH (Registration Evaluation Authorization and reaction of Chemicals), PRTR (pollution Release and Transfer Register) method, VOC (Volatile Organic Compounds) regulation and the like, and the amounts used and the treatment methods are strictly regulated. These compounds are sometimes used as a solvent in the production of each component or the like used in the coloring composition of the present invention, and mixed into the coloring composition as a residual solvent. From the viewpoint of safety to humans and environmental concerns, it is preferable to reduce these substances as much as possible. As a method for reducing the environmental controlled substance, there is a method in which the inside of the system is heated and depressurized to a boiling point of the environmental controlled substance or higher, and the environmental controlled substance is distilled off from the inside of the system to be reduced. In addition, in the case of removing a small amount of the environmental control substance by distillation, it is also useful to azeotropically dissolve the environmental control substance with a solvent having the same boiling point as the solvent in order to improve efficiency. When a compound having radical polymerizability is contained, a polymerization inhibitor or the like may be added and the mixture may be distilled off under reduced pressure so as to prevent the crosslinking between molecules due to the radical polymerization reaction during the distillation off under reduced pressure. These distillation removal methods can be performed in any of the stage of the raw materials, the stage of the product of reacting the raw materials (for example, the resin solution after polymerization and the polyfunctional monomer solution), or the stage of the coloring composition prepared by mixing these compounds.

< 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 a chromophore is substituted with an acid group, a base group, or a phthalimide methyl group. Examples of the chromophore constituting the pigment derivative include a quinoline skeleton, a benzimidazolone skeleton, a diketopyrrolopyrrole skeleton, an azo skeleton, a phthalocyanine skeleton, an anthraquinone skeleton, a quinacridone skeleton, a dioxazine skeleton, a perinone skeleton, a perylene skeleton, a thioindigo skeleton, an isoindoline skeleton, an isoindolinone skeleton, a quinophthalone skeleton, a threne skeleton, a metal complex skeleton, and the like, and the quinoline skeleton, the benzimidazolone skeleton, the diketopyrrolopyrrole skeleton, the azo skeleton, the quinophthalone skeleton, the isoindoline skeleton, and the phthalocyanine skeleton are preferable, and the azo skeleton and the benzimidazolone skeleton are more preferable. The acid group of the pigment derivative is preferably a sulfonic acid group or a carboxyl group, and more preferably a sulfonic acid group. The base group of the pigment derivative is preferably an amino group, and more preferably a tertiary amino group.

Specific examples of the pigment derivative include compounds disclosed in Japanese patent application laid-open Nos. 56-118462, 63-264674, 01-217077, 03-009961, 03-026767, 03-153780, 03-045662, 04-285669, 06-145546, 06-212088, 201506-240158, 10-030063, 10-195326, 201120112011/024896, 1023/024896, 2017/038252, 2015-0082, 2015-1518208171, 0125262, 2011-17294, 2017/0382565, 2014-2014512, 2014-08512, 2014-2014, 2014-08512, and 2014-08512.

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, still more preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and still more preferably 1 part by mass or more. The upper limit of the range is more preferably 25 parts by mass or less, still more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less. When the content of the pigment derivative is within the above range, the stability with time can be further improved. The pigment derivative may be used alone in 1 kind, or may be used in combination of 2 or more kinds. When 2 or more kinds are used in combination, the total amount of these is preferably within the above range.

< curing accelerators >

In the coloring composition of the present invention, a curing accelerator may be added to accelerate the reaction of the polymerizable compound or to lower the curing temperature. Examples of the curing accelerator include polyfunctional thiol compounds having 2 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, and more preferably a compound represented by the formula (T1).

Formula (T1)

[ chemical formula 21]

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

Further, as the curing accelerator, a methylol compound (for example, a compound exemplified as a crosslinking agent in paragraph 0246 of jp 2015-034963 a), an amine, a phosphonium salt, an amidine salt, an amide compound (above, for example, a curing agent described in paragraph 0186 of jp 20153-041165 a), an alkali generating agent (for example, an ionic compound described in jp 2014-055114 a), a cyanate compound (for example, a compound described in paragraph 0071 of jp 2012-150180 a), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in jp 20153052011-254 a), an onium salt compound (for example, a compound exemplified as an acid agent in paragraph 0216 of jp 2015-034963 a, a compound described in jp 2009-1801809 a), and the like can be used.

When the coloring composition of the present invention contains a curing accelerator, the content of the curing accelerator in the total solid content of the coloring composition is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% 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 2 functional groups different in reactivity in one molecule is preferable. The silane coupling agent is preferably a silane compound having at least 1 group selected from a vinyl group, an epoxy group, a styryl group, a methacrylic group, an amino group, an isocyanurate group, a urea group, a mercapto group, a sulfide group and an isocyanate group, and an alkoxy group. Specific examples of the silane coupling agent include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., manufactured by LTD., KBM-602), N-2- (aminoethyl) -3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., manufactured by LTD., KBM-603), 3-aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., manufactured by LTD., KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., manufactured by LTD., manufactured by KBM-903), 3-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., manufactured by LTD., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shin-Etsu Chemical Co., manufactured by LTD., KBM-503), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., manufactured by LTD., manufactured by KBM-403), and the like. As for the details of the silane coupling agent, reference can be made to the descriptions of paragraphs 0155 to 0158 of japanese patent application laid-open No. 2013-254047, 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 in the total solid content of the coloring composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and particularly preferably 0.1 to 5% by mass. The coloring composition of the present invention may contain only 1 kind of silane coupling agent, or may contain 2 or more kinds. When 2 or more species are contained, the total amount is preferably within the above range.

< polymerization inhibitor >)

The coloring composition of the present invention may contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4 '-thiobis (3-methyl-6-t-butylphenol), 2' -methylenebis (4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxylamine salt (ammonium salt, cerium salt, etc.). When the colored composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass in the total solid content of the colored composition. The coloring composition of the present invention may contain only 1 polymerization inhibitor, or may contain 2 or more polymerization inhibitors. When 2 or more species are contained, the total amount is preferably within the above range.

< ultraviolet 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 salicylic acid compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyl triazine compound, an indole compound, a triazine compound, or the like can be used. For details of these, reference can be made to descriptions in paragraphs 0052 to 0072 of japanese patent application laid-open No. 2012-208374, paragraphs 0317 to 0334 of japanese patent application laid-open No. 2013-068814, and paragraphs 0061 to 0080 of japanese patent application laid-open No. 2016-162946, and these contents are incorporated in the present specification. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by DAITO CHEMICAL CO., LTD). Examples of the benzotriazole compound include MIYOSHI OIL & FAT co, and the MYUA series manufactured by ltd. (journal of chemical industry, 2016, 2 months and 1 day). Further, as the ultraviolet absorber, compounds described in japanese patent No. 6268967, paragraphs 0049 to 0059 can be used. When the coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, and particularly preferably 0.1 to 3% by mass. The ultraviolet absorber may be used in only 1 kind, or may be used in2 or more kinds. When 2 or more species are used, the total amount of these is preferably 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. The surfactant includes surfactants described in international publication nos. 2015/166779, paragraphs 0238 to 0245, and the contents are incorporated in the present specification.

The surfactant is preferably a fluorine-based surfactant. By containing the fluorine-based surfactant in the coloring composition, the liquid characteristics (particularly, fluidity) can be further improved, and the liquid saving property can be further improved. Further, a film with less thickness variation can be formed.

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

Examples of the fluorine-based surfactant include surfactants described in, for example, japanese patent application laid-open nos. 0060 to 0064 (international publication No. 2014/017669, and 0060 to 0064) of 2014-041318, surfactants described in japanese patent application laid-open nos. 0117 to 0132 of 2011-132503, and surfactants described in japanese patent application laid-open No. 2020-008634, and these contents are incorporated in the present specification. Commercially available fluorine-based surfactants include, for example, megaface F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560, F-561, F-563, F-565, F-568, F-575, F-780, EXP, MFS-330, R-01, R-40-LM, R-41-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K, DS-21 (above, DIC Corporation), fluorad FC430, FC431, FC171 (manufactured by Sumitomo 3M Limited, supra), surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (manufactured by AGC Inc., supra), polyFox PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SolutiOhS Inc., supra), ftergent 208G, 215M, 245F, 601AD, 601ADH2, 602A, 610FM, 710FL, 710FM, 710FS, FTX-218 (manufactured by Neos Corporation), and the like.

Further, the fluorine-based surfactant can also preferably use an acrylic compound which has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, the functional group containing a fluorine atom is partially cleaved and the fluorine atom volatilizes. Examples of such a fluorine-containing surfactant include MEGAFACE DS series (chemical industry daily news (2016: 2/22 days), and Industrial news (2016: 2/23 days)), such as MEGAFACE DS-21, manufactured by DIC Corporation.

Further, as the fluorine-based surfactant, 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 is also preferably used. As such a fluorine-based surfactant, a fluorine-based surfactant described in Japanese patent laid-open publication No. 2016-216602 can be mentioned, and the content thereof is incorporated in the present specification.

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

[ chemical formula 22]

The weight average molecular weight of the compound is preferably 3000 to 50000, for example 14000. In the above compounds,% representing the proportion of the repeating unit is mol%.

Further, as the fluorine-based surfactant, a fluoropolymer having a group containing an ethylenically unsaturated bond in a side chain can also be used. Specific examples thereof include compounds described in Japanese patent application laid-open Nos. 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, and MEGAFACE RS-101, RS-102, RS-718K, and RS-72-K manufactured by DIC Corporation. Further, as the fluorine-based surfactant, compounds described in paragraphs 0015 to 0158 of Japanese patent application laid-open No. 2015-117327 can be used.

In addition, from the viewpoint of environmental regulations, it is also preferable to use a surfactant described in international publication No. 2020/084854 in place of a surfactant having a perfluoroalkyl group having 6 or more carbon atoms.

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

[ chemical formula 23]

In the formula (fi-1), m represents 1 or 2, n represents an integer of 1 to 4, and α represents 1 or 2,X ^α+ A metal ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH representing an alpha valence ₄ ⁺ 。

Examples of the nonionic surfactant include glycerol (glycerol), trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerol ethoxylate), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, P ] uronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), solsperse20000 (manufactured by Japan lubrissol Corporation), NCW-101, NCW-1001, NCW-1002 (Wako Pure Industries, ltd., product), PIONIN D-6112, D-6112-W, taketo 15 (manufactured by tamolo 6315), and Chemical Co 1010, and Chemical Co 104, and dust 1010.

Examples of the Silicone surfactant include Toray Silicone DC3PA, toray Silicone SH7PA, toray Silicone DC11PA, toray Silicone SH21PA, toray Silicone SH28PA, toray Si1 Silicone SH29PA, toray Si1 Silicone SH30PA, toray Si1 Silicone SH8400 (see above, manufactured by Dow Corning Materials Inc.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (see above, manufactured by motion Performance Materials Inc.), KP-341, KF-6001, KF-6002 (see above, manufactured by Shin-Etsu Chemical Co., manufactured by LTD), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV-10 (see above, manufactured by Ww Corporation Co., manufactured by Dow Corporation), and so-W2 (manufactured by Dow Corporation), BYK-35K-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV-10 (see above, manufactured by Dow Corporation, fy Co., manufactured by Dow Corporation, fy 2, and so on.

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

[ chemical formula 24]

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The number of the surfactants may be 1 or 2 or more. In the case of 2 or more species, the total amount of these is preferably within the above range.

< other additives >

In the coloring composition of the present invention, various additives, for example, a filler, an adhesion promoter, an antioxidant, an anti-agglomeration agent, and the like can be formulated as necessary. Examples of such additives include those described in Japanese patent laid-open publication Nos. 0155 to 0156 of 2004-295116, and the contents thereof are incorporated in the present specification. As the antioxidant, for example, a phenol compound, a phosphorus compound (e.g., a compound described in paragraph 0042 of jp 2011-090147 a), a thioether compound, or the like can be used. Examples of commercially available products include the Adekastab series (AO-20, AO-30, AO-40, AO-50F, AO-60G, AO-80, AO-330, etc.) manufactured by ADEKA CORPORATION. Further, as the antioxidant, a polyfunctional hindered amine antioxidant described in international publication No. 2017/006600, an antioxidant described in international publication No. 2017/164024, and antioxidants described in japanese patent No. 6268967, paragraphs 0023 to 0048 can be used. The antioxidant may be used in 1 type or 2 or more types. Also, the coloring composition of the present invention may further contain a latent antioxidant, as necessary. As the latent antioxidant, a compound in which a site functioning as an antioxidant is protected with a protecting group, and the protecting group is released by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst to function as an antioxidant can be cited. Specific examples of the potential antioxidant include compounds described in International publication Nos. 2014/021023, 2017/030005 and Japanese patent application laid-open No. 2017-008219. Examples of commercially available products include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). The colored composition of the present invention may contain a sensitizer or photostabilizer as described in paragraph 0078 of Japanese patent application laid-open No. 2004-295116, a thermal polymerization inhibitor as described in paragraph 0081 of Japanese patent application laid-open No. 2004-295116, and a storage stabilizer as described in paragraph 0242 of Japanese patent application laid-open No. 2018-091940.

From the viewpoint of environmental regulations, the use of perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof is limited. In the coloring composition of the present invention, when the content of the above compound is reduced, the content of the perfluoroalkyl sulfonic acid (in particular, perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms of perfluoroalkyl group) and salts thereof, and the content of the perfluoroalkyl carboxylic acid (in particular, perfluoroalkyl carboxylic acid having 6 to 8 carbon atoms of perfluoroalkyl group) and salts thereof is preferably in the range of 0.01ppb to 1,000 ppb, more preferably in the range of 0.05ppb to 500ppb, and still more preferably in the range of 0.1ppb to 300ppb, based on the total solid content of the coloring composition. The coloring composition of the present invention may contain substantially no perfluoroalkyl sulfonic acid and salts thereof, and perfluoroalkyl carboxylic acid and salts thereof. For example, by using a compound capable of substituting for the perfluoroalkyl sulfonic acid and its salt and a compound capable of substituting for the perfluoroalkyl carboxylic acid and its salt, a colored composition substantially free of the perfluoroalkyl sulfonic acid and its salt and the perfluoroalkyl carboxylic acid and its salt can be selected. Examples of the compound that can replace the regulatory compound include compounds that are excluded from the regulatory object due to a difference in the number of carbon atoms in the perfluoroalkyl group. However, the use of perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof is not hindered by the above. 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.

< storage Container >

The container for the coloring composition of the present invention is not particularly limited, and a known container can be used. Further, as the storage container, in order to suppress the mixing of impurities into the raw material or the coloring composition, it is also preferable to use a multilayer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins, or a bottle in which 6 kinds of resins are formed into a 7-layer structure. Examples of such a container include those described in Japanese patent application laid-open No. 2015-123351. Further, in order to prevent elution of metal from the inner wall of the container, to improve the storage stability of the composition, to suppress deterioration of components, and the like, it is also preferable that the inner wall of the container is made of glass, stainless steel, or the like.

< method for producing coloring composition >

The coloring composition of the present invention can be produced by mixing the components. In the production of the coloring composition, all the components may be dissolved and/or dispersed in a solvent at the same time to produce the coloring composition, or each component may be appropriately made into a solution or dispersion of 2 or more, if necessary, and these may be mixed at the time of use (at the time of coating) to produce the coloring composition.

Also, in manufacturing the coloring composition, a process of dispersing the pigment may be included. In the process of dispersing the pigment, the mechanical force for dispersing the pigment may be compression, extrusion, impact, shearing, pitting and the like. Specific examples of these processes include bead milling, sand milling, roll milling, ball milling, paint stirring, microfluidization, high-speed impeller, sand mixing, jet stream mixing, high-pressure wet micronization, ultrasonic dispersion, and the like. In addition, in the pulverization of the pigment by sanding (bead milling), it is preferable to use microbeads having a small diameter and to perform the treatment under the condition that the pulverization efficiency is improved by increasing the filling rate of the microbeads. It is also preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment. Further, as a process and a dispersing machine for dispersing a pigment, a process and a dispersing machine described in "a large collection of dispersion technologies, JOHOKIKO co., ltd. release, 7/15/2005" or "a process and a dispersing machine described in paragraph 0022 of japanese patent application laid-open No. 2015-157893, 10/1978, which is published by the ministry of business and development, which is a comprehensive data set of dispersion technologies centered around suspensions (solid/liquid dispersions) and industrial practical applications can be preferably used. In the process of dispersing the pigment, the particle size reduction treatment can be performed by a salt milling step. For example, the raw materials, facilities, and treatment conditions used in the salt milling step can be described in japanese patent laid-open nos. 2015-194521 and 2012-046629.

In the production of the coloring composition, it is preferable to filter the coloring composition with a filter in order to remove foreign matters, reduce defects, and the like. The filter can be used without any particular limitation as long as it is conventionally used for filtration applications and the like. Examples of the filter include filters made of materials such as fluorine resins such as Polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (e.g., nylon-6 and nylon-6, 6), and polyolefin resins (including high-density and ultrahigh-molecular-weight polyolefin resins) such as Polyethylene and Polypropylene (PP). Of these materials, polypropylene (including high density polypropylene) and nylon are preferred.

The pore diameter of the filter is preferably 0.01 to 7.0. Mu.m, more preferably 0.01 to 3.0. Mu.m, and still more preferably 0.05 to 0.5. Mu.m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably. With regard to the pore size value of the filter, reference can be made to the nominal value of the filter manufacturer. As the FILTER, various FILTERs provided by NIHON PALL ltd. (DFA 4201NIEY, DFA4201NAEY, DFA 420J 006P, etc.), advantec Toyo Kaisha, ltd., japan entris inc.

Further, as the filter, a fibrous filter material is also preferably used. Examples of the fibrous filter material include polypropylene fibers, nylon fibers, and glass fibers. Commercially available products include ROKI TECHNO CO., LTD. SBP type series (SBP 008, etc.), TPR type series (TPR 002, TPR005, etc.), and SHPX type series (SHPX 003, etc.). When filters are used, different filters (e.g., a1 st filter and a2 nd filter, etc.) may be combined. In this case, the filtration with each filter may be performed only 1 time, or may be performed 2 or more times. Also, filters of different pore sizes may be combined within the above range. Further, the dispersion may be filtered only by using the 1 st filter, and after mixing other components, filtered by using the 2 nd filter.

< cured film >

The cured film of the present invention is obtained by curing the above-described colored composition of the present invention. The cured film of the present invention can be used for color filters and the like. Specifically, it can be preferably used as a coloring layer (pixel) of a color filter, and can be more preferably used as a red pixel. The thickness of the cured film of the present invention can be appropriately adjusted according to the 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, and further preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.8 μm or less.

< method for Forming cured film >

Next, a method of forming a cured film will be described.

The method for forming a cured film preferably includes the steps of: a step of applying the colored composition of the present invention to a support to form a colored composition layer; a step of exposing the colored composition layer (exposure step); and a step (post-baking step) of subjecting the exposed colored composition layer to a heat treatment. When the cured film (pixel) is formed in a pattern, the exposure step preferably further includes a step (developing step) of exposing the colored composition layer to light in a pattern and then developing the exposed colored composition layer between the exposure step and the post-baking step.

In the present invention, it is preferable to form the cured film at a temperature of 150 ℃ or lower throughout the entire process. In the present invention, "performed at a temperature of 150 ℃ or lower throughout the entire process" means that all the processes for forming a cured film using the coloring composition are performed at a temperature of 150 ℃ or lower. In the case where the heating step is further set after the development of the exposed colored composition layer, the heating step is also performed at a temperature of 150 ℃ or lower. The details of each step will be described below.

In the step of forming the colored composition layer, the colored composition of the present invention is applied to a support to form the colored 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 polyamideimide substrate, and a polyimide substrate. An organic light emitting layer may be formed on these substrates. Further, a silicon substrate can be used as the support. A Charge Coupled Device (CCD), a Complementary Metal Oxide Semiconductor (CMOS), a transparent conductive film, and the like may be formed on the silicon substrate. In addition, a base layer may be provided on the support to improve adhesion to the upper layer, prevent diffusion of a substance, or planarize the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. When the measurement is performed with water, it is preferably 30 to 80 °. 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 underlayer can be adjusted by, for example, a method of adding a surfactant or the like. The base layer can be formed using a composition obtained by removing a colorant from the coloring composition described in the present specification, a composition containing a resin, a polymerizable compound, a surfactant, and the like described in the present specification, or the like.

As a method for applying the coloring composition, a known method can be used. For example, a dropping method (drop casting); slit coating method; a spraying method; a roll coating method; spin coating (spin coating); tape casting coating method; slit spin coating; a prewet method (for example, a method described in japanese patent laid-open No. 2009-145395); various printing methods such as ink jet (for example, on-demand method, piezoelectric method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; nanoimprint method, and the like. The method of applying the inkjet is not particularly limited, and examples thereof include a method shown in "unlimited possibility in inkjet-patent applicable and usable", published in 2.2005, sumibe Techon Research co., ltd. "(especially from page 115 to page 133), and methods described in japanese patent laid-open publication nos. 2003-262716, 2003-185831, 2003-261827, 2012-126830, and 2006-1699325. In addition, as for the method of applying the coloring composition, reference can be made to the descriptions of international publication No. 2017/030174 and international publication No. 2017/018419, and these contents are incorporated in the present specification.

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

Next, the color matching composition layer is exposed (exposure step). For example, the colored composition layer can be exposed using a stepper, a scanner, or the like. In the case of forming a pattern-like cured film (pixel), the colored composition layer is exposed in a pattern-like manner. For example, the colored composition layer can be exposed in a pattern by exposure through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.

Examples of light that can be used for exposure include ultraviolet rays such as g-rays (wavelength: 436 nm) and i-rays (wavelength: 365 nm). As described in korean laid-open patent publication No. 1020170122130, exposure using i-rays can be performed while cutting off light having a wavelength shorter than that of the i-rays. Light having a wavelength of 300nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300nm or less include KrF rays (wavelength: 248 nm) and ArF rays (wavelength: 193 nm), and KrF rays (wavelength: 248 nm) are preferable. Further, a light source having a long wavelength of 300nm or more can be used.

In the exposure, the exposure may be performed by continuously irradiating light, or may be performed by pulse irradiation (pulse exposure). The pulse exposure is an exposure method of repeating irradiation and suspension of light in a short time (for example, millisecond order or less) cycle to perform exposure.

The dose (exposure dose) is preferably, for example, 0.03 to 2.5J/cm ² More preferably 0.05 to 1.0J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the atmospheric air, for example, exposure may be performed in a low oxygen environment (for example, 15 vol%, 5 vol%, or substantially no oxygen) in which the oxygen concentration is 19 vol% or less, or exposure may be performed in a high oxygen environment (for example, 22 vol%, 30 vol%, or 50 vol%) in which the oxygen concentration exceeds 21 vol%. Further, the exposure illuminance can be appropriately set, and can be usually set from 1000W/m ² ～100000W/m ² (e.g., 5000W/m) ² 、15000W/m ² Or 35000W/m ² ) Is selected. The oxygen concentration and the exposure illuminance may be appropriately combined, and may be set to, for example, an oxygen concentration of 10 vol% and an illuminance of 10000W/m ² An oxygen concentration of 35 vol% and an illuminance of 20000W/m ² And the like.

In the method of forming the cured film, it is also preferable to develop the color composition layer after exposure. In particular, in the exposure step, when the colored composition layer is exposed in a pattern, the unexposed portion of the colored composition layer is removed by development and the cured film is formed in a pattern to form a pixel by developing the exposed colored composition layer. The unexposed portions of the colored composition layer can be removed by development using a developer. In this way, the colored composition layer in the unexposed area in the exposure step is dissolved in the developer, and only the photocured portion remains. The temperature of the developing solution is preferably 20 to 30 ℃. The development time is preferably 20 to 180 seconds. Further, in order to improve the residue removal performance, the step of discharging the developer every 60 seconds and then supplying a new developer may be repeated a plurality of times.

The developing solution includes an organic solvent, an alkali developing solution, and the like, and preferably an alkali developing solution. The alkali developing solution is preferably an alkaline aqueous solution (alkali developing solution) obtained by diluting an alkaline agent with pure water. Examples of the alkali agent include organic basic compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, and 1, 8-diazabicyclo- [5.4.0] -7-undecene, and inorganic basic compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. The alkaline agent is preferably a compound having a large molecular weight 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, and more preferably 0.01 to 1% by mass. The developer may further contain a surfactant. The surfactant includes the above-mentioned surfactants, and preferably a nonionic surfactant. From the viewpoint of convenience in transportation and storage, the developer may be temporarily prepared as a concentrated solution and diluted to a desired concentration when used. The dilution ratio is not particularly limited, and can be set, for example, in the range of 1.5 to 100 times. Further, it is also preferable to perform cleaning (rinsing) with pure water after the development. The rinsing is preferably performed by supplying a 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 that the rinse liquid is discharged by moving a nozzle from the center of the support to the peripheral edge of the support. In this case, the nozzle may be moved while gradually decreasing the moving speed of the nozzle when moving from the center portion to the peripheral portion of the support body of the nozzle. By performing flushing in this way, in-plane variations in flushing can be suppressed. Further, the same effect can be obtained by gradually decreasing the rotation speed of the support body while moving the nozzle from the central portion to the peripheral portion of the support body.

After the development, it is also preferable to perform additional exposure treatment and heating treatment (post-baking) after drying. The additional exposure treatment and the post-baking are curing treatments after development for complete curing.

In the case of post-baking, the heating temperature is preferably 150 ℃ or lower. The upper limit of the heating temperature is more preferably 120 ℃ or less, and still more preferably 100 ℃ or less. The lower limit of the heating temperature is not particularly limited as long as the curing of the composition can be promoted, and is more preferably 50 ℃ or higher, and still more preferably 75 ℃ or higher. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, and further preferably 10 minutes or more. The upper limit is not particularly limited, but from the viewpoint of productivity, it is preferably 20 minutes or less. It is also preferable that the post-baking is performed under an atmosphere of an inert gas. According to this aspect, thermal polymerization can be performed with very high efficiency without being inhibited by oxygen, and even when pixels are manufactured at a temperature of 120 ℃ or lower in the entire process, pixels having good flatness and excellent properties such as solvent resistance can be manufactured. The inert gas includes nitrogen, argon, helium, and the like, and nitrogen is preferable. The oxygen concentration during the post-baking is preferably 100ppm or less.

When the additional exposure treatment is performed, it is preferable to perform exposure by irradiating light having a wavelength of 254 to 350 nm. In a more preferred embodiment, in the step of exposing the colored composition layer to light in a pattern (exposure before development), the colored composition layer is preferably exposed by irradiating the colored composition layer with light having a wavelength of more than 350nm and 380nm or less (preferably, light having a wavelength of 355 to 370nm, more preferably, i-ray), and in the additional exposure treatment (exposure after development), the colored composition layer after development is preferably exposed by irradiating the colored composition layer with light having a wavelength of 254 to 350nm (preferably, light having a wavelength of 254 nm). According to this aspect, the colored composition layer can be appropriately cured by the first exposure (exposure before development) and the entire colored composition layer can be almost completely cured by the next exposure (exposure after development), and therefore, as a result, the colored composition layer can be sufficiently cured even under low temperature conditions, and pixels having excellent characteristics such as solvent resistance, adhesiveness, and rectangularity of pattern can be formed. In the case of performing the exposure in2 stages as described above, it is preferable to use a composition containing, as a photopolymerization initiator, a compound having an absorption coefficient of 1.0X 10 at a wavelength of 365nm in methanol ³ A photopolymerization initiator having a concentration of mL/gcm or more and an absorption coefficient at 365nm in methanol of 1.0X 10 ² mL/gcm or less and an absorption coefficient at a wavelength of 254nm of 1.0X 10 ³ A photopolymerization initiator having a concentration of mL/gcm or more.

The exposure after the development can be performed using, for example, an ultraviolet photoresist curing apparatus. Light having a wavelength of 254 to 350nm and light other than this (i-ray, for example) can be irradiated from the ultraviolet photoresist curing apparatus.

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

< color Filter >

Next, the color filter of the present invention will be explained. The color filter of the present invention has the cured film of the present invention. The cured film of the present invention is preferably provided as a color pixel of a color filter, more preferably as a red pixel.

The color filter of the present invention preferably 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 a blue pixel, a green pixel, a yellow pixel, a magenta pixel, and a cyan pixel. A preferred embodiment of the color filter of the present invention includes an embodiment having red pixels, green pixels, and blue pixels formed of the cured film of the present invention.

In the coloring composition for forming blue pixels, which is preferably used in combination with the pixels of the cured film of the present invention, the maximum value A of the absorbance with respect to light having a wavelength of 400 to 450nm ^max11 And the minimum value A of absorbance of light having a wavelength of 475 to 575nm ^min12 Ratio of A ^max11 /A ^min11 Preferably 15 or more, more preferably 20 or more, and still more preferably 25 or more.

When the absorbance of the green pixel-forming colored composition for light having a wavelength of 450nm is 1, the wavelength at which the absorbance becomes 0.3 is preferably in the range of 455 to 505nm, more preferably in the range of 460 to 500nm, even more preferably in the range of 465 to 495nm, and particularly preferably in the range of 470 to 490 nm.

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

When the absorbance of the colored composition for forming a blue pixel with respect to light having a wavelength of 600nm is 1, the wavelength at which the absorbance becomes 0.3 is preferably in the range of 475 to 555nm, more preferably in the range of 480 to 540nm, still more preferably in the range of 485 to 525nm, 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 imaging element such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), and the like.

In the color filter of the present invention, the film thickness of the cured film of the present invention can be appropriately adjusted according to the 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, and further preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and still more preferably 1.8 μm or less.

In the color filter of the present invention, the line width (pattern size) of the pixel is preferably 2.0 to 10.0 μm. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and 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, and further preferably 2.75 μm or more.

In the color filter of the present invention, a protective layer may be provided on the surface of the cured film of the present invention. By providing the protective layer, various functions such as oxidation resistance, low reflection, hydrophilicity/hydrophobicity, and shielding of light having a specific wavelength (ultraviolet rays, near infrared rays, and the like) can be provided. The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Examples of the method for forming the protective layer include a method of coating a resin composition dissolved in an organic solvent, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive material. Examples of the component constituting the protective layer include (meth) acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polystyrene resin, polyarylene ether phosphine oxide resin, 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, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, si, C, W, al, and the like ₂ O ₃ 、Mo、SiO ₂ 、Si ₂ N ₄ Etc., two or more of these components may be contained. For example, in the case of a protective layer for the purpose of blocking oxygen, the protective layer preferably contains a polyol resin, siO ₂ 、Si ₂ N ₄ . In the case of a protective layer for reducing reflection, the protective layer preferably contains a (meth) acrylic resin and a fluororesin.

When the protective layer is formed by applying the resin composition, a known method such as a spin coating method, a casting method, a screen printing method, or an ink jet method can be used as a method for applying the resin composition. As the organic solvent contained in the resin composition, a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. In the case of forming the protective layer by a chemical vapor deposition method, a known chemical vapor deposition method (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) can be used as the chemical vapor deposition method.

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

Further, as the protective layer, the protective layers described in paragraphs 0073 to 0092 of japanese patent application laid-open No. 2017-151176 can also be used.

The color filter may have a base layer. The surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. When the measurement is performed with water, it is preferably 30 to 80 °. 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 underlayer can be adjusted by, for example, a method of adding a surfactant or the like.

The color filter may have a structure in which each colored pixel is embedded in a space divided by a partition into, for example, a lattice shape.

< display device >

The image display device of the present invention has the cured film of the present invention described above. Examples of the display device include a liquid crystal display device and an organic electroluminescence display device. The definition of the display device or the details of each display device are described in, for example, "electronic display device (published in Kogyo chess Publishing co., ltd., 1990)", "display device (published in yobo japan publication co., ltd., 1989)", and the like. The liquid crystal display device is described in, for example, "next generation liquid crystal display technology (edited by infiniband man, kogyo Chosakai Publishing co., ltd., 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, liquid crystal display devices of various types described in the "next generation liquid crystal display technology" described above.

The organic electroluminescent display device may have a light source composed of a white organic electroluminescent element. The white organic electroluminescent element is preferably of tandem (tandem) structure. The tandem structure of organic electroluminescent elements is described in japanese patent application laid-open No. 2003-045676, the third best practice, "the first line of development of organic EL technology — high brightness, high precision, long lifetime, and skill set-", technical Information Institute co., ltd., pages 326 to 328, 2008, and the like. The spectrum of white light emitted from the organic EL element preferably has strong maximum emission peaks in the blue region (430 nm to 485 nm), green region (530 nm to 580 nm), and yellow region (580 nm to 620 nm). In addition to these emission peaks, it is more preferable that the emission peak has a maximum emission peak in a red region (650 nm to 700 nm).

Examples

The present invention will be specifically described below with reference to examples. The materials, amounts used, ratios, contents of treatment, treatment steps and the like shown in the following examples can be appropriately changed without departing from the interest of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

< measurement of weight average molecular weight (Mw) >

The weight average molecular weight (Mw) of the measurement sample was measured by Gel Permeation Chromatography (GPC) under the following conditions.

The types of the pipe columns are as follows: a pipe column formed by connecting TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000 and TOSOH TSKgel Super HZ2000

Developing solvent: tetrahydrofuran (THF)

Temperature of the pipe column: 40 deg.C

Flow rate (sample injection amount): 1.0. Mu.L (sample concentration 0.1 mass%)

Device name: HLC-8220GPC manufactured by TOSOH CORPORATION

A detector: RI (refractive index) detector

Calibration curve base resin: polystyrene resin

< preparation of colorant solution >

After uniformly stirring and mixing the raw materials described in the following table, zirconia beads having a diameter of 1mm were dispersed for 5 hours by an EIGER grinder ("Mini Model M-250MKII" manufactured by EIGER Japan K.K.). Then, the user can use the device to perform the operation, the colorant solution P-R1 was prepared by filtration through a filter having a pore size of 5 μm P-R2, P-R3, P-R4, P-R5 and P-RC1. The amounts of the respective raw materials are shown in parts by mass in the following tables. The blank column indicates nothing to include.

[ Table 1]

The raw materials indicated in the table are as follows.

(Red colorant)

PR177: pigment Red 177 (Red pigment)

PR264: pigment Red 264 (Red pigment)

PR269: pigment Red 269 (Red pigment)

PR254: pigment Red 254 (Red pigment)

PR7: pigment Red 7 (Red pigment)

(yellow colorant)

PY139: c.i. pigment yellow 139 (yellow pigment)

(dispersing agent)

Dispersant 1: solsperse20000 (manufactured by The Lubrizol Corporation)

Dispersant 2: resin solution D2 prepared by the following method

A reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser and a gas inlet tube was charged with 90.0 parts by mass of cyclohexanone, heated to 60 ℃ while injecting nitrogen gas, and a mixture of 20.0 parts by mass of methacrylic acid, 10.0 parts by mass of methyl methacrylate, 55.0 parts by mass of n-butyl methacrylate, 15 parts by mass of benzyl methacrylate and 2.5 parts by mass of 2,2' -azobisisobutyronitrile was dropped at the same temperature over 2 hours to carry out polymerization reaction. After the completion of the dropwise addition, and after 1 hour of reaction at 60 ℃, a solution obtained by dissolving 0.5 part by mass of 2,2' -azobisisobutyronitrile 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 resin solution was diluted with cyclohexanone, thereby obtaining a resin solution D2 having a solid content concentration of 20%. The weight average molecular weight of the obtained resin (copolymer) was 30000.

(pigment derivative)

Pigment derivative 1: a compound of the structure

[ chemical formula 25]

< preparation of coloring composition >

The following raw materials were mixed and stirred, and then filtered using a nylon filter (manufactured by Nihon Pall ltd.) having a pore size of 0.45 μm to prepare a colored composition.

[ Table 2]

The raw materials indicated in the table are as follows.

(colorant solution)

P-R1 to P-R5, P-Rc1: the colorant solutions P-R1 to P-R5 and P-Rc1 prepared as described above

(photopolymerization initiator)

I-1: irgacure OXE02 (a compound having the following structure, manufactured by BASF Co., ltd.)

I-2: omnirad 2959 (Compound of the following structure, manufactured by IGM Resins B.V. Co.)

I-3: a compound of the structure.

[ chemical formula 26]

(resin solution)

A-1 to A-9: 40% by mass PGMEA solution of a resin having the following structure

The resin solution A-1 was prepared by the following method. Specifically, 207 parts by mass of PGMEA was put into a reaction vessel in which a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device were attached to a separable 4-necked flask, the temperature was raised to 80 ℃, the interior of the reaction vessel was replaced with nitrogen, and then a mixture of 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 1.33 parts by mass of 2,2' -azobisisobutyronitrile was dropped into the dropping tube over 2 hours. After the completion of the dropwise addition, the reaction was further continued for 3 hours, thereby obtaining a resin having the following structure. After cooling to room temperature, the solution was diluted with PGMEA to adjust the solid content concentration to 40 mass%, thereby preparing a resin solution a-1.

The resin solutions A-2 to A-9 were prepared in the same manner as the resin solution A-1, respectively.

[ chemical formula 27]

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

[ chemical formula 28]

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

[ chemical formula 29]

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

[ chemical formula 30]

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

[ chemical formula 31]

The weight average molecular weight, the content of cyclic ether group, the content of acid group, and the content of group in which acid group is protected by protecting group of each resin are shown in the following tables. The values of the ratios of the contents of cyclic ether groups to the contents of acid groups in the resins A-1 to A-10, A-12 and D-1 are shown in the columns of content ratios. In addition, in 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 shown in the content ratio column.

[ Table 3]

(polymerizable Compound)

M-1: ARONIX M-402 (TOAGOSEI co., ltd., manufactured, mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

M-2: a compound of the following structure (a + b + c = 3)

[ chemical formula 32]

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

(solvent)

S-1: propylene Glycol Monomethyl Ether Acetate (PGMEA)

S-2: propylene Glycol Monomethyl Ether (PGME)

< evaluation of spectral analysis >

Each of the colored compositions was applied onto a glass substrate using a spin coater so that the film thickness after drying became 2 μm, and dried on a hot plate at 100 ℃ for 2 minutes. Then, an ultra-high pressure mercury lamp was used under an exposure of 20mW/cm ² The exposure amount was 1J/cm ² The exposure was performed under the conditions of (1). Then, the film was heated on a heating plate at 100 ℃ for 20 minutes and allowed to cool naturally, thereby forming a cured film. In the production of the cured film, the temperature of the substrate is in the range of 20 to 100 ℃ throughout the entire process. With respect to the obtained cured film, an ultraviolet-visible near-infrared spectrophotometer (UV 3600, manufactured by Shimadzu Corporation) was used, a reference source circuit (reference) was used as a glass substrate,measuring the absorbance of light with a wavelength of 300-800 nm, and determining the maximum value A of the absorbance relative to the light with a wavelength of 400-500 nm ^max1 And the minimum value A of absorbance with respect to light having a wavelength of 550 to 700nm ^min1 Ratio of A ^max1 /A ^min1 (hereinafter referred to as absorbance ratio 1) and absorbance at a wavelength of 500nm was 1, and the wavelength at which the absorbance became 0.3 (hereinafter referred to as wavelength 1) was measured.

< evaluation of color mixture >

Each of the colored compositions was applied onto a glass substrate using a spin coater so that the film thickness after drying became 2 μm, and dried on a hot plate at 100 ℃ for 2 minutes. Then, an ultra-high pressure mercury lamp was used under an exposure of 20mW/cm ² The exposure amount was 100mJ/cm ² The exposure was performed under the conditions of (1). Next, puddle development was performed at 23 ℃ for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Then, the film was washed with a rotating shower and further with pure water. Then, the film was heated on a heating plate at 100 ℃ for 20 minutes and allowed to cool naturally, thereby forming a cured film. The transmittance (T1) of light having a wavelength of 450nm of the obtained cured film was measured using MCPD-3000 (manufactured by Otsuka electronics co., ltd.).

Next, a color composition for color mixture evaluation was applied on the cured film using a spin coater so that the film thickness after drying became 2 μm, and the film was dried on a hot plate at 100 ℃ for 2 minutes to form a coating film of the color composition for color mixture evaluation, thereby forming a laminated film. As the color composition for color mixture evaluation, a blue color composition used for forming a blue pixel in example 1001 described later was used.

Next, the glass substrate on which the laminated film was formed was placed on a horizontal rotary table of a rotary/shower developing machine (DW-30 model, manufactured by Chemitronics co., ltd.), and was subjected to puddle development for 60 seconds at 23 ℃ using a 60% dilution of CD-2000 (manufactured by FUJIFILM Electronic Materials co., ltd.), and the coating film of the color composition for color mixture evaluation formed on the cured film was removed by development. Next, the glass substrate was fixed to a horizontal rotary table by a vacuum chuck method, while being rotated at a rotation speed of 50rpm by a rotating device, pure water was supplied from a nozzle in a shower shape from above the rotation center of the glass substrate, and the glass substrate was subjected to a rinsing treatment, and then spray-dried.

The transmittance (T2) of light having a wavelength of 450nm of the cured film after the coating film of the color composition for color mixture evaluation was removed by development was measured using MCPD-3000 (manufactured by Otsuka Electronics co., ltd.).

The rate of change in transmittance was calculated from the following formula, and the color mixture was evaluated according to the following evaluation criteria.

Rate of change in transmittance (%) = { | transmittance (T1) -transmittance (T2) |/transmittance (T1) } × 100

S: the change rate of the transmissivity is less than 0.1 percent

A: the change rate of the transmittance is more than 0.1% and less than 0.25%

B: the change rate of the transmittance is more than 0.25% and less than 1%

C: the change rate of the transmittance is more than 1% and less than 2.5%

D: the change rate of the transmittance is more than 2.5% and less than 5%

E: the change rate of the transmittance is more than 5%

< evaluation of storage stability >

The viscosity (V) of the coloring composition immediately after manufacture obtained above was measured using "RE-85L" manufactured by TOKI SANGYO CO ₁ ). After the coloring composition was allowed to stand at a temperature of 40 ℃ for 3 days, the viscosity (V) was measured ₂ ). The thickening ratio 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 ℃. The evaluation criteria are as follows, and the evaluation results are shown in the following table.

Thickening ratio (%) = { (viscosity (V) ₂ ) Viscosity (V) ₁ ) Viscosity (V)/viscosity (V) ₁ )}×100

S: the tackifying rate is less than 0.1 percent

A: the viscosity increasing rate is more than 0.1 percent and less than 0.25 percent

B: the viscosity increasing rate is more than 0.25 percent and less than 1 percent

C: the tackifying rate is more than 1 percent and less than 2.5 percent

D: the viscosity increasing rate is more than 2.5 percent and less than 5 percent

E: the thickening rate is more than 5 percent

[ Table 4]

	Absorbance ratio 1	Wavelength 1 (nm)	Color mixing	Storage stability
					Example 1	230	589	A	A
Example 2	195	576	A	B
					Example 3	195	580	A	A
Example 4	180	577	A	B
					Example 5	170	608	A	A
Example 6	230	589	A	A
					Example 7	230	589	A	B
Example 8	230	589	S	C
					Example 9	230	589	B	D
Example 10	230	589	A	B
					Example 11	230	589	C	A
Example 12	230	589	B	B
					Example 13	230	589	C	B
Example 14	230	589	B	S
					Example 15	230	589	B	S
Example 16	230	589	A	A
					Example 17	230	589	A	A
Example 18	230	589	A	A
					Example 19	230	589	A	A
Example 20	230	589	A	A
					Example 21	230	589	B	A
Comparative example 1	23	532	A	E
					Comparative example 2	230	589	E	A

As shown in the above table, the embodiment can 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-colored composition was applied to a silicon wafer by a spin coating method so that the film thickness after film formation became 1.0. Mu.m. Next, the plate was heated at 100 ℃ for 2 minutes using a hot plate. Next, an i-ray step exposure apparatus FPA-3000i5+ (manufactured by Canon Inc.) was used at 1000mJ/cm ² The exposure amount of (2) was exposed through a mask having a dot pattern of 12 μm square. Next, a puddle development was performed for 60 seconds at 23 ℃ using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH). Then, the film was washed with a rotating shower and further with pure water. Subsequently, the substrate was heated on a hot plate at 100 ℃ for 20 minutes and naturally cooled, thereby forming a green colored pattern (green pixel). Similarly, the red-colored composition and the blue-colored composition were patterned in this order to form a red-colored pattern (red pixels) and a blue-colored pattern (blue pixels), respectively, to fabricate a color filter.

As the red-colored composition, the colored composition of example 1 was used. The green-colored composition and the blue-colored composition will be described later. The obtained color filter is assembled into an organic electroluminescent display device according to a well-known method. The organic electroluminescent display device has a preferable image recognition capability.

[ Green coloring composition ]

The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nihon Pall Ltd.) having a pore size of 0.45 μm to prepare a green colored composition.

Green pigment dispersion liquid of 823085 weight portions

Photopolymerization initiator (Irgacure OXE02, manufactured by BASF Corp.) \ 8230: \8230: \ 1.04 parts by mass

Photopolymerization initiator (Omnirad 2959, IGM Resins B.V.; 8230; 0.77 parts by mass

Resin solution 1, 82300, 82300.9 weight portions

Solution of furyl-containing compound 1 of 823082301 part by mass

Polymerizable compound (compound having the following structure) \\8230; \8230; 2.04 parts by mass

[ chemical formula 33]

Surfactant (compound of the following structure, mw =14000, numerical value of% representing proportion of repeating unit is mole%, fluorine-based surfactant) \ 8230 \ 8230; 0.008 part by mass

[ chemical formula 34]

Propylene glycol monomethyl ether acetate (8230); 82309; 8.8 parts by mass)

[ blue coloring composition ]

The following components were mixed and stirred, and then filtered through a nylon filter (manufactured by Nihon Pall Ltd.) having a pore size of 0.45 μm to prepare a blue colored composition.

Blue pigment dispersion liquid (8230) \\ 8230;' 8230; 51.0 parts by mass

Photopolymerization initiator (Irgacure OXE01, manufactured by BASF Corp.) \ 8230; \ 8230; (2.17 parts by mass)

Photopolymerization initiator (Omnirad 2959, IGM Resins B.V., ltd.) \8230; 0.83 parts by mass

Resin solution 1 of 823070, 4.1 weight portions of 8230

Solution of compound containing furyl 1 \ 8230: \ 8230and 6.2 parts by mass

Polymerizable compound (compound having the following structure) \\8230; \8230; 2.5 parts by mass

[ chemical formula 35]

Surfactant (KF-6001, shin-Etsu Chemical Co., manufactured by LTD) \8230; 0.008 parts by mass

Butyl acetate (8230); 823033.2 weight portions

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

(Green pigment Dispersion)

A mixed solution containing 7.4 parts by mass of c.i. pigment green 36, 5.2 parts by mass of c.i. 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 and dispersed by a bead mill (zirconia beads having a diameter of 0.3 mm) over 3 hours to prepare a pigment dispersion. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., ltd.) having a decompression mechanism was further used at 2000kg/cm ³ Was subjected to dispersion treatment at a flow rate of 500g/min under the pressure of (1). This dispersion treatment was repeated 10 times to obtain a Green pigment dispersion.

Pigment derivative 1: a compound of the structure

[ chemical formula 36]

Dispersant 1: a resin having the following structure. The numerical value indicated by parentheses in the main chain represents the molar ratio of each repeating unit, and the numerical value indicated by parentheses in the side chain represents the number of repeating units. The weight average molecular weight is 24000.

[ chemical formula 37]

(B ] ue pigment Dispersion liquid)

By a bead mill (zirconia beads having a diameter of 0.3 mm), a mixture containing 9.5 parts by mass of c.i. pigment blue 15:6. a mixed solution of 5.0 parts by mass of c.i. pigment violet 23, 5.5 parts by mass of dispersant 1, and 80.0 parts by mass of PGMEA was prepared to prepare a pigment dispersion. Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., ltd.) having a decompression mechanism was further used at 2000kg/cm ³ Was subjected to dispersion treatment at a flow rate of 500g/min under the pressure of (1). This dispersion treatment was repeated 10 times to obtain a Blue pigment dispersion.

(resin solution 1)

A30% by mass PGMEA solution of resin A synthesized by the following method

After a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device was charged with 70.0 parts by mass of cyclohexanone, the temperature was raised to 80 ℃ and the inside of the flask was replaced 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 a mixture of 7.4 parts by mass of p-cumylphenol ethylene oxide-modified acrylate (toagaei osco, ltd., ARONIX M110) and 0.4 part by mass of 2,2' -azobisisobutyronitrile was dropped through the dropping tube over 2 hours. After the end of the dropwise addition, the reaction was continued for further 3 hours to synthesize resin a (Mw = 26000), and dilution was performed with PGMEA, thereby obtaining a 30 mass% PGMEA solution of resin a.

(Compound solution containing furyl group 1)

A20% by mass PGMEA solution of Compound F1 containing a furyl group synthesized by the following method

A reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser and a gas inlet tube was charged with 90.0 parts by mass of PGMEA, heated to 60 ℃ while injecting nitrogen gas, and a mixture of 50.0 parts by mass of furfuryl methacrylate, 26.7 parts by mass of 2-methacryloyloxyethylsuccinic acid, 23.3 parts by mass of 2-hydroxyethyl methacrylate and 2.5 parts by mass of 2,2' -azobis (2, 4-dimethylvaleronitrile) was dropped at the same temperature over 2 hours to conduct polymerization. After the completion of the dropwise addition, and after 1 hour of reaction at 60 ℃, a substance obtained by dissolving 0.5 part by mass of 2,2' -azobis (2, 4-dimethylvaleronitrile) in 10.0 parts by mass of PGMEA was added, and then stirring was continued at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, dilution was performed with PGMEA, thereby obtaining a 20 mass% PGMEA solution of the compound F1 containing a furyl group (Mw = 52000).

Claims

1. A coloring composition comprising a coloring agent containing a red coloring agent, a resin, a polymerizable compound and a photopolymerization initiator,

the resin comprises a resin EP comprising a repeating unit A having at least one cyclic ether group A selected from the group represented by the formula (e-1) and the group represented by the formula (e-2) and a repeating unit B selected from at least one of 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, the maximum value A of absorbance relative to light with the wavelength of 400 nm-500 nm ^max1 And the minimum value A of absorbance with respect to light having a wavelength of 550nm to 700nm ^min1 Ratio of A ^max1 /A ^min1 The content of the organic acid is more than 25,

when the absorbance for light having a wavelength of 500nm is 1, the wavelength at which the absorbance becomes 0.3 is in the range of 570nm to 620nm,

in the formula (e-2), ring A ^R1 Represents a monocyclic aliphatic hydrocarbon ring and represents a connecting bond.

2. The coloring composition according to claim 1,

in the resin EP, the content of the cyclic ether group A is 2.0mmol/g to 6.5mmol/g, and the total of the content of the acid group and the content of the group in which the acid group is protected by the protecting group is 0.45mmol/g to 2.35mmol/g.

3. The coloring composition according to claim 1 or 2,

the content of the cyclic ether group A, the content of the acid group and the content of the group in which the acid group is protected by a protecting group in the resin EP satisfy the condition of the following formula (1),

1.0. Ltoreq. The content of the cyclic ether group A of the resin EP/(the content of the acid group of the resin EP + the content of the group of the acid group of the resin EP which is protected with a protecting group) is 14.0. Ltoreq.14.0, wherein the unit of the content is mmol/g (1).

4. The coloring composition according to any one of claims 1 to 3,

the acid group is a phenolic hydroxyl group or a carboxyl group.

5. The coloring composition according to any one of claims 1 to 4,

the protecting group is a group represented by any one of formulae (Y1) to (Y5),

formula (Y1): -C (R) ^Y1 )(R ^Y2 )(R ^Y3 )

Formula (Y2): -C (= O) OC (R) ^Y4 )(R ^Y5 )(R ^Y6 )

Formula (Y3): -C (R) ^Y7 )(R ^Y8 )(OR ^Y9 )

Formula (Y4): -C (R) ^Y10 )(H)(Ar ^Y1 )

Formula (Y5): -C (= O) (R) ^Y11 )

In the formula (Y1), R ^Y1 ～R ^Y3 Each independently represents an alkyl group, R ^Y1 ～R ^Y3 2 of which are optionally bonded to form a ring,

in the formula (Y2), R ^Y4 ～R ^Y6 Each independently represents an alkyl group, R ^Y4 ～R ^Y6 2 of which are optionally bonded to form a ring,

in the formula (Y3), R ^Y7 And R ^Y8 Each independently represents a hydrogen atom, an alkyl group or an aryl group, R ^Y7 And R ^Y8 At least one of which is alkyl or aryl, R ^Y9 Represents alkyl or aryl, R ^Y7 Or R ^Y8 And R ^Y9 Optionally bonded to form a ring,

in the formula (Y5), R ^Y11 Represents an alkyl group or an aryl group.

6. The coloring composition according to any one of claims 1 to 5,

the colorant further comprises a yellow colorant.

7. The coloring composition according to any one of claims 1 to 6,

the content of the red colorant in the colorant is 70% by mass or more.

8. 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 ℃ or less throughout the process.

9. The colored composition according to any one of claims 1 to 8, which is used for a color filter.

10. The coloring composition according to any one of claims 1 to 9, which is used for a display device.

11. A cured film obtained by curing the coloring composition according to any one of claims 1 to 10.

12. A color filter having the cured film of claim 11.

13. A display device having the cured film of claim 11.