KR20220044580A - Coloring composition, cured film, color filter and display device - Google Patents

Abstract

The coloring composition containing the coloring agent containing a red coloring agent, resin, a polymeric compound, and a photoinitiator. The resin includes resin BI having a repeating unit containing a blocked isocyanate group. In the coloring composition, the ratio A ^max1 /A ^min1 of the maximum absorbance value A ^max1 with respect to the light of a wavelength of 400 to 500 nm and the minimum value A ^min1 of the absorbance with respect to the light having a wavelength of 550 to 700 nm is 25 or more, and the light with a wavelength of 500 nm When the absorbance is 1, the wavelength at which the absorbance is 0.3 exists in the range of 570 to 620 nm. The cured film obtained by hardening|curing the coloring composition mentioned above, and the color filter and display apparatus containing the cured film mentioned above.

Description

Coloring composition, cured film, color filter and display device

The present invention relates to a coloring composition. In more detail, it is related with the coloring composition used for red pixel formation of a color filter, etc. Moreover, this invention relates to the cured film using a coloring composition, a color filter, and a display apparatus.

In various display devices, a color filter is generally used for colorizing a display image. For example, in Patent Document 1, a repeating unit derived from p-acetoxystyrene and a repeating unit derived from 2-(3,5-dimethyl-1H-pyrazole-1-carboxyamide)ethyl methacrylate are It describes manufacturing a color filter etc. using the coloring composition containing resin, a coloring agent, a polymeric compound, and a photoinitiator contained.

Patent Document 1: Korean Patent Publication No. 10-2017-0118438

In general, a color filter has pixels of a plurality of colors. The color filter which has such a multiple-color pixel pattern-forms the coloring composition for pixel formation of each color sequentially, and forms the pixel of each color, and is manufactured.

On the other hand, in recent years, a color filter may be formed on the member with low heat resistance (For example, organic-semiconductor elements, such as an organic electroluminescent display element). Since such a member has low heat resistance, it is preferable to form the pixel of the color filter in a low-temperature process of, for example, 150° C. or less to suppress thermal damage to the support.

However, when a pixel is formed in a low-temperature process, the degree of hardening of the pixel may be insufficient, and when forming a pixel of a different color, color mixing with the coloring composition of the other color occurs and the spectral characteristics are liable to fluctuate. tended to Moreover, according to examination of this inventor, also in the coloring composition of patent document 1, it turned out that there exists room for further improvement with respect to mixing with other colors.

Therefore, the objective of this invention is providing the coloring composition which can form the cured film by which color mixing with other colors was suppressed, a cured film, a color filter, and a display apparatus.

According to examination of this inventor, it discovered that the said objective can be achieved by using the coloring composition mentioned later, and came to complete this invention. The present invention provides the following.

<1> A coloring composition containing a colorant containing a red colorant, a resin, a polymerizable compound, and a photoinitiator, comprising:

The resin comprises a resin BI having a repeating unit comprising a block isocyanate group,

The said coloring composition, ratio A ^max1 /A ^min1 of the maximum value A ^max1 of the absorbance with respect to the light of wavelength 400-500 nm, and the minimum value A ^min1 of the absorbance with respect to the light of wavelength 550-700 nm is 25 or more,

When the absorbance with respect to the light of wavelength 500nm is made into 1, the wavelength from which the absorbance becomes 0.3 exists in the range of 570-620 nm.

<2> The block isocyanate group is an isocyanate group, an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide The coloring composition as described in <1> which is group which has the structure protected with the blocking agent chosen from a compound.

<3> The coloring composition as described in <2> whose molecular weight of the said blocking agent is 50-200.

<4> The coloring composition according to any one of <1> to <3>, wherein the repeating unit containing the block isocyanate group is a repeating unit represented by the following formula (B-1);

[Formula 1]

In the formula (B-1), R ^b1 to R ^b3 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R ^b4 to R ^b7 each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. or an aryl group, and L ^b1 represents a single bond or a hydrocarbon group.

<5> The coloring composition according to any one of <1> to <4>, wherein the resin BI includes a repeating unit having a group in which an acid group is protected by a protecting group.

<6> The coloring composition according to <5>, wherein the acid group is a phenolic hydroxyl group or a carboxy group.

<7> The coloring composition according to <5> or <6>, wherein the protecting group is a group that is decomposed and detached by the action of an acid or a base.

<8> The coloring composition according to any one of <5> to <7>, wherein the protecting group is a group represented by any one of formulas (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 to R ^Y3 each independently represent an alkyl group, and two of R ^Y1 to R ^Y3 may be bonded to each other to form a ring;

In the formula (Y2), R ^Y4 to R ^Y6 each independently represent an alkyl group, and two of R ^Y4 to R ^Y6 may be bonded to each other to form a ring;

In the formula (Y3), R ^Y7 and R ^Y8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^Y7 and R ^Y8 is an alkyl group or an aryl group, and R ^Y9 represents an alkyl group or an aryl group , R ^Y7 or R ^Y8 and R ^Y9 may combine to form a ring;

In formula (Y4), Ar ^Y1 represents an aryl group and R ^Y10 represents an alkyl group or an aryl group;

In formula (Y5), R ^Y11 represents an alkyl group or an aryl group.

<9> The coloring composition according to any one of <5> to <8>, wherein the repeating unit having a group in which the acid group is protected by a protecting group is a repeating unit represented by the following formula (B-2);

[Formula 2]

In formula (B-2), R ^b11 to R ^b13 each independently represent a hydrogen atom, a halogen atom or an alkyl group, L ^b11 represents a single bond or a divalent linking group, and X ^b11 represents a formula (X-1) Or group represented by Formula (X-2) is shown;

[Formula 3]

In formulas (X-1) and (X-2), Y ^b1 represents a protecting group, and the broken line represents a portion bonded to L ^b11 .

<10> The coloring composition according to any one of <1> to <9>, wherein the coloring agent further contains a yellow coloring agent.

The coloring composition in any one of <1>-<10> whose content of the said red coloring agent in the <11> said coloring agent is 70 mass % or more.

The coloring composition in any one of <1>-<11> used in order to form a cured film at the temperature of 150 degrees C or less through <12> all processes.

The coloring composition in any one of <1>-<12> which is for <13> color filters.

<14> The coloring composition in any one of <1>-<13> which is for display devices.

<15> Cured film obtained by hardening|curing the coloring composition in any one of <1>-<14>.

<16> The color filter which has a cured film as described in <15>.

<17> A display device having the cured film according to <15>.

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

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

In the description of the group (atomic group) in the present specification, the description not describing substitution and unsubstitution includes a group having a substituent (atomic group) together with a group having no substituent (atomic group). For example, "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

In the present specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams in exposure unless otherwise specified. Moreover, as light used for exposure, actinic rays or radiation, such as a bright-line spectrum of a mercury vapor lamp, and far ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and an electron beam, generally represented by an excimer laser.

In this specification, the numerical range indicated using "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit.

In this specification, total solid means the total mass of the component except the solvent from all the components of a composition.

In this specification, "(meth)acrylate" represents both, or either of acrylate and methacrylate, and "(meth)acryl" represents both, or either of acryl and methacryl. represents, "(meth)allyl" represents both of allyl and methacryloyl, or either, "(meth)acryloyl" represents both of acryloyl and methacryloyl, or either indicates.

In the present specification, the term "process" is included in this term as long as the desired action of the process is achieved even if it is not clearly distinguishable from other processes as well as independent processes.

In this specification, a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).

<Coloring composition>

The coloring composition of this invention is a coloring composition containing the coloring agent containing a red coloring agent, resin, a polymeric compound, and a photoinitiator,

The resin comprises a resin BI having a repeating unit comprising a block isocyanate group,

The said coloring composition, ratio A ^max1 /A ^min1 of the maximum value A ^max1 of the absorbance with respect to the light of wavelength 400-500 nm, and the minimum value A ^min1 of the absorbance with respect to the light of wavelength 550-700 nm is 25 or more,

When the absorbance for light having a wavelength of 500 nm is 1, the wavelength at which the absorbance is 0.3 is characterized in that it exists in the range of 570 to 620 nm.

ADVANTAGE OF THE INVENTION According to the coloring composition of this invention, the cured film by which color mixing with other colors was suppressed can be formed. In particular, even when the cured film is formed at a low temperature of 150°C or lower (preferably 120°C or lower, more preferably 100°C or lower), a cured film in which color mixing with other colors is suppressed can be formed.

Although the detailed reason for obtaining such an effect is not clear, when resin BI having a repeating unit containing a block isocyanate group is contained in the coloring composition having the above spectral properties, heat is released when the coloring composition is cured by heating. For the reason that it is difficult to do so, by effectively using heat, the protecting group (blocking agent) is detached from the blocked isocyanate group of the resin BI, so that the isocyanate group is easily generated, and the curing of the coloring composition proceeds quickly, so that at a relatively low temperature It is estimated that the cured film fully hardened|cured also by heating of can be formed. For this reason, according to the coloring composition of this invention, the cured film by which color mixing with other colors was suppressed can be formed.

Moreover, at the time of formation of a cured film, when a protective group (blocking agent) detach|desorbs from a block isocyanate group, a film thickness can also be reduced more and it is a thin film, and a cured film with a high color value can also be formed. Here, generally, a red coloring agent has many things with a low color value compared with the coloring agent of another color. As one means for achieving thin film formation, maintaining the desired spectral characteristic in a color filter, the method of raising the density|concentration of the coloring agent in the coloring composition used for formation of a color filter is known. When the density|concentration of the coloring agent in a coloring composition is raised, it is necessary to reduce components other than a coloring agent, and there exists a possibility that the film forming property, pattern formability, etc. may arise, or the freedom degree of prescription design may become narrow. For this reason, it was said that thin film formation was difficult about the red pixel of a color filter. According to the coloring composition of this invention, since a film thickness can be reduced at the time of formation of a cured film and thin film formation can be aimed at, the coloring composition of this invention has high utility value especially in thin film formation of the red pixel of a color filter.

The absorbance Aλ at a predetermined wavelength λ is defined by the following formula (Ab1).

Aλ=-log(Tλ/100) … (Ab1)

Aλ is the absorbance at the wavelength λ, and Tλ is the transmittance (%) of light at the wavelength λ.

In this invention, the value measured in the state of a solution may be sufficient as the value of the light absorbency of a coloring composition, and the value of the cured film formed into a film using the coloring composition may be sufficient as it. When measuring the absorbance in the state of a cured film, a coloring composition is apply|coated by methods, such as spin coating, on a glass substrate, 100 degreeC using a hotplate etc., and drying for 2 minutes, Then, light intensity 20mW/cm ² , It is preferable to measure using a film (cured film) obtained by exposing i-line under the conditions of an exposure amount of 1 J/cm ² , then heating it on a hot plate at 100° C. for 20 minutes, and allowing it to cool to room temperature. Absorbance can be measured using a conventionally known spectrophotometer.

Ratio A ^max1 /A ^min1 of the maximum value A ^max1 of the absorbance with respect to the light of wavelength 400-500 nm, and the minimum value A ^min1 of the absorbance with respect to the light of wavelength 550-700 nm is 25 or more, and, as for the coloring composition of this invention, it is preferable that it is 50 or more and more preferably 100 or more. As the value of the ratio A ^max1 /A ^min1 is higher, the effect of the present invention described above can be obtained more conspicuously, and furthermore, it is easy to obtain a red pixel excellent in color separation properties from other colors. For this reason, although there is no limitation in particular about the upper limit of the value of the said ratio ^Amax1 / ^Amin1 , For example, it may be set as 10000 or less, may be set as 5000 or less, and may be set as 1000 or less.

When the absorbance with respect to the light of wavelength 500nm which the coloring composition of this invention shows is 1, the wavelength at which the absorbance becomes 0.3 exists in the range of 570-620 nm, It is preferable to exist in the range of 575-615 nm, 580- It is more preferable to exist in the range of 610 nm, and it is more preferable to exist in the range of 585-605 nm.

When the absorbance with respect to the light of wavelength 500nm shown by the coloring composition of this invention is made into 1, the wavelength at which the absorbance becomes 0.5, it is preferable to exist in the range of 565-605 nm, It is more preferable to exist in the range of 570-600 nm Preferably, it is more preferable to exist in the range of 575-595 nm.

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

It is preferable that ratio A ^max1 /A600 of the maximum value A ^max1 of the absorbance with respect to the light of wavelength 400-500 nm, and the absorbance A600 with respect to the light of wavelength ^600nm is 5-15, and, as for the coloring composition of this invention, it is ^6.5-13.5 It is more preferable, and it is more preferable that it is 8-12.

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

When the coloring composition of this invention forms the cured film of 0.5-3.0 micrometers in film thickness, the maximum value of the transmittance|permeability with respect to the light of wavelength 550-700 nm in the thickness direction of a film is 85 % or more, and an average transmittance is 50 % or more, the maximum transmittance of light having a wavelength of 550 to 700 nm in the thickness direction of the film is 90% or more, and it is more preferable that the average transmittance is 55% or more.

When the coloring composition of this invention forms a cured film with a film thickness of 0.5-3.0 micrometers, it is preferable that the transmittance|permeability with respect to the light of wavelength 500nm is 1 % or less, It is more preferable that it is 0.75 % or less, It is more preferable that it is 0.5 % or less Do. Moreover, it is preferable that it is 1 % or less, and, as for the maximum value of the transmittance|permeability with respect to the light of wavelength 400-500 nm, it is more preferable that it is 0.75 % or less, It is more preferable that it is 0.5 % or less.

It is preferable that solid content concentration of the coloring composition of this invention is 5-25 mass %. 22.5 mass % or less is preferable, as for an upper limit, 20 mass % or less is more preferable, and its 18 mass % or less is more preferable. If the solid content concentration is within the above range, even if the cured film (pixel) is formed at a temperature of 150 ° C. or less (preferably a temperature of 120 ° C or less) through the previous process, a cured film (pixel) having excellent flatness can be formed. there is.

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

The coloring composition of this invention can be used suitably as a coloring composition for display apparatuses. In more detail, it can use suitably as a coloring composition for pixel formation of the color filter for display devices, and can use it more preferably as a coloring composition for red pixel formation of the color filter for display devices. Although there is no limitation in particular as a kind of display apparatus, The display apparatus etc. which have organic-semiconductor elements, such as an organic electroluminescent display apparatus, are mentioned as a light source.

Moreover, the coloring composition of this invention can also be used as a coloring composition for solid-state image sensors. In more detail, it can use suitably as a coloring composition for pixel formation of the color filter for solid-state imaging elements, It can use more preferably as a coloring composition for red pixel formation of the color filter for solid-state imaging elements.

It is also preferable that the coloring composition of this invention is what is used in order to form a cured film at the temperature of 150 degrees C or less (preferably the temperature of 120 degrees C or less) through all processes. In addition, in this specification, forming a cured film at the temperature of 150 degrees C or less through all processes means performing all the processes of forming a cured film using a coloring composition at the temperature of 150 degrees C or less.

It is preferable that the thickness of the cured film and pixel formed with the coloring composition of this invention is 0.5-3.0 micrometers. 0.8 micrometer or more is preferable, as for a minimum, 1.0 micrometer or more is more preferable, and 1.1 micrometer or more is still more preferable. 2.5 micrometers or less are preferable, as for an upper limit, 2.0 micrometers or less are more preferable, and 1.8 micrometers or less are still more preferable.

Moreover, it is preferable that the line|wire width (pattern size) of the pixel formed with the coloring composition of this invention is 2.0-10.0 micrometers. 7.5 micrometers or less are preferable, as for an upper limit, 5.0 micrometers or less are more preferable, and 4.0 micrometers or less are still more preferable. 2.25 micrometers or more are preferable, as for a minimum, 2.5 micrometers or more are more preferable, and 2.75 micrometers or more are still more preferable.

Hereinafter, the coloring composition of this invention is demonstrated in detail.

<<Colorant>>

The coloring composition of this invention contains a coloring agent. As a coloring agent, chromatic coloring agents, such as a red coloring agent, a green coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent, and an orange coloring agent, are mentioned. In this invention, a pigment may be sufficient as a coloring agent, and dye may be sufficient as it. You may use a pigment and dye together. Moreover, any of an inorganic pigment and an organic pigment may be sufficient as a pigment. Moreover, as a pigment, the inorganic pigment or the material which substituted a part of organic-inorganic pigment with the organic chromophore can also be used. By substituting an inorganic pigment or an organic-inorganic pigment with an organic chromophore, color design can be facilitated. When the thing containing a pigment is used as a coloring agent, it is easy to form the cured film excellent in durability, such as heat resistance and light resistance. When the thing containing dye is used as a coloring agent, it is easy to form the cured film with a higher red color reproduction area|region. Moreover, generally, although the cured film obtained using dye tends to produce color mixture more easily than the cured film obtained using a pigment, according to this invention, even when dye is used as a coloring agent, even if it is a case where color transition is suppressed, the cured film Since it can form, it is especially effective in the case where the thing containing a dye is used as a coloring agent.

As for the average primary particle diameter of a pigment, 1-200 nm is preferable. 5 nm or more is preferable and, as for a minimum, 10 nm or more is more preferable. 180 nm or less is preferable, as for an upper limit, 150 nm or less are more preferable, and its 100 nm or less is still more preferable. The dispersion stability of the pigment in a coloring composition is favorable as the average primary particle diameter of a pigment is the said range. In addition, in this invention, the primary particle diameter of a pigment can be calculated|required from the image photograph obtained by observing the primary particle of a pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is calculated, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment. In addition, let the average primary particle diameter in this invention be the arithmetic average value of the primary particle diameters with respect to the primary particle of 400 pigments. In addition, the primary particle of a pigment means independent particle|grains without aggregation.

A dye multimer can also be used for a coloring agent. It is preferable that a dye multimer is a dye used by melt|dissolving in a solvent. Moreover, the dye multimer may form particle|grains. When a dye multimer is particle|grains, it is used in the state disperse|distributed to the solvent normally. A particle-form dye multimer can be obtained by emulsion polymerization, for example, The compound and manufacturing method of Unexamined-Japanese-Patent No. 2015-214682 are mentioned as a specific example. A dye multimer has two or more dye structures in 1 molecule, and it is preferable to have three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The plurality of dye structures in one molecule may have the same dye structure or different dye structures. As for the weight average molecular weight (Mw) of a dye multimer, 2000-50000 are preferable. As for a minimum, 3000 or more are more preferable, and 6000 or more are still more preferable. 30000 or less are more preferable, and, as for an upper limit, 20000 or less are still more preferable. The dye multimer is disclosed in Japanese Patent Application Laid-Open No. 2011-213925, Japanese Patent Application Laid-Open No. 2013-041097, Japanese Patent Application Laid-Open No. 2015-028144, Japanese Patent Application Laid-Open No. 2015-030742, International Publication No. 2016/031442, etc. It is also possible to use the compounds described.

(red colorant)

The coloring composition of this invention contains a red coloring agent. A pigment may be sufficient as a red coloring agent, and dye may be sufficient as it. You may use a pigment and dye together.

As a red colorant, it is at least 1 sort(s) selected from a xanthene compound, an anthraquinone compound, a monoazo compound, a diazo compound, an azomethine compound, an aminoketone compound, a quinacridone compound, a perylene compound, and a diketopyrrolopyrrole compound. Preferably, it is at least one selected from an anthraquinone compound, a quinacridone compound, a perylene compound, and a diketopyrrolopyrrole compound, more preferably an anthraquinone compound, a perylene compound, and a diketopyrrolopyrrole compound It is more preferably at least one type, and even more preferably at least one type selected from an anthraquinone compound and a diketopyrrolopyrrole compound, it is a compound having absorption on the longer wave side, and the effect of the present invention can be obtained more significantly It is especially preferable that it is an anthraquinone compound from the reason of easiness.

As a red pigment, 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 (xanthene compound, Organo Ultramarine, Bluish Red), 295 (monoazo compound), 296 (diazo compound), and 297 (amino ketone type).

As a 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.

As a red colorant, a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in Japanese Patent Application Laid-Open No. 2017-201384, and a diketopyrrolopyrrole compound described in Paragraph Nos. 0016 to 0022 of Japanese Patent Publication No. 6248838 , the diketopyrrolopyrrole compound described in International Publication No. 2012/102399, the diketopyrrolopyrrole compound described in International Publication No. 2012/117965, the naphtholazo compound described in Japanese Patent Application Laid-Open No. 2012-229344, Japan The red colorant described in Patent Publication No. 6516119, the red colorant described in Japanese Patent Publication No. 6525101, etc. can also be used. Moreover, as a red coloring agent, the compound which has a structure in which the aromatic ring group into which the group which the oxygen atom, the sulfur atom, or the nitrogen atom couple|bonded group couple|bonded with the aromatic ring couple|bonded with the diketopyrrolopyrrole skeleton can also be used.

As the red colorant, from the viewpoint of spectral characteristics and durability, etc., C. I. Pigment Red 122, 177, 179, 202, 254, 264, 269 is preferable, and C. I. Pigment Red 177, 179, 202, 254, 264 is more preferable, C. I. Pigment Red 177, 254, 264 are more preferred.

(other colorants)

It is preferable that the coloring composition of this invention contains other coloring agents other than a red coloring agent further. Examples of the other colorant to be used in combination include a yellow colorant, a green colorant, a purple colorant, a blue colorant, an orange colorant, and the like, and a yellow colorant is preferable because it is easy to form a cured film having spectral properties more suitable for red.

As a yellow colorant, an azo compound, a quinophthalone compound, an isoindolinone compound, an isoindoline compound, an anthraquinone compound, etc. are mentioned, An isoindoline compound, an azo compound, and a quinophthalone compound are preferable, and isoin A doline compound and an azo compound are more preferable, and an isoindoline compound is especially preferable.

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 (metaphosphorus), 233 (quinoline), 234 (aminoketone) ), 235 (amino ketone type), 236 (amino ketone type), etc. yellow pigments are mentioned.

Moreover, as a yellow coloring agent, the compound described in Unexamined-Japanese-Patent No. 2017-201003, the compound of Unexamined-Japanese-Patent No. 2017-197719, Paragraph No. 0011 - 0062 of Unexamined-Japanese-Patent No. 2017-171912, 0137 - The compound of 0276 , the compound described in Paragraph Nos. 0010 to 0062 and 0138 to 0295 of Japanese Unexamined Patent Publication No. 2017-171913, the compounds described in Paragraph Nos. 0011 to 0062 and 0139 to 0190 of Japanese Unexamined Patent Publication No. 2017-171914, Japanese Patent Application Laid-Open No. 2017-171915 Paragraph Nos. 0010 to 0065, the compounds described in 0142 to 0222 of Japanese Patent Application Laid-Open No. 2013-054339, the quinophthalone compounds described in Paragraph Nos. 0011 to 0034, and the quinophthalone compounds described in Paragraph Nos. 0013 to 0058 of Japanese Patent Application Laid-Open No. 2014-026228 Nophthalone compound, the isoindoline compound described in JP-A-2018-062644, the quinophthalone compound described in JP-A-2018-203798, the quinophthalone compound described in JP-A 2018-062578, Japan The quinophthalone compound described in Patent Publication No. 6432076, the quinophthalone compound described in Japanese Patent Application Laid-Open No. 2018-155881, the quinophthalone compound described in Japanese Patent Application Laid-Open No. 2018-111757, Japanese Patent Application Laid-Open No. 2018-040835 The quinophthalone compound described in , the quinophthalone compound described in Japanese Patent Application Laid-Open No. 2017-197640, the quinophthalone compound described in Japanese Patent Application Laid-Open No. 2016-145282, The quinophthalone described in Japanese Patent Application Laid-Open No. 2014-085565 The compound, the quinophthalone compound described in Unexamined-Japanese-Patent No. 2014-021139, the quinophthalone compound of Unexamined-Japanese-Patent No. 2013-209614, The quinophthalone compound of Unexamined-Japanese-Patent No. 2013-209435, Unexamined-Japanese-Patent No. The quinophthalone compound described in Japanese Patent Application Laid-Open No. 2013-181015, Japanese Patent Application Laid-Open No. 2013-061622 The described quinophthalone compound, the quinophthalone compound of Unexamined-Japanese-Patent No. 2013-032486, The quinophthalone compound of Unexamined-Japanese-Patent No. 2012-226110, The quinophthalone compound of Unexamined-Japanese-Patent No. 2008-074987 , The quinophthalone compound described in Unexamined-Japanese-Patent No. 2008-081565, the quinophthalone compound of Unexamined-Japanese-Patent No. 2008-074986, The quinophthalone compound of Unexamined-Japanese-Patent No. 2008-074985, Unexamined-Japanese-Patent No. The quinophthalone compound described in 2008-050420, the quinophthalone compound described in Japanese Unexamined Patent Publication No. 2008-031281, the quinophthalone compound described in Japanese Unexamined Patent Publication No. 48-032765, Japanese Unexamined Patent Publication No. 2019-008014 The quinophthalone compound described in, the compound represented by the following formula (QP1), the metaine dye described in JP-A-2019-073695, the meta-dye described in JP-A-2019-073696, JP-A 2019- The compound represented by the metaine dye of 073697, the metaine dye of Unexamined-Japanese-Patent No. 2019-073698, and a following formula (QP2) can also be used.

[Formula 4]

In formula (QP1), X ¹ to X ¹⁶ each independently represents a hydrogen atom or a halogen atom, and Z ¹ represents an alkylene group having 1 to 3 carbon atoms. As a specific example of the compound represented by Formula (QP1), the compound described in Paragraph No. 0016 of Unexamined-Japanese-Patent No. 6443711 is mentioned.

[Formula 5]

In formula (QP2), each of Y ¹ to Y ³ independently represents a halogen atom. n and m represent the integers of 0-6, and p represents the integer of 0-5. (n+m) is 1 or more. As a specific example of the compound represented by Formula (QP2), the compound described in Paragraph No. 0047 - 0048 of Unexamined-Japanese-Patent No. 6432077 is mentioned.

As a yellow colorant, from a viewpoint of a spectral characteristic, durability, etc., C.I. Pigment Yellow 139, 150, 185 are preferable, C. I. Pigment Yellow 139, 150 are more preferable, C. I. Pigment Yellow 139 is still more preferable.

As the green colorant, C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine-based), 65 (phthalocyanine-based), 66 (phthalocyanine-based), etc. of green pigments. Further, as the green colorant, a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 may be used. there is. As a specific example, the compound of International Publication No. 2015/118720 is mentioned. Moreover, as a green colorant, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound which has the phosphoric acid ester described in International Publication No. 2012/102395 as a ligand, and the phthalocyanine described in Unexamined-Japanese-Patent No. 2019-008014. An amine compound, the phthalocyanine compound described in Unexamined-Japanese-Patent No. 2018-180023, the compound of Unexamined-Japanese-Patent No. 2019-038958, etc. can also be used.

As the green colorant, from the viewpoint of spectral characteristics and durability, etc., C. I. Pigment Green 7, 36, 37, 58, 59, 65 is preferable, C. I. Pigment Green 7, 36, 58, 65 is more preferable, C. I. Pigment Green 7 , 36 is more preferable.

As a 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 (monoazo type) and blue pigments, such as 88 (metaphosphorus type), are mentioned. Moreover, as a blue coloring agent, the aluminum phthalocyanine compound which has a phosphorus atom can also be used. As a specific example, Paragraph No. 0022 - 0030 of Unexamined-Japanese-Patent No. 2012-247591, Paragraph No. 0047 of Unexamined-Japanese-Patent No. 2011-157478 are mentioned.

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

As a purple colorant, purple pigments, such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triaryl methane type), 61 (xanthene type), are mentioned.

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 and orange pigments such as 71 and 73.

As for content of a coloring agent, 5-70 mass % is preferable in total solid of a coloring composition. 10 mass % or more is preferable, as for a minimum, 15 mass % or more is more preferable, and 20 mass % or more is still more preferable. 60 mass % or less is preferable, as for an upper limit, 55 mass % or less is more preferable, and 50 mass % or less is still more preferable.

It is preferable that content of the red coloring agent in a coloring agent is 70 mass % or more, It is more preferable that it is 80 mass % or more, It is more preferable that it is 90 mass % or more.

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

<<Resin>>

The coloring composition of this invention contains resin. Resin is mix|blended for the use which disperse|distributes a pigment etc. in a coloring composition, and the use of a binder, for example. In addition, resin mainly used in order to disperse|distribute a pigment etc. in a coloring composition is also called a dispersing agent. However, such a use of resin is an example, and resin can also be used for purposes other than such a use.

(Suzy BI)

The coloring composition of this invention contains resin (henceforth resin BI) which has a repeating unit containing a block isocyanate group.

As a block isocyanate group which resin BI has, it is preferable that it is a group which can produce|generate an isocyanate group with heat, and it is more preferable that it is a group which can produce|generate an isocyanate group with a heat|fever of 70-150 degreeC. As a blocked isocyanate group, group of the structure in which the isocyanate group was chemically protected by the blocking agent is mentioned.

A blocked isocyanate group is a group in which the isocyanate group has a structure protected by a compound called a blocking agent, and does not show reactivity as an isocyanate group at room temperature (for example, 10 to 30°C), but is heated It is a group of a structure in which a blocking agent is detached from a blocked isocyanate group and an isocyanate group is generated.

As a block isocyanate group which resin BI has, it is more preferable that it is a group which can produce|generate an isocyanate group with the heat|fever of 70-150 degreeC. That is, it is preferable that the isocyanate formation temperature (desorption temperature of a blocking agent) of a blocked isocyanate group is 70-150 degreeC. It is preferable that it is 75 degreeC or more from a viewpoint of storage stability, and, as for the lower limit of the isocyanate formation temperature, it is more preferable that it is 80 degreeC or more. It is preferable that it is 130 degrees C or less from a sclerosis|hardenability viewpoint, and, as for the upper limit of the isocyanate formation temperature, it is more preferable that it is 120 degrees C or less.

Examples of the blocking agent for protecting the isocyanate group of the blocked isocyanate group include an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imidazole compound. od compound, etc., and from the viewpoint of the easiness of the protection reaction and deprotection reaction, an oxime compound, a lactam compound, an active methylene compound, and a pyrazole compound are preferable, and an oxime compound, an active methylene compound and a pyrazole compound are more preferable. and an oxime compound is more preferable.

As an oxime compound, acetoxime, form aldoxime, cyclohexane oxime, methyl ethyl ketone oxime, cyclohexanone oxime, benzophenone oxime, etc. are mentioned.

Examples of the lactam compound include ε-caprolactam and γ-butyrolactam.

Examples of the phenol compound include phenol, naphthol, cresol, xyleneol, and halogen-substituted phenol.

Examples of the alcohol compound include methanol, ethanol, propanol, butanol, cyclohexanol, ethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, and alkyl lactate.

Primary amines and secondary amines are mentioned as an amine compound. The amine compound may be any of aromatic amine, aliphatic amine, and alicyclic amine, and specific examples thereof include aniline, diphenylamine, ethyleneimine, and polyethyleneimine.

Examples of the active methylene compound include diethyl malonate, dimethyl malonate, ethyl acetoacetate, and methyl acetoacetate.

Examples of the pyrazole compound include pyrazole, methylpyrazole, and dimethylpyrazole.

Examples of the mercaptan compound include alkyl mercaptan and aryl mercaptan.

Examples of the imidazole compound include imidazole, 1-methylimidazole, 1-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-methyl. imidazole, 1-benzyl-2-phenylimidazole, etc. are mentioned.

Examples of the imide compound include maleimide, succinimide, phthalimide, and derivatives thereof.

It is preferable that it is 50-200, as for the molecular weight of a blocking agent, it is more preferable that it is 50-160, It is more preferable that it is 50-120. Desorption of the blocking agent at room temperature can be suppressed as the molecular weight of a blocking agent is 50 or more, and the storage stability of a coloring composition can be improved. When the molecular weight of the blocking agent is 200 or less, the blocking agent is easily removed by heat treatment at low temperature (for example, 150° C. or less) to advance a curing reaction, and it is easy to form a sufficiently cured cured film. For this reason, it is easy to form the cured film by which the color transition with another color was suppressed.

As the blocking agent, methyl ethyl ketone oxime, cyclohexanone oxime, acetoxime, diethyl malonate, ethyl acetoacetate, ε-caprolactam, γ-butyrolactam and pyrazole are preferable, and methyl ethyl ketone oxime and acetoxime are preferable. , diethyl malonate and pyrazole are more preferable, and methyl ethyl ketone oxime is still more preferable.

As a repeating unit containing a block isocyanate group, the repeating unit represented by a following formula (Bi-1) is mentioned.

[Formula 6]

In the formula (Bi-1), X ¹ represents the main chain of the repeating unit, L ¹ represents a single bond or a divalent linking group, and Z ¹ represents a block isocyanate group.

In formula (Bi-1), there is no limitation in particular as a main chain of the repeating unit represented by X< ¹ >. There is no restriction|limiting in particular if it is a coupling group formed from a well-known polymerizable monomer. For example, poly (meth) acrylic coupling group, polyalkyleneimine coupling group, polyester coupling group, polyurethane coupling group, polyurea coupling group, polyamide coupling group, polyether coupling group, polystyrene coupling group, etc. and a poly(meth)acrylic-based linking group and a polystyrene-based linking group are preferable, and a poly(meth)acrylic-based linking group is more preferable.

In the formula (Bi-1), as the divalent linking group represented by L ¹ , 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-, -COO-, -OCO-, -S-, and the group formed by combining two or more of these is mentioned. Any of linear, branched, and cyclic|annular form may be sufficient as an alkylene group, and linear or branched form is preferable. Moreover, the alkylene group may have a substituent, and unsubstituted may be sufficient as it. A hydroxyl group, an alkoxy group, etc. are mentioned as a substituent.

In the formula (Bi-1), Z ¹ represents a blocked isocyanate group.

As an aspect of the repeating unit represented by Formula (Bi-1), the repeating unit represented by a following formula (B-1) is mentioned.

[Formula 7]

In the formula (B-1), R ^b1 to R ^b3 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R ^b4 to R ^b7 each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. or an aryl group, and L ^b1 represents a single bond or a hydrocarbon group.

Examples of the halogen atom represented by R ^b1 to R ^b7 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

1-20 are preferable, as for carbon number of the alkyl group represented by ^Rb1 - ^Rb7 , 1-10 are more preferable, and 1-5 are still more preferable. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched.

1-20 are preferable, as for carbon number of the alkoxy group which ^{Rb4-Rb7 represents} , 1-10 are more preferable, and 1-5 are still more preferable.

6-20 are preferable, as for carbon number of the aryl group which ^{Rb4-Rb7 represents} , 6-15 are more preferable, and 6-10 are still more preferable.

Examples of the hydrocarbon group represented by L ^b1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), and a group combining these groups.

In Resin BI, the content of the repeating unit containing a block isocyanate group is preferably 45% by mass or more, more preferably 50% by mass or more, and still more preferably 55% by mass or more, based on the total repeating units of Resin BI. Do. The upper limit may be 100 mass %, 95 mass % or less, and may be 85 mass % or less.

The resin BI preferably includes a repeating unit having a group in which an acid group is protected by a protecting group. According to this aspect, advancing of reaction of resin BI at the time of preservation|save of a coloring composition, etc. can be suppressed, and storage stability of a coloring composition can be improved.

As said acid group, a phenolic hydroxyl group, a carboxy group, a sulfo group, and a phosphoric acid group are mentioned, It is preferable that they are a phenolic hydroxyl group and a carboxy group, Since the reactivity with the isocyanate group after deprotection is high, it is a carboxy group more preferably.

Examples of the protecting group include a group that is decomposed and detached by the action of an acid or a base. The protecting group is preferably a group represented by any one of the formulas (Y1) to (Y5), and more preferably a group represented by the formulas (Y3) and (Y5) from the viewpoint of being easy to deprotect.

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 to R ^Y3 each independently represent an alkyl group, and two of R ^Y1 to R ^Y3 may be bonded to each other to form a ring;

In the formula (Y2), R ^Y4 to R ^Y6 each independently represent an alkyl group, and two of R ^Y4 to R ^Y6 may be bonded to each other to form a ring;

In the formula (Y3), R ^Y7 and R ^Y8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^Y7 and R ^Y8 is an alkyl group or an aryl group, and R ^Y9 represents an alkyl group or an aryl group , R ^Y7 or R ^Y8 and R ^Y9 may combine to form a ring;

In formula (Y4), Ar ^Y1 represents an aryl group and R ^Y10 represents an alkyl group or an aryl group;

In formula (Y5), R ^Y11 represents an alkyl group or an aryl group.

1-12 are preferable, as for carbon number of the alkyl group which R ^Y1 -R ^Y3 of Formula (Y1) represents, 1-6 are more preferable, and 1-4 are still more preferable. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched. In the formula (Y1), two of R ^Y1 to R ^Y3 may combine to form a ring. Examples of the ring formed by bonding two of R ^Y1 to R ^Y3 include a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. A cyclic cycloalkyl group is mentioned, It is preferable that it is a C5-C6 monocyclic cycloalkyl group. Further, in the cycloalkyl group, one of the methylene groups constituting the ring may be substituted with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group.

1-12 are preferable, as for carbon number of the alkyl group which R ^Y4 -R ^Y6 of Formula (Y2) represents, 1-6 are more preferable, and 1-4 are still more preferable. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched. It is preferable that at least 2 of R ^Y4 -R ^Y6 of Formula (Y2) are a methyl group. In the formula (Y2), two of R ^Y4 to R ^Y6 may be bonded to form a ring. As a ring to be formed, the ring demonstrated by Formula (Y1) is mentioned.

In the formula (Y3), R ^Y7 and R ^Y8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^Y7 and R ^Y8 is an alkyl group or an aryl group, and R ^Y9 represents an alkyl group or an aryl group , R ^Y7 or R ^Y8 and R ^Y9 may combine to form a ring.

The alkyl group may be linear, branched, or cyclic. It is preferable that carbon number of an alkyl group is 1-12, It is more preferable that it is 1-6, It is more preferable that it is 1-4. 6-20 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable. Examples of the ring formed by bonding R ^Y7 or R ^Y8 and R ^Y9 to each other include a tetrahydrofuranyl group and a tetrahydropyranyl group. In the formula (Y3), it is preferable that R ^Y7 or R ^Y8 and R ^Y9 are bonded to each other to form a ring. Moreover, it is preferable that one of R ^Y7 and R ^Y8 is a hydrogen atom.

In formula (Y4), Ar ^Y1 represents an aryl group, R ^Y10 represents an alkyl group or an aryl group, and Ar ^Y1 and R ^Y10 may be bonded to each other to form a ring. It is preferable that carbon number of an alkyl group is 1-12, It is more preferable that it is 1-6, It is more preferable that it is 1-4. 6-20 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable. In formula (Y4), it is preferable that R ^Y10 is an alkyl group.

In formula (Y5), R ^Y11 represents an alkyl group or an aryl group, and is preferably an alkyl group. It is preferable that carbon number of an alkyl group is 1-12, It is more preferable that it is 1-6, It is more preferable that it is 1-4. 6-20 are preferable and, as for carbon number of an aryl group, 6-12 are more preferable.

It is preferable that it is 40-200, as for the molecular weight of a protecting group, it is more preferable that it is 40-150, It is more preferable that it is 40-120. If the molecular weight of a protecting group is the said range, it can be set as the coloring composition excellent in storage stability and excellent in sclerosis|hardenability in low temperature.

Specific examples of the protecting group include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-n-butoxyethyl group, 1-t-butoxyethyl group, 1-cyclopentyloxyethyl group, 1- Cyclohexyloxyethyl group, cyclohexyl (methoxy)methyl group, α-methoxybenzyl group, α-ethoxybenzyl group, α-n-propoxybenzyl group, 2-phenyl-1-methoxyethyl group, 2-phenyl- 1-ethoxyethyl group, 2-phenyl-1-i-propoxyethyl group, 2-tetrahydrofuranyl group, 2-tetrahydropyranyl group, 1-ethoxyethyl group, 1-cyclohexyloxyethyl group, 2 -Tetrahydrofuranyl group and 2-tetrahydropyranyl group are preferable, and 1-ethoxyethyl group and 1-cyclohexyloxyethyl group are more preferable.

Examples of the repeating unit having a group in which an acid group is protected by a protecting group include a repeating unit represented by the following formula (Bi-2).

[Formula 8]

In the formula (Bi-2), X ² represents the main chain of the repeating unit, L ² represents a single bond or a divalent linking group, and Z ² represents a group in which an acid group is protected by a protecting group.

In the formula (Bi-2), the main chain of the repeating unit represented by X ² is not particularly limited. There is no restriction|limiting in particular if it is a coupling group formed from a well-known polymerizable monomer. For example, poly (meth) acrylic coupling group, polyalkyleneimine coupling group, polyester coupling group, polyurethane coupling group, polyurea coupling group, polyamide coupling group, polyether coupling group, polystyrene coupling group, etc. and a poly(meth)acrylic-based linking group and a polystyrene-based linking group are preferable, and a poly(meth)acrylic-based linking group is more preferable.

In the formula (Bi-2), as the divalent linking group represented by L ² , 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-, -COO-, -OCO-, -S-, and the group formed by combining two or more of these is mentioned. Any of linear, branched, and cyclic|annular form may be sufficient as an alkylene group, and linear or branched form is preferable. Moreover, the alkylene group may have a substituent, and unsubstituted may be sufficient as it. A hydroxyl group, an alkoxy group, etc. are mentioned as a substituent.

In the formula (Bi-2), Z ² represents a group in which an acid group is protected by a protecting group.

As an aspect of the repeating unit represented by Formula (Bi-2), the repeating unit represented by a following formula (B-2) is mentioned.

[Formula 9]

In formula (B-2), R ^b11 to R ^b13 each independently represent a hydrogen atom, a halogen atom or an alkyl group, L ^b11 represents a single bond or a divalent linking group, and X ^b11 represents a formula (X-1) Or group represented by Formula (X-2) is shown;

[Formula 10]

In formulas (X-1) and (X-2), Y ^b1 represents a protecting group, and the broken line represents a portion bonded to L ^b11 .

Examples of the halogen atom represented by R ^b11 to R ^b13 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

1-20 are preferable, as for carbon number of the alkyl group represented by ^Rb11 - ^Rb13 , 1-10 are more preferable, and 1-5 are still more preferable. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched.

Examples of the divalent linking group represented by L ^b11 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S-, and the group formed by combining two or more of these are mentioned. Any of linear, branched, and cyclic|annular form may be sufficient as an alkylene group, and linear or branched form is preferable. Moreover, the alkylene group may have a substituent, and unsubstituted may be sufficient as it. A hydroxyl group, an alkoxy group, etc. are mentioned as a substituent.

Examples of the protecting group represented by Y ^b1 in formulas (X-1) and (X-2) include groups represented by any one of formulas (Y1) to (Y5) described above. When X ^b11 of Formula (B-2) is group represented by Formula (X-1), it is preferable that Y ^b1 is Formula (Y5). When X ^b11 of Formula (B-2) is group represented by Formula (X-2), it is preferable that Y ^b1 is Formula (Y3).

When X ^b11 of Formula (B-2) is group represented by Formula (X-1), the storage stability of a coloring composition can be improved more. When X ^b11 of Formula (B-2) is group represented by Formula (X-2), it can be set as the coloring composition excellent in sclerosis|hardenability in low temperature.

It is preferable that content of the repeating unit in which the acidic radical has the group protected by the protecting group in resin BI is 25-45 mass % with respect to all the repeating units of resin BI. It is preferable that it is 42.5 mass % or less, and, as for an upper limit, it is more preferable that it is 40 mass % or less. 27.5 mass % or more is preferable and, as for a minimum, 30 mass % or more is more preferable.

Resin BI may contain the repeating unit which has an acidic radical. According to this aspect, the effect of reducing the residue at the time of image development can be expected. When the resin BI contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the resin BI is preferably 10 to 20% by mass based on the total repeating units of the resin BI. It is preferable that it is 18 mass % or less, and, as for an upper limit, it is more preferable that it is 16 mass % or less. 12 mass % or more is preferable and, as for a minimum, 14 mass % or more is more preferable.

It is also preferable that resin BI does not contain the repeating unit which has an acidic radical substantially. According to this aspect, the effect that storage stability and sclerosis|hardenability in low temperature can be made to a higher level can be anticipated. That the resin BI does not substantially contain a repeating unit having an acid group means that the content of the repeating unit having an acid group in the resin BI is 1% by mass or less of the total repeating units of the resin BI, and 0.5% by mass or less It is preferable, and it is more preferable that it is 0.1 mass % or less, and it is more preferable that it does not contain it.

Resin BI may contain a repeating unit (hereinafter also referred to as another repeating unit) other than a repeating unit containing a blocked isocyanate group, a repeating unit having a group protected by an acid group, and a repeating unit having an acid group. The content of the other repeating units is preferably 40% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less in all the repeating units of Resin BI.

(other resins)

The resin composition of the present invention may further contain a resin (hereinafter, also referred to as other resin) other than the above-mentioned resin BI. As for the weight average molecular weight (Mw) of other resin, 2000-200000 are preferable. 1000000 or less are preferable and, as for an upper limit, 500000 or less are more preferable. 3000 or more are preferable, as for a minimum, 4000 or more are more preferable, and 5000 or more are still more preferable.

As other resin, for example, (meth)acrylic resin, (meth)acrylamide resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether Tersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, etc. are mentioned. .

It is also preferable that other resin is resin which has an acidic radical. As an acidic radical, a carboxy group, a phosphoric acid group, a sulfo group, phenolic hydroxyl group etc. are mentioned, for example. Resin which has an acidic radical can also be used as alkali-soluble resin and a dispersing agent. As for the acid value of resin which has an acidic radical, 30-500 mgKOH/g is preferable. As for a minimum, 50 mgKOH/g or more is more preferable, and 70 mgKOH/g or more is more preferable. The upper limit is more preferably 400 mgKOH/g or less, still more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

Resin which has an acidic radical may have the repeating unit derived from a maleimide compound. As a maleimide compound, N-alkyl maleimide, N-aryl maleimide, etc. are mentioned. As a repeating unit derived from a maleimide compound, the repeating unit represented by Formula (C-mi) is mentioned.

[Formula 11]

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

Another resin is a resin containing a repeating unit derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”). desirable.

[Formula 12]

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.

[Formula 13]

In formula (ED2), R represents a hydrogen atom or a C1-C30 organic group. As a specific example of Formula (ED2), description of Unexamined-Japanese-Patent No. 2010-168539 can be referred.

About the specific example of an ether dimer, Paragraph No. 0317 of Unexamined-Japanese-Patent No. 2013-029760 can be considered into consideration, and this content is integrated in this specification.

It is also preferable that other resin is resin containing the repeating unit which has a polymeric group. As a polymeric group, ethylenically unsaturated bond containing groups, such as a vinyl group, a (meth)allyl group, and a (meth)acryloyl group, are mentioned.

It is also preferable that other resin contains resin containing the repeating unit derived from the compound represented by Formula (III).

[Formula 14]

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0 to 15. It is preferable that carbon number of the alkylene group which ^R21 and ^R22 represent is 1-10, It is more preferable that it is 1-5, It is more preferable that it is 1-3, It is especially preferable that it is 2 or 3. It is preferable that n is an integer of 0-5, It is more preferable that it is an integer of 0-4, It is more preferable that it is an integer of 0-3.

As a compound represented by Formula (III), the ethylene oxide or propylene oxide modified|denatured (meth)acrylate of paracumyl phenol, etc. are mentioned. As a commercial item, Aronix M-110 (made by Toagosei Co., Ltd.) etc. are mentioned.

It is also preferable that other resin is a dispersing agent. As a dispersing agent, an acidic dispersing agent (acidic resin) and a basic dispersing agent (basic resin) are mentioned. Here, an acidic dispersing agent (acidic resin) shows resin with more quantity of an acidic radical than the quantity of a basic group. As the acidic dispersant (acidic resin), a resin in which the amount of acidic groups accounts for 70 mol% or more when the total amount of the amount of acidic groups and the amount of basic groups is 100 mol% is preferable, and a resin substantially composed of only acidic groups is more preferable . As for the acidic radical which an acidic dispersing agent (acidic resin) has, a carboxy group is preferable. As for the acid value of an acidic dispersing agent (acidic resin), 10-105 mgKOH/g is preferable. Moreover, a basic dispersing agent (basic resin) shows resin with more quantity of a basic group than the quantity of an acidic radical. As a basic dispersing agent (basic resin), when the total amount of the quantity of an acidic radical and the quantity of a basic group makes 100 mol%, resin in which the quantity of a basic group exceeds 50 mol% is preferable. As for the basic group which a basic dispersing agent has, an amino group is preferable.

It is preferable that resin used as a dispersing agent contains the repeating unit which has an acidic radical. When resin used as a dispersing agent contains the repeating unit which has an acidic radical, when pattern-forming by the photolithographic method, generation|occurrence|production of a developing residue can be suppressed more.

It is also preferable that resin used as a dispersing agent is a graft resin. For the detail of graft resin, Paragraph No. 0025 of Unexamined-Japanese-Patent No. 2012-255128 - description of 0094 can be considered into consideration, and this content is integrated in this specification.

It is also preferable that resin used as a dispersing agent is a polyimine type dispersing agent which contains a nitrogen atom in at least one of a main chain and a side chain. As the polyimine-based dispersant, a resin having a main chain having a partial structure having a functional group with a pKa of 14 or less, 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 is preferable. There is no restriction|limiting in particular as long as a basic nitrogen atom is a nitrogen atom which shows basicity. About a polyimine type dispersing agent, Paragraph No. 0102 of Unexamined-Japanese-Patent No. 2012-255128 - description of 0166 can be considered into consideration, and this content is integrated in this specification.

It is also preferable that resin used as a dispersing agent is resin of the structure in which the several polymer chain couple|bonded with the core part. As a specific example of such resin, Paragraph No. 0196 of Unexamined-Japanese-Patent No. 2013-043962 - the polymeric compounds C-1 - C-31 of 0209, etc. are mentioned.

It is also preferable that resin used as a dispersing agent is resin containing the repeating unit which has an ethylenically unsaturated bond containing group in a side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10-80 mol%, and still more preferably 20-70 mol%, based on the total repeating units of the resin. .

A dispersing agent is also available as a commercial item, As such a specific example, the Disperbyk series (for example, Disperbyk-111, 2001 etc.) manufactured by Bikchemi, and Solsperse series made by Nippon Lubrizol Co., Ltd. (for example, , Solsperse 20000, 76500, etc.), Ajinomoto Fine Techno Co., Ltd. Ajisper series, etc. are mentioned. Moreover, the product of Paragraph No. 0129 of Unexamined-Japanese-Patent No. 2012-137564, and the product of Paragraph No. 0235 of Unexamined-Japanese-Patent No. 2017-194662 can also be used as a dispersing agent. Moreover, as a dispersing agent, the resin containing the resin of Paragraph 0041 - 0060 of Unexamined-Japanese-Patent No. 2017-206689, and the hindered amine quaternary salt of Unexamined-Japanese-Patent No. 2019-095548 can also be used suitably.

It is preferable that content of resin is 5-50 mass % in total solid of a coloring composition. It is preferable that it is 40 mass % or less, and, as for an upper limit, it is more preferable that it is 30 mass % or less. It is preferable that it is 7.5 mass % or more, and, as for a minimum, it is more preferable that it is 10 mass % or more.

Moreover, it is preferable that content of resin BI mentioned above is 5-50 mass % in total solid of a coloring composition. It is preferable that it is 40 mass % or less, and, as for an upper limit, it is more preferable that it is 30 mass % or less. It is preferable that it is 7.5 mass % or more, and, as for a minimum, it is more preferable that it is 10 mass % or more.

Moreover, it is preferable that content of resin BI mentioned above in resin contained in a coloring composition is 80-100 mass %. It is preferable that it is 97.5 mass % or less, and, as for an upper limit, it is more preferable that it is 95 mass % or less. It is preferable that it is 82.5 mass % or more, and, as for a minimum, it is more preferable that it is 85 mass % or more.

<<Polymerizable compound>>

The coloring composition of this invention contains a polymeric compound. As a polymeric compound, the compound etc. which have an ethylenically unsaturated bond containing group are mentioned. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group. It is preferable that the polymeric compound used by this invention is a radically polymerizable compound.

Although any of chemical forms, such as a monomer, a prepolymer, and an oligomer, may be sufficient as a polymeric compound, A monomer is preferable. As for the molecular weight of a polymeric compound, 100-3000 are preferable. As for an upper limit, 2000 or less are more preferable, and 1500 or less are still more preferable. 150 or more are more preferable, and, as for a minimum, 250 or more are still more preferable.

It is preferable that the ethylenically unsaturated bond-containing group (henceforth C=C number) of a polymeric compound is 2-14 mmol/g from a viewpoint of the aging stability of a coloring composition. It is preferable that a minimum is 3 mmol/g or more, It is more preferable that it is 4 mmol/g or more, It is more preferable that it is 5 mmol/g or more. It is preferable that it is 12 mmol/g or less, and, as for an upper limit, it is more preferable that it is 10 mmol/g or less, It is more preferable that it is 8 mmol/g or less. The C=C value of the polymerizable compound was calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.

It is preferable that a polymeric compound is a compound containing 3 or more ethylenically unsaturated bond containing groups, It is more preferable that it is a compound containing 3-15 ethylenically unsaturated bond containing groups, It is 3-6 ethylenically unsaturated bond containing groups. It is more preferable that it is a compound containing dogs. Moreover, it is preferable that it is a 3-15 functional (meth)acrylate compound, and, as for a polymeric compound, it is more preferable that it is a 3-6 functional (meth)acrylate compound. As a specific example of a polymeric compound, Paragraph Nos. 0095 to 0108 of Unexamined-Japanese-Patent No. 2009-288705, Paragraph 0227 of Unexamined-Japanese-Patent No. 2013-029760, Paragraph Nos. 0254 to 0257 of Unexamined-Japanese-Patent No. 2008-292970, Unexamined-Japanese-Patent No. Paragraph Nos. 0034 to 0038 of 2013-253224, Paragraph No. 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048367, Japanese Patent Publication No. 6057891, Japanese Patent Publication No. 6031807, Japanese Patent Application Laid-Open No. 2017 -194662, the contents of which are incorporated herein by reference.

Examples of the polymerizable compound include dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), and dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; Nippon Kayaku Co., Ltd.) ), dipentaerythritol penta (meth) acrylate (as a commercial item, KAYARAD D-310; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa(meth) acrylate (as a commercial item, KAYARAD DPHA; Co., Ltd., NK ester A-DPH-12E; Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups are bonded through ethylene glycol and/or propylene glycol residues A compound of the structure (eg, SR454, SR499, commercially available from Sartomer) is preferable. Moreover, as a polymeric compound, diglycerol EO (ethylene oxide) modified|denatured (meth)acrylate (M-460 as a commercial item; manufactured by Toagosei), pentaerythritol tetraacrylate (Shin-Nakamura Chemical Co., Ltd. product, NK) Ester A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Doa) Made by Kosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Daisei Fine Chemicals Co., Ltd.), light acrylate POB-A0 (Kyo) Eisha Chemical Co., Ltd. product) etc. can also be used.

Examples of the polymerizable compound include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocya It is also preferable to use trifunctional (meth)acrylate compounds, such as nuric-acid ethylene oxide modified|denatured tri(meth)acrylate and pentaerythritol tri(meth)acrylate. As a commercial item of a trifunctional (meth)acrylate compound, Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305 , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK Ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) ) and the like.

As the polymerizable compound, a polymerizable compound having an acid group can also be used. By using the polymeric compound which has an acidic radical, the coloring composition of an unexposed part is easy to remove at the time of image development, and generation|occurrence|production of the image development residue can be suppressed. As an acidic radical, a carboxy group, a sulfo group, a phosphoric acid group, etc. are mentioned, A carboxy group is preferable. As a commercial item of the polymeric compound which has an acidic radical, Aronix M-305, M-510, M-520, Aronix TO-2349 (made by Toagosei Co., Ltd.), etc. are mentioned. As a preferable acid value of the polymeric compound which has an acidic radical, it is 0.1-40 mgKOH/g, More preferably, it is 5-30 mgKOH/g. If the acid value of a polymeric compound is 0.1 mgKOH/g or more, the solubility to a developing solution is favorable, and if it is 40 mgKOH/g or less, it is advantageous on manufacture and handling.

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

As a polymeric compound, the polymeric compound which has 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, 3 to 6 having 4 to 20 ethyleneoxy groups Functional (meth)acrylate compounds are more preferred. As a commercial item of the polymeric compound which has an alkyleneoxy group, KAYARAD RP-1040 (made by Nippon Kayaku Co., Ltd.) etc. are mentioned.

As the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. As a commercial item of the polymeric compound which has a fluorene skeleton, Ogsol EA-0200, EA-0300 (The Osaka Gas Chemical Co., Ltd. product, (meth)acrylate monomer which has a fluorene skeleton) etc. are mentioned.

It is also preferable to use the compound which does not contain environmental control substances, such as toluene, substantially as a polymeric compound. As a commercial item of such a compound, KAYARAD DPHA LT, KAYARAD DPEA-12 LT (made by Nippon Kayaku Co., Ltd.), etc. are mentioned.

As the polymerizable compound, as described in Japanese Patent Application Laid-Open No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. Hei 02-032293, and Japanese Unexamined Patent Publication No. Hei 02-016765. Urethane acrylates and ethylene oxide described in Japanese Patent Publication No. 58-049860, Japanese Publication No. 56-017654, Japanese Publication No. 62-039417, and Japanese Publication No. 62-039418 A urethane compound having a system skeleton is also suitable. Moreover, it is also preferable to use the polymeric compound which has an amino structure or a sulfide structure in a molecule|numerator as described in Unexamined-Japanese-Patent No. 63-277653, Unexamined-Japanese-Patent No. 63-260909, and Unexamined-Japanese-Patent No. Hei01-105238. . The polymerizable compound is UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600 , T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.

It is preferable that content of a polymeric compound is 5.0-35 mass % in total solid of a coloring composition. It is preferable that it is 30 mass % or less, and, as for an upper limit, it is more preferable that it is 25 mass % or less. It is preferable that it is 7.5 mass % or more, and, as for a minimum, it is more preferable that it is 10 mass % or more.

<<Photoinitiator>>

The coloring composition of this invention contains a photoinitiator. There is no restriction|limiting in particular as a photoinitiator, It can select suitably from well-known photoinitiators. It is preferable that a photoinitiator is a photoradical polymerization initiator.

Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (eg, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound, hexaarylbiimidazole, an oxime compound, an organic peroxide, thi o compounds, ketone compounds, aromatic onium salts, hydroxyalkylphenone compounds, aminoalkylphenone compounds, and the like. A photoinitiator is a trihalomethyltriazine compound, a benzyldimethyl ketal compound, a hydroxyalkylphenone compound, an aminoalkylphenone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, from a viewpoint of exposure sensitivity, Oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadiene-benzene-iron complex, halomethyloxadiazole compound and 3-aryl substituted coumarin compound It is preferable that it is a compound chosen from an oxime compound, a hydroxyalkylphenone compound, an aminoalkylphenone compound, and an acylphosphine compound, It is more preferable that it is an oxime compound. Moreover, as a photoinitiator, Paragraph 0065 of Unexamined-Japanese-Patent No. 2014-130173 - 0111, the compound of Unexamined-Japanese-Patent No. 6301489, MATERIAL STAGE 37-60p, vol. 19, No. 3, the peroxide-based photopolymerization initiator described in 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179, the photopolymerization initiator described in Japanese Patent Application Laid-Open No. 2019-043864, The photoinitiator of Unexamined-Japanese-Patent No. 2019-044030 is mentioned, This content is integrated in this specification.

As an aminoalkylphenone compound, the aminoalkylphenone compound of Unexamined-Japanese-Patent No. 10-291969 is mentioned, for example. In addition, as commercially available aminoalkylphenone compounds, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (above, manufactured by BASF), etc. can

As an acylphosphine compound, the acylphosphine compound of Unexamined-Japanese-Patent No. 4225898, etc. are mentioned. Specific examples include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide. As a commercial item of an acylphosphine compound, Omnirad 819, Omnirad TPO (above, IGM Resins B.V. company make), Irgacure 819, Irgacure TPO (above, BASF company make) etc. are mentioned.

As a hydroxyalkylphenone compound, the compound represented by a following formula (V) is mentioned.

Formula (V)

[Formula 15]

In the formula, Rv ¹ represents a substituent, 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 is an integer of 0 to 5 indicates

Examples of the substituent represented by Rv ¹ include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms). A straight chain or branch is preferable and, as for an alkyl group and an alkoxy group, a straight chain is more preferable. Unsubstituted may be sufficient as the alkyl group and alkoxy group which Rv< ¹ > represents, and may have a substituent. As a substituent, a hydroxyl group, the group etc. which have a hydroxyalkylphenone structure are mentioned. As group which has a hydroxyalkylphenone structure, the group which removed ^one hydrogen atom from the benzene ring to which ^Rv1 in Formula (V) couple|bonded, or Rv1 is mentioned.

Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent. As the substituent, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferable. Further, Rv ² and Rv ³ may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms). A straight chain or branch is preferable and, as for an alkyl group, a straight chain is more preferable.

The following compound is mentioned as a specific example of the compound represented by Formula (V).

[Formula 16]

Examples of commercially available hydroxyalkylphenone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above, manufactured by BASF), etc. there is.

As an oxime compound, the compound of Unexamined-Japanese-Patent No. 2001-233842, the compound of Unexamined-Japanese-Patent No. 2000-080068, the compound of Unexamined-Japanese-Patent No. 2006-342166, J.C.S. Perkin II (1979, pp.1653) -1660), the compound described in J. C. S. Perkin II (1979, pp.156-162), the compound described in the Journal of Photopolymer Science and Technology (1995, pp.202-232), JP-A 2000- The compound described in 066385, the compound described in JP 2004-534797 A, the compound described in JP 2006-342166 , the compound described in JP 2017-019766 , the compound described in JP 6065596 A Compound, the compound described in International Publication No. 2015/152153, the compound described in International Publication No. 2017/051680, the compound described in Japanese Patent Application Laid-Open No. 2017-198865, Paragraph No. 0025 of International Publication No. 2017/164127 The compound of 0038, the compound of International Publication No. 2013/167515, etc. are mentioned. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one , 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials Co., Ltd.); Adeka optomer N-1919 (made by ADEKA Corporation, the photoinitiator 2 of Unexamined-Japanese-Patent No. 2012-014052) is mentioned. Moreover, as an oxime compound, it is also preferable to use the compound without coloring property, and the compound which transparency is high and is hard to change color. As a commercial item, ADEKA ARCL's NCI-730, NCI-831, NCI-930 (above, ADEKA Co., Ltd. make) etc. are mentioned.

As a photoinitiator, the oxime compound which has a fluorene ring can also be used. As a specific example of the oxime compound which has a fluorene ring, the compound of Unexamined-Japanese-Patent No. 2014-137466 is mentioned.

As a photoinitiator, the oxime compound which has frame|skeleton in which the at least 1 benzene ring of a carbazole ring became a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound of international publication 2013/083505 is mentioned.

As a photoinitiator, the oxime compound which has a fluorine atom can also be used. As for the oxime compound containing a fluorine atom, the compound represented by Formula (OX-1) is preferable.

(OX-1)

[Formula 17]

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

A monocyclic ring may be sufficient as the aromatic hydrocarbon ring which Ar1 and Ar2 ^of Formula (OX- ¹ ) represent, and a condensed ring may be sufficient as it. 6-20 are preferable, as for the number of carbon atoms which comprises the ring of an aromatic hydrocarbon ring, 6-15 are more preferable, 6-10 are especially preferable. As for the aromatic hydrocarbon ring, a benzene ring and a naphthalene ring are preferable. Among them, Ar ¹ is preferably a benzene ring. It is preferable that Ar2 is ^a benzene ring or a naphthalene ring, and it is more preferable that it is a naphthalene ring.

Examples of the substituent which Ar ¹ and Ar ² may have include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR ^X1 , -SR ^X1 , -COR ^X1 , -COOR ^X1 , -OCOR ^X1 , -NR ^X1 R ^X2 , -NHCOR ^X1 , -CONR ^X1 R ^X2 , -NHCONR ^X1 R ^X2 , -NHCOOR ^X1 , -SO ₂ R ^X1 , -SO ₂ OR ^X1 , -NHSO ₂ R ^X1 etc. are mentioned. . R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

As for a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. are mentioned, A fluorine atom is preferable. As for carbon number of the alkyl group as a substituent, and the alkyl group which R ^X1 and R ^X2 represent, 1-30 are preferable. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched. In the alkyl group, some or all of the hydrogen atoms may be substituted with a halogen atom (preferably a fluorine atom). Moreover, in the alkyl group, a part or all of hydrogen atoms may be substituted by the said substituent. 6-20 are preferable, as for carbon number of the aryl group as a substituent, and the aryl group which R ^X1 and R ^X2 represent, 6-15 are more preferable, and 6-10 are still more preferable. A monocyclic ring may be sufficient as an aryl group, and a condensed ring may be sufficient as it. Moreover, in the aryl group, part or all of the hydrogen atoms may be substituted by the said substituent. The heterocyclic group as a substituent and the heterocyclic group represented by R ^X1 and R ^X2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be monocyclic or a condensed ring may be sufficient as it. 3-30 are preferable, as for the number of carbon atoms which comprise a heterocyclic group, 3-18 are more preferable, 3-12 are more preferable. The number of hetero atoms constituting the heterocyclic group is preferably 1-3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom, or a sulfur atom. Moreover, in the heterocyclic group, part or all of the hydrogen atoms may be substituted by the said substituent.

The aromatic hydrocarbon ring represented by Ar ¹ is preferably an unsubstituted aromatic hydrocarbon ring. It is preferable that the aromatic hydrocarbon ring represented by Ar ² has a substituent. As a substituent, -COR ^X1 is preferable. An alkyl group, an aryl group, or a heterocyclic group is preferable, and, as for R ^X1 , an aryl group is more preferable. The aryl group may have a substituent and may be unsubstituted. As a substituent, a C1-C10 alkyl group etc. are mentioned.

R ¹ in formula (OX-1) represents an aryl group having a fluorine atom-containing group. 6-20 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are still more preferable. The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing group). As the fluorine-containing group, -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 At least one group selected from , —SO ₂ R ^F1 , —SO ₂ OR ^F1 and —NHSO ₂ R ^F1 is preferred. R ^F1 represents a fluorinated alkyl group, and R ^F2 represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, an aryl group or a heterocyclic group. The fluorine-containing group is preferably -OR ^F1 .

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

6-20 are preferable, as for carbon number of the aryl group which R ^F2 represents, 6-15 are more preferable, 6-10 are still more preferable.

The heterocyclic group represented by R ^F2 is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be monocyclic or a condensed ring may be sufficient as it. 2-8 are preferable, as for the number of condensation, 2-6 are more preferable, 3-5 are still more preferable, and 3-4 are especially preferable. 3-40 are preferable, as for the number of carbon atoms which comprise a heterocyclic group, 3-30 are more preferable, 3-20 are more preferable. The number of hetero atoms constituting the heterocyclic group is preferably 1-3. A nitrogen atom, an oxygen atom, or a sulfur atom is preferable, and, as for the hetero atom which comprises a heterocyclic group, a nitrogen atom is more preferable.

It is preferable that the group containing a fluorine atom has a terminal structure represented by Formula (1) or (2). * in the formula represents a linking hand.

*-CHF ₂ (1)

*-CF ₃ (2)

R ² in formula (OX-1) represents an alkyl group or an aryl group, and an alkyl group is preferable. Unsubstituted may be sufficient as an alkyl group and an aryl group, and may have a substituent. Examples of the substituent include the substituents described above for the substituents Ar ¹ and Ar ² may have. 1-20 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, 1-10 are still more preferable, and 1-4 are especially preferable. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched. 6-20 are preferable, as for carbon number of an aryl group, 6-15 are more preferable, and 6-10 are still more preferable.

R ³ of formula (OX-1) represents an alkyl group or an aryl group, and an alkyl group is preferable. Unsubstituted may be sufficient as an alkyl group and an aryl group, and may have a substituent. Examples of the substituent include the substituents described above for the substituents Ar ¹ and Ar ² may have. 1-20 are preferable, as for carbon number of the alkyl group which R< ³ > represents, 1-15 are more preferable, and 1-10 are still more preferable. The alkyl group may be any of linear, branched, and cyclic, but is preferably linear or branched. 6-20 are preferable, as for carbon number of the aryl group which R< ³ > represents, 6-15 are more preferable, and 6-10 are still more preferable.

As a specific example of the oxime compound which has a fluorine atom, the compound described in Unexamined-Japanese-Patent No. 2010-262028, the compound 24 of Unexamined-Japanese-Patent No. 2014-500852, 36-40, and the compound of Unexamined-Japanese-Patent No. 2013-164471. (C-3) etc. are mentioned.

As a photoinitiator, the oxime compound which has a nitro group can be used. It is also preferable to use the oxime compound which has a nitro group as a dimer. As a specific example of the oxime compound which has a nitro group, Paragraph Nos. 0031 to 0047 of Unexamined-Japanese-Patent No. 2013-114249, Paragraph Nos. 0008 to 0012, 0070 to 0079 of Unexamined-Japanese-Patent No. 2014-137466, Japanese Patent Publication The compound described in Paragraph No. 0007-0025 of 4223071, Adeka Arcles NCI-831 (made by ADEKA Corporation) is mentioned.

As a photoinitiator, the oxime compound which has benzofuran frame|skeleton can also be used. As a specific example, OE-01 - OE-75 described in International Publication No. 2015/036910 are mentioned.

As a photoinitiator, the oxime compound which the substituent which has the hydroxyl group couple|bonded with the carbazole skeleton can also be used. As such a photoinitiator, the compound of International Publication No. 2019/088055, etc. are mentioned.

Although the specific example of the oxime compound used preferably in this invention is shown below, this invention is not limited to these.

[Formula 18]

[Formula 19]

In the present invention, as the photopolymerization initiator, a photopolymerization initiator A1 having an extinction coefficient at a wavelength of 365 nm in methanol of 1.0×10 ³ mL/g·cm or more, and an extinction coefficient at a wavelength of 365 nm in methanol of 1.0×10 ² mL/g·cm Below, it is preferable to use together photoinitiator A2 whose extinction coefficient of wavelength 254nm is 1.0x10 ³ mL/g*cm or more. According to this aspect, it is easy to fully harden a coloring composition by exposure, and flatness is favorable in a low-temperature process (for example, the temperature of 150 degrees C or less, Preferably the temperature of 120 degrees C or less throughout the whole process), A cured film excellent in properties such as solvent resistance can also be formed. As photoinitiator A1 and photoinitiator A2, it is preferable to select and use the compound which has said extinction coefficient from the above-mentioned compound.

In addition, in this invention, the extinction coefficient in the said wavelength of a photoinitiator is the value measured as follows. That is, it computed by dissolving a photoinitiator in methanol, preparing the measurement solution, and measuring the absorbance of the measurement solution mentioned above. Specifically, the above-described measurement solution is placed in a glass cell having a width of 1 cm, absorbance is measured using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies, and applied to the following formula, at a wavelength of 365 nm and a wavelength of 254 nm The extinction coefficient (mL/g·cm) was calculated.

[Equation 1]

In the above formula, ε is an extinction coefficient (mL/g·cm), A is an absorbance, c is a concentration of a photopolymerization initiator (g/mL), and l is an optical path length (cm).

The extinction coefficient of the photoinitiator A1 in methanol at a wavelength of 365 nm is 1.0×10 ³ mL/g·cm or more, preferably 1.0×10 ⁴ mL/g·cm or more, and 1.1×10 ⁴ mL/g·cm or more. cm or more, more preferably 1.2×10 ⁴ to 1.0×10 ⁵ mL/g·cm, still more preferably 1.3×10 ⁴ to 5.0×10 ⁴ mL/g·cm, and 1.5× It is particularly preferable that it is 10 ⁴ to 3.0×10 ⁴ mL/g·cm.

Moreover, it is preferable that the extinction coefficient of the light of wavelength 254nm in methanol of photoinitiator A1 is 1.0x10 ⁴ -1.0x10 ⁵ mL/g*cm, and it is 1.5x10 ⁴ -9.5x10 ⁴ mL/g*cm. More preferably, 3.0×10 ⁴ to 8.0×10 ⁴ mL/g·cm is more preferable.

As photoinitiator A1, an oxime compound, an aminoalkylphenone compound, and an acylphosphine compound are preferable, an oxime compound and an acylphosphine compound are more preferable, an oxime compound is still more preferable, Compatibility with other components contained in the composition It is especially preferable that it is an oxime compound containing a fluorine atom from a viewpoint. As a specific example of photoinitiator A1, 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)] (As a commercial item, Irgacure OXE01, the BASF make, for example, ), ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (As a commercially available product, for example, Irgacure OXE02 , made by BASF), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (as a commercial item, for example, Omnirad 819 (manufactured by IGM Resins B.V.), Irgacure 819 (manufactured by BASF)), said oxime (C-13), (C-14), etc. shown in the specific example of a compound are mentioned.

The extinction coefficient of light with a wavelength of 365 nm in methanol of the photoinitiator A2 is 1.0×10 ² mL/g·cm or less, preferably 10 to 1.0×10 ² mL/g·cm, and 20 to 1.0×10 ² mL It is more preferable that it is /g*cm. Moreover, the difference between the extinction coefficient of the light with a wavelength of 365 nm in methanol of the photoinitiator A1 and the light extinction coefficient of the light with a wavelength of 365 nm in methanol of the photoinitiator A2 is 9.0×10 ² mL/g·cm or more, and 1.0×10 ³ mL It is preferably at least /g·cm, more preferably 5.0×10 ³ to 3.0×10 ⁴ mL/g·cm, and still more preferably 1.0×10 ⁴ to 2.0×10 ⁴ mL/g·cm. In addition, the extinction coefficient of the light with a wavelength of 254 nm in methanol of the photoinitiator A2 is 1.0×10 ³ mL/g·cm or more, preferably 1.0×10 ³ to 1.0×10 ⁶ mL/g·cm, 5.0× It is more preferable that it is 10 ³ -1.0×10 ⁵ mL/g·cm.

As the photoinitiator A2, a hydroxyalkylphenone compound, a phenylglyoxylate compound, an aminoalkylphenone compound, and an acylphosphine compound are preferable, and a hydroxyalkylphenone compound and a phenylglyoxylate compound are more preferable, and hydroxy Alkylphenone compounds are more preferred. Moreover, as a hydroxyalkylphenone compound, the compound represented by Formula (V) mentioned above is preferable. Specific examples of the photopolymerization initiator A2 include 1-hydroxy-cyclohexyl-phenyl-ketone (as a commercial product, for example, Omnirad 184 (manufactured by IGM Resins B.V.), Irgacure 184 (manufactured by BASF)), 1-[4-(2) -Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (as a commercial item, for example, Omnirad 2959 (manufactured by IGM Resins B.V.), Irgacure 2959 (manufactured by BASF)) and the like.

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

It is preferable that content of a photoinitiator is 0.1-17.5 mass % in total solid of a coloring composition. It is preferable that it is 0.5 mass % or more, and, as for a minimum, it is more preferable that it is 1.0 mass % or more, It is more preferable that it is 1.5 mass % or more. It is preferable that it is 15.0 mass % or less, and, as for an upper limit, it is more preferable that it is 12.5 mass % or less, It is more preferable that it is 10.0 mass % or less.

Moreover, it is preferable that the coloring composition of this invention contains 1.0-50 mass parts of photoinitiators with respect to 100 mass parts of polymeric compounds. It is preferable that it is 40 mass parts or less, and, as for an upper limit, it is more preferable that it is 30 mass parts or less. It is preferable that it is 2.5 mass parts or more, and, as for a minimum, it is more preferable that it is 5.0 mass parts or more. According to this aspect, the pattern shape after image development is favorable.

The coloring composition of this invention WHEREIN: When using the above-mentioned photoinitiator A1 as a photoinitiator, it is preferable that content of photoinitiator A1 is 0.1-17.5 mass % in total solid of a coloring composition. It is preferable that it is 0.5 mass % or more, and, as for a minimum, it is more preferable that it is 1.0 mass % or more, It is more preferable that it is 1.5 mass % or more. It is preferable that it is 15.0 mass % or less, and, as for an upper limit, it is more preferable that it is 12.5 mass % or less, It is more preferable that it is 10.0 mass % or less.

The coloring composition of this invention WHEREIN: When using the above-mentioned photoinitiator A2 as a photoinitiator, it is preferable that content of photoinitiator A2 is 0.1-10.0 mass % in total solid of a coloring composition. It is preferable that it is 0.5 mass % or more, and, as for a minimum, it is more preferable that it is 1.0 mass % or more, It is more preferable that it is 1.5 mass % or more. It is preferable that it is 9.0 mass % or less, and, as for an upper limit, it is more preferable that it is 8.0 mass % or less, It is more preferable that it is 7.0 mass % or less.

The coloring composition of this invention WHEREIN: When the above-mentioned photoinitiator A1 and photoinitiator A2 are used as a photoinitiator, the coloring composition of this invention is 50-200 mass parts of photoinitiator A2 with respect to 100 mass parts of photoinitiator A1. It is preferable to contain It is preferable that it is 175 mass parts or less, and, as for an upper limit, it is more preferable that it is 150 mass parts or less. It is preferable that it is 60 mass parts or more, and, as for a minimum, it is more preferable that it is 70 mass parts or more. According to this aspect, the cured film excellent in characteristics, such as solvent resistance, can be formed in a low-temperature process (For example, the temperature of 150 degrees C or less through a previous process, Preferably it is a temperature of 120 degrees C or less).

The coloring composition of this invention WHEREIN: When the above-mentioned photoinitiator A1 and photoinitiator A2 are used as a photoinitiator, content of the total of photoinitiator A1 and photoinitiator A2 in total solid of a coloring composition is 0.1-20.0 mass % It is preferable to be It is preferable that a minimum is 1.0 mass % or more, It is more preferable that it is 2.0 mass % or more, It is more preferable that it is 2.5 mass % or more. It is preferable that it is 17.5 mass % or less, and, as for an upper limit, it is more preferable that it is 15.0 mass % or less, It is more preferable that it is 12.5 mass % or less.

<<curing catalyst >>

The coloring composition of this invention can contain a curing catalyst further. According to this aspect, it can be set as the coloring composition excellent in low temperature sclerosis|hardenability. As a curing catalyst, a tin compound, a titanium compound, a bismuth compound, a zirconium compound, an aluminum compound, etc. are mentioned, It is preferable that they are a bismuth compound, a zirconium compound, and an aluminum compound. Specific examples of the curing catalyst include K-CAT 348, 4205, 5218, XK-635, XK-640, and A-209 (manufactured by KING INDUSTRIES).

It is preferable that content of a curing catalyst is 0.1-5 mass parts with respect to 100 mass parts of resin BI, It is more preferable that it is 0.15-4 mass parts, It is more preferable that it is 0.2-3 mass parts. The said coloring composition may contain only 1 type of curing catalyst, and may contain it 2 or more types. When two or more types of curing catalysts are included, it is preferable that those total amounts become the said range.

<<Furyl group-containing compound>>

The coloring composition of this invention can contain the compound (henceforth a furyl group containing compound) containing a furyl group. According to this aspect, it can be set as the coloring composition excellent in low-temperature hardening.

The structure of the furyl group-containing compound is not particularly limited as long as it further contains a furyl group (group in which one hydrogen atom has been removed from furan). For the furyl group-containing compound, the compounds described in Paragraph Nos. 0049 to 0089 of JP-A-2017-194662 can be used. In addition, Japanese Patent Application Laid-Open No. 2000-233581, JP 1994-271558 , JP 1994-293830 , JP 1996-239421 , JP 1998-508655 , Japanese Patent Application Laid-Open No. Japanese Patent Application Laid-Open No. 2000-001529, Japanese Patent Application Laid-Open No. 2003-183348, JP 2006-193628 , JP 2007-186684 , JP 2010-265377 , JP 2011-170069 . The compound described in etc. can also be used.

A monomer may be sufficient as a furyl group containing compound, and a polymer may be sufficient as it. It is preferable that it is a polymer from the reason that it is easy to improve the durability of the film|membrane obtained. In the case of a polymer, as for a weight average molecular weight, 2000-70000 are preferable. 60000 or less are preferable and, as for an upper limit, 50000 or less are more preferable. 3000 or more are preferable, as for a minimum, 4000 or more are more preferable, and 5000 or more are still more preferable. In addition, a polymer type furyl group containing compound is a component corresponding also to resin in the coloring composition of this invention.

It is preferable that content of a furyl group containing compound is 0.1-70 mass % in total solid of a coloring composition. It is preferable that it is 2.5 mass % or more, and, as for a minimum, it is more preferable that it is 5.0 mass % or more, It is more preferable that it is 7.5 mass % or more. It is preferable that it is 65 mass % or less, and, as for an upper limit, it is more preferable that it is 60 mass % or less, It is more preferable that it is 50 mass % or less. The furyl group containing compound may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<<Compound having an epoxy group>>

The coloring composition of this invention can contain the compound which has an epoxy group further. As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferable. It is preferable to have 2-100 epoxy groups in 1 molecule. The upper limit may be, for example, 10 or less, or 5 or less. The epoxy equivalent of the compound having an epoxy group (= molecular weight of the compound having an epoxy group/number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 to 400 g/eq, and still more preferably 100 to 300 g/eq. . The compound having an epoxy group may be a low molecular weight compound (for example, molecular weight less than 1000), or a macromolecular compound (for example, molecular weight 1000 or more, in the case of a polymer, a weight average molecular weight of 1000 or more) do. 200-100000 are preferable and, as for the molecular weight (in the case of a polymer, a weight average molecular weight) of the compound which has an epoxy group, 500-50000 are more preferable. 3000 or less are preferable, as for the upper limit of molecular weight (in the case of a polymer, weight average molecular weight), 2000 or less are more preferable, and 1500 or less are still more preferable.

As a compound which has an epoxy group, Paragraph Nos. 0034 to 0036 of Unexamined-Japanese-Patent No. 2013-011869, Paragraph Nos. 0147 to 0156 of Unexamined-Japanese-Patent No. 2014-043556, Paragraph Nos. 0085 to 0092 of Unexamined-Japanese-Patent No. 2014-089408 Compounds , a compound described in Japanese Patent Application Laid-Open No. 2017-179172 can also be used. These contents are incorporated herein by reference.

When the coloring composition of this invention contains the compound which has an epoxy group, it is preferable that content of the compound which has an epoxy group is 0.1-40 mass % in total solid of a coloring composition. As for a minimum, 0.5 mass % or more is more preferable, and 1 mass % or more is still more preferable. 30 mass % or less is more preferable, and, as for an upper limit, 20 mass % or less is still more preferable. The compound which has an epoxy group may be individual 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that a total amount becomes the said range.

<<Solvent>>

It is preferable that the coloring composition of this invention contains a solvent. As a solvent, an organic solvent is mentioned. A solvent will not have a restriction|limiting in particular in particular, if the solubility of each component and the applicability|paintability of a coloring composition are satisfy|filled basically. Examples of the organic solvent include an ester solvent, a ketone solvent, an alcohol solvent, an amide solvent, an ether solvent, and a hydrocarbon solvent. For details of these, reference may be made to paragraph 0223 of International Publication No. 2015/166779, the content of which is incorporated herein by reference. Moreover, the ester type solvent by which the cyclic alkyl group was substituted, and the ketone type solvent by which the cyclic alkyl group was substituted can also be used preferably. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl Ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene Glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, etc. are mentioned. However, there are cases where it is preferable to reduce the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent for reasons such as environmental reasons (for example, 50 mass ppm ( parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

In this invention, it is preferable that a boiling point is an organic solvent of 160 degrees C or less as a solvent from a viewpoint of volatilizing a solvent efficiently. It is more preferable that it is 140 degrees C or less, and, as for the boiling point of the organic solvent, it is still more preferable that it is 130 degrees C or less. Although the lower limit in particular of a boiling point is not restrict|limited, For example, it is preferable that it is 100 degreeC or more. Examples of such an organic solvent include butyl acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, and ethyl lactate, and butyl acetate and propylene glycol Monomethyl ether and propylene glycol monomethyl ether acetate are preferable.

In this invention, it is preferable to use the solvent with little metal content, and it is preferable that the metal content of a solvent is 10 mass ppb (parts per billion) or less, for example. If necessary, a solvent having a mass ppt (parts per trillion) level may be used, and such a high-purity solvent is provided by, for example, Toyo Kosei Corporation (Kagaku Kogyo Nippo, November 13, 2015).

As a method of removing impurities, such as a metal, from a solvent, distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter is mentioned, for example. As a filter pore diameter of the filter used for filtration, 10 micrometers or less are preferable, 5 micrometers or less are more preferable, and 3 micrometers or less are still more preferable. The material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.

The solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be contained and multiple types of isomers may be contained.

In this invention, it is preferable that the content rate of the peroxide in an organic solvent is 0.8 mmol/L or less, and it is more preferable that a peroxide is not included substantially.

It is preferable that content of the solvent in a coloring composition is 60-95 mass %. Moreover, it is preferable that it is 90 mass % or less, and, as for an upper limit, it is more preferable that it is 87.5 mass % or less, It is more preferable that it is 85 mass % or less. Moreover, it is preferable that it is 65 mass % or more, and, as for a minimum, it is more preferable that it is 70 mass % or more, It is more preferable that it is 75 mass % or more. A solvent may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that those total amounts become the said range.

Moreover, it is preferable that the coloring composition of this invention does not contain an environmental regulation substance substantially from a viewpoint of environmental regulation. In addition, in this invention, it means that content of the environmental control substance in a coloring composition is 50 mass ppm or less, It is preferable that it is 30 mass ppm or less, It is 10 mass ppm or less that it does not contain an environmental control substance substantially in this invention. It is more preferable, and it is especially preferable that it is 1 mass ppm or less. Environmentally regulated substances include, for example, benzene; alkylbenzenes such as toluene and xylene; Halogenated benzenes, such as chlorobenzene, etc. are mentioned. They are registered as environmentally regulated substances based on REACH (Registration Evaluation Authorization and Restriction of CHemicals) rules, PRTR (Pollutant Release and Transfer Register) laws, VOC (Volatile Organic Compounds) regulations, etc., and their usage and handling methods are strict. is tightly regulated. These compounds may be used as a solvent when manufacturing each component etc. used for the coloring composition of this invention, and may mix in a coloring composition as a residual solvent. From the viewpoint of safety for humans and consideration for the environment, it is desirable to reduce these substances as much as possible. As a method of reducing an environmentally regulated substance, the method of heating or depressurizing the inside of a system to make it more than the boiling point of an environmentally regulated substance, and distilling and reducing an environmental regulated substance from the inside of a system is mentioned. Moreover, in the case of distilling off a small amount of environmentally regulated substances, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to increase efficiency. Moreover, when it contains the compound which has radical polymerizability, in order to suppress that a radical polymerization reaction advances and bridge|crosslinks between molecules during vacuum distillation, you may add a polymerization inhibitor etc. and vacuum distillation. These distillation removal methods can be performed at any stage of the stage of the raw material, the stage of the product reacted with the raw material (for example, a resin solution or polyfunctional monomer solution after polymerization), or the stage of the coloring composition prepared by mixing these compounds. .

<<Pigment Derivatives>>

The coloring composition of this invention can contain a pigment derivative. Examples of the pigment derivative include compounds having a structure in which a part of the chromophore is substituted with an acid group, a basic group, or a phthalimidemethyl 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, Perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, threne skeleton, metal complex skeleton, etc. are mentioned, Quinoline skeleton, benzimidazolone skeleton, diketopyrrolo A pyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferable, and an azo skeleton and a benzimidazolone skeleton are more preferable. As an acidic radical which a pigment derivative has, a sulfo group and a carboxy group are preferable and a sulfo group is more preferable. As a basic group which a pigment derivative has, an amino group is preferable and a tertiary amino group is more preferable.

As a specific example of a pigment derivative, Unexamined-Japanese-Patent No. 56-118462, Unexamined-Japanese-Patent No. 63-264674, Unexamined-Japanese-Patent No. Hei 01-217077, Unexamined-Japanese-Patent No. Hei 03-009961, Unexamined-Japanese-Patent No. Hei 03-026767, Japanese Unexamined Patent Publication No. Hei 03-153780, Japanese Unexamined Patent Publication No. Hei 03-045662, Japanese Unexamined Patent Publication No. Hei 04-285669, Japanese Unexamined Patent Publication No. Hei 06-145546, Japanese Unexamined Patent Publication Paragraph Nos. 0086 to 0098 of Japanese Patent Application Laid-Open No. Hei06-212088, Japanese Unexamined Patent Publication No. Hei06-240158, Japanese Patent Application Laid-Open No. Hei10-030063, Japanese Unexamined Patent Publication No. Hei10-195326, International Publication No. 2011/024896; Paragraph Nos. 0063 to 0094 of International Publication No. 2012/102399, Paragraph No. 0082 of International Publication No. 2017/038252, Paragraph No. 0171 of Japanese Patent Application Laid-Open No. 2015-151530, Paragraph No. 0162 to of Japanese Unexamined Patent Publication No. 2011-252065 0183, Japanese Patent Application Laid-Open No. 2003-081972, Japanese Patent Application Laid-Open No. 5299151, Japanese Patent Application Laid-Open No. 2015-172732, Japanese Patent Application Laid-Open No. 2014-199308, Japanese Patent Application Laid-Open No. 2014-085562, Japanese Patent Application Laid-Open No. 2014 -035351, Unexamined-Japanese-Patent No. 2008-081565, Unexamined-Japanese-Patent No. 2019-109512, The compound of Unexamined-Japanese-Patent No. 2019-133154 is mentioned.

As for content of a pigment derivative, 0.1-30 mass parts is preferable with respect to 100 mass parts of pigments. As for the lower limit of this range, it is more preferable that it is 0.25 mass part or more, It is still more preferable that it is 0.5 mass part or more, It is especially preferable that it is 0.75 mass part or more, It is still more preferable that it is 1 mass part or more. Moreover, as for the upper limit of this range, it is more preferable that it is 25 mass parts or less, It is more preferable that it is 20 mass parts or less, It is especially preferable that it is 15 mass parts or less. When content of a pigment derivative exists in the said range, there exists an effect that aging stability improves more. Only 1 type may be used for a pigment derivative, and may use 2 or more types together. When using 2 or more types together, it is preferable that those total amounts become the said range.

<<curing accelerator>>

The coloring composition of this invention accelerates|stimulates reaction of a polymeric compound, or may add a hardening accelerator for the purpose of lowering|hanging hardening temperature. As a hardening accelerator, the polyfunctional thiol compound etc. which have two or more mercapto groups in a molecule|numerator are mentioned. The polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesiveness, and the like. It is preferable that it is secondary alkanethiols, and, as for a polyfunctional thiol compound, it is more preferable that it is a compound represented by Formula (T1).

Formula (T1)

[Formula 20]

In formula (T1), n represents the integer of 2-4, and L represents a 2-4 valent coupling group. In formula (T1), it is preferable that coupling group L is a C2-C12 aliphatic group, n is 2, and it is especially preferable that L is a C2-C12 alkylene group.

Further, the curing accelerator is a methylol compound (eg, a compound exemplified as a crosslinking agent in Paragraph No. 0246 of JP 2015-034963 A), amines, phosphonium salts, amidine salts, amide compounds (above, eg For example, the hardening|curing agent described in Paragraph No. 0186 of Unexamined-Japanese-Patent No. 2013-041165), a base generator (For example, the ionic compound described in Unexamined-Japanese-Patent No. 2014-055114), a cyanate compound (For example, The compound described in Paragraph No. 0071 of Unexamined-Japanese-Patent No. 2012-150180), an alkoxysilane compound (For example, the alkoxysilane compound which has the epoxy group described in Unexamined-Japanese-Patent No. 2011-253054), an onium salt compound (For example, For example, the compound illustrated as an acid generator in Paragraph No. 0216 of Unexamined-Japanese-Patent No. 2015-034963, the compound of Unexamined-Japanese-Patent No. 2009-180949) etc. can also be used.

When the coloring composition of this invention contains a hardening accelerator, 0.3-8.9 mass % is preferable in total solid of a coloring composition, and, as for content of a hardening accelerator, 0.8-6.4 mass % is more preferable.

<<Silane Coupling Agent>>

The coloring composition of this invention can contain a silane coupling agent. As a silane coupling agent, the silane compound which has a functional group from which at least 2 types of reactivity differ in 1 molecule is preferable. The silane coupling agent is at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, an ureido group, a mercapto group, a sulfide group, and an isocyanate group; , a silane compound having an alkoxy group is preferable. As a specific example of a silane coupling agent, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (Shinetsu Chemical Co., Ltd. product, KBM-602), N-2-(aminoethyl) )-3-Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), 3-aminopropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903) ), 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM) -503) and 3-glycidoxypropyl trimethoxysilane (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.). About the detail of a silane coupling agent, Paragraph No. 0155 of Unexamined-Japanese-Patent No. 2013-254047 - description of 0158 can be considered into consideration, and this content is integrated in this specification. When the coloring composition of this invention contains a silane coupling agent, 0.001-20 mass % is preferable in total solid of a coloring composition, as for content of a silane coupling agent, 0.01-10 mass % is more preferable, 0.1 mass % - 5 mass % are especially preferable. The coloring composition of this invention may contain 1 type, and may contain 2 or more types of silane coupling agents. When 2 or more types are included, it is preferable that those total amounts become the said range.

<<Polymerization inhibitor>>

The coloring composition of this invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, and 4,4'-thiobis(3-methyl-6). -t-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, cerium salt, etc.), etc. are mentioned. there is. When the coloring composition of this invention contains a polymerization inhibitor, as for content of a polymerization inhibitor, 0.0001-5 mass % is preferable in total solid of a coloring composition. The coloring composition of this invention may contain 1 type, and may contain 2 or more types of polymerization inhibitors. When 2 or more types are included, it is preferable that those total amounts become the said range.

<<Ultraviolet absorbent>>

The coloring composition of this invention can contain a ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound, etc. may be used. can About these details, Paragraph Nos. 0052 to 0072 of Unexamined-Japanese-Patent No. 2012-208374, Paragraph Nos. 0317-0334 of Unexamined-Japanese-Patent No. 2013-068814, Paragraph No. 0061 of Unexamined-Japanese-Patent No. 2016-162946 description of 0080 reference, the contents of which are incorporated herein by reference. As a commercial item of a ultraviolet absorber, UV-503 (made by Daito Chemical Co., Ltd.) etc. is mentioned, for example. Moreover, as a benzotriazole compound, the MYUA series (Kagaku Kogyo Nippo, February 1, 2016) manufactured by Miyoshi Yushi is mentioned. Moreover, the compound of Paragraph No. 0049 - 0059 of Unexamined-Japanese-Patent No. 6268967 can also be used as a ultraviolet absorber. When the coloring composition of this invention contains a ultraviolet absorber, 0.1-10 mass % is preferable in total solid of a coloring composition, as for content of a ultraviolet absorber, 0.1-5 mass % is more preferable, 0.1-3 mass % is Especially preferred. Moreover, only 1 type may be used for a ultraviolet absorber, and 2 or more types may be used for it. When using 2 or more types, it is preferable that those total amounts become the said range.

<<Surfactant>>

The coloring composition of this invention can contain surfactant. As surfactant, various surfactants, such as a fluorochemical surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone type surfactant, can be used. About surfactant, Paragraph No. 0238 of International Publication No. 2015/166779 - the surfactant of 0245 is mentioned, This content is integrated in this specification.

It is preferable that surfactant is a fluorochemical surfactant. By containing a fluorine-type surfactant in a coloring composition, liquid characteristic (especially fluidity|liquidity) can improve more and liquid saving property can be improved more. Moreover, a film|membrane with a small thickness dispersion|variation can also be formed.

As for the fluorine content rate in a fluorine-type surfactant, 3-40 mass % is suitable, More preferably, it is 5-30 mass %, Especially preferably, it is 7-25 mass %. The fluorine-containing surfactant having a fluorine content in this range is effective from the viewpoints of the uniformity of the thickness of the coating film and the liquid-saving properties, and the solubility in the coloring composition is also good.

As a fluorochemical surfactant, Paragraph No. 0060-0064 of Unexamined-Japanese-Patent No. 2014-041318 (paragraph No. 0060-0064 of Corresponding International Publication No. 2014/017669) etc., Paragraph number of Unexamined-Japanese-Patent No. 2011-132503 The surfactants described in 0117-0132 are mentioned, These content is integrated in this specification. Examples of commercially available fluorine-based surfactants include Megapac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS-330 (above, manufactured by DIC Corporation), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Corporation), Sufflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by AGC Corporation), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA), etc. are mentioned. .

In addition, the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and when heat is applied, a portion of the functional group containing a fluorine atom is cleaved, and an acrylic compound in which the fluorine atom is volatilized can also be suitably used. As such a fluorine-based surfactant, Megapac DS series manufactured by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shinbun (February 23, 2016)), for example, Megapac DS -21 can be mentioned.

Moreover, it is also preferable to use the polymer of the fluorine atom containing vinyl ether compound which has a fluorinated alkyl group or a fluorinated alkylene ether group, and a hydrophilic vinyl ether compound as a fluorine-type surfactant. As for such a fluorine-type surfactant, the fluorine-type surfactant of Unexamined-Japanese-Patent No. 2016-216602 is mentioned, This content is integrated in this specification.

A block polymer can also be used for a fluorochemical surfactant. The fluorine-based surfactant has two or more (preferably 5 or more) repeating units derived from a (meth)acrylate compound having a fluorine atom and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) (meth) ) A fluorine-containing high molecular compound containing a repeating unit derived from an acrylate compound can also be preferably used. Moreover, the fluorine-containing surfactant of Paragraph No. 0016 - 0037 of Unexamined-Japanese-Patent No. 2010-032698, and the following compound are also illustrated as a fluorochemical surfactant used by this invention.

[Formula 21]

The weight average molecular weight of said compound becomes like this. Preferably it is 3000-50000, for example, it is 14000. Among the above compounds, % indicating the proportion of the repeating unit is mol%.

Further, as the fluorine-containing surfactant, a fluorinated polymer having an ethylenically unsaturated bond-containing group in a side chain may be used. As a specific example, the compound of Paragraph Nos. 0050 to 0090 and Paragraph Nos. 0289 to 0295 of Unexamined-Japanese-Patent No. 2010-164965, DIC Corporation Megapac RS-101, RS-102, RS-718K, RS-72- K etc. are mentioned. Moreover, Paragraph No. 0015 of Unexamined-Japanese-Patent No. 2015-117327 - the compound of 0158 can also be used for a fluorine-type surfactant.

Examples of the nonionic surfactant include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), 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, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (Japan) Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Junyaku Kogyo Co., Ltd. product), Pionein D-6112, D-6112-W, D-6315 (Takemoto Yushi) Co., Ltd.), Olfin E1010, Surfinol 104, 400, 440 (manufactured by Nisshin Chemical Industry Co., Ltd.), and the like.

As a silicone type surfactant, For example, Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, new S-Silicone Co., Ltd. make), BYK307, BYK323, BYK330 (above, the product made by Big Chemi), etc. are mentioned.

0.001-5.0 mass % is preferable and, as for content of surfactant in the total solid of a coloring composition, 0.005-3.0 mass % is more preferable. One type may be sufficient as surfactant, and 2 or more types may be sufficient as it. In the case of 2 or more types, it is preferable that those total amounts become the said range.

<<Other additives>>

Various additives, for example, a filler, an adhesion promoter, antioxidant, aggregation inhibitor, etc. can be mix|blended with the coloring composition of this invention as needed. As these additives, Paragraph No. 0155 of Unexamined-Japanese-Patent No. 2004-295116 - the additive of 0156 are mentioned, This content is integrated in this specification. Moreover, as antioxidant, a phenol compound, a phosphorus compound (For example, the compound of Paragraph No. 0042 of Unexamined-Japanese-Patent No. 2011-090147), a thioether compound, etc. can be used, for example. As a commercial item, For example, ADEKA Co., Ltd. ADEKA STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO) -330, etc.). Moreover, as antioxidant, the polyfunctional hindered amine antioxidant described in International Publication No. 2017/006600, the antioxidant described in International Publication No. 2017/164024, Paragraph Nos. 0023 to 0048 of Japanese Patent Publication No. 6268967 Antioxidants may also be used. Only 1 type may be used for antioxidant, and 2 or more types may be used for it. Moreover, the coloring composition of this invention may contain a latent antioxidant as needed. As a latent antioxidant, the site functioning as an antioxidant is a compound protected by a protecting group, and the protecting group is detached by heating at 100 to 250 ° C. or by heating at 80 to 200 ° C. in the presence of an acid/base catalyst to function as an antioxidant. compounds can be mentioned. As a specific example of a latent antioxidant, the compound of International Publication No. 2014/021023, International Publication No. 2017/030005, and Unexamined-Japanese-Patent No. 2017-008219 is mentioned. As a commercial item, Adeka Arcles GPA-5001 (made by ADEKA Corporation) etc. are mentioned. Moreover, as for the coloring composition of this invention, the sensitizer and light stabilizer of Paragraph 0078 of Unexamined-Japanese-Patent No. 2004-295116, the thermal polymerization inhibitor of Paragraph 0081 of the same publication, Paragraph No. 0242 of Unexamined-Japanese-Patent No. 2018-091940. It may contain storage stabilizers.

<Receiving container>

There is no limitation in particular as a container for the coloring composition of this invention, A well-known container can be used. In addition, for the purpose of suppressing the mixing of impurities into the raw material or the coloring composition as the container, a multi-layer bottle in which the inner wall of the container is composed of 6 types of 6 layers of resin, or a bottle with 7 layers of 6 types of resins is used. It is also desirable As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example. Further, the inner wall of the container is preferably made of glass, stainless steel, or the like for the purpose of preventing metal elution from the inner wall of the container, enhancing storage stability of the composition, or suppressing component deterioration.

<Method for producing a coloring composition>

The coloring composition of this invention can mix and manufacture the above-mentioned component. In the production of the coloring composition, the coloring composition may be prepared by simultaneously dissolving and/or dispersing all the components in a solvent. You may mix these with and may manufacture a coloring composition.

Moreover, in the case of manufacture of a coloring composition, you may include the process of disperse|distributing a pigment. In the process of dispersing the pigment, examples of the mechanical force used for dispersing the pigment include compression, compression, impact, shear, and cavitation. Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high-speed impellers, sand grinders, flow jet mixers, high-pressure wet atomization, and ultrasonic dispersion. Moreover, in the grinding|pulverization of the pigment in a sand mill (bead mill), it is preferable to process under the conditions which improved grinding|pulverization efficiency by using small diameter beads, increasing the filling rate of beads, etc. In addition, it is preferable to remove the coarse particles by filtration, centrifugation, or the like after the pulverization treatment. In addition, the process and disperser for dispersing pigments are "Dispersion Technology Exhibition, Published by Johokiko Co., Ltd., July 15, 2005" and "Practical synthesis of dispersion technology and industrial applications centered on suspension (open/liquid dispersion system)" The process and disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used. Moreover, in the process of dispersing a pigment, you may perform the refinement|miniaturization process of particle|grains by a salt milling process. As for the material, apparatus, processing conditions, etc. used in the salt milling process, description of Unexamined-Japanese-Patent No. 2015-194521 and Unexamined-Japanese-Patent No. 2012-046629 can be referred, for example.

Manufacture of a coloring composition WHEREIN: It is preferable to filter a coloring composition with a filter for the objective of removal of a foreign material, reduction of a defect, etc. As a filter, if it is a filter conventionally used for a filtration use, etc., it will not specifically limit, It can be used. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (eg nylon-6, nylon-6,6), polyolefin resins such as polyethylene and polypropylene (PP) ( and a filter using a material such as high-density and ultra-high molecular weight polyolefin resin). Among these materials, polypropylene (including high-density polypropylene) and nylon are preferable.

0.01-7.0 micrometers is preferable, as for the pore diameter of a filter, 0.01-3.0 micrometers is more preferable, 0.05-0.5 micrometers is still more preferable. If the hole diameter of a filter is the said range, a fine foreign material can be removed more reliably. For the pore diameter value of the filter, the nominal value of the filter maker can be referred to. As the filter, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Integris Co., Ltd. (formerly Nippon Microliss Co., Ltd.) and Kits Microfilter Co., Ltd. can be used.

Moreover, it is also preferable to use a fiber-form filter medium as a filter. As a fibrous filter medium, a polypropylene fiber, a nylon fiber, a glass fiber, etc. are mentioned, for example. As a commercial item, the SBP type series (SBP008 etc.), the TPR type series (TPR002, TPR005 etc.) made by a Rocky Techno company, and the SHPX type series (SHPX003 etc.) are mentioned. When using a filter, you may combine different filters (for example, a 1st filter, a 2nd filter, etc.). In that case, the filtration using each filter may be performed only once, and may be performed 2 times or more. Moreover, you may combine filters of different pore diameters within the above-mentioned range. Moreover, after performing filtration using a 1st filter only with respect to a dispersion liquid, and mixing another component, you may filter with a 2nd filter.

<Cured film>

The cured film of this invention is a film|membrane obtained by hardening|curing the coloring composition of this invention mentioned above. The cured film of this invention can be used for a color filter etc. Specifically, it can be preferably used as a colored layer (pixel) of a color filter, and is used more preferably as a red pixel. Although the film thickness of the cured film of this invention can be suitably adjusted according to the objective, it is preferable that it is 0.5-3.0 micrometers. 0.8 micrometer or more is preferable, as for a minimum, 1.0 micrometer or more is more preferable, and 1.1 micrometer or more is still more preferable. 2.5 micrometers or less are preferable, as for an upper limit, 2.0 micrometers or less are more preferable, and 1.8 micrometers or less are still more preferable.

<Method of forming a cured film>

Next, the formation method of a cured film is demonstrated.

The formation method of a cured film apply|coats the coloring composition of this invention on a support body, The process of forming a coloring composition layer, The process of exposing this coloring composition layer (exposure process), The process of heat-processing the coloring composition layer after exposure It is preferable to include (post-baking process). Moreover, when forming a pattern-shaped cured film (pixel), the said exposure process WHEREIN: The process of exposing a coloring composition layer in pattern shape, and developing the coloring composition layer after exposure between an exposure process and a post-baking process. It is preferable to further include (development process).

In forming a cured film, in this invention, it is preferable to carry out at the temperature of 150 degrees C or less through all processes. In addition, in this invention, "it carries out at the temperature of 150 degrees C or less through all processes" means performing all of the processes of forming a cured film using a coloring composition at the temperature of 150 degrees C or less. After developing the coloring composition layer after exposure, when providing the process of heating further, it means performing this heating process also at the temperature of 150 degrees C or less. Hereinafter, each process is demonstrated in detail.

At the process of forming a coloring composition layer, the coloring composition of this invention is apply|coated on a support body, and a coloring composition layer is formed. As a support body, a glass substrate, a resin substrate, etc. are mentioned. 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. Moreover, as a support body, a silicon substrate can also be used. A charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Moreover, the base layer may be provided in the support body in order to improve adhesiveness with an upper layer, to prevent the diffusion of a substance, or to planarize a board|substrate surface. It is preferable that the surface contact angle of a base layer is 20-70 degrees when measured with diiodomethane. Moreover, when it measures with water, it is preferable that it is 30-80 degrees. The wettability of a coloring composition is favorable as the surface contact angle of a base layer is the said range. Adjustment of the surface contact angle of the base layer can be performed, for example, by a method such as addition of a surfactant. A base layer may be formed using the composition which removed the coloring agent from the coloring composition described in this specification, the composition containing resin, polymeric compound, surfactant, etc. described in this specification.

As a coating method of a coloring composition, a well-known method can be used. For example, the drip method (drop cast); slit coat method; spray method; roll coat method; spin coating (spin coating); soft coating method; slit and spin method; free-wet method (for example, the method described in Unexamined-Japanese-Patent No. 2009-145395); Various printing methods, such as discharge system printing, such as inkjet (For example, an on-demand method, a piezo method, a thermal method), a nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and the metal mask printing method; a transfer method using a mold or the like; The nanoimprint method etc. are mentioned. The method of application in inkjet is not particularly limited, and for example, the method shown in "Diffuse and usable inkjet -infinite possibilities viewed as a patent -, published in February 2005, Sumibe Techno Research" (particularly page 115) ~133 pages), Japanese Unexamined Patent Publication No. 2003-262716, Japanese Unexamined Patent Publication No. 2003-185831, Japanese Unexamined Patent Publication No. 2003-261827, Japanese Unexamined Patent Publication No. 2012-126830, Japanese Unexamined Patent Publication No. 2006-169325 The method described in etc. is mentioned. Moreover, about the application|coating method of a coloring composition, description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be considered into consideration, and these content is integrated in this specification.

The coloring composition layer formed on the support body may be dried (prebaked). When prebaking, 80 degrees C or less is preferable, as for prebaking temperature, 70 degrees C or less is more preferable, 60 degrees C or less is still more preferable, and 50 degrees C or less is especially preferable. The lower limit can be, for example, 40°C or higher. As for prebaking time, 10 to 3600 second is preferable. Pre-baking can be performed with a hot plate, an oven, etc.

Next, the coloring composition layer is exposed (exposure process). For example, it can carry out using a stepper exposure machine, a scanner exposure machine, etc. with respect to a coloring composition layer. When forming a patterned cured film (pixel), a coloring composition layer is exposed in pattern shape. For example, a coloring composition layer can be pattern-exposed by exposing through the mask which has a predetermined|prescribed mask pattern. Thereby, an exposure part can be hardened|cured.

Examples of the light usable in exposure include ultraviolet rays such as g-line (wavelength 436 nm) and i-line (wavelength 365 nm). The exposure using the i-line may be performed while cutting light having a wavelength shorter than that of the i-line, as described in Korean Patent Application Laid-Open No. 1020170122130. Moreover, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180-300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), and KrF line (wavelength 248 nm) is preferable. In addition, a light source having a long wavelength of 300 nm or more can also be used.

Moreover, in the case of exposure, you may expose by irradiating light continuously, and you may irradiate and expose by pulse (pulse exposure). In addition, pulse exposure is an exposure method of the system of repeating exposure of light irradiation and pause in a cycle of a short time (for example, a millisecond level or less).

The irradiation amount (exposure amount) is, for example, preferably 0.03 to 2.5 J/cm ² , and more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration at the time of exposure can be appropriately selected, and in addition to carrying out under the atmosphere, for example, in a low-oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially anoxic), or exposure in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume. Moreover, exposure illuminance can be set suitably, ^and can select from the range ^of 1000W/ ^m2-100000W /m2 (for example, 5000W/m2, ^15000W /m2, or ^35000W /m2) normally. . The oxygen concentration and exposure illuminance may suitably combine conditions, for example, an illuminance of 10000 W/m ^{2 with an oxygen concentration of 10 vol%, an illuminance of 20,000 W/m 2 with} an oxygen concentration of 35 vol%, or the like.

In the formation method of a cured film, it is also preferable to develop the coloring composition layer after exposure. In particular, in the exposure step, when the coloring composition layer is exposed in a pattern shape, by developing the coloring composition layer after exposure, the unexposed portion of the coloring composition layer is developed and removed to form a cured film in a pattern shape to form a pixel. there is. The image development removal of the unexposed part of a coloring composition layer can be performed using a developing solution. Thereby, the coloring composition layer of the unexposed part in an exposure process elutes to a developing solution, and only the photocured part remains. As for the temperature of a developing solution, 20-30 degreeC is preferable, for example. As for image development time, 20 to 180 second is preferable. Moreover, in order to improve residue removability, you may repeat the process of shaking off a developing solution every 60 second and supplying a new developing solution several times more.

As a developing solution, an organic solvent, an alkali developing solution, etc. are mentioned, It is preferable that it is an alkali developing solution. As an alkali developing solution, the alkaline aqueous solution (alkali developing solution) which diluted the alkali agent with pure water is preferable. Examples of the alkali agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, and tetraethylammonium hydroxide. hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, Organic alkaline compounds such as pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate Inorganic alkaline compounds, such as these are mentioned. The alkali agent is preferably a compound having a large molecular weight from the viewpoint of environment and safety. 0.001-10 mass % is preferable and, as for the density|concentration of the alkali agent of alkaline aqueous solution, 0.01-1 mass % is more preferable. Moreover, the developing solution may contain surfactant further. As surfactant, the surfactant mentioned above is mentioned, A nonionic surfactant is preferable. The developer may be once prepared as a concentrate from the viewpoints of transport and storage convenience, and then diluted to a concentration required at the time of use. Although the dilution ratio is not specifically limited, For example, it can set in the range of 1.5-100 times. Moreover, it is also preferable to wash|clean (rinse) with pure water after image development. Moreover, it is preferable to supply and perform rinsing liquid to the coloring composition layer after image development, rotating the support body in which the coloring composition layer after image development was formed. It is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral portion of the support. At this time, in moving from the center part of the support body of a nozzle to a peripheral part, you may move, reducing the moving speed of a nozzle gradually. By rinsing in this way, in-plane unevenness of rinsing can be suppressed. Moreover, the same effect is acquired even if it reduces the rotation speed of a support body gradually, moving a nozzle from a support body center part to a peripheral part.

It is also preferable to perform an additional exposure process or a heat process (post-baking) after drying after image development. An additional exposure process and a post-baking are hardening processes after image development for making hardening complete.

When performing post-baking, 150 degrees C or less of heating temperature is preferable. As for the upper limit of heating temperature, 120 degrees C or less is more preferable, and 100 degrees C or less is still more preferable. The lower limit of the heating temperature is not particularly limited as long as curing of the composition can be promoted, and 50°C or more is more preferable, and 75°C or more is still more preferable. 1 minute or more is preferable, as for heating time, 5 minutes or more are more preferable, and 10 minutes or more are still more preferable. Although the upper limit is not specifically limited, 20 minutes or less is preferable from a viewpoint of productivity. It is also preferable to perform post-baking in the atmosphere of an inert gas. According to this aspect, thermal polymerization can proceed with very high efficiency without being inhibited by oxygen, and even when the pixel is manufactured at a temperature of 120° C. or less through the entire process, flatness is good, solvent resistance, etc. It is possible to manufacture a pixel having excellent properties. Nitrogen gas, argon gas, helium gas, etc. are mentioned as an inert gas, It is preferable that it is nitrogen gas. It is preferable that the oxygen concentration at the time of a post-baking is 100 ppm or less.

When performing an additional exposure process, it is preferable to irradiate and expose with the light of wavelength 254-350 nm. As a more preferable aspect, the process of exposing the coloring composition layer in pattern shape (exposure before development) is light with a wavelength of more than 350 nm and 380 nm or less with respect to the coloring composition layer (preferably light with a wavelength of 355-370 nm, More preferably is performed by irradiating and exposing the i-line), and the additional exposure treatment (exposure after development) is performed by irradiating and exposing the colored composition layer after development with light having a wavelength of 254 to 350 nm (preferably light having a wavelength of 254 nm). desirable. According to this aspect, the coloring composition layer can be properly cured by the first exposure (exposure before development), and the entire coloring composition layer can be almost completely cured by the subsequent exposure (exposure after development). As a result, the low temperature Even under conditions, a coloring composition layer can fully be hardened|cured and the pixel excellent in characteristics, such as solvent resistance, adhesiveness, and the rectangularity of a pattern, can be formed. When exposure is performed in two steps as described above, in the coloring composition, as a photopolymerization initiator, an extinction coefficient at a wavelength of 365 nm in methanol is 1.0×10 ³ mL/g·cm or more, and an extinction coefficient at a wavelength of 365 nm in methanol is It is 1.0x10 ² mL/g*cm or less, and it is preferable to use what contains the photoinitiator whose extinction coefficient of wavelength 254nm is 1.0x10 ³ mL/g*cm or more.

Exposure after development can be performed using, for example, an ultraviolet photoresist curing device. From an ultraviolet photoresist hardening apparatus, you may irradiate light (for example, i line|wire) other than that with the light of wavelength 254-350 nm, for example.

30-4000 mJ/cm< ² > is preferable and, as for the exposure amount (irradiation amount) in exposure after image development, 50-3500 mJ/cm< ² > is more preferable. It is preferable that it is 200 nm or less, and, as for the difference of the wavelength of the light used by the exposure before image development, and the wavelength of the light used by the exposure after image development, it is more preferable that it is 100-150 nm.

<Color filter>

Next, the color filter of this invention is demonstrated. The color filter of this invention has the cured film of this invention mentioned above. Preferably, it is a colored pixel of a color filter, More preferably, it has the cured film of this invention as a red pixel.

It is preferable that the color filter of this invention has the colored pixel of another hue other than the pixel of the cured film of this invention. As a color pixel of another color, a blue pixel, a green pixel, a yellow pixel, a magenta pixel, a cyan pixel, etc. are mentioned. As a preferable aspect of the color filter of this invention, the aspect which has a red pixel comprised from the cured film of this invention, a green pixel, and a blue pixel is mentioned.

The coloring composition for green pixel formation which it is preferable to use in combination with the pixel of the cured film of this invention is ^ratio of the maximum value A max11 of the absorbance with respect to the light of wavelength 400-450 nm, and the minimum value A ^min12 of the absorbance with respect to the light of wavelength 475-575 nm It is preferable that A ^max11 /A ^min11 is 15 or more, It is more preferable that it is 20 or more, It is more preferable that it is 25 or more.

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

Ratio A of the maximum value A ^max21 of the absorbance with respect to the light of wavelength 550-650 nm, and the minimum value Amin21 of the light absorbency with respect to the light of wavelength 400-500 nm, as for the coloring composition for blue pixel formation which it is preferable to use in combination with the pixel of the cured film of this invention It is preferable that ^max21 /A ^min21 is 10 or more, It is more preferable that it is 12.5 or more, It is more preferable that it is 15 or more.

Moreover, when the absorbance with respect to the light of wavelength 600nm shown by the said coloring composition for blue pixel formation is set to 1, it is preferable that the wavelength at which the absorbance becomes 0.3 exists in the range of 475-555 nm, and in the range of 480-540 nm It is more preferably present, more preferably in the range of 485 to 525 nm, and particularly preferably in the range of 490 to 510 nm.

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

In the color filter of this invention, although the film thickness of the cured film of this invention can be adjusted suitably according to the objective, it is preferable that it is 0.5-3.0 micrometers. 0.8 micrometer or more is preferable, as for a minimum, 1.0 micrometer or more is more preferable, and 1.1 micrometer or more is still more preferable. 2.5 micrometers or less are preferable, as for an upper limit, 2.0 micrometers or less are more preferable, and 1.8 micrometers or less are still more preferable.

The color filter of this invention WHEREIN: It is preferable that the line width (pattern size) of a pixel is 2.0-10.0 micrometers. 7.5 micrometers or less are preferable, as for an upper limit, 5.0 micrometers or less are more preferable, and 4.0 micrometers or less are still more preferable. As for a lower limit, 2.25 micrometers or more are preferable, 2.5 micrometers or more are more preferable, and 2.75 micrometers or more are still more preferable.

As for the color filter of this invention, the protective layer may be provided in the surface of the cured film of this invention. By providing the protective layer, various functions such as oxygen blocking, low reflection, hydrophobicization, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be provided. As thickness of a protective layer, 0.01-10 micrometers is preferable and 0.1-5 micrometers is more preferable. Examples of the method for forming the protective layer include a method of applying and forming a resin composition dissolved in an organic solvent, a chemical vapor deposition method, a method of affixing the molded resin with an adhesive, and the like. As a component constituting the protective layer, (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, poly Arylene 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, Aramide resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polycarbonate resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ , etc. are mentioned, and two or more types 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 includes a polyol resin, SiO ₂ , and Si ₂ N ₄ . Moreover, in the case of the protective layer aimed at reducing reflection, it is preferable that a protective layer contains a (meth)acrylic resin and a fluororesin.

In the case where 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, and an inkjet method can be used as a method for applying the resin composition. As the organic solvent contained in the resin composition, a known organic solvent (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by a chemical vapor deposition method, a known chemical vapor deposition method (thermochemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used as the chemical vapor deposition method.

The protective layer may contain additives such as organic/inorganic microparticles, an absorber of light of a specific wavelength (eg, ultraviolet, near-infrared, etc.), a refractive index modifier, an antioxidant, an adhesive, and a surfactant, if necessary. Examples of the organic/inorganic fine particles include, for example, polymer fine particles (eg, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, oxynitride Titanium, magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, etc. are mentioned. A well-known absorber can be used for the light absorber of a specific wavelength. Although content of these additives can be adjusted suitably, 0.1-70 mass % is preferable with respect to the total mass of a protective layer, and 1-60 mass % is more preferable.

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

The color filter may have a base layer. A base layer can also be formed using the composition etc. which removed the coloring agent from the coloring composition of this invention mentioned above, for example. It is preferable that the surface contact angle of a base layer is 20-70 degrees when measured with diiodomethane. Moreover, when it measures with water, it is preferable that it is 30-80 degrees. The wettability of a resin composition is favorable in the surface contact angle of a base layer being the said range. Adjustment of the surface contact angle of the base layer can be performed, for example, by a method such as addition of a surfactant.

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

<Display device>

The display device of this invention has the cured film of this invention mentioned above. As a display device, a liquid crystal display device, an organic electroluminescent display device, etc. are mentioned. For the definition of a display device and the details of each display device, see, for example, "Electronic Display Device (author Akio Sasaki, Kokocho Chosakai, published in 1990)", "Display device (author Sumiaki Ibuki, Tosho Sangyo) Note) published in the first year of the Heisei year)", etc. Moreover, about a liquid crystal display device, it describes, for example in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Kokocho Chosakai, published in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied, and for example, the present invention can be applied to various types of liquid crystal display devices described in "Next-generation liquid crystal display technology".

The organic electroluminescent display device may have a light source which consists of a white organic electroluminescent element. As a white organic electroluminescent element, it is preferable that it is a tandem structure. Regarding the tandem structure of organic electroluminescent devices, Japanese Patent Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Forefront of organic EL technology development - high luminance, high precision, long life, know-how-", Kijutsu Joho Kyo Kai, pp. 326-328, 2008 et al. The spectrum of white light emitted by the organic EL device preferably has a strong maximum emission peak in the blue region (430 nm-485 nm), the green region (530 nm-580 nm), and the yellow region (580 nm-620 nm). In addition to these emission peaks, it is more preferable to further have a maximum emission peak in the red region (650 nm to 700 nm).

Example

Hereinafter, the present invention will be described in detail with reference to Examples. Materials, amounts of use, ratios, processing contents, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit 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.

Column type: TOSOH TSKgel Super HZM-H, TOSOH TSKgel Super HZ4000, and TOSOH TSKgel Super HZ2000

Development solvent: tetrahydrofuran

Column temperature: 40°C

Flow rate (sample injection volume): 1.0 μL (sample concentration 0.1% by mass)

Device name: HLC-8220GPC manufactured by Tosoh Corporation

Detector: RI (Refractive Index) Detector

Calibration curve base resin: polystyrene resin

<Preparation of colorant solution>

After uniformly stirring and mixing the raw materials described in the table below, using zirconia beads having a diameter of 1 mm, they were dispersed in an Eiger motor mill ("Mini Model M-250MKII" manufactured by Eiger Japan) for 5 hours. Then, it filtered with the filter of 5 micrometers in pore diameter, and the coloring agent solution P-R1 - P-R11, P-RC1 was prepared. In the table below, the blending amount of each raw material is shown in parts by mass.

[Table 1]

The raw materials shown by the abbreviation in a table|surface are as follows.

(red colorant)

PR254: C. I. Pigment Red 254

PR177: C. I. Pigment Red 177

PR264: C. I. Pigment Red 264

PR269: C. I. Pigment Red 269

PR7: C. I. Pigment Red 7

AR249: C. I. Acid Red 249

(yellow colorant)

PY139: C. I. Pigment Yellow 139

PY150: C. I. Pigment Yellow 150

PY185: C. I. Pigment Yellow 185

SY162: C. I. Solvent Yellow 162

(dispersant)

Dispersant 1: Solsperse 20000 (manufactured by Nippon Lubrizol)

Dispersant 2: Resin solution D2 prepared by the following method

90.0 parts by mass of cyclohexanone was put into a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux condenser, and a gas introduction tube, heated to 60° C. while injecting nitrogen gas into the vessel, and 20.0 parts by mass of methacrylic acid at the same temperature; A mixture of 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 is added dropwise over 2 hours and polymerized reaction was carried out. After completion|finish of dripping, after making it react at 60 degreeC for 1 hour further, what melt|dissolved 0.5 mass parts of 2,2'- azobisisobutyronitrile 10.0 mass parts of propylene glycol monomethyl ether acetate (PGMEA) was added After that, stirring was continued at the same temperature for 3 hours to obtain a resin (copolymer). After cooling to room temperature, resin solution D2 having a solid content concentration of 20% was obtained by diluting with cyclohexanone. The weight average molecular weight of the obtained resin (copolymer) was 30000.

(pigment derivative)

Pigment derivative 1: a compound of the structure

[Formula 22]

<Preparation of a coloring composition>

After mixing and stirring the raw materials shown below, it filtered using the nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometers, and the coloring composition was prepared.

[Table 2]

The raw materials shown by the abbreviation in a table|surface are as follows.

(colorant solution)

P-R1 to P-R11, P-RC1: Colorant solution prepared above P-R1 to P-R11, P-RC1

(Photoinitiator)

I-1: Irgacure OXE02 (The compound of the following structure, manufactured by BASF, has an extinction coefficient of 7749 mL/g·cm in methanol at a wavelength of 365 nm.)

I-2: Omnirad 2959 (manufactured by IGM Resins BV, a compound of the following structure, the extinction coefficient in methanol at a wavelength of 365 nm is 48.93 mL/g·cm, and the extinction coefficient at a wavelength of 254 nm is 3.0 × 10 ⁴ mL/ g cm.)

I-3: Compound of the following structure (The extinction coefficient of light with a wavelength of 365 nm in methanol is 18900 mL/g·cm.)

[Formula 23]

(profit)

B-1: Resin of the following structure (resin having a repeating unit containing a block isocyanate group. Numerical values appended to the main chain are mass ratios.)

[Formula 24]

Put propylene glycol monomethyl ether acetate (PGMEA) in a reaction vessel, and 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a thermal polymerization initiator thereto; 2.0 mass parts of 1-dodecanethiol was added as a molecular weight regulator. Next, 60 parts by mass of the monomer (bm-2) and 40 parts by mass of benzyl methacrylate were put into the reaction vessel, and then 60° C. was maintained in a nitrogen atmosphere to react for 12 hours to synthesize Resin B-1. The weight average molecular weight of the synthesized resin B-1 was 7000.

B-2: Resin of the following structure (resin having a repeating unit containing a block isocyanate group and a repeating unit having a group in which an acid group is protected by a protecting group. Numerical values indicated in the main chain are mass ratios.)

[Formula 25]

Put propylene glycol monomethyl ether acetate (PGMEA) in a reaction vessel, and 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a thermal polymerization initiator thereto; 2.0 mass parts of 1-dodecanethiol was added as a molecular weight regulator. Then, 34 parts by mass of the monomer (bm-1), 59 parts by mass of the monomer (bm-2), and 7 parts by mass of benzyl methacrylate were put into the reaction vessel, and then maintained at 60° C. under a nitrogen atmosphere, It was made to react for 12 hours, and resin B-2 was synthesize|combined. The weight average molecular weight of the synthesized resin B-2 was 7500.

B-3: Resin of the following structure (resin having a repeating unit containing a block isocyanate group and a repeating unit having a group in which an acid group is protected by a protecting group. Numerical values indicated in the main chain are mass ratios.)

[Formula 26]

Put propylene glycol monomethyl ether acetate (PGMEA) in a reaction vessel, and 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a thermal polymerization initiator thereto; 2.0 mass parts of 1-dodecanethiol was added as a molecular weight regulator. Then, 34 parts by mass of the monomer (bm-1), 59 parts by mass of the monomer (bm-3), and 7 parts by mass of benzyl methacrylate were put into the reaction vessel, and then maintained at 60° C. under a nitrogen atmosphere, It was made to react for 12 hours, and resin B-3 was synthesize|combined. The weight average molecular weight of the synthesized resin B-3 was 7200.

B-4: Resin of the following structure (resin having a repeating unit containing a block isocyanate group and a repeating unit having a group in which an acid group is protected by a protecting group. Numerical values indicated in the main chain are mass ratios.)

[Formula 27]

Put propylene glycol monomethyl ether acetate (PGMEA) in a reaction vessel, and 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a thermal polymerization initiator thereto; 2.0 mass parts of 1-dodecanethiol was added as a molecular weight regulator. Then, 34 parts by mass of the monomer (bm-1), 59 parts by mass of the monomer (bm-4), and 7 parts by mass of benzyl methacrylate were put into the reaction vessel, and then maintained at 60° C. under a nitrogen atmosphere, It was made to react for 12 hours, and resin B-4 was synthesize|combined. The weight average molecular weight of the synthesized resin B-4 was 6900.

B-5: Resin of the following structure (resin having a repeating unit containing a block isocyanate group and a repeating unit having a group in which an acid group is protected by a protecting group. Numerical values indicated in the main chain are mass ratios.)

[Formula 28]

Put propylene glycol monomethyl ether acetate (PGMEA) in a reaction vessel, and 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a thermal polymerization initiator thereto; 2.0 mass parts of 1-dodecanethiol was added as a molecular weight regulator. Then, 34 parts by mass of the monomer (bm-5), 59 parts by mass of the monomer (bm-3), and 7 parts by mass of benzyl methacrylate were put into the reaction vessel, and then maintained at 60° C. under a nitrogen atmosphere, It was made to react for 12 hours, and resin B-5 was synthesize|combined. The weight average molecular weight of the synthesized resin B-5 was 7100.

B-6: Resin of the following structure (resin having a repeating unit containing a block isocyanate group and a repeating unit having a group in which an acid group is protected by a protecting group. Numerical values indicated in the main chain are mass ratios.)

[Formula 29]

Put propylene glycol monomethyl ether acetate (PGMEA) in a reaction vessel, and 5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) as a thermal polymerization initiator thereto; 2.0 mass parts of 1-dodecanethiol was added as a molecular weight regulator. Then, 34 parts by mass of the monomer (bm-6), 59 parts by mass of the monomer (bm-3), and 7 parts by mass of benzyl methacrylate were put into the reaction vessel, and then maintained at 60° C. under a nitrogen atmosphere, It was made to react for 12 hours, and resin B-6 was synthesize|combined. The weight average molecular weight of the synthesized resin B-6 was 7400.

The monomers (bm-1) to (bm-6) used in the synthesis of the resins B-1 to B-6 are compounds of the following structures.

[Formula 30]

(Polymerizable compound)

M-1: Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

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

[Formula 31]

(solvent)

S-1: propylene glycol monomethyl ether acetate (PGMEA)

S-2: propylene glycol monomethyl ether (PGME)

<Evaluation of Spectral>

Using a spin coater, each coloring composition was apply|coated on the glass substrate so that the film thickness after drying might be set to 2 micrometers, and it was made to dry for 2 minutes on a 100 degreeC hotplate. Next, using the ultrahigh pressure mercury lamp, it exposed on the conditions of exposure illuminance 20mW/cm< ² >, and exposure amount 1J/cm< ² >. And on a 100 degreeC hotplate, it heated for 20 minutes, stood to cool, and formed the cured film. Production of a cured film WHEREIN: The temperature of a board|substrate is the range of 20-100 degreeC through all processes. About the obtained cured film, using the ultraviolet-visible near-infrared spectrophotometer (UV3600, Shimadzu Corporation make), the absorbance of light in the range of wavelength 300-800 nm is measured using the reference glass substrate, and wavelength 400- Ratio A ^max1 /A ^min1 (hereinafter referred to as absorbance ratio 1) of the maximum absorbance value A ^max1 for light of 500 nm and the minimum value A ^min1 of absorbance for light with a wavelength of 550 to 700 nm, the absorbance for light with a wavelength of 500 nm is 1 When it is set as , the wavelength at which the absorbance becomes 0.3 (hereinafter referred to as wavelength 1) was measured, respectively.

<Evaluation of color mixing>

Using a spin coater, each coloring composition was apply|coated on the glass substrate so that the film thickness after drying might be set to 2 micrometers, and it was made to dry for 2 minutes on a 100 degreeC hotplate. Next, using the ultrahigh pressure mercury lamp, it exposed under the conditions of exposure illuminance 20mW/cm< ² >, and exposure amount 100mJ/cm< ² >. Then, using 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), puddle image development was performed at 23 degreeC for 60 second. Thereafter, it was rinsed with a spin shower and further washed with pure water. And it heated for 20 minutes on a 100 degreeC hotplate, stood to cool, and formed the cured film. The transmittance (T1) of light with a wavelength of 450 nm of the obtained cured film was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.).

Next, on this cured film, the coloring composition for color mixing evaluation is applied using a spin coater so that the film thickness after drying becomes 2 µm, dried on a hot plate at 100°C for 2 minutes, and a coating film of the colored composition for color mixing evaluation was formed to form a laminated film. The blue coloring composition used for formation of the blue pixel of Example 1001 mentioned later was used for the coloring composition for color mixing evaluation.

Next, the glass substrate on which this laminated film was formed was placed on a horizontal rotary table of a spin/shower developing machine (DW-30 type, manufactured by Chemtronics Co., Ltd.), and CD-2000 (Fujifilm Electronics Materials Co., Ltd.) was produced. Puddle development was performed at 23 degreeC for 60 second using a 60% dilution liquid, and the coating film of the coloring composition for color mixing evaluation formed on the cured film was removed. Next, the above-described glass substrate is fixed to a horizontal rotation table by a vacuum chuck method, and while the glass substrate is rotated at a rotation speed of 50 rpm by a rotation device, pure water is supplied from the upper side of the rotation center to the shower phase from the jet nozzle and rinsed and spray-drying after that.

The transmittance (T2) of the light with a wavelength of 450 nm of the said cured film after developing and removing the coating film of the coloring composition for color mixing evaluation was measured using MCPD-3000 (made by Otsuka Electronics Co., Ltd.).

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

Change in transmittance (%) = {|Transmittance (T1) - Transmittance (T2)|/Transmittance (T1)}×100

S: The rate of change of transmittance is less than 0.1%

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

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

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

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

E: The rate of change of transmittance is 5% or more

<Evaluation of storage stability>

The viscosity (V1) _of the coloring composition immediately after manufacture obtained above was measured with "RE-85L" by Toki Sangyo Co., Ltd. product. After leaving this coloring composition still on 40 degreeC temperature conditions for 3 days, the viscosity ( _V2 ) was measured. The thickening rate was computed from the following formula, and storage stability was evaluated according to the following evaluation criteria. The viscosity of the coloring composition was measured in the state which temperature-controlled at 23 degreeC. Evaluation criteria were as follows, and evaluation results were described in the table below.

Thickening rate (%)={(Viscosity (V ₂ )-Viscosity (V ₁ ))/Viscosity (V ₁ )}×100

S: The thickening rate is less than 0.1%

A: The thickening rate is 0.1% or more and less than 0.25%.

B: The thickening rate is 0.25% or more and less than 1%.

C: The thickening rate is 1% or more and less than 2.5%.

D: The thickening rate is 2.5% or more and less than 5%

E: The thickening rate is 5% or more

[Table 3]

As shown in the said table|surface, the Example was excellent in evaluation of color mixing.

<Example 1001>

On the silicon wafer, the green coloring composition was apply|coated by the spin coating method so that the film thickness after film formation might be set to 1.0 micrometer. Then, it heated at 100 degreeC for 2 minute(s) using the hotplate. Next, using an i-line stepper exposure apparatus FPA-3000i5+ (manufactured by Canon Co., Ltd.), exposure was performed at an exposure amount of 1000 mJ/cm ² through a mask of a dot pattern having a square dot pattern having a side of 12 μm. Next, using 0.3 mass % aqueous solution of tetramethylammonium hydroxide (TMAH), puddle development was performed at 23 degreeC for 60 second. Thereafter, it was rinsed with a spin shower and further washed with pure water. Then, it heated for 20 minutes on a 100 degreeC hotplate, and stood to cool, and the green coloring pattern (green pixel) was formed. Similarly, the red coloring composition and the blue coloring composition were sequentially patterned, the red coloring pattern (red pixel), the blue coloring pattern (blue pixel) were formed, respectively, and the color filter was produced.

As a red coloring composition, the coloring composition of Example 11 was used. A green coloring composition and a blue coloring composition are mentioned later. The obtained color filter was introduced into an organic electroluminescent display device according to a known method. This organic electroluminescent display device had a suitable image recognition ability.

[Green Coloring Composition]

After mixing and stirring the following components, it filtered with the nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometers, and the green coloring composition was prepared.

Green Pigment Dispersion … 85 parts by mass

Photoinitiator (Irgacure OXE02, manufactured by BASF) … 1.04 parts by mass

Photoinitiator (Omnirad 2959, manufactured by IGM Resins B.V.) … 0.77 parts by mass

resin solution 1 … 0.9 parts by mass

Furyl group-containing compound solution 1 … 1.4 parts by mass

Polymerizable compound (compound of the following structure) … 2.04 parts by mass

[Formula 32]

Surfactant (a compound of the following structure, Mw = 14000, the numerical value of % representing the proportion of repeating units is mole %, fluorine-based surfactant) … 0.008 parts by mass

[Formula 33]

Propylene glycol monomethyl ether acetate … 8.8 parts by mass

[Blue coloring composition]

After mixing and stirring the following components, it filtered with the nylon filter (made by Nippon Pole Co., Ltd.) with a pore diameter of 0.45 micrometers, and the blue coloring composition was prepared.

Blue pigment dispersion … 51.0 parts by mass

Photoinitiator (Irgacure OXE01, manufactured by BASF) … 2.17 parts by mass

Photoinitiator (Omnirad 2959, manufactured by IGM Resins B.V.) … 0.83 parts by mass

resin solution 1 … 4.1 parts by mass

Furyl group-containing compound solution 1 … 6.2 parts by mass

Polymerizable compound (compound of the following structure) … 2.5 parts by mass

[Formula 34]

Surfactant (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd.) … 0.008 parts by mass

butyl acetate … 33.2 parts by mass

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

(Green pigment dispersion)

A mixture consisting of 7.4 parts by mass of CI Pigment Green 36, 5.2 parts by mass of CI Pigment Yellow 185, 1.4 parts by mass of pigment derivative 1, 4.86 parts by mass of dispersant 1, and 81.14 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter ) was mixed and dispersed for 3 hours to prepare a pigment dispersion. After that, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BI Co., Ltd.) with a pressure reducing mechanism, dispersion treatment was performed at a flow rate of 500 g/min under a pressure of 2000 kg/cm ³ . This dispersion treatment was repeated 10 times to obtain a green pigment dispersion.

Pigment derivative 1: a compound of the structure

[Formula 35]

Dispersant 1: A resin of the following structure. Numerical values in parentheses of the main chain indicate the molar ratio of each repeating unit, and numerical values in parentheses in side chains indicate the number of repeating units in the side chain. The weight average molecular weight is 24000.

[Formula 36]

(Blue pigment dispersion)

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

(resin solution 1)

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

70.0 parts by mass of cyclohexanone was put into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, the temperature was raised to 80° C., the inside of the flask was replaced with nitrogen, and then from the dropping tube, n-butyl methacrylate 13.3 parts by mass, 2-hydroxyethyl methacrylate 4.6 parts by mass, methacrylic acid 4.3 parts by mass, paracumylphenol ethylene oxide modified acrylate (manufactured by Toagosei Co., Ltd., Aronix M110) 7.4 The mixture of mass parts and 0.4 mass parts of 2,2'- azobisisobutyronitrile was dripped over 2 hours. After completion|finish of dripping, reaction was continued for 3 hours, and resin A (Mw=26000) was synthesize|combined, and the 30 mass % PGMEA solution of resin A was obtained by diluting with PGMEA.

(Furyl group-containing compound solution 1)

20% by mass PGMEA solution of furyl group-containing compound F1 synthesized by the following method

Putting 90.0 parts by mass of PGMEA into a reaction vessel equipped with a stirrer, thermometer, dropping device, reflux condenser, and gas introduction tube, and heating to 60° C. while injecting nitrogen gas into the vessel, 50.0 parts by mass of furyl methacrylate at the same temperature, A mixture of 26.7 parts by mass of 2-methacryloyloxyethyl succinic acid, 23.3 parts by mass of 2-hydroxyethyl methacrylate, and 2.5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) Polymerization reaction was performed by dripping over 2 hours. After completion|finish of dripping, after making it react at 60 degreeC for 1 hour, what melt|dissolved 0.5 mass parts of 2,2'- azobis (2, 4- dimethylvaleronitrile) 10.0 mass parts of PGMEA is added, after that Stirring was continued for 3 hours at the same temperature to obtain a copolymer. The 20 mass % PGMEA solution of the furyl group containing compound F1 (Mw=52000) was obtained by diluting with PGMEA after cooling to room temperature.

Claims (17)

A coloring composition comprising a colorant containing a red colorant, a resin, a polymerizable compound, and a photoinitiator, comprising:
The resin comprises a resin BI having a repeating unit comprising a block isocyanate group,
In the coloring composition, the ratio A ^max1 /A ^min1 of the maximum value A ^max1 of the absorbance with respect to light having a wavelength of 400 to 500 nm and the minimum value A ^min1 of the absorbance with respect to the light having a wavelength of 550 to 700 nm is 25 or more,
When the absorbance with respect to the light of wavelength 500nm is made into 1, the wavelength from which the absorbance becomes 0.3 exists in the range of 570-620 nm, the coloring composition. The method according to claim 1,
The block isocyanate group is selected from the group consisting of an isocyanate group, an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. A group having a structure protected by a blocking agent to be used, a coloring composition. 3. The method according to claim 2,
The molecular weight of the said blocking agent is 50-200, The coloring composition. 4. The method according to any one of claims 1 to 3,
The coloring composition whose repeating unit containing the said block isocyanate group is a repeating unit represented by a following formula (B-1);
[Formula 1]

In the formula (B-1), R ^b1 to R ^b3 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and R ^b4 to R ^b7 each independently represent a hydrogen atom, a halogen atom, an alkyl group, or an alkoxy group. or an aryl group, and L ^b1 represents a single bond or a hydrocarbon group. 5. The method according to any one of claims 1 to 4,
The resin BI is a coloring composition comprising a repeating unit having a group in which an acid group is protected by a protecting group. 6. The method of claim 5,
The said acid group is a phenolic hydroxyl group or a carboxy group, The coloring composition. 7. The method according to claim 5 or 6,
The said protecting group is a group which is decomposed|disassembled by the action of an acid or a base, and is a group, the coloring composition. 8. The method according to any one of claims 5 to 7,
The said protecting group is group represented by any one of Formula (Y1)-(Y5), Color composition;
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 to R ^Y3 each independently represent an alkyl group, and two of R ^Y1 to R ^Y3 may be bonded to each other to form a ring;
In the formula (Y2), R ^Y4 to R ^Y6 each independently represent an alkyl group, and two of R ^Y4 to R ^Y6 may be bonded to each other to form a ring;
In the formula (Y3), R ^Y7 and R ^Y8 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ^Y7 and R ^Y8 is an alkyl group or an aryl group, and R ^Y9 represents an alkyl group or an aryl group , R ^Y7 or R ^Y8 and R ^Y9 may combine to form a ring;
In formula (Y4), Ar ^Y1 represents an aryl group and R ^Y10 represents an alkyl group or an aryl group;
In formula (Y5), R ^Y11 represents an alkyl group or an aryl group. 9. The method according to any one of claims 5 to 8,
a coloring composition in which the repeating unit having a group in which the acid group is protected by a protecting group is a repeating unit represented by the following formula (B-2);
[Formula 2]

In formula (B-2), R ^b11 to R ^b13 each independently represent a hydrogen atom, a halogen atom or an alkyl group, L ^b11 represents a single bond or a divalent linking group, and X ^b11 represents a formula (X-1) Or group represented by Formula (X-2) is shown;
[Formula 3]

In formulas (X-1) and (X-2), Y ^b1 represents a protecting group, and the broken line represents a portion bonded to L ^b11 . 10. The method according to any one of claims 1 to 9,
The colorant further comprises a yellow colorant, the coloring composition. 11. The method according to any one of claims 1 to 10,
The coloring composition whose content of the said red coloring agent in the said coloring agent is 70 mass % or more. 12. The method according to any one of claims 1 to 11,
A coloring composition used to form a cured film at a temperature of 150° C. or less through the entire process. 13. The method according to any one of claims 1 to 12,
A coloring composition for a color filter. 14. The method according to any one of claims 1 to 13,
The coloring composition for display devices. The cured film obtained by hardening|curing the coloring composition in any one of Claims 1-14. The color filter which has the cured film of Claim 15. The display device which has the cured film of Claim 15.