KR20220127879A - Coloring composition, film, color filter, solid-state image sensor and image display device - Google Patents

Abstract

A coloring composition comprising a color material containing a pigment, a photoinitiator, a polymerizable compound, and a resin, wherein the pigment is an aromatic ring group in which an electron-donating group is introduced into an aromatic ring Ar ^D1 is bonded to a diketopyrrolopyrrole skeleton A coloring composition comprising a pigment DPP having a structure, wherein the photoinitiator comprises an oxime compound OX having an aromatic ring group Ar ^OX1 in which an electron withdrawing group is introduced into an aromatic ring. Films, color filters, solid-state imaging devices, and image display devices.

Description

Coloring composition, film, color filter, solid-state image sensor and image display device

This invention relates to the coloring composition containing a pigment. Moreover, this invention relates to the film|membrane which used the coloring composition, a color filter, a solid-state image sensor, and an image display apparatus.

In recent years, from the spread of digital cameras and camera-equipped mobile phones, the demand for solid-state imaging devices such as charge-coupled device (CCD) image sensors is increasing significantly. A color filter is used as a key device of a display or an optical element. A color filter is usually provided with pixels of three primary colors of red, green, and blue, and plays a role of decomposing transmitted light into three primary colors.

The colored pixel of each color of a color filter is manufactured using the coloring composition containing color materials, such as a pigment. Moreover, diketopyrrolopyrrole pigment etc. are used as a color material for the coloring composition for red pixel formation (for example, patent document 1 etc.).

Patent Document 1: Japanese Patent Application Laid-Open No. 2019-200343

As a result of the inventors intensively examining the coloring composition containing the diketopyrrolopyrrole pigment, the film formed using the coloring composition containing the diketopyrrolopyrrole pigment at a higher temperature (for example, 230 ° C. or higher) etc.), it was found that crystals derived from diketopyrrolopyrrole pigment tend to precipitate as foreign substances in the film. In addition, as a result of the present inventor examining the coloring composition described in the Example of Patent Document 1, when the film formed using this coloring composition is heated to a high temperature of 230 ° C. or higher, the diketopyrrolopyrrole pigment derived from the film is It turned out that a crystal|crystallization is easy to precipitate as a foreign material, and there exists room for further improvement.

Moreover, in recent years, the request|requirement with respect to the characteristic of the film|membrane used for a color filter etc. is increasing. As such a required characteristic, the thing excellent in light resistance, the thing excellent in adhesiveness with a support body, etc. are calculated|required. Moreover, as a result of this inventor examining about the coloring composition described in the Example of patent document 1, it turns out that the film|membrane formed using this coloring composition has room for further improvement with respect to light resistance and adhesiveness with a support body. there was.

Accordingly, it is an object of the present invention to provide a coloring composition, a film, a color filter, a solid-state image sensor, and an image display device that is excellent in light resistance and adhesiveness and can form a film in which precipitation of foreign substances is suppressed even after heat treatment. have.

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

<1> A coloring composition containing a color material containing a pigment, a photoinitiator, a polymerizable compound, and a resin, comprising:

The pigment includes a pigment DPP having a structure in which an aromatic ring group Ar ^D1 in which an electron-donating group is introduced into an aromatic ring is bonded to a diketopyrrolopyrrole skeleton,

The said photoinitiator contains the oxime compound OX which has the aromatic ring group ^ArOX1 in which the electron withdrawing group was introduce|transduced into the aromatic ring, The coloring composition.

<2> The coloring composition according to <1>, wherein the electron withdrawing group included in the aromatic ring group Ar ^OX1 is at least one selected from an acyl group and a nitro group.

<3> The coloring composition according to <1>, wherein the electron withdrawing group included in the aromatic ring group Ar ^OX1 is an acyl group.

<4> The coloring composition according to any one of <1> to <3>, wherein the aromatic ring group Ar ^OX1 is a group represented by the formula (OR-1);

[Formula 1]

In the formula, R ^OX1 represents a substituent, R ^OX2 represents an electron withdrawing group, n represents an integer of 0 to 4, and a broken line represents a bond.

<5> The said oxime compound OX has at least 1 sort(s) of group chosen from the group represented by a formula (OR-11), and a group represented by a formula (OR-12), In any one of <1>-<4> in any one of description coloring composition;

[Formula 2]

wherein R ^OX11 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group;

R ^OX12 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group , an acyloxy group or an amino group,

The dashed line indicates the bonding hand.

<6> The coloring composition according to any one of <1> to <5>, wherein the oxime compound OX is at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2);

[Formula 3]

In the formula, R ^X1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group;

R ^X2 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group , an acyloxy group or an amino group,

R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;

However, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

<7> The electron-donating group of the aromatic ring group Ar ^D1 is at least one selected from a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, and an amino group, <1> to <6> The coloring composition in any one of.

<8> The said aromatic ring group Ar ^D1 is group represented by Formula (AR-1), The coloring composition in any one of <1>-<7>;

[Formula 4]

In the formula, R ^D1 represents a substituent, R ^D2 represents an electron-donating group, n represents an integer of 0 to 4, and a broken line represents a bond with a diketopyrrolopyrrole skeleton.

<9> The coloring composition according to any one of <1> to <8>, wherein the pigment DPP is a compound represented by a formula (DPP1);

[Formula 5]

In the formula, R ^D11 and R ^D12 each independently represents a substituent,

R ^D21 and R ^D22 each independently represent an electron-donating group,

n11 and n12 each independently represent an integer of 0-4.

<10> The coloring composition according to any one of <1> to <9>, wherein the pigment DPP contains at least one selected from color index pigment red 264 and color index pigment red 272.

The coloring composition in any one of <1>-<10> whose content of the color material in the total solid of a <11> coloring composition is 50 mass % or more.

<12> The colored composition according to any one of <1> to <11>, which is for a solid-state imaging device.

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

<14> The film|membrane obtained using the coloring composition in any one of <1>-<13>.

<15> The color filter which has the film|membrane as described in <14>.

<16> A solid-state imaging device having the film according to <14>.

<17> An image display device having the film according to <14>.

ADVANTAGE OF THE INVENTION According to this invention, it is excellent in light resistance and adhesiveness, and can provide the coloring composition, film|membrane, color filter, solid-state image sensor, and image display apparatus which can form the film|membrane by which precipitation of foreign material was suppressed even after heat processing.

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

In this specification, "~" is used in the meaning including the numerical value described before and after that as a lower limit and an upper limit.

In the description of the group (atomic group) in this specification, the description which does not describe substitution and unsubstituted includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent. 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 lamp, and a deep ultraviolet ray represented by an excimer laser, extreme ultraviolet (EUV light), X-ray, an electron beam, are mentioned.

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

In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

In this specification, a weight average molecular weight and a number average molecular weight are polystyrene conversion values measured by the GPC (gel permeation chromatography) method.

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, a pigment means the compound which is hard to melt|dissolve with respect to a solvent.

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.

<Coloring composition>

The coloring composition of this invention,

A coloring composition containing a color material containing a pigment, a photoinitiator, a polymerizable compound, and a resin, comprising:

The pigment includes a pigment DPP having a structure in which an aromatic ring group Ar ^D1 in which an electron-donating group is introduced into an aromatic ring is bonded to a diketopyrrolopyrrole skeleton,

The photopolymerization initiator is characterized in that it contains an oxime compound OX having an aromatic ring group Ar ^OX1 in which an electron withdrawing group is introduced into the aromatic ring.

ADVANTAGE OF THE INVENTION According to the coloring composition of this invention, it is excellent in light resistance and adhesiveness, and can form the film|membrane by which precipitation of the foreign material was suppressed even after heat processing. The reason such an effect is acquired is estimated that it is based on the following. In the coloring composition of the present invention, the pigment DPP described above has an electron-donating group, and since the oxime compound OX used as a photopolymerization initiator has an electron-withdrawing group, in the coloring composition, the pigment DPP and the oxime compound OX are close to each other presumed to exist. For this reason, it is estimated that the hardening reaction of a polymeric compound advances in the vicinity of pigment DPP by light irradiation at the time of exposure. For this reason, it is estimated that the film|membrane excellent in adhesiveness with a support body was able to be formed. In addition, diketopyrrolopyrrole pigment has high crystallinity and tends to agglomerate by heating. As a result, even if the obtained film|membrane was heat-processed, the aggregation etc. of a diketopyrrolopyrrole pigment could be suppressed, and it is estimated that the film|membrane in which precipitation of the foreign material was suppressed was able to be formed. In addition, the oxime compound OX used as a photoinitiator in the coloring composition of the present invention has an aromatic ring group Ar ^OX1 in which an electron withdrawing group is introduced into the aromatic ring, and the portion of the aromatic ring group Ar ^OX1 acts as an ultraviolet absorber. It is estimated that it did, and as a result, it is estimated that the film|membrane excellent in light resistance was able to be formed.

Moreover, since the said pigment DPP used for the coloring composition of this invention has a red color value higher than the conventional red pigment, even if it is a thin film, it can form the cured film which has a desired spectral characteristic. Since the pigment DPP has a structure in which the aromatic ring group Ar ^D1 is bonded to the diketopyrrolopyrrole skeleton, the HOMO (Highest Occupied Molecular Orbital)-LUMO (Lowest Unoccupied Molecular Orbital) transition elongates to increase the transition moment, and as a result, the pigment DPP Since the molar extinction coefficient ε in the red wavelength region (eg, 450 to 600 nm) increased, it is estimated that the color value of red is high. In addition, since the pigment DPP has a higher color value of red than that of a conventional red pigment, the desired spectroscopy can be achieved with a compounding amount smaller than that required to achieve spectral properties equivalent to that of a conventional red pigment. The compounding quantity of a component can also be raised, and the freedom degree of prescription design is high.

The coloring composition of this invention can be used suitably as a coloring composition for solid-state image sensors. Moreover, the coloring composition of this invention can be used suitably as a coloring composition for color filters. Specifically, it can use suitably as a coloring composition for pixel formation of a color filter, and can use it more preferably as a coloring composition for red pixel formation of a color filter. Moreover, the coloring composition of this invention can be used suitably as a coloring composition for pixel formation of the color filter used for a solid-state image sensor.

Hereinafter, each component used for the coloring composition of this invention is demonstrated.

<<Color material>>

The coloring composition of this invention contains the color material containing a pigment. It is preferable that content of the pigment in a color material is 50 mass % or more, It is more preferable that it is 70 mass % or more, It is more preferable that it is 80 mass % or more, It is especially preferable that it is 90 mass % or more. Moreover, only a pigment may be sufficient as a color material.

As the pigment, one containing a pigment DPP (hereinafter also referred to as pigment DPP) having a structure in which an aromatic ring group Ar ^D1 having an electron-donating group introduced into the aromatic ring is bonded to a diketopyrrolopyrrole skeleton is used. Pigment DPP is a diketopyrrolopyrrole pigment. In addition, in this specification, an electron-donating group is an atomic group which donates an electron to the substituted atomic group by a cause effect or a resonance effect in organic electron theory. Examples of the electron-donating group include those taking a negative value as the substituent constant (?p+) of Hammett's formula. The substituent constant (σp+) of Hammett's formula can be quoted from page 175 of the first edition of Organic Chemistry I. Molecular Structure and Reaction and Organometallic Chemistry in a graduate lecture. As for the electron-donating group, it is preferable that the substituent constant (?p+) of Hammett's formula is a group of -0.01 or less, it is more preferable that it is a group of -0.15 or less, and it is still more preferable that it is a group of -0.3 or less.

In the pigment DPP, examples of the electron-donating group of the aromatic ring group Ar ^D1 include a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, and an amino group.

1-10 are preferable and, as for carbon number of an alkyl group, an alkoxy group, and an alkylthio group, 1-5 are more preferable. Any of linear, branched, and cyclic|annular chain may be sufficient as these groups, and linear or branched is preferable.

6-20 are preferable and, as for carbon number of an aryl group and an aryloxy group, 6-10 are more preferable.

Examples of the amino group include a group represented by -NRa ¹ Ra ² . Ra ¹ and Ra ² each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Ra ¹ and Ra ² may combine to form a ring. 1-30 are preferable, as for carbon number ^of the alkyl group which Ra1 and Ra2 represent, ^1-15 are more preferable, and 1-8 are still more preferable. Any of linear, branched, and cyclic|annular chain may be sufficient as an alkyl group, A linear or branched is preferable, and a linear is more preferable. 6-30 are preferable, as for carbon number ^of the aryl group which ^Ra1 and Ra2 represent, 6-20 are more preferable, and 6-12 are still more preferable. The heterocyclic group represented by Ra ¹ and Ra ² may be monocyclic or may be a condensed ring. The heterocyclic group is preferably a monocyclic or condensed ring having 2 to 4 condensed rings. As for the number of the hetero atoms which comprise the ring of a heterocyclic group, 1-3 are preferable. As for the hetero atom which comprises the ring of a heterocyclic group, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable. 3-30 are preferable, as for the number of the carbon atoms which comprise the ring of a heterocyclic group, 3-18 are more preferable, 3-12 are more preferable.

As the electron-donating group, an alkyl group, an alkoxy group, an aryl group and an amino group are preferable, and an alkyl group, an alkoxy group and an aryl group are more preferable, and an alkyl group and an aryl group are more preferable because a film having spectral properties suitable for red color is easily obtained; Alkyl groups are particularly preferred.

It is preferable that the said aromatic ring group Ar ^D1 is group represented by Formula (AR-1).

[Formula 6]

In the formula, R ^D1 represents a substituent, R ^D2 represents an electron-donating group, n represents an integer of 0 to 4, and a broken line represents a bond with a diketopyrrolopyrrole skeleton.

In the formula (AR-1), examples of the substituent represented by R ^D1 include a group selected from the group of the substituent T described later and the electron-donating group described above, and an electron-donating group is preferable. When n is 2 or more, n pieces of R ^D1 may be the same or each may be different.

In the formula (AR-1), examples of the electron-donating group represented by R ^D2 include the groups described above, and their preferred ranges are also the same.

In formula (AR-1), n represents the integer of 0-4, it is preferable that it is an integer of 0-3, It is more preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1.

In the formula (AR-1), the broken line represents a bond with the diketopyrrolopyrrole skeleton. In addition, diketopyrrolopyrrole skeleton means the following structures. A broken line shows the bond with substituents, such as group represented by Formula (AR-1). As a substituent other than group represented by Formula (AR-1), an aryl group etc. are mentioned. The aryl group may have a substituent. As a substituent, the group chosen from the group of the substituent T mentioned later is mentioned.

[Formula 7]

It is preferable that it is a compound represented by a formula (DPP1), and, as for pigment DPP, it is more preferable that it is a compound represented by a formula (DPP2) from the reason that the effect of this invention is acquired remarkably.

[Formula 8]

In the above formula, R ^D11 and R ^D12 each independently represents a substituent,

R ^D21 and R ^D22 each independently represent an electron-donating group,

n11 and n12 each independently represent an integer of 0-4.

Examples of the substituent represented by R ^D11 and R ^D12 include a group selected from the group of the substituent T described later and the electron-donating group described above, and an electron-donating group is preferable. When n11 is 2 or more, n11 pieces of R ^D11 may be the same, and each may differ. Moreover, when n12 is 2 or more, n12 pieces of R ^D12 may be same, and each may differ.

Examples of the electron-donating group represented by R ^D21 and R ^D22 include the groups described above, and their preferred ranges are also the same.

n11 and n12 each independently represent the integer of 0-4, it is preferable that it is an integer of 0-3, It is more preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1, It is especially preferable that it is 0.

(substituent T)

Examples of the substituent T include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² , - NRt ³ CORt ¹ , -CONRt ¹ Rt ² , -NRt ³ CONRt ¹ Rt ² , -NRt ³ COORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NRt ³ SO ₂ Rt ¹ or - SO ₂ NRt ¹ Rt ² . R ^t1 to R ^t3 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. Rt ¹ and Rt ² may combine to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

1-30 are preferable, as for carbon number of an alkyl group, 1-15 are more preferable, and 1-8 are still more preferable. Although linear, branched, or cyclic any may be sufficient as an alkyl group, a linear or branched is preferable and a linear is more preferable.

2-30 are preferable, as for carbon number of an alkenyl group, 2-15 are more preferable, 2-8 are still more preferable. Although linear, branched, and cyclic any may be sufficient as an alkenyl group, a linear or branched is preferable, and a linear is more preferable.

6-30 are preferable, as for carbon number of an aryl group, 6-20 are more preferable, and 6-12 are still more preferable.

The heterocyclic group may be monocyclic or a condensed ring may be sufficient as it. The heterocyclic group is preferably a monocyclic or condensed ring having 2 to 4 condensed rings. As for the number of the hetero atoms which comprise the ring of a heterocyclic group, 1-3 are preferable. As for the hetero atom which comprises the ring of a heterocyclic group, a nitrogen atom, an oxygen atom, or a sulfur atom is preferable. 3-30 are preferable, as for the number of the carbon atoms which comprise the ring of a heterocyclic group, 3-18 are more preferable, 3-12 are more preferable.

The alkyl group, the aryl group, and the heterocyclic group may have a substituent and may be unsubstituted. As a substituent, the group chosen from the group of the substituent T mentioned above is mentioned.

As a specific example of pigment DPP, the compound of the following structure is mentioned. The compound of the structure represented by Formula (R1) is color index (C.I.) Pigment Red 272, and the compound of the structure represented by Formula (R10) is C.I. Pigment Red 264. Pigment DPP preferably contains at least one selected from C. I. Pigment Red 264 and C. I. Pigment Red 272, and more preferably contains C. I. Pigment Red 272.

[Formula 9]

The color material used for the coloring composition of this invention can contain further color materials (henceforth another color material) other than the pigment DPP mentioned above. A pigment may be sufficient as another color material, and dye may be sufficient as it. You may use a pigment and dye together. It is preferable that another color material contains a pigment. Moreover, an organic pigment may be sufficient as a pigment, and an inorganic pigment may be sufficient as it. 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 organic chromophore for an inorganic pigment or an organic-inorganic pigment, color design can be facilitated.

It is preferable that a yellow color material is included as another color material, and, as for the coloring composition of this invention, it is more preferable that a yellow pigment is included. According to this aspect, it is easy to form the film|membrane which has the spectral characteristic suitable for a red pixel. Moreover, when a yellow pigment is used as another color material, the storage stability of a coloring composition can also be improved.

Examples of the yellow color material include a quinophthalone compound, an isoindoline compound, an azo compound, an azomethine compound, a benzimidazolone compound, a pteridine compound, and a quinoxaline compound, and a quinophthalone compound, an isoindoline compound , an azo compound, an azomethine compound, and a pteridine compound are preferable, an isoindoline compound and an azo compound are more preferable, and an isoindoline compound because it is easy to form a film having spectral properties more suitable for red color This is particularly preferred.

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

Moreover, as a yellow color material, the compound of Unexamined-Japanese-Patent No. 2017-201003, the compound of Unexamined-Japanese-Patent No. 2017-197719, Paragraph Nos. 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 Patent Application Laid-Open 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, the quinophthalone compounds described in Paragraph Nos. 0011 to 0034 of Japanese Patent Application Laid-Open No. 2013-054339, 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-218-203798, the quinophthalone compound described in JP-A-2018-062578, Japan The quinophthalone compound described in Patent Publication No. 6432077, the quinophthalone compound described in Japanese 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 A quinophthalone compound, the quinophthalone compound described in Unexamined-Japanese-Patent No. 2018-040835, the quinophthalone compound described in Unexamined-Japanese-Patent No. 2017-197640, the quinophthalone compound described in Unexamined-Japanese-Patent No. 2016-145282, The quinophthalone compound of Unexamined-Japanese-Patent No. 2014-085565, the quinophthalone compound of Unexamined-Japanese-Patent No. 2014-021139, The quinophthalone compound of Unexamined-Japanese-Patent No. 2013-209614, Unexamined-Japanese-Patent No. 2013 -The quinophthalone compound described in -209435, the quino described in Japanese Unexamined-Japanese-Patent No. 2013-181015. A phthalone compound, the quinophthalone compound of Unexamined-Japanese-Patent No. 2013-061622, the quinophthalone compound of Unexamined-Japanese-Patent No. 2013-054339, The quinophthalone compound of Unexamined-Japanese-Patent No. 2013-032486, Japan The quinophthalone compound described in Unexamined-Japanese-Patent No. 2012-226110, the quinophthalone compound of Unexamined-Japanese-Patent No. 2008-074987, The quinophthalone compound of Unexamined-Japanese-Patent No. 2008-081565, Unexamined-Japanese-Patent No. 2008- The quinophthalone compound described in 074986, the quinophthalone compound described in Unexamined-Japanese-Patent No. 2008-074985, the quinophthalone compound described in Unexamined-Japanese-Patent No. 2008-050420, The quin of Unexamined-Japanese-Patent No. 2008-031281. Nophthalone compound, the quinophthalone compound described in Japanese Unexamined Patent Publication No. 48-032765, the quinophthalone compound described in Japanese Unexamined Patent Publication No. 2019-008014, the compound represented by the formula (QP1), the compound represented by the formula (QP2) , the compound described in Korean Patent Application Laid-Open No. 10-2014-0034963, the compound described in Japanese Patent Application Laid-Open No. 2017-095706, the compound described in Taiwan Patent Application Laid-Open No. 201920495, the compound described in Japanese Patent Application Laid-Open No. 6607427 can also be used. Moreover, what multimerized these compounds is also used preferably from a viewpoint of color value improvement.

[Formula 10]

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 11]

In the formula (QP2), Y ¹ to Y ³ each independently represent 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 the other color material, a red color material other than the pigment DPP (hereinafter, also referred to as another red color material) may be used. It is preferable that another red color material is a pigment. Examples of other red color materials include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, etc. It is preferably an iketopyrrolopyrrole compound, an anthraquinone compound, or an azo compound, and more preferably a diketopyrrolopyrrole compound from the viewpoint of forming a red pixel with higher color separation performance. As a specific example of another red color material, 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, 269, 270 Red pigments, such as 279, 291, 294 (xanthene type, Organo Ultramarine, Bluish Red), 295 (monoazo type), 296 (diazo type), 297 (amino ketone type), are mentioned. The other red color material is preferably C.I. Pigment Red 254 from the viewpoint of being able to form a red pixel having higher color separation performance.

Chromatic color materials, such as an orange color material, a green color material, a purple color material, and a blue color material, can also be used for another color material. What is shown below is mentioned as these specific examples.

C. I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 light (above, orange pigment),

C. I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine-based), 65 (phthalocyanine-based), 66 (phthalocyanine-based), etc. (above, green pigment),

C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60 (triarylmethane-based), 61 (xanthene-based), etc. (above, purple pigment);

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 (monoa crude), 88 (metaphosphorus), etc. (above, blue pigment).

As the green color material, a zinc halide 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. have. As a specific example, the compound of International Publication No. 2015/118720 is mentioned. Moreover, as a green color material, the compound described in Chinese Patent Application No. 106909027, the phthalocyanine compound which has the phosphate 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.

Moreover, as a blue color material, the aluminum phthalocyanine compound which has a phosphorus atom can also be used. As a specific example, Paragraph 0022 - 0030 of Unexamined-Japanese-Patent No. 2012-247591, Paragraph 0047 of Unexamined-Japanese-Patent No. 2011-157478 are mentioned.

Moreover, dye can also be used as another color material. There is no restriction|limiting in particular as dye, A well-known dye can be used. For example, a pyrazolazo compound, an anilinoazo compound, a triarylmethane compound, an anthraquinone compound, an anthrapyridone compound, a benzylidene compound, an oxonol compound, a pyrazolotriazolazo compound, a pyridonazo compound, an anin compound, a phenothiazine compound, a pyrrolopyrazolazomethine compound, a xanthene compound, a phthalocyanine compound, a benzopyran compound, an indigo compound, and a pyrromethene compound. Moreover, the thiazole compound of Unexamined-Japanese-Patent No. 2012-158649, the azo compound of Unexamined-Japanese-Patent No. 2011-184493, and the azo compound of Unexamined-Japanese-Patent No. 2011-145540 can also be used preferably. Moreover, as dye, a dye multimer can also be used. 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 JP 2011-213925 , JP 2013-041097 , JP 2015-028144 , JP 2015-030742 , JP 2016-102191 , The compounds described in International Publication No. 2016/031442 and the like can also be used.

The content of the color material in the total solid content of the coloring composition is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 45% by mass or more, 50 It is especially preferable that it is mass % or more. Moreover, it is preferable that it is 80 mass % or less, and, as for the upper limit of content of the color material in the total solid of a coloring composition, it is more preferable that it is 70 mass % or less, It is more preferable that it is 60 mass % or less.

Further, the content of the pigment in the total solid content of the coloring composition is preferably 20 mass % or more, more preferably 30 mass % or more, still more preferably 40 mass % or more, still more preferably 45 mass % or more, , 50% by mass or more is particularly preferred. Moreover, it is preferable that it is 80 mass % or less, and, as for the upper limit of content of the pigment in the total solid of a coloring composition, it is more preferable that it is 70 mass % or less, It is more preferable that it is 60 mass % or less.

The content of the pigment DPP in the total solid content of the coloring composition is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass or more, still more preferably 20% by mass or more, It is especially preferable that it is 25 mass % or more. Moreover, it is preferable that it is 70 mass % or less, and, as for the upper limit of content of pigment DPP in the total solid of a coloring composition, it is more preferable that it is 60 mass % or less, It is still more preferable that it is 55 mass % or more.

It is preferable that content of the pigment DPP in the total mass of the color material contained in a coloring composition is 20-100 mass %, It is more preferable that it is 30-95 mass %, It is more preferable that it is 40-90 mass %.

When the color material contained in the coloring composition contains a yellow color material, the content of the yellow color material is preferably 5 to 100 parts by mass, more preferably 10 to 60 parts by mass, and 15 to 40 parts by mass with respect to 100 parts by mass of the pigment DPP. It is more preferable that it is a mass part.

When the color material contained in the coloring composition contains a red color material other than the pigment DPP, the content of the red color material other than the pigment DPP is preferably 5 to 100 parts by mass with respect to 100 parts by mass of the pigment DPP, and 10 to 60 parts by mass It is more preferable, and it is still more preferable that it is 15-40 mass parts.

<<Photoinitiator>>

The coloring composition of this invention contains a photoinitiator. As a photoinitiator, the thing containing the oxime compound OX (henceforth an oxime compound OX) which has the aromatic ring group ^ArOX1 in which the electron withdrawing group was introduce|transduced into the aromatic ring is used. In the oxime compound OX, the aromatic ring group Ar ^OX1 is preferably bonded to a moiety containing the oxime structure of the oxime compound OX through the aromatic ring to which the electron withdrawing group is bonded. That is, it is preferable that the electron withdrawing group of the aromatic ring group Ar ^OX1 is couple|bonded with the site|part containing the oxime structure of oxime compound OX via the aromatic ring which electron withdraw|attracted by the electron withdrawing group. Specifically, it is preferable that the aromatic ring side of the aromatic ring group Ar ^OX1 is the bonding side with the moiety containing the oxime structure of the oxime compound OX. In addition, in this specification, an electron withdrawing group is an atomic group which withdraw|retracts an electron from the substituted atomic group by a cause effect or a resonance effect in organic electron theory. Examples of the electron withdrawing group include those taking a positive value as the substituent constant (?p-) of Hammett's formula. The substituent constant (σp-) of the Hammett formula can be quoted from page 175 of the graduate course in Organic Chemistry I. Molecular Structure and Reaction and Organometallic Chemistry, first edition. The electron withdrawing group is preferably a group having a substituent constant (?p-) of the Hammett formula of 0.01 or more, more preferably a group of 0.1 or more, and still more preferably a group of 0.3 or more.

In the oxime compound OX, examples of the electron withdrawing group possessed by the aromatic ring group Ar ^OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. , preferably an acyl group and a nitro group, more preferably an acyl group, and still more preferably a benzoyl group, for the reason that it is easy to form a film having more excellent light resistance. The benzoyl group may have a substituent. Examples of the substituent include a group selected from the group of the above-described substituent T, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, and a heterocyclic group. It is preferably an oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group or an amino group, which is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. more preferably, an alkoxy group, an alkylsulfanyl group, or an amino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkenyl group, alkylsulfanyl group, arylsulfanyl group, acyl group and amino group include the groups described as these groups represented by R ^OX11 described later. .

It is preferable that the said aromatic ring group Ar ^OX1 is group represented by Formula (OR-1). According to this aspect, the effect of this invention mentioned above is exhibited more notably.

[Formula 12]

In the formula, R ^OX1 represents a substituent, R ^OX2 represents an electron withdrawing group, n represents an integer of 0 to 4, and a broken line represents a bond.

Examples of the substituent represented by R ^OX1 in the formula (OR-1) include a group selected from the group of the substituent T and the electron withdrawing group described above, and an electron withdrawing group is preferable. When n is 2 or more, n pieces of R ^OX1 may be the same or each may be different.

In formula (OR-1), as an electron withdrawing group which ^ROX2 represents, the group mentioned above is mentioned, and a preferable range is also the same.

In formula (OR-1), n represents the integer of 0-4, it is preferable that it is an integer of 0-3, It is more preferable that it is an integer of 0-2, It is more preferable that it is 0 or 1, It is 0 Especially preferred.

In Formula (OR-1), a broken line represents a bond. At the position of the broken line in formula (OR-1), it bonds with the other atomic group which comprises oxime compound OX, and comprises oxime compound OX.

It is preferable to have at least 1 sort(s) of group chosen from group represented by a formula (OR-11), and group represented by a formula (OR-12), as for oxime compound OX, it is more preferable to have group represented by a formula (OR-12). do.

[Formula 13]

wherein R ^OX11 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group;

R ^OX12 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group , an acyloxy group or an amino group,

The dashed line indicates the bonding hand.

R ^OX11 is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heterocyclic group, more preferably an alkyl group, an aryl group or a heterocyclic group, and still more preferably an alkyl group. R ^OX12 is preferably an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group or an acyloxy group, more preferably an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. , it is more preferably an alkyl group.

The above-mentioned groups represented by R ^OX11 and R ^OX12 may further have a substituent. As an additional substituent, the group selected from the group of the above-mentioned substituent T is mentioned.

1-18 are preferable, as for carbon number of the alkyl group which ^ROX11 and ^ROX12 represent, 1-15 are more preferable, and 1-8 are still more preferable. The alkyl group may be linear, branched, or cyclic. When carbon number of an alkyl group is 2 or more, the ether bond may be included between carbon atoms. Specific examples of the alkyl group represented by R ^OX11 and R ^OX12 include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, an octadecyl group, and an isopropyl group. , isobutyl group, isopentyl group, sec-butyl group, tert-butyl group, sec-pentyl group, tert-pentyl group, tert-octyl group, neopentyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, A cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, 4-decylcyclohexyl group, etc. are mentioned. Moreover, as a specific example of the alkyl group containing an ether bond between carbon atoms, -CH ₂ -O-CH ₃ , -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -CH ₂ -CH ₂ -CH ₂ - O-CH ₂ -CH ₃ , -(CH ₂ -CH ₂ -O) _n -CH ₃ (wherein n is 1 to 8), -(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (wherein m is 1 to 5), -CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ -, -CH ₂ -CH-(OCH ₃ ) ₂ , and groups shown below.

[Formula 14]

2-18 are preferable, as for carbon number of the alkenyl group which ^ROX11 and ^ROX12 represent, 2-15 are more preferable, 2-8 are still more preferable. The alkenyl group may be linear, branched, or cyclic. Specific examples of the alkenyl group include vinyl group, 1-propenyl group, allyl group, 2-butenyl group, 3-butenyl group, isopropenyl group, isobutenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentene Diary, 4-pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, cyclopentenyl group, cyclohexenyl group, 1,3-butadienyl group, cyclo A hexadienyl group, a cyclopentadienyl group, etc. are mentioned.

1-18 are preferable, as for carbon number of the alkoxy group which ^ROX11 and ^ROX12 represent, 1-15 are more preferable, and 1-8 are still more preferable. The alkoxy group may be linear, branched, or cyclic. When carbon number of an alkoxy group is 2 or more, the ether bond may be included between carbon atoms. Specific examples of the alkoxy group represented by R ^OX11 and R ^OX12 include a methyloxy group, an ethyloxy group, a propyloxy group, a butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, and a de Siloxy group, dodecyloxy group, octadecyloxy group, isopropyloxy group, isobutyloxy group, isopentyloxy group, sec-butyloxy group, tert-butyloxy group, sec-pentyloxy group, tert-pentyloxy group , tert- octyloxy group, neopentyloxy group, cyclopropyloxy group, cyclobutyloxy group, cyclopentyloxy group, cyclohexyloxy group, adamantyloxy group, norbornyloxy group, boronyloxy group, 4-decylcyclohexyl group A siloxy group etc. are mentioned. Moreover, as a specific example of the alkoxy group containing an ether bond between carbon atoms, -O-CH ₂ -O-CH ₃ , -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -O-CH ₂ -CH ₂ -CH ₂ -O-CH ₂ -CH ₃ , -O-(CH ₂ -CH ₂ -O) _n -CH ₃ (wherein n is 1 to 8), -O-(CH ₂ -CH ₂ -CH ₂ -O) _m -CH ₃ (wherein m is 1 to 5), -O-CH ₂ -CH(CH ₃ )-O-CH ₂ -CH ₃ -, -O-CH ₂ -CH -(OCH ₃ ) ₂ and groups shown below are mentioned.

[Formula 15]

6-24 are preferable and, as for carbon number of the aryl group which ^ROX11 and ^ROX12 represent, 6-12 are more preferable. Specific examples of the aryl group include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 9-anthryl group, 2-phenanthryl group, 3-phenanthryl group, 9-phenanthryl group, 1- Pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azulenyl group, 1-acenaphthyl group, 2-fluorenyl group, 9-fluorenyl group, 3-peryleneyl group, o-tolyl group, m -Tolyl group, p-tolyl group, 2,3-xylyl group, 2,5-xylyl group, mesityl group, p-cumenyl group, p-dodecylphenyl group, p-cyclohexylphenyl group, 4-biphenyl group, o- Fluorophenyl group, m-chlorophenyl group, p-bromophenyl group, p-hydroxyphenyl group, m-carboxyphenyl group, o-mercaptophenyl group, p-cyanophenyl group, m-nitrophenyl group, m-azidephenyl group, etc. can be heard

6-24 are preferable and, as for carbon number of the aryloxy group which ^ROX11 and ^ROX12 represent, 6-12 are more preferable. Specific examples of the aryloxy group include a phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 9-anthryloxy group, 9-phenanthryloxy group, 1-pyrenyloxy group, 5-naphthacenyloxy group, 1 -indenyloxy group, 2-azulenyloxy group, 1-acenaphthyloxy group, 9-fluorenyloxy group, etc. are mentioned.

The heterocycle of the heterocyclic group and the heterocyclic oxy group represented by R ^OX11 and R ^OX12 may be monocyclic or may be a condensed ring. The heterocyclic ring is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings. The number of heteroatoms constituting the heterocyclic ring is preferably 1-3. The hetero atom constituting the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom. 3-30 are preferable, as for the number of the carbon atoms which comprise a heterocyclic ring, 3-18 are more preferable, 3-12 are more preferable.

Specific examples of the heterocyclic group include 2-thienyl group, 2-benzothienyl group, naphtho[2,3-b]thienyl group, 3-thianthrenyl group, 2-thianthrenyl group, 2-furyl group , 2-benzofuryl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxacyinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, Pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, 2-indolyl group, 3-indolyl group, 1H-indazolyl group, purinyl group, 4H-quinolizinyl group, isoquinolyl group , quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxalinyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, β- Carbolinyl group, phenanthridinyl group, 2-acridinyl group, periimidinyl group, phenanthroline group, phenazinyl group, phenarazine group, isothiazolyl group, phenothiazineyl group, isoxazolyl group, fu Razanyl group, 3-phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group, pyrazolinyl group, piperidyl group , piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanetolyl group, 4-quinolinyl group, 4-isoquinolyl group, 3-phenothiazinyl group, 2-pe Noxacyin diary, 3-coumarin diary, etc. are mentioned. Specific examples of the heterocyclic oxy group include 2-furanyloxy group, 2-thienyloxy group, 2-indolyloxy group, 3-indolyloxy group, 2-benzofuryloxy group, 2-benzothienyloxy group, 2- A carbazolyloxy group, 3-carbazolyloxy group, 4-carbazolyloxy group, 9-acridinyloxy group, etc. are mentioned.

1-18 are preferable, as for carbon number of the alkylsulfanyl group which ^ROX11 and ^ROX12 represent, 1-15 are more preferable, and 1-8 are still more preferable. The alkylsulfanyl group may be either linear or branched. Specific examples of the alkylsulfanyl group include methylthio group, ethylthio group, propylthio group, butylthio group, pentylthio group, hexylthio group, octylthio group, decylthio group, dodecylthio group, octadecylthio group, etc. can be heard

As for carbon number of the arylsulfanyl group which ^ROX11 and ^ROX12 represent, 6-18 are preferable. Specific examples of the arylsulfanyl group include a phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group, 9-phenanthrylthio group, and the like.

1-20 are preferable, as for carbon number of the alkylsulfinyl group which ^ROX11 and ^ROX12 represent, 1-15 are more preferable, and 1-8 are still more preferable. The alkylsulfinyl group may be either linear or branched. Specific examples of the alkylsulfinyl group include methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexylsulfinyl group, cyclohexylsulfinyl group, octylsulfinyl group, 2-ethylhexylsulfinyl group, decanoyl group A sulfinyl group, a dodecanoyl sulfinyl group, an octadecanoyl sulfinyl group, a cyanomethyl sulfinyl group, a methyloxymethyl sulfinyl group, etc. are mentioned.

The number of carbon atoms of the arylsulfinyl group represented by R ^OX11 and R ^OX12 is preferably 6 to 30. Specific examples of the arylsulfinyl group include phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group, 2-methylphenylsulfinyl group, 2-methyloxyphenylsulfinyl group, 2-butyloxy Phenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group, 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group a diyl group, 4-methyloxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenylsulfinyl group, 4-dimethylaminophenylsulfinyl group, etc. are mentioned.

1-20 are preferable, as for carbon number of the alkylsulfonyl group which ^ROX11 and ^ROX12 represent, 1-15 are more preferable, and 1-8 are still more preferable. The alkylsulfonyl group may be either linear or branched. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group, a cyclohexylsulfonyl group, an octylsulfonyl group, a 2-ethylhexylsulfonyl group, and a decanoyl group. A sulfonyl group, a dodecanoyl sulfonyl group, an octadecanoyl sulfonyl group, a cyanomethyl sulfonyl group, a methyloxymethyl sulfonyl group, etc. are mentioned.

The number of carbon atoms of the arylsulfonyl group represented by R ^OX11 and R ^OX12 is preferably 6 to 30. Specific examples of the arylsulfonyl group include phenylsulfonyl group, 1-naphthylsulfonyl group, 2-naphthylsulfonyl group, 2-chlorophenylsulfonyl group, 2-methylphenylsulfonyl group, 2-methyloxyphenylsulfonyl group, 2-butyloxy Phenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group, 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group Diyl, 4-methyloxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylaminophenylsulfonyl group, etc. are mentioned.

Examples of the acyl group represented by R ^OX11 include a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, and an aryl group having 6 to 18 carbon atoms in a carbonyl group. and a group to which an aryloxy group or a heterocyclic group of is bonded. Specific examples of the acyl group include formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, palmitoyl group, stearoyl group, cyclo Pentylcarbonyl group, cyclohexylcarbonyl group, acryloyl group, methacryloyl group, crotonoyl group, isocrotonoyl group, oleoyl group, cinnamoyl group, benzoyl group, methyloxycarbonyl group, ethyloxycarbonyl group, propyloxy group Carbonyl group, butyloxycarbonyl group, hexyloxycarbonyl group, octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, benzoyl group, toluyl group, 1-naphthoyl group, 2-naphthoyl group, 9-anthrylcarbonyl group, phenyloxycarbonyl group, 4-methylphenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 2-methylsulfanylphenyl group oxycarbonyl group, 1-naphthoyloxycarbonyl group, 2-naphthoyloxycarbonyl group, 9-anthryloxycarbonyl group, 3-furoyl group, 2-thenoyl group, nicotinyl group, isonicotinyl group, etc. are mentioned. have.

As for carbon number of the acyloxy group which ^ROX11 and ^ROX12 represent, 2-20 are preferable. Specific examples of the acyloxy group include acetyloxy group, propanoyloxy group, butanoyloxy group, pentanoyloxy group, trifluoromethylcarbonyloxy group, benzoyloxy group, 1-naphthylcarbonyloxy group, 2-naphthylcarbonyloxy group and the like.

Examples of the amino group represented by R ^OX11 and R ^OX12 include -NH ₂ , an alkylamino group, a dialkylamino group, an arylamino group, a diarylamino group, an alkylarylamino group, a benzylamino group, and a dibenzylamino group. Examples of the alkylamino group include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, a dodecylamino group, an octadecylamino group, an isopropylamino group, an isobutylamino group, Isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cyclo Heptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group, etc. are mentioned. Examples of the dialkylamino group include dimethylamino group, diethylamino group, dipropylamino group, dibutylamino group, dipentylamino group, dihexylamino group, diheptylamino group, dioctylamino group, dinonylamino group, didecylamino group, didodecylamino group, Dioctadecylamino group, diisopropylamino group, diisobutylamino group, diisopentylamino group, methylethylamino group, methylpropylamino group, methylbutylamino group, methylisobutylamino group, cyclopropylamino group, pyrrolidino group, piperidino group, A piperazino group etc. are mentioned. Examples of the arylamino group include anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-bi phenylamino group, 4-biphenylamino group, 1-fluoreneamino group, 2-fluoreneamino group, 2-thiazoleamino group, p-terphenylamino group, etc. are mentioned. Examples of the diarylamino group include diphenylamino group, ditolylamino group, N-phenyl-1-naphthylamino group, N-phenyl-2-naphthylamino group, and the like. Examples of the alkylarylamino group include N-methylanilino group, N-methyl-2-pyridino group, N-ethylanilino group, N-propylanilino group, N-butylanilino group, N-isopropyl, N- A pentyl anilino group, N-ethyl anilino group, N-methyl-1- naphthylamino group, etc. are mentioned.

As for carbon number of the phosphinoyl group represented by R ^OX11 , 2-50 are preferable. Specific examples of the phosphinoyl group include a dimethylphosphinoyl group, a diethylphosphinoyl group, a dipropylphosphinoyl group, a diphenylphosphinoyl group, a dimethoxyphosphinoyl group, a diethoxyphosphinoyl group, and a dibenzoylphosphinoyl group. , a bis(2,4,6-trimethylphenyl)phosphinoyl group, and the like.

As for carbon number of the carbamoyl group represented by R ^OX11 , 2-30 are preferable. Specific examples of the carbamoyl group include N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-butylcarbamoyl group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2-chlorophenylcarbamoyl group, N- 2-isopropoxyphenylcarbamoyl group, N-2-(2-ethylhexyl)phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3- Cyanophenylcarbamoyl group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group and a moyl group, N-methyl-N-phenylcarbamoyl group, N,N-dimethylcarbamoyl group, N,N-dibutylcarbamoyl group, and N,N-diphenylcarbamoyl group.

As for carbon number of the sulfamoyl group represented by R ^OX11 , 0-30 are preferable. Specific examples of the sulfamoyl group include sulfamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, N,N-dialkylsulfamoyl group, N,N-diarylsulfamoyl group, N-alkyl-N - an arylsulfamoyl group, etc. are mentioned. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfamoyl group, N- Octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2-methylphenylsulfamoyl group, N-2- Chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methyl Sulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl group, N-methyl-N-phenylsulfamoyl group, N,N-dimethylsulfamoyl group, N,N-dibutylsulfamoyl group, N,N-diphenylsulfamoyl group, etc. are mentioned.

In formulas (OR-11) and (OR-11), the broken line represents a bond. At the position of the broken line in the formula (OR-11) and the position of the broken line in the formula (OR-12), it bonds with other atomic groups constituting the oxime compound OX to form the oxime compound OX.

The oxime compound OX is preferably at least one selected from the group consisting of the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and is a compound represented by the formula (OX2) from the viewpoint of forming a film having more excellent adhesion. more preferably.

[Formula 16]

In the formula, R ^X1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group;

R ^X2 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group , an acyloxy group or an amino group,

R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;

However, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

In the above formula, R ^X1 is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group or a heterocyclic group, more preferably an alkyl group, an aryl group or a heterocyclic group, and still more preferably an alkyl group. Further, R ^X2 is preferably an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group or an acyloxy group, more preferably an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. , it is more preferably an alkyl group.

R ^X1 in the above formula has the same meaning as R ^OX11 in the above formulas (OR-11) and (OR-12), and the preferable range is also the same.

R ^X2 in the above formula has the same meaning as R ^OX12 in the above formulas (OR-11) and (OR-12), and the preferable range is also the same.

R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent.

Examples of the substituent represented by R ^X3 to R ^X9 include a group selected from the group of the substituent T described above, a group represented by the formula (OR-11), and a group represented by the formula (OR-12).

R ^X3 to R ^X5 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkyl It is preferably a sulfanyl group, an arylsulfanyl group, an acyl group, or an amino group, more preferably a hydrogen atom, a halogen atom, a nitro group, an alkyl group, an aryl group or a heterocyclic group, a hydrogen atom, a nitro group, an alkyl group or It is more preferable that it is an aryl group, and it is especially preferable that it is a hydrogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, acyl group and amino group include the groups described as these groups represented by R ^OX11 described above. . The alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, acyl group and amino group may further have a substituent. As an additional substituent, the group selected from the group of the above-mentioned substituent T is mentioned.

R ^X6 to R ^X10 are each independently a hydrogen atom, a halogen atom, a cyano group, an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an aryl A sulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an amino group, a group represented by the formula (OR-11) or a group represented by the formula (OR-12) is preferable, and a hydrogen atom, It is more preferably a rosen atom, a cyano group, an alkyl group, an aryl group, a heterocyclic group or an amino group, more preferably a hydrogen atom, a cyano group, an alkyl group or an aryl group, still more preferably a hydrogen atom, an alkyl group or an aryl group , a hydrogen atom or an alkyl group is still more preferable, and a hydrogen atom is particularly preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. An alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and an amino group are as described above. Examples of these groups represented by one R ^OX11 include the groups described. Alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group and amino group are substituents may have more As an additional substituent, the group selected from the group of the above-mentioned substituent T is mentioned.

Examples of the substituent represented by R ^X10 to R ^X14 include a group selected from the group of the substituent T described above and the electron withdrawing group described above. However, at least one of R ^X10 to R ^X14 is an electron withdrawing group.

The substituents represented by R ^X10 to R ^X14 include a nitro group, a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group, and an aryl group. It is preferable that they are a sulfanyl group, an acyl group, and an amino group. Examples of the alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkenyl group, alkylsulfanyl group, arylsulfanyl group, acyl group and amino group include the groups described as these groups represented by R ^OX11 described above. . The alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkenyl group, alkylsulfanyl group, arylsulfanyl group, acyl group and amino group may further have a substituent. As an additional substituent, the group selected from the group of the above-mentioned substituent T is mentioned.

Examples of the electron withdrawing group represented by R ^X10 to R ^X14 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group. An actual group and a nitro group are preferable, and since it is easy to form the film|membrane which is more excellent in light resistance, it is more preferable that it is an acyl group, and it is more preferable that it is a benzoyl group. The benzoyl group may have a substituent. Examples of the substituent include a group selected from the group of the above-described substituent T, a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, and a heterocyclic group. It is preferably an oxy group, an alkenyl group, an alkylsulfanyl group, an arylsulfanyl group, an acyl group or an amino group, which is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group or an amino group. more preferably, an alkoxy group, an alkylsulfanyl group, or an amino group. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkenyl group, alkylsulfanyl group, arylsulfanyl group, acyl group and amino group include the groups described as these groups represented by R ^OX11 described above. .

In the above formula, it is preferable that R ^X12 is an electron withdrawing group and R ^X10 , R ^X11 , R ^X13 , and R ^X14 are hydrogen atoms.

As a specific example of the oxime compound OX, the compound of the following structure, and the compound of Paragraph No. 0083 - 0105 of Unexamined-Japanese-Patent No. 4600600 are mentioned.

[Formula 17]

[Formula 18]

[Formula 19]

The photoinitiator contained in the coloring composition of this invention may further contain other photoinitiators (henceforth another photoinitiator) other than the oxime compound OX mentioned above.

Examples of other photopolymerization initiators 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, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, and the like, trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compound, acylphosphine compound, phosphine oxide compound, metallocene compound, oxime compound, triarylimidazole dimer, onium compound, benzothiazole compound, benzophenone compound, acetophenone compound, cyclopentadi It is preferably an ene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, and is selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound. It is more preferable that it is a compound, and it is more preferable that it is an oxime compound or (alpha)-amino ketone compound from the reason of high initiator efficiency. Moreover, as another 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, These content is integrated in this specification.

Examples of commercially available α-hydroxyketone 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). can As a commercial item of α-aminoketone compound, 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. have. 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 an oxime compound used as another photoinitiator, 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), J. C. S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232), The compound described in Unexamined-Japanese-Patent No. 2000-066385, the compound described in Unexamined-Japanese-Patent No. 2004-534797, the compound described in Unexamined-Japanese-Patent No. 2006-342166, the compound of Unexamined-Japanese-Patent No. 2017-019766, Japanese Patent The compound described in Publication No. 6065596, 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, International Publication No. 2017/ Paragraph Nos. 0025 to 0038 of 164127, the compound of International Publication No. 2013/167515, etc. are mentioned. Examples of commercially available oxime compounds used as other photopolymerization initiators include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04 (above, manufactured by BASF), TR-PBG-304 (Changzhou Tronly New Electronic Materials) Co., Ltd.) can be mentioned.

As an oxime compound used as another 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 an oxime compound used as another 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 No. 2013/083505 is mentioned.

As an oxime compound used as another photoinitiator, the oxime compound which has a fluorine atom can also be used. 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, 36-40 of Unexamined-Japanese-Patent No. 2014-500852, and the compound of Unexamined-Japanese-Patent No. 2013-164471. (C-3) etc. are mentioned.

As an oxime compound used as another 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 an oxime compound used as another photoinitiator, the oxime compound which the substituent which has a 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.

As for content of the photoinitiator in the total solid of a coloring composition, 0.1-30 mass % is preferable. 0.5 mass % or more is preferable, as for a minimum, 1 mass % or more is more preferable, and it is still more preferable that it is 1.5 mass % or more. 20 mass % or less is preferable and, as for an upper limit, 15 mass % or less is more preferable.

As for content of the oxime compound OX in the total solid of a coloring composition, 0.1-30 mass % is preferable. 0.5 mass % or more is preferable and, as for a minimum, 1 mass % or more is more preferable. 20 mass % or less is preferable and, as for an upper limit, 15 mass % or less is more preferable.

It is preferable that content of the oxime compound OX in the total mass of the photoinitiator contained in a coloring composition is 20-100 mass %, It is more preferable that it is 35-100 mass %, It is more preferable that it is 40-100 mass % And, it is still more preferable that it is 50-100 mass %, and it is especially preferable that it is 60-100 mass %.

As one preferable aspect of the photoinitiator contained in a coloring composition, the aspect whose photoinitiator is substantially only oxime compound OX is mentioned. According to this aspect, interaction with pigment DPP is strong, and crystallization by heating can be suppressed more effectively. In addition, in this specification, when a photoinitiator is substantially only oxime compound OX, it means that content of oxime compound OX in the total mass of a photoinitiator is 99 mass % or more, It is preferable that it is 99.9 mass % or more, and photopolymerization It is more preferable that the initiator is only the oxime compound OX.

As another preferable aspect of the photoinitiator contained in a coloring composition, the aspect in which a photoinitiator contains oxime compound OX and other photoinitiators other than oxime compound OX is mentioned. According to this aspect, it is easy to harden a film|membrane more uniformly, and sclerosis|hardenability of the whole film|membrane can be improved more. This aspect WHEREIN: As another photoinitiator, it is preferable that it is at least 1 sort(s) chosen from an oxime compound and (alpha)-amino ketone compound from the reason that initiator efficiency is high. Moreover, it is preferable that content of another photoinitiator is 10-200 mass parts with respect to 100 mass parts of oxime compound OX, It is more preferable that it is 20-100 mass parts, It is more preferable that it is 30-80 mass parts.

<<Polymerizable compound>>

The coloring composition of this invention contains a polymeric compound. As the polymerizable compound, a known compound that can be crosslinked by radical, acid or heat can be used. In this invention, it is preferable that a polymeric compound is a compound which has an ethylenically unsaturated bond containing group, for example. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, vinylphenyl group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acrylamide group, etc. These are mentioned, It is preferable that it is a (meth)acryloyloxy 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. As for a minimum, 150 or more are more preferable, and 250 or more are still more preferable.

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 - 0108 of Unexamined-Japanese-Patent No. 2009-288705, Paragraph 0227 of Unexamined-Japanese-Patent No. 2013-029760, Paragraph Nos. 0254 - 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 Unexamined Patent Application Publication No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048367, Japanese Patent Publication No. 6057891, and the compound described in Japanese Patent Publication No. 6031807 , the contents of which are incorporated herein by reference.

Examples of the polymerizable compound include dipentaerythritol tri(meth)acrylate (KAYARAD D-330 as a commercially available product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (KAYARAD D-320 as a commercially available product; Nippon Kayaku Co., Ltd. product), dipentaerythritol penta (meth) acrylate (KAYARAD D-310 as a commercial product; Nippon Kayaku Co., Ltd. product), dipentaerythritol hexa(meth) acrylate (KAYARAD as a commercial product) DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and these (meth)acryloyl groups are ethylene glycol and/or propylene glycol residues Compounds having a structure bonded via Moreover, as a polymeric compound, diglycerol EO (ethylene oxide) modified (meth)acrylate (as a commercial item, M-460; Toagosei make), 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) Kosei Co., Ltd.), NK Oligo UA-7200 (Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH -600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (above, manufactured by Daisei Fine Chemicals), light acrylate POB -A0 (manufactured by Kyoeisha Chemical Co., Ltd.) or the like can also be used.

Moreover, to a polymeric compound, trimethylol propane tri(meth)acrylate, trimethylol propane propylene oxide modified|denatured tri(meth)acrylate, trimethylol propane ethylene oxide modified|denatured tri(meth)acrylate, iso Trifunctional (meth)acrylate compounds, such as cyanuric-acid ethylene oxide modified|denatured tri(meth)acrylate and pentaerythritol tri(meth)acrylate, can also be used. 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.

Moreover, the compound which has an acidic radical can also be used for a polymeric compound. By using the polymeric compound which has an acidic radical, the polymeric compound 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 carboxyl group, a sulfo group, a phosphoric acid group, etc. are mentioned, A carboxyl group is preferable. As a commercial item of the polymeric compound which has an acidic radical, Aronix 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, solubility with respect to a developing solution is favorable, and if it is 40 mgKOH/g or less, it is advantageous on manufacture and handling.

Moreover, the compound which has a caprolactone structure can also be used for a polymeric compound. As a commercial item of the polymeric compound which has a caprolactone structure, KAYARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120 (above, Nippon Kayaku Co., Ltd. product) etc. are mentioned.

Moreover, the polymeric compound which has an alkyleneoxy group can also be used for a polymeric compound. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an ethyleneoxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an ethyleneoxy group, and 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, SR-494 which is a tetrafunctional (meth)acrylate which has four ethyleneoxy groups made by Sartomer, for example, isobutyleneoxy group manufactured by Nippon Kayaku Co., Ltd. KAYARAD TPA-330 which is a trifunctional (meth)acrylate which has three, etc. are mentioned.

Moreover, as a polymeric compound, the polymeric compound which has 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.

It is preferable that content of the polymeric compound in the total solid of a coloring composition is 0.1-50 mass %. As for a minimum, 0.5 mass % or more is more preferable, and 1 mass % or more is still more preferable. 40 mass % or less is more preferable, and, as for an upper limit, 30 mass % or less is still more preferable. Single 1 type may be sufficient as a polymeric compound, and 2 or more types may be used together. When using 2 or more types together, it is preferable that those sum total becomes the said range.

<<Resin>>

The coloring composition of this invention contains resin. Resin is mix|blended for the use which disperse|distributes a pigment in a coloring composition, and the use of a binder, for example. In addition, resin mainly used in order to disperse|distribute a pigment 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.

As for the weight average molecular weight (Mw) of 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 and, as for a minimum, 5000 or more are more preferable.

As the resin, (meth)acrylic resin, epoxy resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene Etherphosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, etc. are mentioned. From these resins, 1 type may be used individually, and 2 or more types may be mixed and used for them.

It is also preferable that the coloring composition of this invention contains resin which has an acidic radical. As an acidic radical, a carboxyl group, a phosphoric acid group, a sulfo group, phenolic hydroxyl group etc. are mentioned, for example. Only 1 type may be sufficient as these acidic radicals, and 2 or more types may be sufficient as them. Resin which has an acidic radical can also be used as a dispersing agent. When the coloring composition of this invention contains resin which has an acidic radical, a desired pattern can be formed by alkali image development. As for the acid value of resin which has an acidic radical, 30-500 mgKOH/g is preferable. 50 mgKOH/g or more is preferable and, as for a minimum, 70 mgKOH/g or more is more preferable. The upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

It is also preferable that the coloring composition of this invention contains resin which has a basic group. The resin having a basic group is preferably a resin including a repeating unit having a basic group in the side chain, and more preferably a copolymer having a repeating unit having a basic group in the side chain and a repeating unit not containing a basic group, and a basic group in the side chain It is more preferable that it is a block copolymer which has the repeating unit which has and the repeating unit which does not contain a basic group. Resin which has a basic group can also be used as a dispersing agent. As for the amine titer of resin which has a basic group, 5-300 mgKOH/g is preferable. 10 mgKOH/g or more is preferable and, as for a minimum, 20 mgKOH/g or more is more preferable. 200 mgKOH/g or less is preferable and, as for an upper limit, 100 mgKOH/g or less is more preferable. As a basic group contained in resin which has a basic group, group represented by a formula (a-1), group represented by a formula (a-2), etc. are mentioned.

[Formula 20]

In formula (a-1), R ^a1 and R ^a2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and R ^a1 and R ^a2 may be bonded to each other to form a ring;

In the formula (a-2), R ^a11 represents a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acyl group or an oxy radical, and R ^a12 to R ^a19 are each independently, A hydrogen atom, an alkyl group, or an aryl group is represented.

1-30 are preferable, as for carbon number of the alkyl group represented by R ^a1 , R ^a2 , R ^a11 -R ^a19 , 1-15 are more preferable, 1-8 are still more preferable, 1-5 are especially preferable. Any of linear, branched, and cyclic|annular chain may be sufficient as an alkyl group, A linear or branched is preferable, and a linear is more preferable. The alkyl group may have a substituent. As a substituent, the group chosen from the group of the substituent T mentioned above is mentioned.

6-30 are preferable, as for carbon number of the aryl group represented by R ^a1 , R ^a2 , R ^a11 -R ^a19 , 6-20 are more preferable, and 6-12 are still more preferable. The aryl group may have a substituent. As a substituent, the group chosen from the group of the substituent T mentioned above is mentioned.

1-30 are preferable, as for carbon number of the alkoxy group which R ^a11 represents, 1-15 are more preferable, 1-8 are still more preferable, 1-5 are especially preferable. The alkoxy group may have a substituent. As a substituent, the group chosen from the group of the substituent T mentioned above is mentioned.

6-30 are preferable, as for carbon number of the aryloxy group which R ^a11 represents, 6-20 are more preferable, 6-12 are still more preferable. The aryloxy group may have a substituent. As a substituent, the group chosen from the group of the substituent T mentioned above is mentioned.

2-30 are preferable, as for carbon number of the acyl group which R ^a11 represents, 2-20 are more preferable, 2-12 are still more preferable. The acyl group may have a substituent. As a substituent, the group chosen from the group of the substituent T mentioned above is mentioned.

Commercially available resins having a basic group include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 ( Above, made by Big Chemie Japan), SOLSPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (above, the Nippon Lubrizol company make), Efka PX 4300, 4330, 4046, 4060, 4080 (above, the BASF company make) etc. are mentioned. In addition, the resin having a basic group is the block copolymer (B) described in Paragraph Nos. 0063 to 0112 of Japanese Patent Application Laid-Open No. 2014-219665, and the block copolymer A1 described in Paragraph Nos. 0046 to 0076 of Unexamined Patent Publication No. 2018-156021. may be used, the contents of which are incorporated herein by reference.

It is also preferable that the coloring composition of this invention contains resin which has an acidic radical, and resin which has a basic group, respectively. According to this aspect, the storage stability of a coloring composition can be improved more. When the resin having an acid group and the resin having a basic group are used together, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, with respect to 100 parts by mass of the resin having an acid group, , more preferably 50 to 200 parts by mass.

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

[Formula 21]

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 22]

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.

As resin, it is also preferable to use resin containing the repeating unit which has a polymeric group.

As resin, it is also preferable to use resin containing the repeating unit derived from the compound represented by Formula (X).

[Formula 23]

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. n represents the integer of 0-15, it is preferable that it 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 (X), 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.

As resin, it is also preferable to use resin which has a repeating unit derived from the (meth)acrylate which has an alicyclic ring. It is preferable that it is (meth)acrylate which has alicyclic crosslinking as (meth)acrylate which has an alicyclic ring. As a specific example, the (meth)acrylate which has a dicyclopentanyl group, the (meth)acrylate which has an adamantyl group, etc. are mentioned.

It is also preferable that resin (henceforth resin Ac) which has an aromatic carboxyl group is included as resin. According to this aspect, the film|membrane with which precipitation of the foreign material in after heat processing was suppressed more can be formed. Resin Ac WHEREIN: The aromatic carboxyl group may be contained in the main chain of a repeating unit, and may be contained in the side chain of a repeating unit. It is preferable that the aromatic carboxyl group is contained in the main chain of a repeating unit. In addition, in this specification, an aromatic carboxyl group is group of the structure which 1 or more carboxyl groups couple|bonded with the aromatic ring. Aromatic carboxyl group WHEREIN: It is preferable that it is 1-4, and, as for the number of the carboxyl groups couple|bonded with the aromatic ring, it is more preferable that it is 1-2.

The resin Ac is preferably a resin containing at least one repeating unit selected from the repeating unit represented by the formula (Ac-1) and the repeating unit represented by the formula (Ac-2), and is represented by the formula (Ac-2) It is more preferable that it is resin containing the repeating unit which appears. When resin which has an aromatic carboxyl group is resin which has a repeating unit represented by Formula (Ac-2), this resin is used preferably as a dispersing agent.

[Formula 24]

In formula (Ac-1), Ar ¹ represents a group containing an aromatic carboxyl group, L ¹ represents -COO- or -CONH-, and L ² represents a divalent linking group.

In formula (Ac-2), Ar ¹⁰ represents a group containing an aromatic carboxyl group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, and P ¹⁰ represents a polymer chain.

Examples of the group containing the aromatic carboxyl group represented by Ar ¹ in the formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like. As aromatic tricarboxylic acid anhydride and aromatic tetracarboxylic acid anhydride, the compound of the following structure is mentioned.

[Formula 25]

In the formula, Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, a group represented by the formula (Q-1) Or group represented by Formula (Q-2) is shown.

[Formula 26]

Specific examples of the group containing the aromatic carboxyl group represented by Ar ¹ include a group represented by the formula (Ar-11), a group represented by the formula (Ar-12), and a group represented by the formula (Ar-13).

[Formula 27]

In formula (Ar-11), n1 represents the integer of 1-4, it is preferable that it is 1 or 2, and it is more preferable that it is 2.

In formula (Ar-12), n2 represents the integer of 1-8, it is preferable that it is an integer of 1-4, It is more preferable that it is 1 or 2, It is more preferable that it is 2.

In formula (Ar-13), n3 and n4 each independently represent the integer of 0-4, It is preferable that it is an integer of 0-2, It is more preferable that it is 1 or 2, It is more preferable that it is 1. However, at least one of n3 and n4 is an integer of 1 or more.

In formula (Ar-13), Q ¹ is a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C(CF ₃ ) ₂ -, the formula (Q- Group represented by 1) or group represented by said Formula (Q-2) is shown.

In formulas (Ar-11) to (Ar-13), *1 represents a bonding position with L ¹ .

In formula (Ac-1), L ¹ represents -COO- or -CONH-, and it is preferable to represent -COO-.

Examples of the divalent linking group represented by L ² in the formula (Ac-1) include an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and 2 of these The group which combined more than types is mentioned. 1-30 are preferable, as for carbon number of an alkylene group, 1-20 are more preferable, and 1-15 are still more preferable. The alkylene group may be linear, branched, or cyclic. 6-30 are preferable, as for carbon number of an arylene group, 6-20 are more preferable, and 6-10 are still more preferable. The alkylene group and the arylene group may have a substituent. A hydroxyl group etc. are mentioned as a substituent. It is preferable that the divalent coupling group represented by L ² is a group represented by -L ^2a -O-. L ^2a is an alkylene group; arylene group; a group combining an alkylene group and an arylene group; The group etc. which combined at least 1 type selected from an alkylene group and an arylene group, and at least 1 type selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S- are mentioned. and it is preferably an alkylene group. 1-30 are preferable, as for carbon number of an alkylene group, 1-20 are more preferable, and 1-15 are still more preferable. The alkylene group may be linear, branched, or cyclic. The alkylene group and the arylene group may have a substituent. A hydroxyl group etc. are mentioned as a substituent.

As group containing the aromatic carboxyl group which Ar< ¹⁰ > represents in Formula (Ac-2), it has the same meaning as Ar< ¹ > of Formula (Ac-1), and a preferable range is also the same.

In formula (Ac-2), L ¹¹ represents -COO- or -CONH-, and preferably represents -COO-.

Examples of the trivalent linking group represented by L ¹² in the formula (Ac-2) include a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and two or more thereof. A group combining the above may be mentioned. Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. 1-30 are preferable, as for carbon number of an aliphatic hydrocarbon group, 1-20 are more preferable, and 1-15 are still more preferable. The aliphatic hydrocarbon group may be linear, branched, or cyclic. 6-30 are preferable, as for carbon number of an aromatic hydrocarbon group, 6-20 are more preferable, and 6-10 are still more preferable. The hydrocarbon group may have a substituent. A hydroxyl group etc. are mentioned as a substituent. It is preferable that it is group represented by Formula ( ^L12-1 ), and, as for the trivalent coupling group represented by L12, it is more preferable that it is group represented by Formula (L12-2).

[Formula 28]

In formula (L12-1), L ^12b represents a trivalent linking group, X ¹ represents S, *1 represents a bonding position with L ¹¹ in formula (Ac-2), *2 represents a formula (Ac-) 2) shows the binding position with P ¹⁰ . Examples of the trivalent linking group represented by L ^12b include a hydrocarbon group; a hydrocarbon group and a group obtained by combining at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-, etc. are mentioned, A hydrocarbon group or a hydrocarbon group It is preferable that it is the group which combined -O-.

In formula (L12-2), L ^12c represents a trivalent linking group, X ¹ represents S, *1 represents a bonding position with L ¹¹ in formula (Ac-2), *2 represents a formula (Ac-) 2) shows the binding position with P ¹⁰ . Examples of the trivalent linking group represented by L ^12c include a hydrocarbon group; The group etc. which combined a hydrocarbon group and at least 1 sort(s) chosen from -O-, -CO-, -COO-, -OCO-, -NH-, and -S- are mentioned, It is preferable that it is a hydrocarbon group.

In the formula (Ac-2), P ¹⁰ represents a polymer chain. The polymer chain represented by P ¹⁰ preferably has at least one repeating unit selected from a poly(meth)acryl repeating unit, a polyether repeating unit, a polyester repeating unit, and a polyol repeating unit. As for the weight ^average molecular weight of polymer chain P10, 500-20000 are preferable. The lower limit is preferably 1000 or more. 10000 or less are preferable, as for an upper limit, 5000 or less are more preferable, and 3000 or less are still more preferable. The dispersibility of the pigment in a composition is favorable as the weight ^average molecular weight of P10 is the said range.

The polymer chain represented by P ¹⁰ may contain a crosslinkable group. Examples of the crosslinkable group include an ethylenically unsaturated bond-containing group, a cyclic ether group, and a block isocyanate group, and an ethylenically unsaturated bond-containing group is preferable. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a vinylphenyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, and a (meth)acryloylamide group, ( A meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group are preferable, and a (meth)acryloyloxy group is more preferable. As a cyclic ether group, an epoxy group, oxetanyl group, etc. are mentioned. In addition, the blocked isocyanate group in this invention is a group which can produce|generate an isocyanate group by heat, For example, the group which made the blocking agent and an isocyanate group react, and protected the isocyanate group. It can be exemplified preferably. Examples of the blocking agent 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 imide compound. About a blocking agent, Paragraph No. 0115 of Unexamined-Japanese-Patent No. 2017-067930 - the compound of 0117 are mentioned, This content is integrated in this specification. Moreover, it is preferable that a block isocyanate group is group which can produce|generate an isocyanate group by 90-260 degreeC heat|fever.

In the formula (Ac-2), the polymer chain represented by P ¹⁰ is preferably a polymer chain containing repeating units represented by the following formulas (P-1) to (P-5), and (P-5) It is more preferable that it is a polymer chain containing the repeating unit which appears.

In the formula (Ac-2), the polymer chain represented by P ¹⁰ is preferably a polymer chain containing repeating units represented by the following formulas (P-1) to (P-5), and (P-5) It is more preferable that it is a polymer chain containing the repeating unit which appears.

[Formula 29]

In the above formula, R ^P1 and R ^P2 each represent an alkylene group. As the alkylene group represented by R ^P1 and R ^P2 , a linear or branched alkylene group having 1 to 20 carbon atoms is preferable, a linear or branched alkylene group having 2 to 16 carbon atoms is more preferable, and a straight chain or branched alkylene group having 2 to 16 carbon atoms is more preferable. A chain or branched alkylene group is more preferable.

In the above formula, R ^P3 represents a hydrogen atom or a methyl group.

In the formula, L ^P1 represents a single bond or an arylene group, and L ^P2 represents a single bond or a divalent linking group. It is preferable that L ^P1 is a single bond. Examples of the divalent linking group represented by L ^P2 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-, -NHCO-, -CONH-, and the group formed by combining two or more of these are mentioned.

R ^P4 represents a hydrogen atom or a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, and an ethylenically unsaturated group. A bond-containing group, a cyclic ether group, a blocked isocyanate group, etc. are mentioned.

Further, the polymer chain represented by P ¹⁰ is more preferably a polymer chain having a repeating unit containing an ethylenically unsaturated bond-containing group in a side chain. Moreover, the ratio of the repeating unit containing an ethylenically unsaturated bond-containing group in a side chain in all the repeating units constituting P ¹⁰ is preferably 5 mass % or more, more preferably 10 mass % or more, and 20 mass % More preferably. The upper limit can be 100 mass %, it is preferable that it is 90 mass % or less, and it is more preferable that it is 60 mass % or less.

Moreover, it is also preferable that the polymer chain represented by P< ¹⁰ > has a repeating unit containing an acidic radical. As an acidic radical, a carboxyl group, a phosphoric acid group, a sulfo group, phenolic hydroxyl group, etc. are mentioned. According to this aspect, the dispersibility of coloring agents, such as a pigment in a coloring composition, can be improved more. Furthermore, developability can also be improved more and generation|occurrence|production of the image development residue can be suppressed more. It is preferable that it is 1-30 mass %, as for the ratio of the repeating unit containing an acidic radical, it is more preferable that it is 2-20 mass %, It is more preferable that it is 3-10 mass %.

It is preferable that the weight average molecular weights of resin Ac are 3000-35000. It is preferable that it is 25000 or less, and, as for an upper limit, it is more preferable that it is 20000 or less, It is more preferable that it is 15000 or less. It is preferable that a minimum is 4000 or more, It is more preferable that it is 6000 or more, It is more preferable that it is 7000 or more.

As for the acid value of resin Ac, 5-200 mgKOH/g is preferable. It is preferable that it is 150 mgKOH/g or less, and, as for an upper limit, it is more preferable that it is 100 mgKOH/g or less, It is more preferable that it is 80 mgKOH/g or less. The lower limit is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and still more preferably 20 mgKOH/g or more.

It is preferable that resin contains resin as 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. Moreover, a basic dispersing agent (basic resin) shows resin with more quantity of a basic group than the quantity of an acidic radical.

As an acidic dispersing agent (acidic resin), when the total amount of the quantity of an acidic radical and the quantity of a basic group is 100 mol%, resin whose quantity of an acidic radical is 70 mol% or more is preferable. As for the acidic radical which an acidic dispersing agent (acidic resin) has, a carboxyl group is preferable. As for the acid value of an acidic dispersing agent (acidic resin), 5-200 mgKOH/g is preferable. It is preferable that it is 150 mgKOH/g or less, and, as for an upper limit, it is more preferable that it is 100 mgKOH/g or less, It is more preferable that it is 80 mgKOH/g or less. The lower limit is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and still more preferably 20 mgKOH/g or more.

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 is 100 mol%, resin whose quantity of a basic group is 60 mol% or more is preferable. As for the basic group which a basic dispersing agent has, an amino group is preferable. As for the amine titer of a basic dispersing agent (basic resin), 5-100 mgKOH/g is preferable. It is preferable that it is 80 mgKOH/g or less, and, as for an upper limit, it is more preferable that it is 60 mgKOH/g or less, It is more preferable that it is 45 mgKOH/g or less. The lower limit is preferably 10 mgKOH/g or more, more preferably 15 mgKOH/g or more, and still more preferably 20 mgKOH/g or 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 resin (resin Ac) which has an aromatic carboxyl group. As resin which has an aromatic carboxyl group, the thing mentioned above is mentioned.

It is also preferable that resin used as a dispersing agent is a polyimine type dispersing agent containing 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 of 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 the resin used as a dispersing agent is resin of the structure in which the several polymer chain couple|bonded with the core part. Examples of such resin include dendrimers (including star-shaped polymers). Moreover, as a specific example of a dendrimer, 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. . Moreover, as a dispersing agent, resin of Unexamined-Japanese-Patent No. 2018-087939 can also be used.

A dispersing agent can also be obtained as a commercial item, As such a specific example, the DISPERBYK series made by Bikchemi Japan, the SOLSPERSE series made by Nippon Lubrizol, the Efka series made by BASF, Ajiper series made by Ajinomoto Fine Techno Co., Ltd. and the like. 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, the block copolymers (EB-1) - (EB-9) of Paragraph No. 0219 - 0221 of Unexamined-Japanese-Patent No. 6432077 can also be used for resin used as a dispersing agent.

It is preferable that content of resin in the total solid of a coloring composition is 1-80 mass %. The lower limit is preferably 5 mass % or more, more preferably 10 mass % or more, still more preferably 15 mass % or more, and particularly preferably 20 mass % or more. 70 mass % or less is preferable, as for an upper limit, 60 mass % or less is more preferable, 50 mass % or less is still more preferable, and 40 mass % or less is especially preferable. The coloring composition of this invention may contain 1 type of resin, and may contain it 2 or more types. When 2 or more types of resin are included, it is preferable that those total amounts become the said range.

<<Pigment Derivatives>>

It is preferable that the coloring composition of this invention contains a pigment derivative. As a pigment derivative, the compound which has the structure in which the acidic radical or the basic group couple|bonded with the pigment skeleton is mentioned. As the dye skeleton constituting the pigment derivative, quinoline dye skeleton, benzimidazolone dye skeleton, benzisoindole dye skeleton, benzothiazole dye skeleton, iminium dye skeleton, squarylium dye skeleton, croconium dye skeleton, oxonol Dye skeleton, pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, azo dye skeleton, azomethine dye skeleton, phthalocyanine dye skeleton, naphthalocyanine dye skeleton, anthraquinone dye skeleton, dianthraquinone dye Skeleton, quinacridone pigment skeleton, dioxazine pigment skeleton, perinone pigment skeleton, perylene pigment skeleton, thiazine indigo pigment skeleton, thioindigo pigment skeleton, isoindoline pigment skeleton, isoindolinone pigment skeleton, quinope Talon dye skeleton, iminium dye skeleton, dithiol dye skeleton, triarylmethane dye skeleton, pyromethene dye skeleton, etc. are mentioned, Diketopyrrolopyrrole dye skeleton, benzisoindole dye skeleton, anthraquinone dye skeleton , dianthraquinone dye skeleton, thiazine indigo dye skeleton, azo dye skeleton, quinophthalone dye skeleton, and quinacridone dye skeleton, more preferably diketopyrrolopyrrole dye skeleton. That is, the pigment derivative is preferably a diketopyrrolopyrrole compound. According to this aspect, the film|membrane with a higher red color value can be formed, and it is used more preferably as a coloring composition for red pixels. Examples of the acid group include a sulfo group, a carboxyl group, a phosphoric acid group, and salts thereof. Examples of the atom or group constituting the salt include alkali metal ions (Li ⁺ , Na ⁺ , K ⁺ , etc.), alkaline earth metal ions (Ca ²⁺ , Mg ²⁺ , etc.), ammonium ions, imidazolium ions, and pyridinium ions. , phosphonium ions, and the like. Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, an ammonium group salt, and a phthalimidemethyl group. A hydroxide ion, a halogen ion, a carboxylate ion, a sulfonic acid ion, a phenoxide ion, etc. are mentioned as an atom or atomic group which comprises a salt.

As the pigment derivative, a pigment derivative excellent in visible transparency (hereinafter also referred to as a transparent pigment derivative) may be contained. The maximum value (εmax) of the molar extinction coefficient in the wavelength region of 400 to 700 nm of the transparent pigment derivative is preferably 3000L·mol ^-1 ·cm ^-1 or less, and more preferably 1000L·mol ^-1 ·cm ^-1 or less, , 100L·mol ^-1 ·cm ^-1 or less is more preferable. The lower limit of εmax may be, for example, 1L·mol ^-1 ·cm ^-1 or more, and 10L·mol ^-1 ·cm ^-1 or more.

As a specific example of a pigment derivative, the compound described in the Example mentioned later, 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, Japanese Unexamined Patent Publication No. Hei03-026767, Japanese Unexamined Patent Publication No. Hei03-153780, Japanese Unexamined Patent Publication No. Hei 03-045662, Japanese Unexamined Patent Publication No. Hei04-285669, Japanese Unexamined Patent Publication No. Hei06 -145546, Japanese Unexamined Patent Publication No. Hei 06-212088, Japanese Unexamined Patent Publication No. Hei 06-240158, Japanese Unexamined Patent Publication No. Hei 10-030063, Japanese Unexamined Patent Publication No. Hei 10-195326, International Publication No. 2011/ Paragraph Nos. 0086 to 0098 of 024896, Paragraph Nos. 0063 to 0094 of International Publication No. 2012/102399, Paragraph Nos. 0082 of International Publication No. 2017/038252, Paragraph Nos. 0171 of Japanese Patent Application Laid-Open No. 2015-151530, Japanese Patent Application Laid-Open No. Paragraph Nos. 0162 to 0183 of 2011-252065, Japanese Patent Application Laid-Open No. 2003-081972, Japanese Patent Publication 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, the compound of Unexamined-Japanese-Patent No. 2014-035351, and the compound of Unexamined-Japanese-Patent No. 2008-081565 are mentioned.

When it contains a pigment derivative, 1-30 mass parts is preferable with respect to 100 mass parts of pigments, as for content of a pigment derivative, 1-20 mass parts is more preferable, 2-10 mass parts is still more preferable, 3-8 mass parts Especially preferred. 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 are 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. There will be no restriction|limiting in particular in particular basically, if the kind of solvent satisfy|fills the solubility of each component and the applicability|paintability of a coloring composition. 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 No. 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-dimethylpropaneamide, 3-butoxy-N,N-dimethylpropaneamide, etc. are mentioned. However, there are cases where it is preferable to reduce the aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as the organic solvent for reasons such as environmental reasons (for example, 50 mass ppm based on the total amount of the organic solvent) (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less).

In this invention, it is preferable to use the organic solvent with little metal content, and it is preferable that the metal content of an organic solvent is 10 mass ppb (parts per billion) or less, for example. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic 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 an organic 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 organic 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.

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 10-95 mass %, It is more preferable that it is 20-90 mass %, It is more preferable that it is 30-90 mass %.

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. These 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 a coloring composition, 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 reducing by heating or depressurizing the inside of a system, making it more than the boiling point of an environmentally regulated substance, and distilling off an environmentally regulated substance in a system is mentioned. Moreover, when distilling off a small amount of an environmental control substance, in order to raise efficiency, it is also useful to make it azeotrope with the solvent which has a boiling point equivalent to the said solvent. 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 may distill under reduced pressure. These distillation removal methods can be performed at any stage, such as 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. It is possible.

<<Compound having a cyclic ether group>>

The coloring composition of this invention can contain the compound which has a cyclic ether group. As a cyclic ether group, an epoxy group, oxetanyl group, etc. are mentioned. It is preferable that the compound which has a cyclic ether group is a compound (henceforth an epoxy compound) which has an epoxy group. As an epoxy compound, Paragraph Nos. 0034 - 0036 of Unexamined-Japanese-Patent No. 2013-011869, Paragraph Nos. 0147-0156 of Unexamined-Japanese-Patent No. 2014-043556, Paragraph Nos. 0085 - 0092 of Unexamined-Japanese-Patent No. 2014-089408, Japan The compound described in Unexamined Patent Publication No. 2017-179172 can also be used. These contents are integrated in this specification.

The epoxy compound may be a low molecular weight compound (for example, molecular weight less than 2000, furthermore, molecular weight less than 1000), or a high molecular weight compound (macromolecule) (for example, molecular weight 1000 or more, in the case of a polymer, a weight average molecular weight of 1000 or more ) may be 200-100000 are preferable and, as for the weight average molecular weight of an epoxy compound, 500-50000 are more preferable. 10000 or less are preferable, as for the upper limit of a weight average molecular weight, 5000 or less are more preferable, and 3000 or less are still more preferable.

As the epoxy compound, an epoxy resin can be preferably used. Examples of the epoxy resin include an epoxy resin that is a glycidyl ether of a phenol compound, an epoxy resin that is a glycidyl ether of various novolac resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, A glycidyl ester-based epoxy resin, a glycidylamine-based epoxy resin, an epoxy resin obtained by glycidylating halogenated phenols, a condensate of a silicon compound having an epoxy group and other silicon compounds, and a polymerizable unsaturated compound having an epoxy group and copolymers of other polymerizable unsaturated compounds. It is preferable that it is 310-3300 g/eq, as for the epoxy equivalent of an epoxy resin, it is more preferable that it is 310-1700 g/eq, It is more preferable that it is 310-1000 g/eq.

Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Maproof G-0150M, G-0105SA, G-0130SP, G -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (above, Nichiyu Co., Ltd. product, epoxy group-containing polymer) etc. are mentioned.

As for content of the compound which has a cyclic ether group in total solid of a coloring composition, 0.1-20 mass % is preferable. 0.5 mass % or more is preferable, and, as for a minimum, 1 mass % or more is more preferable, for example. 15 mass % or less is preferable and, as for an upper limit, 10 mass % or less is more preferable, for example. One type may be sufficient as the compound which has a cyclic ether group, 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.

<<curing accelerator>>

The coloring composition of this invention may also contain a hardening accelerator. Examples of the curing accelerator include a thiol compound, a methylol compound, an amine compound, a phosphonium salt compound, an amidine salt compound, an amide compound, a base generator, an isocyanate compound, an alkoxysilane compound, and an onium salt compound. . As a specific example of a hardening accelerator, Paragraph No. 0094 - 0097 of International Publication No. 2018/056189, the compound of Paragraph No. 0246 - 0253 of Unexamined-Japanese-Patent No. 2015-034963 Paragraph number of Unexamined-Japanese-Patent No. 2013-041165 The compound of 0186-0251, the ionic compound of Unexamined-Japanese-Patent No. 2014-055114, the compound of Paragraph No. 0071 of Unexamined-Japanese-Patent No. 2012-150180 - the compound of 0080, The epoxy group of Unexamined-Japanese-Patent No. 2011-253054 The alkoxysilane compound which has, the compound of Paragraph Nos. 0085 - 0092 of Unexamined-Japanese-Patent No. 5765059, the carboxyl group containing epoxy curing agent of Unexamined-Japanese-Patent No. 2017-036379, etc. are mentioned. When it contains a hardening accelerator, 0.3-8.9 mass % is preferable and, as for content of the hardening accelerator in the total solid of a coloring composition, 0.8-6.4 mass % is more preferable.

<<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 As such a compound, Paragraph No. 0038-0052 of Unexamined-Japanese-Patent No. 2009-217221, Paragraph No. 0052 of Unexamined-Japanese-Patent No. 2012-208374, Paragraph No. 0317-0334 of Unexamined-Japanese-Patent No. 2013-068814, Unexamined-Japanese-Patent No. Paragraph Nos. 0061 to 0080 of Publication No. 2016-162946 include the compounds described, the contents of which are incorporated herein by reference. As a specific example of a ultraviolet absorber, the compound of the following structure, etc. are mentioned. 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 for a ultraviolet absorber.

[Formula 30]

When it contains a ultraviolet absorber, 0.01-10 mass % is preferable and, as for content of the ultraviolet absorber in the total solid of a coloring composition, 0.01-5 mass % is more preferable. In this invention, 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 a total amount becomes the said range.

<<Polymerization inhibitor >>

The coloring composition of this invention can contain a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, and 4,4'-thiobis(3-methyl-6). -tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salt (ammonium salt, cerium salt, etc.) are mentioned. . Among them, p-methoxyphenol is preferable. When it contains a polymerization inhibitor, as for content of the polymerization inhibitor in the total solid of a coloring composition, 0.0001-5 mass % is preferable. The number of polymerization inhibitors may be one, and two or more types may be sufficient as them. In the case of two or more types, it is preferable that a total amount becomes the said range.

<<Silane Coupling Agent>>

The coloring composition of this invention can contain a silane coupling agent. In the present invention, the silane coupling agent means a silane compound having a hydrolyzable group and a functional group other than that. Moreover, a hydrolysable group means the substituent which is directly connected to a silicon atom and can generate|occur|produce a siloxane bond by at least any one of a hydrolysis reaction and a condensation reaction. As a hydrolysable group, a halogen atom, an alkoxy group, an acyloxy group, etc. are mentioned, for example, An alkoxy group is preferable. That is, as for a silane coupling agent, the compound which has an alkoxysilyl group is preferable. Moreover, as a functional group other than a hydrolysable group, For example, a vinyl group, (meth)allyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocya A nate group, a phenyl group, etc. are mentioned, An amino group, a (meth)acryloyl group, and an epoxy group are preferable. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ -Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) manufactured by KBE-602), γ-aminopropyl trimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), γ-aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd.) Co., Ltd. product, trade name KBE-903), 3-methacryloxypropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd. product, trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) and the like. Moreover, about the specific example of a silane coupling agent, the compound of Paragraph No. 0018-0036 of Unexamined-Japanese-Patent No. 2009-288703, Paragraph No. 0056-0066 of Unexamined-Japanese-Patent No. 2009-242604 are mentioned, These contents are incorporated herein by reference. When it contains a silane coupling agent, 0.01-15.0 mass % is preferable and, as for content of the silane coupling agent in total solid of a coloring composition, 0.05-10.0 mass % is more preferable. The number of silane coupling agents may be one, and two or more types may be sufficient as them. In the case of two or more types, it is preferable that a total amount becomes 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) improves more and liquid saving property can be improved more. Moreover, a film|membrane with a small thickness nonuniformity 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 fluorine-type surfactant, Paragraph No. 0060 of Unexamined-Japanese-Patent No. 2014-041318 (paragraph No. 0060 of Corresponding International Publication No. 2014/017669) Paragraph No. of Paragraph No. of Unexamined-Japanese-Patent No. 2011-132503 Surfactant etc. and surfactants described in 0117 to 0132, the contents of which are incorporated herein by reference. Examples of commercially available fluorinated 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 31]

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-based surfactant, a fluorinated polymer having an ethylenically unsaturated bond-containing group in the 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 (Fujifilm Wako Junyaku Co., Ltd.), Pionin D-6112, D-6112-W, D-6315 (Yushi Takemoto) Co., Ltd. product), Olfin E1010, Surfinol 104, 400, 440 (made by Nisshin Chemical Industry Co., Ltd.), etc. are mentioned.

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) , Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by Big Chemi), and the like.

When it contains surfactant, 0.001 mass % - 5.0 mass % are 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 two or more types may be sufficient as it. In the case of two or more types, it is preferable that a total amount becomes the said range.

<<Antioxidant>>

The coloring composition of this invention can contain antioxidant. As antioxidant, a phenol compound, a phosphorous acid ester compound, a thioether compound, etc. are mentioned. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. As a preferable phenol compound, a hindered phenol compound is mentioned. The compound which has a substituent in the site|part (orthosite) adjacent to a phenolic hydroxyl group is preferable. As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable. Moreover, as for antioxidant, the compound which has a phenol group and a phosphite group in the same molecule is also preferable. Moreover, as antioxidant, phosphorus antioxidant can also be used suitably. It is preferable that it is 0.01-20 mass %, and, as for content of the antioxidant in total solid of a coloring composition, it is more preferable that it is 0.3-15 mass %. When it contains antioxidant, only 1 type may be used for antioxidant, and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.

<<Other ingredients>>

The coloring composition of this invention is a sensitizer, hardening accelerator, a filler, a thermosetting accelerator, a plasticizer, and other adjuvants (for example, electroconductive particle, a filler, an antifoamer, a flame retardant, a leveling agent, A peeling accelerator, a fragrance|flavor, a surface tension regulator, a chain transfer agent, etc.) may be contained. By containing these components appropriately, properties such as film properties can be adjusted. These components are, for example, after Paragraph No. 0183 of Unexamined-Japanese-Patent No. 2012-003225 (paragraph No. 0237 of U.S. Patent Application Laid-Open No. 2013/0034812) Paragraph No. of Unexamined-Japanese-Patent No. 2008-250074. Reference can be made to descriptions of 0101 to 0104, 0107 to 0109, and the like, the contents of which are incorporated herein by reference. 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 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 of a latent antioxidant, Adeka Arcles GPA-5001 (made by ADEKA Corporation) etc. are mentioned. Moreover, as described in Unexamined-Japanese-Patent No. 2018-155881, you may add C.I. Pigment Yellow 129 for the purpose of improving a weather resistance.

The coloring composition of this invention may contain a metal oxide in order to adjust the refractive index of the film|membrane obtained. _{As a} metal oxide, TiO2, ZrO2, _{Al2O3 ,} SiO2 _, etc. are mentioned. 1-100 nm is preferable, as for the primary particle diameter of a metal oxide, 3-70 nm is more preferable, 5-50 nm is still more preferable. The metal oxide may have a core-shell structure. Moreover, in this case, hollow shape may be sufficient as a core part.

The coloring composition of this invention may also contain a light resistance improving agent. As a light resistance improving agent, Paragraph No. 0036 of Unexamined-Japanese-Patent No. 0036-0037 of Unexamined-Japanese-Patent No. 2017-198787, Paragraph No. 0036 of Unexamined-Japanese-Patent No. 2017-129774 Paragraph No. Compounds described in 0037, 0049 to 0052, Paragraph Nos. 0031 to 0034, 0058 to 0059 of Japanese Patent Application Laid-Open No. 2017-129674, Compounds described in Paragraph Nos. 0036 to 0037, 0051 to 0054 of Japanese Patent Application Laid-Open No. 2017-122803 , the compound described in Paragraph Nos. 0025 to 0039 of International Publication No. 2017/164127, the compound described in Paragraph Nos. 0034 to 0047 of Japanese Patent Application Laid-Open No. 2017-186546, Paragraph Nos. 0019 to 0041 of Japanese Unexamined Patent Publication No. 2015-025116 Compound, Paragraph No. 0101 - 0125 of Unexamined-Japanese-Patent No. 2012-145604 The compound of Paragraph No. 0018 - 0021 of Unexamined-Japanese-Patent No. 2012-103475 Paragraph No. 0015 - 0018 of Unexamined-Japanese-Patent No. 2011-257591 Paragraph Nos. 0103 to 0153 of Unexamined-Japanese-Patent No. 2011-253174, the compound of Paragraph No. 0017 - 0021 of Unexamined-Japanese-Patent No. 2011-191483, the compound of Paragraph No. 0108 - 0116 of Unexamined-Japanese-Patent No. 2011-145668, the compound of description. The compounds described in , etc. are mentioned.

The water content of the coloring composition of this invention is 3 mass % or less normally, 0.01-1.5 mass % is preferable, and it is more preferable that it is the range of 0.1-1.0 mass %. The moisture content can be measured by the Karl Fischer method.

The coloring composition of this invention can be used by adjusting a viscosity for the purpose of adjustment of a film surface top (flatness etc.), adjustment of a film thickness, etc. Although the value of a viscosity can be suitably selected as needed, For example, 0.3 mPa*s - 50 mPa*s are preferable in 25 degreeC, and 0.5 mPa*s - 20 mPa*s are more preferable. As a measuring method of a viscosity, it can measure in the state which temperature-controlled at 25 degreeC using the corn-plate type viscometer, for example.

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 and 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 6 types of resins in a 7-layer structure is also used. desirable. As such a container, the container of Unexamined-Japanese-Patent No. 2015-123351 is mentioned, for example.

<The preparation method of a coloring composition>

The coloring composition of this invention can mix and prepare the above-mentioned component. When preparing 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 prepare a coloring composition.

Moreover, at the time of preparation of a coloring composition, it is preferable to 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. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, etc. after a grinding|pulverization process. In addition, the process and dispersing machine for dispersing pigments are "Dispersion Technology Collection, Published by Johokiko Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid/liquid dispersion system) and practical application of industrial applications" Comprehensive data collection, published by Keiei Kaihatsu Center Publishing Co., Ltd., October 10, 1978", the process and disperser described in Paragraph No. 0022 of Unexamined-Japanese-Patent No. 2015-157893 can be used suitably. 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 raw material, apparatus, processing conditions, etc. used for a salt milling process, description of Unexamined-Japanese-Patent No. 2015-194521 and Unexamined-Japanese-Patent No. 2012-046629 can be referred, for example.

Preparation of a coloring composition WHEREIN: It is preferable to filter a coloring composition with a filter for the purpose 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 Microlith 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.) made by Rocky Techno, TPR type series (TPR002, TPR005 etc.), and 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 or may be performed twice 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.

<act>

The film|membrane of this invention is a film|membrane obtained from the coloring composition of this invention mentioned above. The film|membrane of this invention can be used for a color filter etc. Specifically, it can use suitably as a color pixel of a color filter, More specifically, it can use suitably as a red pixel of a color filter. The film thickness of the film of the present invention can be appropriately adjusted according to the purpose. For example, 5 micrometers or less are preferable, as for a film thickness, 1 micrometer or less is more preferable, and 0.6 micrometer or less is still more preferable. 0.1 micrometer or more is preferable, as for the lower limit of a film thickness, 0.2 micrometer or more is more preferable, and 0.3 micrometer or more is still more preferable.

<Method of forming a pixel>

Next, a method of forming a pixel will be described. The formation method of a pixel apply|coats the coloring composition of this invention mentioned above on a support body, The process of forming a coloring composition layer, The process of exposing a coloring composition layer in pattern shape, Developing the unexposed part of the coloring composition layer after exposure It is preferable to include a step of removing it. Hereinafter, each process is demonstrated.

At the process of forming a coloring composition layer, a coloring composition is apply|coated on a support body, and a coloring composition layer is formed. There is no limitation in particular as a support body, According to a use, it can select suitably. For example, a glass substrate, a silicon substrate, etc. are mentioned, It is preferable that it is a silicon substrate. In addition, 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 black matrix which isolates each pixel may be formed in a silicon substrate. In addition, the silicon substrate may be provided with a base layer in order to improve adhesion with the upper layer, to prevent diffusion of substances, or to planarize the surface of the substrate. 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. If the surface contact angle of a base layer is the said range, the applicability|paintability of a coloring composition is favorable. Adjustment of the surface contact angle of the base layer can be performed, for example, by a method such as addition of a surfactant.

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 coat method; 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, a 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 "Diffused 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 manufacturing a film|membrane by a low-temperature process, it is not necessary to pre-bake. When prebaking, 150 degrees C or less is preferable, as for prebaking temperature, 120 degrees C or less is more preferable, and 110 degrees C or less is still more preferable. The lower limit can be, for example, 50°C or higher, or 80°C or higher. 10-300 second is preferable, as for prebaking time, 40-250 second is more preferable, and 80-220 second is still more preferable. Pre-baking can be performed with a hot plate, an oven, etc.

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

Examples of the radiation (light) that can be used during exposure include g-line, i-line, and the like. 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 in the atmosphere, for example, in a low-oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially anoxic) or 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 appropriately 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.

Next, the unexposed part of the coloring composition layer after exposure is developed and removed (development process). 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 an unexposed part 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 for a developing solution, an organic solvent, an alkali developing solution, etc. are mentioned, An alkali developing solution is used preferably. 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. 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 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. 100-240 degreeC is preferable, and, as for the heating temperature in a post-baking, 200-240 degreeC is more preferable, for example. Post-baking can be performed in a continuous or batch manner, using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater, so that the developed film (pixel) is subjected to the above conditions. . When performing additional exposure processing, it is preferable that the light used for exposure is light with a wavelength of 400 nm or less. Moreover, you may perform an additional exposure process by the method described in Korean Unexamined-Japanese-Patent No. 10-2017-0122130.

In this way, a pixel can be formed.

<Color filter>

Next, the color filter of this invention is demonstrated. The color filter of this invention has the film|membrane of this invention mentioned above. Specifically, it has the film|membrane of this invention as a color pixel of a color filter.

Moreover, it is also preferable that the color filter of this invention has a red pixel obtained using the coloring composition of this invention mentioned above, a blue pixel, and a green pixel.

It is preferable that the color filter of this invention has the film|membrane of this invention as a red pixel of a color filter. The color filter of the present invention can be used for a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an image display device, or the like.

In the color filter of this invention, the film thickness of the film|membrane of this invention can be suitably adjusted according to the objective. 5 micrometers or less are preferable, as for a film thickness, 1 micrometer or less is more preferable, and 0.6 micrometer or less is more preferable. 0.1 micrometer or more is preferable, as for the lower limit of a film thickness, 0.2 micrometer or more is more preferable, and 0.3 micrometer or more is still more preferable.

It is preferable that the width|variety of the pixel contained in a color filter is 0.4-10.0 micrometers. The lower limit is preferably 0.4 µm or more, more preferably 0.5 µm or more, and still more preferably 0.6 µm or more. It is preferable that it is 5.0 micrometers or less, and, as for an upper limit, it is more preferable that it is 2.0 micrometers or less, It is more preferable that it is 1.0 micrometer or less, It is still more preferable that it is 0.8 micrometer or less. Moreover, it is preferable that it is 0.5-20 GPa, and, as for the Young's modulus of a pixel, 2.5-15 GPa is more preferable.

Each pixel included in the color filter preferably has high flatness. Specifically, it is preferable that it is 100 nm or less, and, as for surface roughness Ra of a pixel, it is more preferable that it is 40 nm or less, It is more preferable that it is 15 nm or less. Although a lower limit is not prescribed|regulated, For example, it is preferable that it is 0.1 nm or more. The surface roughness of the pixel can be measured using, for example, AFM (Atomic Force Microscope) Dimension3100 manufactured by Veeco. Moreover, although the contact angle of the water on a pixel can be set to a suitable value suitably, it is the range of 50-110 degrees typically. The contact angle can be measured using, for example, a contact angle meter CV-DT·A type (manufactured by Kyowa Kaimen Chemical Co., Ltd.). Moreover, it is preferable that the volume resistance value of a pixel is high. Specifically, the volume resistance value of the pixel is preferably 10 ⁹ Ω·cm or more, and more preferably 10 ¹¹ Ω·cm or more. Although the upper limit is not prescribed|regulated, it is preferable that it is 10 ¹⁴ ohm*cm or less, for example. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advanced Test Co., Ltd.).

In a color filter, the protective layer may be provided on the surface of the film|membrane (pixel) 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 forming by coating 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 , and the like, and two or more of these components may be included. 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.

When the resin composition is applied to form a protective layer, 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 Nos. 0073 - 0092 of Unexamined-Japanese-Patent No. 2017-151176 can also be used.

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

<Solid-State Imaging Device>

The solid-state imaging device of the present invention has the above-described film of the present invention. Although there will be no limitation in particular as a structure of a solid-state imaging element, if it is a structure provided with the film|membrane of this invention and functioning as a solid-state image sensor, For example, the following structures are mentioned.

A plurality of photodiodes constituting a light receiving area of a solid-state image sensor (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) It has a light-shielding film on the photodiode and the transfer electrode in which only the light-receiving portion of the photodiode is opened, a device protective film made of silicon nitride or the like formed to cover the entire surface of the light-shielding film and the photodiode light-receiving portion on the light-shielding film, and a color filter on the device protective film configuration that has Moreover, the structure which has a light condensing means (for example, microlens etc., the same hereinafter) above a device protective film and below a color filter (side close to a board|substrate), a structure which has a light condensing means on a color filter, etc. may be sufficient. Moreover, the color filter may have the structure in which each color pixel was embedded in the space partitioned by the grid|lattice form by the partition, for example. It is preferable that the partition in this case has a low refractive index with respect to each color pixel. As an example of the imaging device which has such a structure, the apparatus of Unexamined-Japanese-Patent No. 2012-227478, Unexamined-Japanese-Patent No. 2014-179577, and International Publication No. 2018/043654 are mentioned. The imaging device provided with the solid-state imaging element of the present invention can be used not only for a digital camera and an electronic device having an imaging function (such as a mobile phone), but also for an in-vehicle camera or a surveillance camera.

<Image display device>

The image display apparatus of this invention has the film|membrane of this invention mentioned above. As an image display apparatus, a liquid crystal display device, an organic electroluminescent display apparatus, etc. are mentioned. For the definition of an image display apparatus and the details of each image display apparatus, for example, "Electronic display device (author Akio Sasaki, Kokocho Chosakai, published in 1990)", "Display device (author Sumiaki Ibuki, Sangyo)" Tosho Co., Ltd. published in the first year of the Heisei)" and the like. Moreover, about a liquid crystal display device, it describes, for example in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Kogyo 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, it can be applied to various types of liquid crystal display devices described in "Next-generation liquid crystal display technology" above.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples. Materials, usage amounts, 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.

<Preparation of dispersion>

After mixing the materials (pigment, pigment derivative, resin, solvent) described in the table below, 230 parts by mass of zirconia beads having a diameter of 0.3 mm are added, and dispersion treatment is performed for 5 hours using a paint shaker, and the beads are separated by filtration A dispersion was prepared. The numerical value of the compounding quantity of each raw material in the following table|surface is a mass part. In addition, the value of the compounding quantity of resin (dispersing agent) is a value of the compounding quantity in the resin solution of 20 mass % of solid content, respectively.

[Table 1]

[Table 2]

The raw materials described in the above table are as follows.

(pigment)

[Pigment DPP having a structure in which the aromatic ring group Ar ^D1 in which an electron-donating group is introduced into the aromatic ring is bonded to the diketopyrrolopyrrole skeleton]

Pigment R1: Compound (C.I. Pigment Red 272) of the structure represented by the following formula (R1)

Pigment R2: A compound of the structure represented by the following formula (R2)

Pigment R3: A compound of the structure represented by the following formula (R3)

Pigment R4: A compound of the structure represented by the following formula (R4)

Pigment R5: a compound of the structure represented by the following formula (R5)

Pigment R6: A compound of the structure represented by the following formula (R6)

Pigment R7: a compound of the structure represented by the following formula (R7)

Pigment R8: a compound of the structure represented by the following formula (R8)

Pigment R9: a compound of the structure represented by the following formula (R9)

Pigment R10: Compound (C.I. Pigment Red 264) of the structure represented by the following formula (R10)

[Formula 32]

[Pigments other than DPP]

PR254: Color Index Pigment Red 254

PY139: Color Index Pigment Yellow 139

PO71: Color Index Pigment Orange 71

(pigment derivative)

Derivative 1: a compound of the structure

[Formula 33]

Derivative 2: a compound of the structure

[Formula 34]

Derivative 3: a compound of the structure

[Formula 35]

Derivative 4: a compound of the structure

[Formula 36]

Derivative 5: a compound of the structure

[Formula 37]

(Suzy)

A-1: 20% by mass of propylene glycol monomethyl of a resin having the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 24000, acid value 47 mgKOH/g) Ether acetate (PGMEA) solution

[Formula 38]

A-2: 20% by mass PGMEA solution of a resin having the following structure (the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 16000, acid value 67 mgKOH/g)

[Formula 39]

B-1: The resin solution of resin B-1 synthesize|combined by the following method (solid content concentration 20 mass %).

50 parts by mass of methyl methacrylate, 50 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were put into the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of reaction container was heated at 70 degreeC, 6 mass parts of 3-mercapto-1,2- propanediol was added, 0.12 mass parts of AIBN (azobisisobutyronitrile) was further added, and it was made to react for 12 hours. . It was confirmed that 95% reacted by solid content measurement. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and 7 at 120°C time was reacted. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMEA was added, the nonvolatile matter (solid content concentration) was adjusted to 20 mass %, and the resin solution of resin B-1 of the following structure with an acid value of 43 mgKOH/g and a weight average molecular weight of 9000 was obtained.

[Formula 40]

B-2: The resin solution of resin B-2 synthesize|combined by the following method (solid content concentration 20 mass %).

50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of t-butyl methacrylate, and 45.4 parts by mass of PGMEA were put into the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of reaction container was heated at 70 degreeC, 6 mass parts of 3-mercapto-1,2- propanediol was added, 0.12 mass parts of AIBN (azobisisobutyronitrile) was further added, and it was made to react for 12 hours. . It was confirmed that 95% reacted by solid content measurement. Next, 9.7 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and 7 at 120°C time was reacted. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMEA was added, the nonvolatile matter (solid content concentration) was adjusted to 20 mass %, and the resin solution of resin B-2 of the following structure with an acid value of 43 mgKOH/g and a weight average molecular weight of 9000 was obtained.

[Formula 41]

B-3: The resin solution of resin B-3 synthesize|combined by the following method (solid content concentration 20 mass %).

In the synthesis of resin B-2, 20 parts by mass of t-butyl methacrylate was similarly changed to 20 parts by mass of (3-ethyloxetan-3-yl)methyl methacrylate, and an acid value of 43 mgKOH/g, The resin solution of resin B-3 of the following structure with a weight average molecular weight of 9000 was obtained.

[Formula 42]

B-4: The resin solution of resin B-4 synthesize|combined by the following method (solid content concentration 20 mass %).

Synthesis of Resin B-2 WHEREIN: Except having changed 20 mass parts of t-butylmethacrylate into 20 mass parts of Showa Denko "Karensu MOI-BM", in the same manner, acid value 43 mgKOH/g, weight average molecular weight 9000 A resin solution of resin B-4 having the following structure was obtained.

[Formula 43]

B-5: The resin solution of resin B-5 synthesize|combined by the following method (solid content concentration 20 mass %).

3-mercapto-1,2-propanediol 6.0 parts by mass, pyromellitic anhydride 9.5 parts by mass, PGMEA 62 parts by mass, 1,8-diazabicyclo-[5.4.0]-7-undecene 0.2 A mass part was injected|thrown-in to the reaction container, and the atmospheric gas was substituted with nitrogen gas. The inside of the reaction container was heated to 100 degreeC, and it was made to react for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measurement of the acid value, the temperature in the system was cooled to 70° C., 65 parts by mass of methyl methacrylate, 5.0 parts by mass of ethyl acrylate, 15 parts by mass of t-butyl acrylate 53.5 mass parts of PGMEA solutions which melt|dissolved mass parts, 5.0 mass parts of methacrylic acid, 10 mass parts of hydroxyethyl methacrylate, and 0.1 mass parts of 2,2'- azobisisobutyronitrile were added, and it was made to react for 10 hours. The polymerization was confirmed to have progressed to 95% by solid content measurement, and the reaction was terminated. PGMEA was added, the nonvolatile matter (solid content concentration) was adjusted to 20 mass %, and the resin solution of resin B-5 of the following structure with an acid value of 70.5 mgKOH/g and a weight average molecular weight of 10000 was obtained.

[Formula 44]

B-6: The resin solution of resin B-6 synthesize|combined by the following method (solid content concentration 20 mass %).

108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic anhydride, 650 parts by mass of methoxypropyl acetate, and 0.2 parts by mass of monobutyl tin oxide as a catalyst were put into the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. , and reacted at 120° C. for 5 hours (first step). By measuring the acid value, it was confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 mass parts of compounds obtained in the 1st process in conversion of solid content, 200 mass parts of 2-hydroxypropyl methacrylates, 200 mass parts of ethyl acrylates, 150 mass parts of t-butyl acrylates, 2-methoxyethyl 200 parts by mass of acrylate, 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA are put into a reaction vessel, the inside of the reaction vessel is heated to 80° C., and 2,2'-azobis (2, 1.2 mass parts of 4-dimethylvaleronitrile) was added, and it was made to react for 12 hours (2nd process). It was confirmed that 95% reacted by solid content measurement. Finally, 500 parts by mass of a 50 mass % PGMEA solution of the compound obtained in the second step, 27.0 parts by mass of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts by mass of hydroquinone are put into the reaction vessel, and iso The reaction was performed until disappearance of the peak at 2270 cm ^-1 based on the cyanate group was confirmed (third step). After confirming the disappearance of the peak, the reaction solution is cooled, the nonvolatile matter (solid content concentration) is adjusted to 20 mass % by adding PGMEA, an acid value of 68 mgKOH/g, an unsaturated double bond value of 0.62 mmol/g, and a weight average molecular weight of 13000 of the following structure A resin solution of Resin B-6 was obtained.

[Formula 45]

B-7: The resin solution of resin B-7 synthesize|combined by the following method (solid content concentration 20 mass %).

40 parts by mass of methyl methacrylate, 60 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were put into the reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The inside of reaction container was heated at 70 degreeC, 8 mass parts of 3-mercapto-1,2- propanediol was added, 0.12 mass parts of AIBN (azobisisobutyronitrile) was further added, and it was made to react for 12 hours. . It was confirmed that 95% reacted by solid content measurement. Next, 13 parts by mass of pyromellitic anhydride, 70.3 parts by mass of PGMEA, and 0.20 parts by mass of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and 7 at 120°C time was reacted. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. PGMEA was added, the nonvolatile matter (solid content concentration) was adjusted to 20 mass %, and the resin solution of resin B-7 of the following structure with an acid value of 55 mgKOH/g and a weight average molecular weight of 10000 was obtained.

[Formula 46]

C-1: PGMEA solution having a solid content concentration of 20% by mass of DISPERBYK-2001 (resin having a basic group, amine value of 29 mgKOH/g, manufactured by Big Chemie Japan)

C-2: 20% by mass PGMEA solution of the resin having the following structure (the numerical value appended to the main chain is the mass ratio. amine value 71 mgKOH/g, weight average molecular weight 9900)

[Formula 47]

C-3: 20% by mass PGMEA solution of the resin having the following structure (the numerical value appended to the main chain is the mass ratio. amine value 80 mgKOH/g, weight average molecular weight 8500)

[Formula 48]

(solvent)

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

<Preparation of coloring composition>

The raw materials described in the table below were mixed to prepare a coloring composition. In addition, the value of the compounding quantity of resin is the value of the compounding quantity in the resin solution of 20 mass % of solid content.

[Table 3]

[Table 4]

[Table 5]

The raw materials described in the above table are as follows.

(dispersion)

Dispersion R1-R39: Dispersion R1-R39 as described above

(Suzy)

A-3: 20% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 11000, acid value 69 mgKOH/g)

[Formula 49]

A-4: 20% by mass PGMEA solution of a resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 13000)

[Formula 50]

(polymerizable compound)

E-1: dipentaerythritol hexaacrylate

E-2: trimethylol propane ethyleneoxy modified triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-350)

E-3: trimethylol propane triacrylate (manufactured by Toagosei Co., Ltd., Aronix M-309)

E-4: urethane acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., U-6LPA)

(Photoinitiator)

[Oxime compound OX having an aromatic ring group Ar ^OX1 in which an electron withdrawing group is introduced into the aromatic ring]

G-1 to G-4: a compound of the following structure

[Formula 51]

[Photoinitiator other than oxime compound OX]

G-c1: a compound of the following structure (oxime-based photopolymerization initiator)

[Formula 52]

G-c2: a compound of the following structure (benzophenone-based photopolymerization initiator)

[Formula 53]

G-c3: Irgacure OXE02 (manufactured by BASF, oxime-based photopolymerization initiator)

(additive)

H-1: a compound of the following structure (ultraviolet absorber)

[Formula 54]

(Surfactants)

I-1: 1 mass % PGMEA solution of the compound of the following structure (weight average molecular weight 14000). In the following formula, % indicating the proportion of the repeating unit is mol%.

[Formula 55]

(Polymerization inhibitor)

J-1: p-methoxyphenol

(solvent)

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

K-2: propylene glycol monomethyl ether (PGME)

<Evaluation of the performance of the coloring composition>

(light resistance)

On a glass substrate, the coloring composition is applied by a spin coat method, then heat-treated (pre-baked) at 100° C. for 120 seconds using a hot plate, followed by exposure with an i-line at an exposure dose of 1000 mj/cm ² , and then, It heated at 200 degreeC for 5 minutes, and produced the film|membrane with a thickness of 0.6 micrometer. About the obtained film|membrane, the light transmittance (transmittance) of the range of wavelength 400-700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. product. Next, the film produced above was irradiated with light of 100000 Lux for 1000 hours using a light resistance tester (Super Xenon Weather Meter SX75, manufactured by Suga Shikenki Co., Ltd.) (total irradiation amount 100 million Lux·hr). The transmittance|permeability of the film|membrane after light irradiation was measured, and the following reference|standard evaluated light resistance. A to C is the range where there is no problem in use.

A: The integrated value of the transmittance|permeability of the wavelength 400-700 nm of the film|membrane after light irradiation is 99% or more of the integrated value of the transmittance|permeability of the wavelength 400-700 nm of the film|membrane before light irradiation.

B: The integrated value of transmittance at a wavelength of 400 to 700 nm of the film after light irradiation is 97% or more and less than 99% of the integrated value of transmittance at a wavelength of 400 to 700 nm of the film before light irradiation.

C: The integrated value of transmittance at a wavelength of 400 to 700 nm of the film after light irradiation is 95% or more and less than 97% of the integrated value of transmittance at a wavelength of 400 to 700 nm of the film before light irradiation.

D: The integrated value of the transmittance|permeability of the wavelength 400-700 nm of the film|membrane after light irradiation is less than 95% of the integrated value of the transmittance|permeability of the wavelength 400-700 nm of the film|membrane before light irradiation.

(Adhesiveness)

CT-4000 (manufactured by FUJIFILM ELECTRONICS MATERIALS CO., LTD.) was applied on a silicon wafer with a diameter of 8 inches (= 203.2 mm) by spin coating to a film thickness of 0.1 μm, and heated at 220° C. using a hot plate. It heated for 1 hour to form a base layer. Each coloring composition was apply|coated by the spin coating method on this silicon wafer with a base layer, after that, it heated at 100 degreeC for 2 minute(s) using the hotplate, and obtained the composition layer with a film thickness of 0.5 micrometer. For this composition layer, using an i-line stepper FPA-3000i5+ (manufactured by Canon Co., Ltd.), through a mask pattern in which square pixels of 1.1 μm on one side are arranged in an area of 4 mm × 3 mm on the substrate, respectively, the wavelength of 365 nm of light was irradiated with an exposure amount of 500 mJ/cm ² and exposed. With respect to the composition layer after exposure, puddle development was performed at 23 degreeC for 60 second using the 0.3 mass % aqueous solution of tetramethylammonium hydroxide. Then, it rinsed using water by spin shower, and further performed water washing with pure water. Then, after blowing a water droplet with high-pressure air and drying a silicon wafer naturally, it post-baked at 220 degreeC for 300 second using the hotplate, and formed the pixel. About the obtained pixel, it observed using the optical microscope, the number of the pixel in close_contact|adherence among all the pixels was counted, and adhesiveness was evaluated. A to C is the range where there is no problem in use.

A: All the pixels are in close contact.

B: The pixels in close contact are 98% or more and less than 100% of all pixels.

C: The pixels in close contact are 95% or more and less than 98% of all pixels.

D: The number of pixels in close contact is less than 95% of all pixels.

(alien substance)

On a glass substrate, the coloring composition is applied by a spin coat method, then heat-treated (pre-baked) at 100° C. for 120 seconds using a hot plate, followed by exposure with an i-line at an exposure dose of 1000 mj/cm ² , and then, It heated at 200 degreeC for 5 minutes, and produced the film|membrane with a thickness of 0.6 micrometer.

The obtained film was further subjected to heat treatment at 230°C for 30 minutes, at 245°C for 30 minutes, and at 260°C for 30 minutes, respectively. The film after heat treatment was observed with an optical microscope, and the presence or absence of crystal precipitation was judged according to the following reference|standard. A to C is the range where there is no problem in use.

A: There was no crystal precipitation after any heat treatment at 230°C for 30 minutes, 245°C for 30 minutes, and 260°C for 30 minutes.

B: Crystals did not precipitate in the heat treatment at 230°C for 30 minutes and at 245°C for 30 minutes, but crystals were deposited in the heat treatment at 260°C for 30 minutes.

C: No crystals were precipitated in the heat treatment at 230°C for 30 minutes, but crystals were deposited in the heat treatment at 245°C for 30 minutes.

D: Crystals were precipitated by heat treatment at 230°C for 30 minutes.

(spectral properties)

On a glass substrate, the coloring composition is applied by a spin coat method, then heat-treated (pre-baked) at 100° C. for 120 seconds using a hot plate, followed by exposure with an i-line at an exposure dose of 1000 mj/cm ² , and then, It heated at 200 degreeC for 5 minutes, and produced the film|membrane with a thickness of 0.6 micrometer. About the obtained film|membrane, the light transmittance (transmittance) of the range of 400-700 nm was measured using MCPD-3000 manufactured by Otsuka Electronics Co., Ltd. When the average value of the transmittance of 400 to 500 nm was T1, the average value of the transmittance of 500 to 550 nm was T2, and the 50% transmittance was λ50, the spectral characteristics as red were judged according to the following criteria. A case where all of the following three items were satisfied was set as A, a case where only two items were satisfied was set as B, a case where only one item was satisfied was referred to as C, and a case where none of the following items was satisfied was set to D.

· T1 is 5% or less.

· T2 is 5% or less.

·λ50 is in the range of 530 to 590 nm.

[Table 6]

[Table 7]

As shown in the said table|surface, the Example was excellent in light resistance, adhesiveness, and evaluation of a foreign material. On the other hand, the comparative example was inferior to the Example in any one of light resistance, adhesiveness, and a foreign material.

Moreover, the film|membrane obtained from the coloring composition of Examples R1-R62 had a high red color value, and had the spectral characteristic suitable as a red coloring pixel of a color filter.

(Example 1001)

On a 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 carried out through a mask of a rectangular dot pattern having a side of 2 µm at an exposure amount of 1000 mJ/cm ² . Then, 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, the green coloring composition was patterned and the green pixel was formed by heating at 200 degreeC for 5 minute(s) using a hotplate. Similarly, the red coloring composition and the blue coloring composition were patterned by the same process, a red pixel and a blue pixel were formed one by one, and the color filter which has a green pixel, a red pixel, and a blue pixel was formed. In this color filter, the green pixel is formed in the Bayer pattern, and the red pixel and the blue pixel are formed in the area|region adjacent to the island pattern. The obtained color filter was introduce|transduced into the solid-state image sensor according to a well-known method. This solid-state imaging element had suitable image recognition ability. In addition, as a red coloring composition, the coloring composition of Example R1 was used. A green coloring composition and a blue coloring composition are mentioned later.

(Preparation of green coloring composition)

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

Green pigment dispersion: 73.7 parts by mass

Resin 101: 0.3 parts by mass

Polymeric compound 101: 1.2 mass parts

Photoinitiator 101: 0.6 parts by mass

Surfactant 101: 4.2 parts by mass

PGMEA: 19.5 parts by mass

(Preparation of 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: 44.9 parts by mass

Resin 101: 2.1 parts by mass

Polymerizable compound 101: 1.5 parts by mass

Polymeric compound 102: 0.7 mass parts

Photoinitiator 101: 0.8 parts by mass

Surfactant 101: 4.2 parts by mass

PGMEA: 45.8 parts by mass

The raw material used for preparation of a green coloring composition and a blue coloring composition is as follows.

green pigment dispersion

A mixed solution comprising 6.4 parts by mass of CI Pigment Green 36, 5.3 parts by mass of CI Pigment Yellow 150, 5.2 parts by mass of a dispersant (Disperbyk-161, manufactured by BYKChemie), and 83.1 parts by mass of PGMEA was mixed with a bead mill (zirconia beads 0.3 mm diameter), mixed and dispersed for 3 hours to prepare a pigment dispersion. Thereafter, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEI 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.

blue pigment dispersion

A mixed solution comprising 9.7 parts by mass of CI Pigment Blue 15:6, 2.4 parts by mass of CI Pigment Violet 23, 5.5 parts by mass of a dispersant (Disperbyk-161, manufactured by BYKChemie), and 82.4 parts by mass of PGMEA was mixed with a bead mill (zirconia beads). 0.3 mm diameter) by mixing and dispersing for 3 hours. Thereafter, using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEI 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.

Polymeric compound 101: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

Polymeric compound 102: a compound of the structure

[Formula 56]

Resin 101: a resin of the following structure (weight average molecular weight 11000, the numerical value added to the main chain is the molar ratio.)

[Formula 57]

Photoinitiator 101: Irgacure OXE01 (manufactured by BASF)

Surfactant 101: 1 mass % PGMEA solution of the compound of the following structure (weight average molecular weight 14000, the numerical value of % which shows the ratio of a repeating unit is mol%).

[Formula 58]

Claims (17)

A coloring composition containing a color material containing a pigment, a photoinitiator, a polymerizable compound, and a resin, comprising:
The pigment includes a pigment DPP having a structure in which an aromatic ring group Ar ^D1 in which an electron-donating group is introduced into an aromatic ring is bonded to a diketopyrrolopyrrole skeleton,
The said photoinitiator contains the oxime compound OX which has the aromatic ring group ^ArOX1 in which the electron withdrawing group was introduce|transduced into the aromatic ring, The coloring composition. The method according to claim 1,
The electron withdrawing group which the said aromatic ring group ^ArOX1 has is at least 1 sort(s) selected from an acyl group and a nitro group, The coloring composition. The method according to claim 1,
The electron withdrawing group which the said aromatic ring group Ar ^OX1 has is an acyl group, The coloring composition. 4. The method according to any one of claims 1 to 3,
The said aromatic ring group Ar ^OX1 is group represented by Formula (OR-1), Color composition;
[Formula 1]

In the formula, R ^OX1 represents a substituent, R ^OX2 represents an electron withdrawing group, n represents an integer of 0 to 4, and a broken line represents a bond. 5. The method according to any one of claims 1 to 4,
Coloring composition in which the said oxime compound OX has at least 1 sort(s) of group chosen from group represented by a formula (OR-11), and group represented by a formula (OR-12);
[Formula 2]

wherein R ^OX11 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group;
R ^OX12 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group , an acyloxy group or an amino group,
The dashed line indicates the bonding hand. 6. The method according to any one of claims 1 to 5,
The said oxime compound OX is a coloring composition which is at least 1 sort(s) chosen from the compound represented by Formula (OX1), and the compound represented by Formula (OX2);
[Formula 3]

In the formula, R ^X1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acyloxy group, an amino group, a phosphinoyl group, a carbamoyl group or a sulfamoyl group;
R ^X2 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group , an acyloxy group or an amino group,
R ^X3 to R ^X14 each independently represent a hydrogen atom or a substituent;
However, at least one of R ^X10 to R ^X14 is an electron withdrawing group. 7. The method according to any one of claims 1 to 6,
The electron-donating group of the aromatic ring group Ar ^D1 is at least one selected from a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, and an amino group. 8. The method according to any one of claims 1 to 7,
The said aromatic ring group Ar ^D1 is group represented by Formula (AR-1), Color composition;
[Formula 4]

In the formula, R ^D1 represents a substituent, R ^D2 represents an electron-donating group, n represents an integer of 0 to 4, and a broken line represents a bond with a diketopyrrolopyrrole skeleton. 9. The method according to any one of claims 1 to 8,
The said pigment DPP is a coloring composition which is a compound represented by Formula (DPP1);
[Formula 5]

In the formula, R ^D11 and R ^D12 each independently represents a substituent,
R ^D21 and R ^D22 each independently represent an electron-donating group,
n11 and n12 each independently represent an integer of 0-4. 10. The method according to any one of claims 1 to 9,
The said pigment DPP contains at least 1 sort(s) selected from color index pigment red 264 and color index pigment red 272, the coloring composition. 11. The method of any one of claims 1 to 10,
The coloring composition whose content of the color material in the total solid of a coloring composition is 50 mass % or more. 12. The method according to any one of claims 1 to 11,
The coloring composition for solid-state imaging devices. 13. The method according to any one of claims 1 to 12,
A coloring composition for a color filter. The film|membrane obtained using the coloring composition in any one of Claims 1-13. The color filter which has the film|membrane of Claim 14. The solid-state image sensor which has the film|membrane of Claim 14. The image display apparatus which has the film|membrane of Claim 14.