TWI840333B - Photosensitive coloring composition, cured film, pattern forming method, color filter, solid-state imaging element and image display device - Google Patents

Abstract

The present invention provides a photosensitive coloring composition capable of forming a cured film having excellent resistance to discoloration by a developer. In addition, a cured film, a method for forming a pattern, a color filter, a solid-state imaging element, and an image display device are provided. The photosensitive coloring composition contains: a photopolymerization initiator a, the absorption coefficient of light with a wavelength of 365 nm in methanol exceeding 1.0×10 ² mL/gcm; a photopolymerization initiator b, the absorption coefficient of light with a wavelength of 365 nm in methanol being 1.0×10 ² mL/gcm or less, and the absorption coefficient of light with a wavelength of 254 nm being 1.0×10 ³ mL/gcm or more; an alkali-soluble resin; and a coloring material having a polymerizable group. The content of the photopolymerization initiator a in the total solid content of the photosensitive coloring composition is 1.5 mass % or more, and the content of the photopolymerization initiator b is 1.5 mass % or more.

Description

Photosensitive coloring composition, cured film, pattern forming method, color filter, solid-state imaging element and image display device

The present invention relates to a photosensitive coloring composition. More specifically, it relates to a photosensitive coloring composition used to form coloring pixels of a color filter. In addition, it relates to a cured film using the photosensitive coloring composition, a method for forming a pattern, a color filter, a solid-state imaging element, and an image display device.

In recent years, the demand for solid-state imaging components such as charge-coupled device (CCD) image sensors has increased significantly due to the popularity of digital cameras and portable phones with cameras. Color filters are used as key components in displays and optical components.

The color filter is manufactured by coating a colored photosensitive composition for forming pixels of various colors on a support, performing pre-baking at about 100°C, then performing exposure and development to form a pattern, and then performing post-baking. Post-baking is a heat treatment for accelerating the hardening of the developed film, and is performed at a relatively high temperature. For example, in Patent Document 1, the developed film is post-baked at a temperature of more than 200°C.

In recent years, research has been conducted on the use of organic electroluminescence (EL) as a light source in image display devices and organic materials for photoelectric conversion films in image sensors. Most of these components have low heat resistance. Therefore, research has been conducted on the manufacture of color filters at low temperatures. For example, Patent Document 2 describes a method for manufacturing a color filter, which comprises: (i) forming a layer on a substrate using a photosensitive coloring composition; (ii) exposing the photosensitive coloring composition layer to light having a wavelength greater than 350 nm and less than 380 nm; (iii) performing alkaline development on the photosensitive coloring composition layer; and (iv) exposing the photosensitive coloring composition layer to light having a wavelength of 254 to 350 nm, wherein the photosensitive coloring composition comprises (a) a polymerization initiator having an absorbance coefficient of 1.0×10 ³ mL/gcm or more for light having a wavelength of 365 nm in methanol, and (b) a catalyst having an absorbance coefficient of 1.0×10 2 mL/gcm or more for light having a wavelength of 365 nm in methanol ^. mL/gcm or less, and the absorption coefficient of light with a wavelength of 254nm is 1.0×10 ³ mL/gcm or more, (c) a compound having an unsaturated double bond, (d) an alkali-soluble resin, and (e) a colorant, wherein the content of (a) the polymerization initiator is 1.5 to 10 mass % and (b) the content of the polymerization initiator is 1.5 to 7.5 mass % in the total solid content of the photosensitive coloring composition. [Prior art document] [Patent document]

[Patent Document 1] Japanese Patent Publication No. 2015-143330 [Patent Document 2] Japanese Patent Publication No. 2015-041058

As mentioned above, in recent years, research has been conducted on manufacturing color filters at lower temperatures. On the other hand, the inventors of the present invention have studied a photosensitive coloring composition comprising a colorant and an alkali-soluble resin, and found that when the photosensitive coloring composition is cured at a low temperature to form a cured film, the obtained cured film tends to have low resistance to discoloration by a developer.

Thus, the object of the present invention is to provide a photosensitive coloring composition capable of forming a cured film having excellent resistance to discoloration by a developer. Another object is to provide a cured film, a pattern forming method, a color filter, a solid-state imaging element, and an image display device.

As a result of intensive research, the inventors have found that a photosensitive coloring composition comprising a specific photopolymerization initiator and a color material having a polymerizable group described below can form a cured film having excellent resistance to discoloration by a developer even when cured at a low temperature, thereby completing the present invention. That is, the present invention is as follows. <1> A photosensitive coloring composition comprising: a photopolymerization initiator a having an absorbance of more than 1.0×10 ² mL/gcm for light at a wavelength of 365 nm in methanol; a photopolymerization initiator b having an absorbance of less than 1.0×10 ² mL/gcm for light at a wavelength of 365 nm in methanol and an absorbance of more than 1.0×10 ³ mL/gcm for light at a wavelength of 254 nm in methanol; an alkali-soluble resin; and a coloring material having a polymerizable group, wherein the content of the photopolymerization initiator a in the total solid content of the photosensitive coloring composition is 1.5% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more. <2> The photosensitive coloring composition as described in <1>, wherein the absorption coefficient of the photopolymerization initiator a in methanol for light of a wavelength of 365 nm is 1.0×10 ³ mL/gcm or more. <3> The photosensitive coloring composition as described in <1> or <2>, wherein the photopolymerization initiator a is an oxime compound. <4> The photosensitive coloring composition as described in any one of <1> to <3>, wherein the photopolymerization initiator b is a hydroxyacetophenone compound. <5> The photosensitive coloring composition as described in any one of <1> to <4>, which contains 50 to 500 parts by mass of the photopolymerization initiator a relative to 100 parts by mass of the photopolymerization initiator b. <6> The photosensitive coloring composition as described in any one of <1> to <5>, wherein the total content of the photopolymerization initiator a and the photopolymerization initiator b in the total solid content of the photosensitive coloring composition is 3 to 17% by mass. <7> The photosensitive coloring composition as described in any one of <1> to <6>, wherein the coloring material is a pigment polymer. <8> A cured film obtained by curing the photosensitive coloring composition as described in any one of <1> to <7>. <9> A method for forming a pattern, comprising: a step of forming a photosensitive coloring composition layer on a support using the photosensitive coloring composition described in any one of <1> to <7>; a step of irradiating the photosensitive coloring composition layer with light having a wavelength greater than 350 nm and less than 380 nm and exposing it in a pattern; a step of alkaline developing the exposed photosensitive coloring composition layer; and a step of irradiating the developed photosensitive coloring composition layer with light having a wavelength of 254 to 350 nm and exposing it. <10> A color filter having the cured film described in <8>. <11> A solid-state imaging element having the cured film described in <8>. <12> An image display device having the cured film described in <8>. [Invention Effect]

According to the present invention, a photosensitive coloring composition capable of forming a cured film having excellent resistance to discoloration by a developer can be provided. In addition, a cured film, a method for forming a pattern, a color filter, and a solid-state imaging element can be provided.

The content of the present invention is described in detail below. In the marking of the groups (atomic groups) in this specification, the markings that are not marked with substitution and unsubstituted include groups (atomic groups) without substitution and also include groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups). Regarding "exposure" in this specification, unless otherwise specified, it includes not only exposure using light, but also exposure using particle beams such as electron beams and ion beams. In addition, as light used for exposure, the bright line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams and other actinic rays or radiation can generally be listed. In this specification, the numerical range indicated by "to" refers to a range that includes the numerical values recorded before and after the "to" as the lower limit and the upper limit. In this specification, the total solid content refers to the total mass of the components excluding the solvent from the total components of the composition. In this specification, "(meth)acrylate" means both or either acrylate and methacrylate, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid, "(meth)allyl" means both or either allyl and methallyl, and "(meth)acryl" means both or either acryl and methacryl. The term "step" in this specification includes not only independent steps, but also steps that achieve the desired effect of the step even if they cannot be clearly distinguished from other steps. In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene-equivalent values measured by gel permeation chromatography (GPC).

<Photosensitive coloring composition> The photosensitive coloring composition of the present invention contains: a photopolymerization initiator a, whose absorption coefficient for light with a wavelength of 365 nm in methanol exceeds 1.0×10 ² mL/gcm; a photopolymerization initiator b, whose absorption coefficient for light with a wavelength of 365 nm in methanol is 1.0×10 ² mL/gcm or less, and whose absorption coefficient for light with a wavelength of 254 nm is 1.0×10 ³ mL/gcm or more; an alkali-soluble resin; and a coloring material having a polymerizable group. The photosensitive coloring composition is characterized in that the content of the photopolymerization initiator a in the total solid components of the photosensitive coloring composition is 1.5 mass % or more, and the content of the photopolymerization initiator b is 1.5 mass % or more.

The photosensitive coloring composition of the present invention contains the photopolymerization initiator a and the photopolymerization initiator b as photopolymerization initiators in the above-mentioned specific ratio, so that it can be firmly cured to the deep part of the cured film by exposure. In addition, in the present invention, since a color material having a polymerizable group is used, when the photosensitive coloring composition is cured, the polymerizable group of the color material reacts with components other than the color material of the photosensitive coloring composition, and the color easily enters the cured film, and a cured film with excellent resistance to discoloration by a developer can be formed. Therefore, discoloration after development can be effectively suppressed. For example, when a filter having pixels of multiple colors is manufactured by sequentially forming patterns (pixels) of cured films of various colors using photosensitive coloring compositions of multiple colors, when forming pixels of the second color and later, the pixels formed in the previous step are also exposed to the developer, but by using the photosensitive coloring composition of the present invention, a cured film with excellent resistance to discoloration to the developer can be formed, so that when forming pixels of the second color and later, the discoloration of the pixels formed before can be suppressed. In addition, according to the photosensitive coloring composition of the present invention, the photosensitive coloring composition can be properly cured in the initial exposure (exposure before development). Therefore, a pattern with good rectangularity can be formed. Moreover, the entire photosensitive coloring composition can be cured in the next exposure (exposure after development). Therefore, it is also possible to form a pattern having excellent pattern forming properties and excellent resistance to discoloration by a developer. In addition, the photosensitive coloring composition of the present invention achieves particularly remarkable effects when a dye having a polymerizable group is used as a colorant having a polymerizable group. When a dye is used as a colorant, it tends to have a high affinity for the developer and tends to be easily discolored relative to the developer. Therefore, it is necessary to perform a heat treatment at a high temperature in the known photosensitive coloring composition to fully cure the film. However, according to the photosensitive coloring composition of the present invention, by using a dye having a polymerizable group, even at a low temperature, curing can form a cured film having excellent resistance to discoloration by a developer, so the effect of the present invention is particularly remarkable. Furthermore, by using a dye, a cured film having a vivid color and a high color value can be formed.

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

<<Photopolymerization initiator>> The photosensitive coloring composition of the present invention contains a photopolymerization initiator. Examples of the photopolymerization initiator include halogenated alkyl derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbisimidazole compounds, oxime compounds such as oxime derivatives, organic peroxides, hard compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoacetophenone compounds, hydroxyacetophenone compounds, benzoylformate compounds, etc. Specific examples of the photopolymerization initiator include, for example, paragraphs 0265 to 0268 of Japanese Patent Application Publication No. 2013-029760, which are incorporated into this specification.

The present invention can use a photopolymerization initiator with two or more functional groups as the photopolymerization initiator. Specific examples of such photopolymerization initiators include dimers of oxime compounds described in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No. WO2015/004565, paragraphs 0417 to 0412 of Japanese Patent Publication No. 2016-532675, paragraphs 0039 to 0055 of International Publication No. WO2017/033680, compounds (E) and (G) described in Japanese Patent Publication No. 2013-522445, and Cmpd1 to 7 described in International Publication No. WO2016/034963.

Examples of the benzoyl carboxylic acid ester compound include methyl benzoyl carboxylate, and examples of commercially available products include DAROCUR-MBF (manufactured by BASF Corporation).

As the aminoacetophenone compound, for example, there can be mentioned the aminoacetophenone compounds described in Japanese Patent Application Laid-Open No. 10-291969. Also, as the aminoacetophenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF) can be used.

As the acylphosphine compound, there can be mentioned the acylphosphine compounds described in Japanese Patent No. 4225898. As a specific example, there can be mentioned bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide, etc. As the acylphosphine compound, IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF) can also be used.

Examples of the hydroxyacetophenone compound include compounds represented by the following formula (V). Formula (V) [Chemical Formula 1] In the formula, ^Rv1 represents a substituent, ^Rv2 and ^Rv3 each independently represent a hydrogen atom or a substituent, ^Rv2 and ^Rv3 may also be bonded to each other to form a ring, and m represents an integer of 0 to 4.

As the substituent represented by Rv ¹ , alkyl groups (preferably alkyl groups having 1 to 10 carbon atoms) and alkoxy groups (preferably alkoxy groups having 1 to 10 carbon atoms) can be listed. Preferably, the alkyl group and the alkoxy group are straight chain or branched chain, and straight chain is more preferred. The alkyl group and the alkoxy group represented by Rv ¹ may be unsubstituted or may have a substituent. As the substituent, hydroxyl groups and groups having a hydroxyacetophenone structure can be listed. As the group having a hydroxyacetophenone structure, the benzene ring to which Rv ¹ in formula (V) is bonded or a group having a structure in which one hydrogen atom is removed from Rv ¹ can be listed.

^Rv2 and ^Rv3 each independently represent a hydrogen atom or a substituent. As a substituent, an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) is preferred. In addition, ^Rv2 and ^Rv3 may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, and more preferably an aliphatic ring having 4 to 8 carbon atoms). The alkyl group is preferably a straight chain or a branched chain, and a straight chain is more preferred.

As specific examples of the compound represented by formula (V), the following compounds can be cited. [Chemical Formula 2]

As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (product names: all manufactured by BASF) can also be used.

As the oxime compound, for example, the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-080068, and the compounds described in JP-A-2006-342166 can be used. As the oxime compound, compounds described in 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), Japanese Patent Application Publication No. 2000-066385, Japanese Patent Application Publication No. 2000-080068, Japanese Patent Application Publication No. 2004-534797, and Japanese Patent Application Publication No. 2006-342166 can also be used. Specific examples of oxime compounds include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)], ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime), etc. Among commercially available products, IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF) are preferably used. In addition, TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), ADEKA ARKLS NCI-930, ADEKA OPTOMER N-1919 (photopolymerization initiator 2 in Japanese Patent Application Publication No. 2012-014052) (all manufactured by ADEKA CORPORATION) can also be used.

In addition, as the oxime compound, the following compounds can be used, that is, the compounds described in Japanese Patent Publication No. 2009-519904 in which an oxime is linked to the N position of the carbazole ring, the compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced into the benzophenone site, and the compounds described in Japanese Patent Publication No. 2010-015025 and U.S. Patent Publication No. 2009-292 039, ketoxime compounds described in International Publication No. WO2009/131189, compounds described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule, compounds described in Japanese Patent Publication No. 2009-221114 having a maximum absorption at 405 nm and good sensitivity to a g-ray light source, etc. For example, it is preferred to refer to paragraphs 0274 to 0306 of Japanese Patent Publication No. 2013-029760, and the contents are incorporated into this specification.

Furthermore, as the oxime compound, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include compounds described in Japanese Patent Application Laid-Open No. 2014-137466. This content is incorporated into this specification.

Furthermore, as the oxime compound, an oxime compound having a benzofuran skeleton can also be used. As specific examples, compounds OE-01 to OE-75 described in International Publication No. WO2015/036910 can be cited.

Furthermore, as the oxime compound, an oxime compound having a carbazole ring and a skeleton in which at least one benzene ring is a naphthalene ring can also be used. As a specific example of such an oxime compound, the compound disclosed in International Publication No. WO2013/083505 can be cited.

Furthermore, as a photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of oxime compounds having a fluorine atom include compounds described in Japanese Patent Publication No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Publication No. 2014-500852, and compound (C-3) described in Japanese Patent Publication No. 2013-164471. This content is incorporated into this specification.

In addition, as the oxime compound, an oxime compound having a nitro group can be used. It is also preferred that the oxime compound having a nitro group is a dimer. As specific examples of the oxime compound having a nitro group, there can be cited the compounds described in paragraphs 0031 to 0047 of Japanese Patent Publication No. 2013-114249, paragraphs 0008 to 0012, 0070 to 0079 of Japanese Patent Publication No. 2014-137466, the compounds described in paragraphs 0007 to 0025 of Japanese Patent Publication No. 4223071, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION), etc.

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

[Chemical formula 3] [Chemical formula 4]

In the present invention, as photopolymerization initiators, a photopolymerization initiator a (hereinafter, also referred to as photopolymerization initiator a) having an absorbance coefficient of light at a wavelength of 365 nm in methanol of greater than 1.0×10 ² mL/gcm and a photopolymerization initiator b (hereinafter, also referred to as photopolymerization initiator b) having an absorbance coefficient of light at a wavelength of 365 nm in methanol of 1.0×10 ² mL/gcm or less and an absorbance coefficient of light at a wavelength of 254 nm of 1.0×10 ³ mL/gcm or more are used in combination. As photopolymerization initiator a and photopolymerization initiator b, compounds having the above-mentioned absorbance coefficients can be selected from the above-mentioned compounds and used.

In addition, in the present invention, the absorbance coefficient of the photopolymerization initiator at the above wavelength is a value measured as follows. That is, the absorbance coefficient is calculated by preparing a measurement solution by dissolving the photopolymerization initiator in methanol and measuring the absorbance of the measurement solution. Specifically, the measurement solution is added to a glass dish with a width of 1 cm, and the absorbance is measured using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies. The absorbance is substituted into the following formula to calculate the absorbance coefficient (mL/gcm) at a wavelength of 365 nm and a wavelength of 254 nm. [Formula 1] In the above formula, ε represents the absorption coefficient (mL/gcm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g/mL), and l represents the optical path length (cm).

The absorption coefficient of the photopolymerization initiator a for light having a wavelength of 365 nm in methanol is greater than 1.0×10 ² mL/gcm, preferably 1.0×10 ³ mL/gcm or more, more preferably 1.0×10 ³ to 1.0×10 ⁴ mL/gcm, further preferably 2.0×10 ³ to 9.0×10 ³ mL/gcm, and particularly preferably 3.0×10 ³ to 8.0×10 ³ mL/gcm. The extinction coefficient of the photopolymerization initiator a for light having a wavelength of 254 nm in methanol is preferably 1.0×10 ⁴ to 1.0×10 ⁵ mL/gcm, more preferably 1.5×10 ⁴ to 9.5×10 ⁴ mL/gcm, and even more preferably 3.0×10 ⁴ to 8.0×10 ⁴ mL/gcm.

As the photopolymerization initiator a, oxime compounds, aminoacetophenone compounds, and acylphosphine compounds are preferred, oxime compounds and acylphosphine compounds are more preferred, and oxime compounds are further preferred. Specific examples of the photopolymerization initiator a include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyl oxime)] (commercially available products include IRGACURE-OXE01, manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyl oxime) (commercially available products include IRGACURE-OXE02, manufactured by BASF), bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (commercially available products include IRGACURE-819, manufactured by BASF), and the compound (C-13) listed in the specific examples of the above-mentioned oxime compounds.

The extinction coefficient of the light having a wavelength of 365 nm in methanol of the photopolymerization initiator b is 1.0×10 ² mL/gcm or less, preferably 10 to 1.0×10 ² mL/gcm, and more preferably 20 to 1.0×10 ² mL/gcm. Furthermore, the difference between the extinction coefficient of the light having a wavelength of 365 nm in methanol of the photopolymerization initiator a and the extinction coefficient of the light having a wavelength of 365 nm in methanol of the photopolymerization initiator b is preferably 9.0×10 ² mL/gcm or more, more preferably 9.0×10 ² to 1.0×10 ⁵ mL/gcm, and even more preferably 9.0×10 ² to 1.0×10 ⁴ mL/gcm. The absorption coefficient of the photopolymerization initiator b for light having a wavelength of 254 nm in methanol is 1.0×10 ³ mL/gcm or more, preferably 1.0×10 ³ to 1.0×10 ⁶ mL/gcm, more preferably 5.0×10 ³ to 1.0×10 ⁵ mL/gcm, and even more preferably 1.0×10 ⁴ to 5.0×10 ⁵ mL/gcm.

As the photopolymerization initiator b, hydroxyacetophenone compounds, benzoylformate compounds, aminoacetophenone compounds, and acylphosphine compounds are preferred, hydroxyacetophenone compounds and benzoylformate compounds are more preferred, and hydroxyacetophenone compounds are further preferred. In addition, as the hydroxyacetophenone compound, the compound represented by the above formula (V) is preferred. As specific examples of the photopolymerization initiator b, 1-hydroxy-cyclohexyl-phenyl-ketone (as a commercial product, for example, IRGACURE-184, manufactured by BASF), 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (as a commercial product, for example, IRGACURE-2959, manufactured by BASF), etc. can be cited.

As a combination of photopolymerization initiator a and photopolymerization initiator b, from the viewpoint of being able to increase the absorption coefficient of light having a wavelength greater than 350 nm and less than 380 nm and the absorption coefficient of light having a wavelength greater than 254 nm and less than 350 nm, a combination in which photopolymerization initiator a is an oxime compound and photopolymerization initiator b is a hydroxyacetophenone compound is preferred, and a combination in which photopolymerization initiator a is an oxime compound and photopolymerization initiator b is a compound represented by the above formula (V) is more preferred.

The content of photopolymerization initiator a in the total solid content of the photosensitive coloring composition of the present invention is 1.5 mass % or more, preferably 1.5 to 15 mass %. From the perspective of the adhesion of the cured film (pattern) to the support after development, the lower limit of the content of photopolymerization initiator a is preferably 2 mass %, more preferably 3 mass %, and more preferably 5 mass %. From the perspective of miniaturization of the developed pattern, the upper limit of the content of photopolymerization initiator a is preferably 14.5 mass %, more preferably 12.5 mass %, and more preferably 9 mass %. Photopolymerization initiator a may include only one type or two or more types. When two or more photopolymerization initiators a are included, it is preferred that the total of the above range.

The content of the photopolymerization initiator b is 1.5% by mass or more, preferably 1.5 to 10% by mass, in the total solid components of the photosensitive coloring composition of the present invention. From the viewpoint of the discoloration resistance of the obtained cured film, the lower limit of the content of the photopolymerization initiator b is preferably 1.6% by mass or more, more preferably 2% by mass or more, and even more preferably 3% by mass or more. From the viewpoint of miniaturization of the developed pattern, the upper limit of the content of the photopolymerization initiator b is preferably 9.5% by mass or less, more preferably 7.5% by mass or less, and even more preferably 5% by mass or less. The photopolymerization initiator b may contain only one type or two or more types. When two or more types of photopolymerization initiators b are contained, it is preferably that the total of the above range.

The photosensitive coloring composition of the present invention preferably contains 50 to 500 parts by mass of the photopolymerization initiator a relative to 100 parts by mass of the photopolymerization initiator b. From the perspective of easily forming a cured film with excellent discoloration resistance, the upper limit is preferably 400 parts by mass or less, and more preferably 350 parts by mass or less. Furthermore, from the perspective of easily forming a cured film with a high residual film rate after development and excellent adhesion to a support, the lower limit is preferably 100 parts by mass or more, and even more preferably 150 parts by mass or more.

The total content of the photopolymerization initiator a and the photopolymerization initiator b in the total solid content of the photosensitive coloring composition of the present invention is preferably 3 to 17% by mass or more. From the perspective of the temporal stability of the composition, the lower limit is preferably 3.2% by mass or more, more preferably 3.5% by mass or more, and even more preferably 4.5% by mass or more. From the perspective of miniaturization of the developed pattern, the upper limit is preferably 16% by mass or less, more preferably 15% by mass or less, and even more preferably 14% by mass or less.

The photosensitive coloring composition of the present invention can also contain photopolymerization initiators other than photopolymerization initiator a and photopolymerization initiator b (hereinafter, also referred to as other photopolymerization initiators) as photopolymerization initiators, but it is preferred that other photopolymerization initiators are substantially not contained. The situation of substantially not containing other photopolymerization initiators is as follows: relative to the total of 100 parts by mass of photopolymerization initiators a and photopolymerization initiators b, the content of other photopolymerization initiators is preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, and even more preferably 0.1 parts by mass or less, and it is even more preferred that other photopolymerization initiators are not contained.

＜＜Colorant with polymerizable group＞＞ The photosensitive coloring composition of the present invention contains a colorant with a polymerizable group. The colorant with a polymerizable group may be a pigment or a dye, with dyes being preferred. That is, the colorant with a polymerizable group is preferably a dye with a polymerizable group. The cured film obtained using the photosensitive coloring composition containing a dye as a colorant tends to be easily decolorized by a developer, and by using a dye with a polymerizable group, a cured film having excellent decolorization resistance to a developer can be formed even when the film is cured at a low temperature. Therefore, the effect of the present invention is more significant. In addition, in this specification, a dye refers to a pigment compound dissolved in water or an organic solvent. For example, it is preferred that the pigment compound be dissolved in cyclohexanone or propylene glycol monomethyl ether acetate (PGMEA) at 25°C at a concentration of 0.1 mass % or more.

The color material having a polymerizable group has a triarylmethane pigment structure, a dibenzopyran pigment structure, an anthraquinone pigment structure, a cyanine pigment structure, a squarylium salt pigment structure, a quinophthalone pigment structure, a phthalocyanine pigment structure, a subphthalocyanine pigment structure, an azo pigment structure, a pyrazolotriazole pigment structure, a dipyrromethene pigment structure, an isoindoline pigment structure, a thiazole pigment structure, a benzimidazolone pigment structure, a peroxycyclic ketone pigment structure, a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a diammonium pigment structure, a naphthalocyanine pigment structure, a perylene pigment structure, a dibenzofuranone pigment structure, a merocyanine pigment structure, a crotonium pigment structure, and an oxocyanine pigment. A compound having a pigment structure selected from the structure is preferred, and a compound having a pigment structure selected from the group consisting of a triarylmethane pigment structure, a dibenzopyran pigment structure, anthraquinone pigment structure, a cyanine pigment structure, a squarylium pigment structure, a quinophthalone pigment structure, a phthalocyanine pigment structure, a subphthalocyanine pigment structure, an azo pigment structure, a thiazole pigment structure, a pyrazolotriazole pigment structure, and a dipyrromethene pigment structure is more preferred, and a compound having a pigment structure selected from the group consisting of a triarylmethane pigment structure, a dibenzopyran pigment structure, and a dipyrromethene pigment structure is further preferred, and a compound having a triarylmethane pigment structure or a dibenzopyran pigment structure is particularly preferred.

(Compound Having a Triarylmethane Dye Structure) Examples of the compound having a triarylmethane dye structure include compounds represented by the following formula (TP).

Formula (TP) [Chemical formula 5]

In formula (TP), Rtp ¹ to Rtp ⁴ each independently represent a hydrogen atom, an alkyl group or an aryl group. Rtp ⁵ represents a hydrogen atom, an alkyl group, an aryl group or NRtp ⁹ Rtp ¹⁰ (Rtp ⁹ and Rtp ¹⁰ represent a hydrogen atom, an alkyl group or an aryl group). Rtp ⁶ , Rtp ⁷ and Rtp ⁸ represent a substituent. a, b and c represent integers of 0 to 4. When a, b and c are 2 or more, Rtp ⁶ , Rtp ⁷ and Rtp ⁸ may be linked to each other to form a ring. X represents an anion. When X is absent, at least one of Rtp ¹ to Rtp ⁸ contains an anion. At least one of Rtp ¹ to Rtp ⁸ contains a polymerizable group.

Rtp ¹ to Rtp ⁴ are preferably hydrogen atom, linear or branched alkyl group having 1 to 5 carbon atoms, or phenyl group. Rtp ⁵ is preferably hydrogen atom or NRtp ⁹ Rtp ¹⁰ , and NRtp ⁹ Rtp ¹⁰ is particularly preferred. Rtp ⁹ and Rtp ¹⁰ are preferably hydrogen atom, linear or branched alkyl group having 1 to 5 carbon atoms, or phenyl group. The substituent represented by Rtp ⁶ , Rtp ⁷ , and Rtp ⁸ may include the groups or polymerizable groups listed in the substituent group T group described later.

In formula (TP), X represents a counter anion. When X is absent, at least one of Rtp ¹ to Rtp ⁸ contains an anion. There is no particular limitation on the counter anion. It can be an organic anion or an inorganic anion. The counter anion is preferably an organic anion. Examples of the counter anion include fluorine anions, chlorine anions, bromine anions, iodine anions, cyanide anions, perchlorate anions, non-nucleophilic anions, and the like. From the viewpoint of heat resistance, non-nucleophilic anions are preferred. As an example of a counter anion, there can be cited the known non-nucleophilic anions described in paragraph 0075 of Japanese Patent Application Laid-Open No. 2007-310315, and the contents thereof are incorporated into this specification. The non-nucleophilicity refers to the property of not attacking the dye nucleophilically by heating.

The counter anion is preferably an imide anion (e.g., a bis(sulfonyl)imide anion), a tri(sulfonyl)methyl anion, or an anion having a boron atom, more preferably a bis(sulfonyl)imide anion and a tri(sulfonyl)methyl anion, and more preferably a bis(sulfonyl)imide anion. Examples of anions having a boron atom include tetrafluoroborate anions, tetraphenylborate anions, and tetraperfluorophenylborate anions. The molecular weight of the counter anion is preferably 100 to 1,000, and more preferably 200 to 500.

In formula (TP), a, b or c each independently represents an integer of 0 to 4. In particular, a and c are each preferably 0 or 1, more preferably 0. b is preferably an integer of 0 to 2, more preferably 0 or 2.

In formula (TP), when at least one of Rtp ¹ to Rtp ⁷ contains anions, the anions are preferably -SO ₃ ^- , -COO ^- , -PO ₄ ^- , bis(sulfonyl)imide anions, tris(sulfonyl)methide anions and tetraarylborate anions, more preferably bis(sulfonyl)imide anions, tris(sulfonyl)methide anions and tetraarylborate anions, and still more preferably bis(sulfonyl)imide anions and tris(sulfonyl)methide anions. Specifically, structures obtained by replacing at least one of Rtp ¹ to Rtp ⁷ with the formula (P) can be listed. Formula (P) [Chemical Formula 6] In formula (P), L represents a single bond or a divalent linking group, and ^X1 represents an anion.

In formula (P), L represents a single bond or a divalent linking group. As the divalent linking group, -NR ¹⁰ -, -O-, -SO ₂ -, an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, or a group consisting of a combination thereof is preferred. In particular, a group consisting of a combination of -NR ¹⁰ -, -SO ₂ and an alkylene group containing a fluorine atom, a group consisting of a combination of -O- and an arylene group containing a fluorine atom, or a group consisting of a combination of -NR ¹⁰ -, -SO ₂ and an alkylene group containing a fluorine atom is preferred. In -NR ¹⁰ -, R ¹⁰ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom. The alkylene group containing a fluorine atom preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 3 carbon atoms. The alkylene groups are more preferably perfluoroalkylene groups. Specific examples of fluorine-substituted alkylene groups include difluoromethylene, tetrafluorovinyl, hexafluoropropylene, etc. The carbon number of the arylene group containing fluorine atoms is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10. Specific examples of the arylene group containing fluorine atoms include tetrafluorophenylene, hexafluoro-1-naphthylene, hexafluoro-2-naphthylene, etc.

In formula (P), ^X1 represents an anion, preferably one selected from the group consisting of _-SO3- ^{, -COO-} , _-PO4- ^, bis(sulfonyl)imide anion, tri(sulfonyl)methide anion and tetraarylborate anion, more preferably one selected from the group consisting of bis(sulfonyl)imide anion, tri(sulfonyl)methide anion and tetraarylborate anion, and even more preferably bis(sulfonyl)imide anion or tri(sulfonyl)methide anion.

When at least one of Rtp ¹ to Rtp ⁸ contains an anion, at least one of Rtp ¹ to Rtp ⁸ is preferably a structure obtained by substitution with Formula (P-1). Formula (P-1) [Chemical Formula 7] In formula (P-1), ^L1 represents a single bond or a divalent linking group, and a single bond is preferred. Examples of the divalent linking group represented by ^L1 include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, -O-, -S-, or a group composed of these groups. ^L2 represents _-SO2- or -CO-. G represents a carbon atom or a nitrogen atom. When G is a carbon atom, n1 represents 2, and when G is a nitrogen atom, n1 represents 1. ^R6 represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. When n1 is 2, two ^R6s may be the same or different. The alkyl group containing a fluorine atom represented by ^R6 preferably has a carbon number of 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The carbon number of the aryl group containing a fluorine atom represented by R ⁶ is preferably 6 to 20, more preferably 6 to 14, and even more preferably 6 to 10.

(Compound Having a Dibenzopyran Dye Structure) Examples of the compound having a dibenzopyran dye structure include compounds represented by the following formula (J).

(Formula J) [Chemical Formula 8]

In formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, R ⁸⁵ each independently represents a monovalent substituent, and m represents an integer of 0 to 5. X represents a counter anion. When X is absent, at least one of R ⁸¹ to R ⁸⁵ contains an anion. At least one of R ⁸¹ to R ⁸⁵ contains a polymerizable group.

The substituents that may be present in R ⁸¹ to R ⁸⁵ in formula (J) include the groups or polymerizable groups listed in the substituent T described later. R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ , and R ⁸⁵ when m is 2 or more in formula (J) may independently bond to each other to form a 5-, 6-, or 7-membered saturated ring, or a 5-, 6-, or 7-membered unsaturated ring. Examples of the ring formed include pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, pyridine ring, and oxazine ring, and preferably include benzene ring and pyridine ring. When the ring formed is a further substitutable group, it may be substituted by the substituents described for R ⁸¹ to R ^85. When it is substituted by two or more substituents, the substituents may be the same or different.

In formula (J), X represents a counter anion. Examples of the counter anion include the counter anions described in formula (TP). When X is absent, at least one of R ⁸¹ to R ⁸⁵ includes an anion. In formula (J), when at least one of R ⁸¹ to R ⁸⁵ includes an anion, examples of the anion include the anions described in formula (TP).

(Compounds having a dipyrromethene structure) As compounds having a dipyrromethene structure, dipyrromethene compounds and dipyrromethene metal complex compounds obtained from dipyrromethene compounds and metals or metal compounds are preferred. For example, dipyrromethene pigments represented by formula (PM) are preferred. Formula (PM) [Chemical formula 9] In the formula, ^R1 , ^R2 , ^R3 , ^R4 , ^R5 and ^R6 each independently represent a hydrogen atom or a substituent, and ^R7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group or a heterocyclic group. Examples of the substituent include the substituent group T described below. At least one of ^R1 to ^R7 contains a polymerizable group.

The metal or metal compound that forms the dipyrromethene metal complex compound is described. The metal or metal compound may be any metal atom or metal compound that can form a complex, including a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or a divalent metal chloride. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., it also includes metal chlorides such as AlCl, InCl, FeCl, TiCl ₂ , SnCl, SiCl ₂ , GeCl ₂ , metal oxides such as TiO, VO, and metal hydroxides such as Si(OH) ₂ . Among them, from the viewpoints of stability of the complex, spectral characteristics, heat resistance, light resistance and manufacturing suitability, Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B or VO is preferred, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B or VO is further preferred, and Fe, Zn, Cu, Co, B or VO (V=O) is the most preferred. Among them, Zn is particularly preferred.

The details of the dipyrromethene pigment structure can be found in paragraphs 0045 to 0095 of Japanese Patent Application Publication No. 2014-132348 and paragraphs 0033 to 0136 of Japanese Patent Application Publication No. 2011-095732, and the contents are incorporated into the present specification.

(Substituent T group) As the substituent T group, the following groups can be listed. Alkyl (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl (preferably an alkynyl group having 2 to 30 carbon atoms), aryl (preferably an aryl group having 6 to 30 carbon atoms), amino (preferably an amino group having 0 to 30 carbon atoms), alkoxy (preferably an alkoxy group having 1 to 30 carbon atoms), aryloxy (preferably an aryloxy group having 6 to 30 carbon atoms), heteroaryloxy, acyl (preferably an acyl group having 1 to 30 carbon atoms) ), alkoxycarbonyl (preferably an alkoxycarbonyl having 2 to 30 carbon atoms), aryloxycarbonyl (preferably an aryloxycarbonyl having 7 to 30 carbon atoms), acyloxy (preferably an acyloxy having 2 to 30 carbon atoms), amide (preferably an amide having 2 to 30 carbon atoms), alkoxycarbonylamino (preferably an alkoxycarbonylamino having 2 to 30 carbon atoms), aryloxycarbonylamino (preferably an aryloxycarbonylamino having 7 to 30 carbon atoms), sulfonylamine (preferably Preferably, the group is an aminosulfonyl group having 0 to 30 carbon atoms), an aminoformyl group (preferably an aminoformyl group having 1 to 30 carbon atoms), an alkylthio group (preferably an alkylthio group having 1 to 30 carbon atoms), an arylthio group (preferably an arylthio group having 6 to 30 carbon atoms), a heteroarylthio group (preferably a carbon number of 1 to 30 carbon atoms), an alkylsulfonyl group (preferably a carbon number of 1 to 30 carbon atoms), an arylsulfonyl group (preferably a carbon number of 6 to 30 carbon atoms), a heteroarylsulfonyl group (preferably a carbon number of 1 to 30 carbon atoms), an alkyl Sulfinyl group (preferably having 1 to 30 carbon atoms), arylsulfinyl group (preferably having 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably having 1 to 30 carbon atoms), urea group (preferably having 1 to 30 carbon atoms), hydroxyl group, carboxyl group, sulfonic acid group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imidic acid group, hydrazine group, alkylsulfinyl group, arylsulfinyl group, hydrazine group, imino group, heteroaryl group (preferably having 1 to 30 carbon atoms). When these groups are groups that can be further substituted, they may also have substituents. As substituents, the groups described in the above substituent T can be listed.

Examples of the polymerizable group possessed by the color material include olefinic unsaturated groups such as vinyl, (meth)allyl, and (meth)acryloyl.

Since it is easy to form a cured film with excellent resistance to discoloration by a developer, the color material having a polymerizable group is preferably a pigment polymer. A pigment polymer is a pigment compound having two or more pigment structures in one molecule, preferably having three or more pigment structures. The upper limit is not particularly limited and can be set to 100 or less. The pigment structure in one molecule can be the same pigment structure or different pigment structures. In addition, in the present invention, different pigment structures refer not only to pigment structures with different pigment skeletons, but also to pigment structures with the same pigment skeleton but different types of substituents bonded to the pigment skeleton.

The pigment multimer is preferably a pigment multimer comprising at least one of a repeating unit represented by the formula (A) described below, a repeating unit represented by the formula (B), and a repeating unit represented by the formula (C), or a pigment multimer represented by the formula (D) described below. That is, the pigment multimer is preferably a pigment multimer having a repeating unit represented by the formula (A) (also referred to as a pigment multimer (A)), a pigment multimer having a repeating unit represented by the formula (B) (also referred to as a pigment multimer (B)), a pigment multimer having a repeating unit represented by the formula (C) (also referred to as a pigment multimer (C)), and a pigment multimer represented by the formula (D) (also referred to as a pigment multimer (D)), and more preferably, the pigment multimer (A) or the pigment multimer (D).

(Dye polymer (A)) The dye polymer (A) preferably contains a repeating unit represented by formula (A). The ratio of the repeating unit represented by formula (A) is preferably 10% by mass or more of all the repeating units constituting the dye polymer (A), more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit can be set to 100% by mass or less, and can also be set to 95% by mass or less. [Chemical formula 10] In formula (A), ^X1 represents the main chain of the repeating unit, ^L1 represents a single bond or a divalent linking group, and ^D1 represents a pigment structure.

In formula (A), ^X1 represents a main chain of repeating units. ^X1 may be a linking group formed by polymerization reaction, and preferably a main chain derived from a compound having a (meth)acrylic group, a styrene group, a vinyl group, or an ether group. Also preferably, the main chain has a cyclic alkylene group. There is no particular limitation on ^X1 as long as it is a linking group formed by a known polymerizable monomer. The linking group represented by the following (XX-1) to (XX-25) is preferred, more preferably selected from (XX-1), (XX-2), (XX-10) to (XX-17), (XX-18), (XX-19), (XX-24) and (XX-25), and even more preferably selected from (XX-1), (XX-2), (XX-10) to (XX-17), (XX-24) and (XX-25).

In the following formulae, * represents a bonding site with ^L1 in formula (A). Me represents a methyl group. In (XX-18) and (XX-19), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

[Chemical formula 11]

^L1 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, _-SO2- , and a linking group formed by linking two or more of these groups. R represents independently a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

The number of carbon atoms in the alkylene group is preferably 1 to 30. The upper limit is preferably 25 or less, and 20 or less is further preferred. The lower limit is preferably 2 or more, and 3 or more is further preferred. The alkylene group may be any of a linear chain, a branched chain, and a cyclic group. The alkylene group may have a substituent or may be unsubstituted. As a substituent, the groups described in the substituent group T group may be listed. The number of carbon atoms in the arylene group is preferably 6 to 20, and 6 to 12 is more preferred. The arylene group may have a substituent or may be unsubstituted. As a substituent, the groups described in the substituent group T group may be listed. The heterocyclic connecting group is preferably a 5-membered ring or a 6-membered ring. The hetero atom possessed by the heterocyclic connecting group is preferably an oxygen atom, a nitrogen atom, and a sulfur atom. The number of heteroatoms in the heterocyclic linking group is preferably 1 to 3. The heterocyclic linking group may have a substituent or may be unsubstituted. As the substituent, the groups described in the substituent group T can be cited.

^D1 represents a pigment structure. The type of the pigment structure represented by ^D1 is not particularly limited. Examples thereof include a triarylmethane pigment structure, a phthalocyanine pigment structure, an anthraquinone pigment structure, a cyanine pigment structure, a squarylium pigment structure, a quinophthalone pigment structure, a phthalocyanine pigment structure, a subphthalocyanine pigment structure, an azo pigment structure, a pyrazolotriazole pigment structure, a dipyrromethene pigment structure, an isoindoline pigment structure, a thiazole pigment structure, a benzimidazolone pigment structure, a violaceous copper pigment structure, a pyrrolopyrrole pigment structure, a diketopyrrolopyrrole pigment structure, a diammonium pigment structure, a naphthacyanine pigment structure, a retinol pigment structure, a dibenzofuranone pigment structure, a merocyanine pigment structure, a crotonium pigment structure, and an oxocyanine pigment structure. The pigment structure represented by ^D1 may contain a polymerizable group.

The pigment multimer (A) preferably has a repeating unit containing a polymerizable group in addition to the repeating unit represented by the formula (A). In addition, when the pigment structure represented by ^D1 in the above formula (A) does not have a polymerizable group, the pigment multimer (A) has a repeating unit containing a polymerizable group.

The pigment polymer (A) may contain other repeating units in addition to the repeating units represented by the formula (A). The other repeating units may contain functional groups such as polymerizable groups and acid groups. They may not contain functional groups. In addition, when the pigment structure represented by ^D1 in the above formula (A) does not have a polymerizable group, the pigment polymer (A) has a repeating unit containing a polymerizable group.

The ratio of the repeating unit having a polymerizable group is preferably 0 to 50 mass % of all the repeating units constituting the dye multimer (A). The lower limit is more preferably 1 mass % or more, and more preferably 3 mass % or more. The upper limit is more preferably 35 mass % or less, and more preferably 30 mass % or less.

Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group. The acid group may include only one type or two or more types. The ratio of the repeating unit having an acid group is preferably 0 to 50% by mass of all the repeating units constituting the pigment multimer (A). The lower limit is more preferably 1% by mass, and more preferably 3% by mass. The upper limit is more preferably 35% by mass or less, and more preferably 30% by mass or less.

As other functional groups, groups containing 2 to 20 repeated unsubstituted alkylene oxide chains, lactone, acid anhydride, amide, cyano and other development-promoting groups, long-chain and cyclic alkyl, aralkyl, aryl, polyalkylene, hydroxyl, cis-butenediimide, amino and other hydrophilicity adjusting groups can be introduced appropriately. In the group containing 2 to 20 repeated unsubstituted alkylene oxide chains, the number of repeated alkylene oxide chains is preferably 2 to 15, more preferably 2 to 10. One alkylene oxide chain is represented by -(CH ₂ ) _n O-, where n is an integer, preferably 1 to 10, more preferably 1 to 5, and more preferably 2 or 3.

Specific examples of other repeating units are shown, but the present invention is not limited thereto. In the following structural formula, Me represents a methyl group and Et represents an ethyl group. [Chemical Formula 12] [Chemical formula 13]

(Pigment polymer (B)) The pigment polymer (B) contains a repeating unit represented by formula (B). The ratio of the repeating unit represented by formula (B) is preferably 10% by mass or more of all the repeating units constituting the pigment polymer (B), more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit can be set to 100% by mass or less, and can also be set to 95% by mass or less. [Chemical formula 14] In formula (B), ^X2 represents the main chain of the repeating unit, ^L2 represents a single bond or a divalent linking group, ^D2 represents a pigment structure having a group capable of ionically bonding or coordinately bonding with ^Y2 , and ^Y2 represents a group capable of ionically bonding or coordinately bonding with ^D2 ;

^X2 has the same meaning as ^X1 in formula (A), and the preferred range is also the same. ^L2 represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, _-SO2- , and a linking group formed by linking two or more of these groups. R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. The details of the divalent linking group are the same as those of ^L1 in formula (A). L ² is a single bond, or an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, or a divalent linking group obtained by combining two or more of these groups.

Y ² can be any group as long as it can form an ionic bond or a coordination bond with D ^2. For example, anionic groups and cationic groups can be listed. Examples of anionic groups include -SO ₃ ^- , -COO ^- , -PO ₄ ^- , -PO ₄ H ^- , bis(sulfonyl)imide anions, tri(sulfonyl)methide anions, and tetraarylborate anions. Examples of cationic groups include substituted or unsubstituted onium cations (e.g., ammonium, pyridinium, imidazolium, and phosphonium), and ammonium cations are particularly preferred. As the ammonium cation, -N(R) ₃ ⁺ can be cited. R each independently represents a hydrogen atom or an alkyl group, and at least one of R represents an alkyl group. The carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 5. The alkyl group may be any of a straight chain, a branched chain, and a cyclic chain, and a straight chain is preferred.

^D2 represents a pigment structure having a group capable of ionically bonding or coordinately bonding with ^Y2 . The type of pigment structure is not particularly limited, and the types of pigment structures described in ^D1 can be listed. As the group capable of ionically bonding or coordinately bonding with ^Y2 possessed by ^D2 , the anionic group and cationic group described in ^Y2 can be listed. In addition, when the charge balance of ^D2 is biased toward either the cation or the anion, it can also bond with ^Y2 in the cationic part or the anionic part of ^D2 . The pigment structure represented by ^D2 may have a polymerizable group.

The pigment multimer (B) may contain other repeating units described for the pigment multimer (A) in addition to the repeating units represented by the formula (B). Furthermore, it may contain repeating units represented by the above formula (A) and repeating units represented by the formula (C) described later. In addition, when the pigment structure represented by ^D2 in the above formula (B) does not have a polymerizable group, the pigment multimer (B) has a repeating unit containing a polymerizable group.

(Dye polymer (C)) The dye polymer (C) preferably contains a repeating unit represented by formula (C). The ratio of the repeating unit represented by formula (C) is preferably 10% by mass or more of all the repeating units constituting the dye polymer (C), more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 50% by mass or more. The upper limit can be set to 100% by mass or less, and can also be set to 95% by mass or less. [Chemical Formula 15] In formula (C), L ³ represents a single bond or a divalent linking group, D ³ represents a pigment structure, and m represents 0 or 1.

In formula (C), L ³ represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group having 1 to 30 carbon atoms, an arylene group having 6 to 30 carbon atoms, a heterocyclic linking group, -CH=CH-, -O-, -S-, -C(=O)-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO ₂ -, and a linking group formed by linking two or more of these groups. R each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The carbon number of the alkyl group and the alkylene group is preferably 1 to 30. The upper limit is preferably 25 or less, and 20 or less is further preferred. The lower limit is preferably 2 or more, and 3 or more is further preferred. The alkyl group and the alkylene group may be any of a straight chain, a branched chain, and a ring. The carbon number of the aryl group and the arylene group is preferably 6 to 20, and 6 to 12 is more preferred. The heterocyclic connecting group and the heterocyclic group are preferably 5-membered rings or 6-membered rings. The heteroatoms possessed by the heterocyclic connecting group and the heterocyclic group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms possessed by the heterocyclic connecting group and the heterocyclic group is preferably 1 to 3. The alkylene group, arylene group, heterocyclic linking group, alkyl group, aryl group and heterocyclic group may be unsubstituted or may have a substituent. As the substituent, a polymerizable group and an acid group may be listed. In addition, a group containing 2 to 20 repeated unsubstituted alkylene oxide chains, a developing promoting group such as a lactone, an acid anhydride, an amide, and a cyano group, a long chain and cyclic alkyl group, an aralkyl group, an aryl group, a polyalkylene group, a hydroxyl group, a cis-butylene diimide group, an amine group and the like may be used as a substituent.

^L3 is preferably an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, -S-, or a linking group obtained by combining two or more of these groups. ^D3 represents a pigment structure. The type of the pigment structure is not particularly limited, and the pigment structure of the type described in ^D1 can be listed. The pigment structure represented by ^D3 may have a polymerizable group. m represents 0 or 1, and 1 is preferred.

The pigment polymer (C) contains the other repeating units described for the pigment polymer (A) in addition to the repeating units represented by the general formula (C).

(Dye polymer (D)) The dye polymer (D) is preferably represented by the formula (D). [Chemical formula 16] In formula (D), ^L4 represents a (n+k)-valent linking group, ^L41 and ^L42 each independently represent a single bond or a divalent linking group, ^D4 represents a pigment structure, ^P4 represents a substituent; n represents 2 to 15, k represents 0 to 13, and n+k is 2 to 15. n ^D4s may be different from each other or the same. When k is 2 or more, a plurality of ^P4s may be different from each other or the same.

n is preferably 2 to 14, more preferably 2 to 8, particularly preferably 2 to 7, and further preferably 2 to 6. k is preferably 1 to 13, more preferably 1 to 10, further preferably 1 to 8, particularly preferably 1 to 7, and further preferably 1 to 6.

L ⁴¹ and L ⁴² each independently represent a single bond or a divalent linking group. The divalent linking group includes a group consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms, which may be unsubstituted or have a substituent. Specific examples of the divalent linking group include the following structural units or groups consisting of two or more of the following structural units combined.

[Chemical formula 17]

As the (n+k)-valent linking group represented by L ⁴ , there are groups consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms and 0 to 20 sulfur atoms. As the (n+k)-valent linking group, the following structural units or groups consisting of two or more of the following structural units combined (which may also form a ring structure) can be listed.

[Chemical formula 18]

Specific examples of the (n+k)-valent linking group include the linking group described in paragraphs 0071 to 0072 of Japanese Patent Application Laid-Open No. 2008-222950 and the linking group described in paragraph 0176 of Japanese Patent Application Laid-Open No. 2013-029760.

In the general formula (D), ^D4 represents a pigment structure. The type of the pigment structure is not particularly limited, and the pigment structures described for ^D1 can be exemplified. The pigment structure represented by ^D4 may contain a polymerizable group.

In formula (D), as the substituent represented by P ⁴ , an acid group, a polymerizable group, etc. can be listed. In addition, the substituent represented by P ⁴ can be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound. When k is 2 or more, the k P ^4s may be the same or different. When the pigment structure represented by D ⁴ does not contain a polymerizable group, one or more of the k P ^4s represent a polymerizable group.

The pigment polymer represented by formula (D) is preferably a structure represented by formula (D-1). [Chemical Formula 19]

In formula (D-1), L ⁴ represents a (n+k)-valent linking group. n represents 2 to 15, and k represents 0 to 13. D ⁴ represents a pigment structure, and P ⁴ represents a substituent. B ⁴¹ and B ⁴² each independently represent a single bond, -O-, -S-, -CO-, -NR-, -O ₂ C-, -CO ₂ -, -NROC-, or -CONR-. R represents a hydrogen atom, an alkyl group, or an aryl group. C ⁴¹ and C ⁴² each independently represent a single bond or a divalent linking group. S represents a sulfur atom. n D ^4s may be different from each other or the same. When k is 2 or more, a plurality of P ^4s may be different from each other or the same. n+k is 2 to 15.

L ⁴ , D ⁴ and P ⁴ in formula (D-1) have the same meanings as L ⁴ , D ⁴ and P ⁴ in formula (D). B ⁴¹ and B ⁴² in formula (D-1) are preferably a single bond, -O-, -CO-, -O ₂ C-, -CO ₂ -, -NROC- or -CONR-, more preferably a single bond, -O-, -CO-, -O ₂ C- or -CO ₂ -. R represents a hydrogen atom, an alkyl group or an aryl group.

As the divalent linking group represented by ^C41 and ^C42 in formula (D-1), an alkylene group, an arylene group, and a group formed by combining these groups are preferred. The carbon number of the alkylene group is preferably 1 to 30, and more preferably 1 to 10. The alkylene group may be any of a linear chain, a branched group, and a ring. The carbon number of the arylene group is preferably 6 to 30, and more preferably 6 to 12.

The weight average molecular weight (Mw) of the pigment polymer is preferably 2000 to 50000. The lower limit is more preferably 3000 or more, and more preferably 6000 or more. The upper limit is more preferably 30000 or less, and more preferably 20000 or less. By keeping within the above range, it is easy to produce a cured film with excellent discoloration resistance.

The content of the color material having a polymerizable group in the total solid content of the photosensitive coloring composition is preferably 5 to 40 mass %. The lower limit is 6 mass % or more, which is more preferably, and 10 mass % or more is further preferably. The upper limit is 35 mass % or less, which is more preferably, and 30 mass % or less is further preferably. In addition, the content of the color material having a polymerizable group is preferably 25 to 500 mass parts relative to 100 mass parts in total of the photopolymerization initiator a and the photopolymerization initiator b. The lower limit is 30 mass parts or more, which is more preferably, 50 mass parts or more is further preferably, and 100 mass parts or more is particularly preferably. The upper limit is 450 mass parts or less, which is more preferably, 400 mass parts or less is further preferably, and 350 mass parts or less is particularly preferably. Within this range, a cured film having excellent resistance to discoloration by a developer can be more easily obtained.

＜＜Other colorants＞＞ The photosensitive coloring composition of the present invention can also contain a colorant that does not have a polymerizable group (hereinafter, also referred to as other colorants). The other colorant can be any of a pigment and a dye. As the pigment, inorganic pigments and organic pigments can be listed, and organic pigments are preferred. As the average particle size of the pigment, 20 to 300 nm is preferred, 25 to 250 nm is more preferred, and 30 to 200 nm is further preferred. The "average particle size" mentioned here refers to the average particle size of the secondary particles formed by the aggregation of the primary particles of the pigment. In addition, the particle size distribution of the secondary particles of the pigment (hereinafter, also referred to as "particle size distribution") is that the secondary particles entering (average particle size ± 100) nm account for more than 70% by mass of the whole, and preferably more than 80% by mass. In addition, the particle size distribution of secondary particles can be measured using the scattering intensity distribution. In addition, the average particle size of primary particles is determined by observing the particle size of 100 particles in the non-agglomerated part using a scanning electron microscope (SEM) or a transmission electron microscope (TEM) and calculating the average value.

As organic pigments, for example, the following can be listed. Color Index (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, etc. (the above are yellow pigments), C.I.Pigment Orange2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. (the above are orange pigments), C.I.Pigment Red1, 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, 1 49, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, 279, etc. (the above are red pigments), C.I.Pigment Green7, 10, 36, 37, 58, 59, etc. (the above are green pigments), C.I.Pigment Violet1, 19, 23, 27, 32, 37, 42, etc. (the above are purple pigments), C.I.Pigment Blue1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80, etc. (the above are blue pigments).

Furthermore, as a green pigment, a zinc phthalocyanine halogenide pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can be used. As a specific example, the compound described in the international publication WO2015/118720 can be cited. Furthermore, as a blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. As a specific example, the compound described in paragraphs 0022 to 0030 of Japanese Patent Publication No. 2012-247591 and paragraph 0047 of Japanese Patent Publication No. 2011-157478 can be cited.

The dye is not particularly limited, and known dyes can be used. As the chemical structure, dyes such as pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxocyanine, pyrazolotriazole azo, pyridone azo, cyanine, phenothioin, pyrrolopyrazole azoimine, phthalocyanine, benzopyran, indigo, and pyrromethene can be used. In addition, thiazole compounds described in Japanese Patent Publication No. 2012-158649, azo compounds described in Japanese Patent Publication No. 2011-184493, and azo compounds described in Japanese Patent Publication No. 2011-145540 can also be preferably used. Furthermore, as the yellow dye, quinophthalone compounds described in paragraphs 0011 to 0034 of JP-A-2013-054339, quinophthalone compounds described in paragraphs 0013 to 0058 of JP-A-2014-026228, and the like can also be used.

When the photosensitive coloring composition of the present invention contains other colorants, the content of the other colorants is preferably 5 to 50 mass % in the total solid content of the photosensitive coloring composition. The lower limit is 6 mass % or more, which is more preferably, and 10 mass % or more is further preferably. The upper limit is 45 mass % or less, which is more preferably, and 40 mass % or less is further preferably. In addition, the content of the pigment of other colorants is preferably 50 mass % or more, 70 mass % or more is more preferably, and 80 mass % or more is further preferably. In addition, the total amount of the colorant having a polymerizable group and other colorants is preferably 20 to 70 mass % in the total solid content of the photosensitive coloring composition. The lower limit is 25 mass % or more, which is more preferably, and 30 mass % or more is further preferably. The upper limit is preferably 70% by mass or less, and 55% by mass or less is further preferred. In addition, the content of the dye in the coloring material (the total of the coloring material having a polymerizable group and other coloring materials) contained in the photosensitive coloring composition of the present invention is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more.

＜＜Resin＞＞ The photosensitive coloring composition of the present invention includes a resin. Examples of the resin include alkali-soluble resins. The resin is mixed for the purpose of dispersing particles such as pigments in the composition or for the purpose of a binder. In addition, a resin mainly used to disperse particles such as pigments is also called a dispersant. However, these uses of the resin are just examples, and the resin can also be used for purposes other than these uses.

In the photosensitive coloring composition of the present invention, the content of the resin is preferably 1 to 80 mass % in the total solid content of the photosensitive coloring composition. The lower limit is more preferably 5 mass % or more, and more preferably 10 mass % or more. The upper limit is more preferably 70 mass % or less, and more preferably 60 mass % or less.

(Alkali-soluble resin) The photosensitive coloring composition of the present invention includes an alkali-soluble resin. The alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali dissolution. Examples of the group that promotes alkali dissolution (hereinafter, also referred to as an acid group) include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, and a carboxyl group is preferred. The type of acid group possessed by the alkali-soluble resin may be only one type, or may be two or more types.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5000 to 100,000. The number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 to 20,000.

The acid value of the alkali-soluble resin is preferably 25 to 200 mgKOH/g. The lower limit is more preferably 30 mgKOH/g or more, and more preferably 40 mgKOH/g or more. The upper limit is more preferably 150 mgKOH/g or less, and more preferably 120 mgKOH/g or less, and particularly preferably 100 mgKOH/g or less.

As the alkali-soluble resin, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic acid/acrylamide copolymer resins are preferred from the viewpoint of heat resistance. Also, acrylic resins, acrylamide resins, and acrylic acid/acrylamide copolymer resins are preferred from the viewpoint of controlling the developing property.

As the alkali-soluble resin, a polymer having a carboxyl group in the side chain is preferred. For example, copolymers having repeating units derived from monomers such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, succinic acid, 2-carboxyethyl (meth)acrylic acid, vinyl benzoic acid, and partially esterified succinic acid, alkali-soluble phenolic resins such as novolac resins, acidic cellulose derivatives having a carboxyl group in the side chain, polymers having a hydroxyl group, and polymers of acid anhydride addition. In particular, copolymers of (meth)acrylic acid and other monomers that can be copolymerized therewith are preferred as alkali-soluble resins. As other monomers that can be copolymerized with (meth)acrylic acid, alkyl (meth)acrylates, aryl (meth)acrylates, vinyl compounds, etc. can be listed. Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, and the like. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomers, polymethyl methacrylate macromonomers, and the like. The other monomers copolymerizable with the (meth)acrylic acid may be only one kind or two or more kinds.

The alkali-soluble resin may have a repeating unit derived from a cis-butylenediimide compound. Examples of the cis-butylenediimide compound include N-alkyl cis-butylenediimide and N-aryl cis-butylenediimide. Examples of the repeating unit derived from the cis-butylenediimide compound include a repeating unit represented by the formula (C-mi). [Chemical Formula 20]

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

As the alkali-soluble resin, a copolymer containing benzyl (meth)acrylate/(meth)acrylic acid, a copolymer containing benzyl (meth)acrylate/(meth)acrylic acid/2-hydroxyethyl (meth)acrylate, or a multi-component copolymer containing benzyl (meth)acrylate/(meth)acrylic acid/other monomers can be preferably used. In addition, copolymers obtained by copolymerizing 2-hydroxyethyl (meth)acrylate and other monomers, 2-hydroxypropyl (meth)acrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymers described in Japanese Patent Application Laid-Open No. 7-140654, 2-hydroxy-3-phenoxypropyl acrylate/polymethyl methacrylate macromonomer/benzyl methacrylate/methacrylic acid copolymers, 2-hydroxyethyl methacrylate/polystyrene macromonomer/methyl methacrylate/methacrylic acid copolymers, 2-hydroxyethyl methacrylate/polystyrene macromonomer/benzyl methacrylate/methacrylic acid copolymers, and the like can also be preferably used.

Alkali-soluble resins may also be alkali-soluble resins having a polymerizable group. Examples of the polymerizable group include (meth)allyl group and (meth)acryloyl group. Among alkali-soluble resins having a polymerizable group, those having a polymerizable group in a side chain are useful. Examples of commercially available alkali-soluble resins having a polymerizable group include DIANAL NR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer 6173 (polyurethane acrylate oligomer containing a carboxyl group, manufactured by Diamond Shamrock Co., Ltd.), VISCOAT R-264, KS RESIST 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (e.g., ACA230AA), PLACCEL CF200 series (both manufactured by Daicel Corporation), Ebecry 13800 (manufactured by DAICEL UCB CO., LTD.), ACRYCURE RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.), and DP-1305 (manufactured by FUJIFILM Finechemicals Co., Ltd.).

As the alkali-soluble resin, an alkali-soluble resin containing a repeating unit having a hydroxyl group is preferred. In this manner, the affinity with the developer is improved, and a pattern with excellent rectangularity is easily formed. Among the alkali-soluble resins containing a repeating unit having a hydroxyl group, a hydroxyl value of 30 to 100 mgKOH/g is preferably used as the alkali-soluble resin. A lower limit of 35 mgKOH/g or more is more preferred, and a value of 40 mgKOH/g or more is further preferred. An upper limit of 80 mgKOH/g or less is more preferred. If the hydroxyl value of the alkali-soluble resin is within the above range, a pattern with excellent rectangularity is easily formed. As an alkali-soluble resin containing a repeating unit having a hydroxyl group, a resin having the following structure can be exemplified. [Chemical Formula 21]

The alkali-soluble resin preferably comprises a polymer obtained by polymerizing a monomer component comprising at least one compound selected from the group consisting of a compound represented by the following formula (ED1) and a compound represented by formula (1) in JP-A-2010-168539 (hereinafter, these compounds may also be referred to as "ether dimers").

[Chemical formula 22]

In formula (ED1), ^R1 and ^R2 each independently represent a hydrogen atom or a alkyl group having 1 to 25 carbon atoms which may have a substituent.

As a specific example of the ether dimer, for example, reference can be made to paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-029760, the contents of which are incorporated herein. The ether dimer may be of only one kind or of two or more kinds.

As a polymer obtained by polymerizing a monomer component including an ether dimer, for example, a polymer having the following structure can be cited. [Chemical Formula 23]

The alkali-soluble resin may also contain repeating units derived from a compound represented by the following formula (X). [Chemical Formula 24] In formula (X), _R1 represents a hydrogen atom or a methyl group, _R2 represents an alkylene group having 2 to 10 carbon atoms, and _R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.

For the alkali-soluble resin, reference can be made to paragraphs 0558 to 0571 of Japanese Patent Application Publication No. 2012-208494 (paragraphs 0685 to 0700 of the corresponding U.S. Patent Application Publication No. 2012/0235099), the contents of which are incorporated into the present specification. In addition, the copolymer (B) described in paragraphs 0029 to 0063 of Japanese Patent Application Publication No. 2012-032767 and the alkali-soluble resin used in the examples, the adhesive resin described in paragraphs 0088 to 0098 of Japanese Patent Application Publication No. 2012-208474 and the adhesive resin used in the examples, and the adhesive described in paragraphs 0022 to 0032 of Japanese Patent Application Publication No. 2012-137531 can also be used. Resins and adhesive resins used in the examples, adhesive resins described in paragraphs 0132 to 0143 of Japanese Patent Application Publication No. 2013-024934 and adhesive resins used in the examples, paragraphs 0092 to 0098 of Japanese Patent Application Publication No. 2011-242752 and adhesive resins used in the examples, and adhesive resins described in paragraphs 0030 to 0072 of Japanese Patent Application Publication No. 2012-032770. These contents are incorporated into this specification.

The content of the alkali-soluble resin in the total solid content of the photosensitive coloring composition is preferably 1 to 50 mass %. The lower limit is more preferably 2 mass %, and more preferably 3 mass %. The upper limit is more preferably 40 mass %, and more preferably 35 mass %. The photosensitive coloring composition of the present invention may contain only one alkali-soluble resin, or may contain two or more alkali-soluble resins. When containing two or more alkali-soluble resins, the total is preferably within the above range.

(Dispersant) The photosensitive coloring composition of the present invention may contain a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and alkaline dispersants (alkaline resins).

Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of alkaline groups. As the acidic dispersant (acidic resin), when the total amount of the amount of acid groups and the amount of alkaline groups is set to 100 mol%, the resin in which the amount of acid groups accounts for 70 mol% or more is preferred, and the resin substantially containing only acid groups is more preferred. The acid groups possessed by the acidic dispersant (acidic resin) are preferably carboxyl groups. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. In addition, the alkaline dispersant (alkaline resin) refers to a resin in which the amount of alkaline groups is greater than the amount of acid groups. As the alkaline dispersant (alkaline resin), when the total amount of the acid group and the amount of the alkaline group is 100 mol%, the resin having the amount of the alkaline group exceeding 50 mol% is preferred. The alkaline group of the alkaline dispersant is preferably an amine group.

Examples of dispersants include polymer dispersants [e.g., polyamides and their salts, polycarboxylic acids and their salts, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly(meth)acrylates, (meth)acrylic acid copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphates, polyoxyethylene alkylamines, alkanolamines, etc. Polymer dispersants can be further classified into linear polymers, terminal modified polymers, grafted polymers, and block polymers based on their structures. Polymer dispersants are adsorbed on the surface of the pigment to prevent reagglomeration. Therefore, terminal modified polymers, grafted polymers, and block polymers having a fixed site on the surface of the pigment can be cited as preferred structures. Furthermore, the dispersants described in paragraphs 0028 to 0124 of Japanese Patent Application Laid-Open No. 2011-070156 and the dispersants described in Japanese Patent Application Laid-Open No. 2007-277514 are also preferably used. These contents are incorporated into this specification.

In the present invention, a graft copolymer can also be used as a dispersant. The details of the graft copolymer can refer to the description of paragraphs 0131 to 0160 of Japanese Patent Publication No. 2012-137564, and the content is incorporated into this specification. In addition, in the present invention, a resin containing nitrogen atoms on the main chain can also be used as a dispersant. The resin containing nitrogen atoms on the main chain (hereinafter, also referred to as oligoimine resin) preferably contains at least one repeating unit with nitrogen atoms selected from poly (lower alkylene imine) repeating units, polyallylamine repeating units, polydiallylamine repeating units, meta-xylene diamine-epichlorohydrin condensate repeating units and polyvinylamine repeating units. Regarding the oligoimine resin, reference can be made to paragraphs 0102 to 0174 of Japanese Patent Application Laid-Open No. 2012-255128, the contents of which are incorporated into the present specification.

The dispersant may be a commercial product. For example, the product described in paragraph 0129 of Japanese Patent Application Publication No. 2012-137564 may be used as the dispersant. For example, the DISPERBYK series (for example, DISPERBYK-161, etc.) manufactured by BYK Chemie GmbH may be cited. In addition, the resin described as the dispersant may be used for purposes other than the dispersant. For example, it may be used as an adhesive.

The content of the dispersant is preferably 1 to 200 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 5 parts by mass or more, and more preferably 10 parts by mass or more. The upper limit is preferably 150 parts by mass or less, and more preferably 100 parts by mass or less.

(Other resins) The photosensitive coloring composition of the present invention may contain resins other than the above-mentioned dispersants and alkali-soluble resins (also referred to as other resins) as resins. Examples of other resins include (meth) acrylic resins, (meth) acrylamide resins, ene thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamide imide resins, polyolefin resins, cycloolefin resins, polyester resins, styrene resins, silicone resins, and the like. The other resins may be used alone or in combination of two or more kinds.

＜＜Polymerizable compound＞＞ The photosensitive coloring composition of the present invention preferably contains a polymerizable compound in addition to a colorant having a polymerizable group. Examples of polymerizable compounds include compounds having olefinic unsaturated groups. Examples of ethylenic unsaturated groups include vinyl, (meth)allyl, (meth)acryloyl, etc. Polymerizable compounds are preferably compounds that can be polymerized by free radicals (free radical polymerizable compounds). In addition, in this specification, polymerizable compounds are compounds different from colorants having polymerizable groups. Polymerizable compounds are preferably compounds that do not have a pigment structure.

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

The polymerizable compound is preferably a compound containing 3 or more ethylenic unsaturated groups, more preferably a compound containing 3 to 15 ethylenic unsaturated groups, and further preferably a compound containing 3 to 6 ethylenic unsaturated groups. In addition, the free radical polymerizable compound is preferably a 3 to 15-functional (meth)acrylate compound, and more preferably a 3 to 6-functional (meth)acrylate compound. As specific examples of free radical polymerizable compounds, there can be cited the compounds described in paragraphs 0095 to 0108 of Japanese Patent Publication No. 2009-288705, paragraph 0227 of Japanese Patent Publication No. 2013-029760, and paragraphs 0254 to 0257 of Japanese Patent Publication No. 2008-292970, and the contents are incorporated into this specification.

The polymerizable compound is dipentatriol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU CO., Ltd.), dipentatriol tetraacrylate (commercially available as KAYARAD D-320; manufactured by NIPPON KAYAKU CO., Ltd.), dipentatriol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., Ltd.), dipentatriol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by NIPPON KAYAKU CO., Ltd., NK ester A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., Ltd.), and a compound having a structure in which the (meth)acryloyl group is bonded to an ethylene glycol and/or propylene glycol residue (for example, a compound manufactured by SARTOMER Company, Inc.) is preferred. Such oligomer types can also be used. In addition, as a radical polymerizable compound, NK ESTER A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. In addition, as a radical polymerizable compound, trifunctional (meth)acrylate compounds such as trihydroxymethylpropane tri(meth)acrylate, trihydroxymethylpropylene oxide modified tri(meth)acrylate, trihydroxymethylpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and neopentyltriol tri(meth)acrylate are also preferably used. Commercially available products of the trifunctional (meth)acrylate compound include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305, M-303, M-452, and 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, and TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, and PET-30 (manufactured by Nippon Kayaku Co., Ltd.).

The polymerizable compound may have an acid group. Examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and a carboxyl group is preferred. Examples of commercially available free radical polymerizable compounds having an acid group include ARONIX M-510, M-520, and ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.).

The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g. If the acid value of the polymerizable compound is 0.1 mgKOH/g or more, the solubility in the developer is good, and if it is 40 mgKOH/g or less, it is advantageous in production or handling.

The polymerizable compound is preferably a compound having a caprolactone structure. The polymerizable compound having a caprolactone structure is commercially available, for example, from NIPPON KAYAKU CO., Ltd. as KAYARAD DPCA series, including DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

The polymerizable compound is preferably a compound having an alkoxy group. The polymerizable compound having an alkoxy group is preferably a compound having an ethyloxy group and/or a propyloxy group, more preferably a compound having an ethyloxy group, and further preferably a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyloxy groups. Commercially available polymerizable compounds having an alkoxy group include, for example, SR-494, a tetrafunctional (meth)acrylate having four ethoxy groups, and KAYARAD TPA-330, a trifunctional (meth)acrylate having three isobutyloxy groups, manufactured by Sartomer Company, Inc.

As the polymerizable compound, urethane acrylates described in Japanese Patent Publication No. 48-041708, Japanese Patent Publication No. 51-037193, Japanese Patent Publication No. 2-032293, and Japanese Patent Publication No. 2-016765, or urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also preferred. In addition, it is also preferred to use a polymerizable compound having an amino structure or a thioether structure in the molecule as described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 1-105238. Commercially available products include UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.). In addition, as the polymerizable compound, 8UH-1006, 8UH-1012 (the above, manufactured by TAISEI FINE CHEMICAL Co., Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), etc. are also preferably used. In addition, as the polymerizable compound, the compounds described in Japanese Patent Publication No. 2017-048367, Japanese Patent No. 6057891, and Japanese Patent No. 6031807 can also be used.

The content of the polymerizable compound in the total solid content of the photosensitive coloring composition is preferably 0.1 to 50 mass %. The lower limit is preferably 0.5 mass % or more, and 1 mass % or more is further preferably. The upper limit is preferably 45 mass % or less, and 40 mass % or less is further preferably. In addition, the content of the polymerizable compound is preferably 25 to 500 mass parts relative to 100 mass parts of the color material having a polymerizable base. The lower limit is preferably 30 mass parts or more, and 50 mass parts or more is further preferably. The upper limit is preferably 450 mass parts or less, and 300 mass parts or less is further preferably. If the content of the polymerizable compound is within the above range, a finer developed pattern can be expected. Furthermore, the total amount of the polymerizable compound and the colorant having a polymerizable group is preferably 20 to 80 mass % in the total solid content of the photosensitive coloring composition. It is more preferable that the lower limit is 25 mass % or more, and it is further preferable that it is 40 mass % or more. It is more preferable that the upper limit is 75 mass % or less, and it is further preferable that it is 60 mass % or less. If the above total amount is within the above range, it is easy to obtain a cured film with better adhesion to the support. Furthermore, the total amount of the polymerizable compound and the colorant having a polymerizable group is preferably 25 to 500 mass parts relative to 100 mass parts of the total of the photopolymerization initiator a and the photopolymerization initiator b. It is more preferable that the lower limit is 30 mass % or more, and it is further preferable that it is 50 mass % or more. The upper limit is preferably 450 parts by mass or less, and even more preferably 300 parts by mass or less. Within this range, a cured film having excellent resistance to discoloration by a developer or excellent adhesion to a support can be easily obtained.

<<Compounds having epoxy groups>> The photosensitive coloring composition of the present invention preferably further contains a compound having an epoxy group. In this manner, the mechanical strength of the obtained cured film can be improved. As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferred. It is preferred to have 2 to 100 epoxy groups in one molecule. The upper limit can be set to, for example, 10 or less, or 5 or less.

The epoxy equivalent (= molecular weight of the compound having an epoxy group/number of epoxy groups) of the compound having an epoxy group is preferably 500 g/eq or less, more preferably 100 to 400 g/eq, and even more preferably 100 to 300 g/eq.

The compound having an epoxy group may be a low molecular weight compound (e.g., a molecular weight of less than 1,000) or a high molecular weight compound (e.g., a polymer having a molecular weight of 1,000 or more, a weight average molecular weight of 1,000 or more). The molecular weight (the weight average molecular weight in the case of a polymer) of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the molecular weight (the weight average molecular weight in the case of a polymer) is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,500 or less.

As the compound having an epoxy group, the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408 can also be used. These contents are incorporated into this specification.

When the photosensitive coloring composition of the present invention contains a compound having an epoxy group, the content of the compound having an epoxy group in the total solid content of the photosensitive composition is preferably 0.1 to 40 mass %. The lower limit is, for example, 0.5 mass % or more, which is more preferably, and 1 mass % or more is further preferably. The upper limit is, for example, 30 mass % or less, which is more preferably, and 20 mass % or less is further preferably. The compound having an epoxy group may be a single type, or two or more types may be used at the same time. When two or more types are used at the same time, the total amount is preferably within the above range. In addition, the content of the compound having an epoxy group is preferably 1 to 400 mass parts, more preferably 1 to 100 mass parts, and further preferably 1 to 50 mass parts relative to 100 mass parts of the polymerizable compound.

<<Solvent>> The photosensitive coloring composition of the present invention preferably contains a solvent. The solvent is preferably an organic solvent. The solvent is not particularly limited as long as it satisfies the solubility of each component and the coating property of the photosensitive coloring composition.

Examples of organic solvents include the following. Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetates (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkoxypropionates (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, methyl 3-methoxypropionate, etc.) ethyl ethoxypropionate, etc.)), alkyl 2-alkoxypropionates (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetylacetate, ethyl acetylacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl solvent acetate, ethyl solvent acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc. Examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, etc. Examples of aromatic hydrocarbons include preferably toluene, xylene, etc. However, the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as solvents may be reduced for environmental reasons (for example, it can be set to 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less relative to the total amount of the organic solvent).

The organic solvent may be used alone or in combination of two or more. When two or more organic solvents are used in combination, a mixed solution consisting of two or more selected from the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl solvent acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is particularly preferred.

In the present invention, the organic solvent preferably has a peroxide content of 0.8 mmol/L or less, and more preferably contains substantially no peroxide. In addition, it is preferred to use an organic solvent with a low metal content, for example, an organic solvent with a metal content of 10 parts per billion or less. If necessary, an organic solvent with a metal content of ppt (parts per trillion) can also be used. Such a high-purity solvent is provided by TOYO Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

The content of the solvent is preferably 5 to 80% by mass of the total solid content of the photosensitive coloring composition. The lower limit is preferably 10% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 50% by mass or less, and even more preferably 40% by mass or less.

＜＜Hardening accelerator＞＞ In order to promote the reaction of the polymerizable compound or to lower the curing temperature, a hardening accelerator may be added to the photosensitive coloring composition of the present invention. As a hardening accelerator, there can be listed polyfunctional thiol compounds having two or more alkyl groups in the molecule. The polyfunctional thiol compound can also be added for the purpose of improving stability, odor, resolution, developing properties, adhesion, etc. The polyfunctional thiol compound is preferably a dialkyl thiol, and the compound represented by formula (T1) is more preferably. Formula (T1) [Chemical Formula 25] (In formula (T1), n represents an integer of 2 to 4, and L represents a 2- to 4-valent linking group.)

In formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, and n is 2 and L is particularly preferably an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulae (T2) to (T4), and compounds represented by formula (T2) are particularly preferred. These polyfunctional thiol compounds may be used alone or in combination of a plurality of them.

[Chemical formula 26]

The curing accelerator may include hydroxymethyl compounds (for example, compounds listed as crosslinking agents in paragraph 0246 of Japanese Patent Application Laid-Open No. 2015-034963), amines, phosphonium salts, amidine salts, amide compounds (for example, the curing agents described in paragraph 0186 of Japanese Patent Application Laid-Open No. 2013-041165), alkali generators (for example, ionic compounds described in Japanese Patent Application Laid-Open No. 2014-055114), cyanate compounds (for example, Such as the compound described in paragraph 0071 of Japanese Patent Publication No. 2012-150180), alkoxysilane compounds (for example, the alkoxysilane compounds having an epoxy group described in Japanese Patent Publication No. 2011-253054), onium salt compounds (for example, the compounds exemplified as acid generators in paragraph 0216 of Japanese Patent Publication No. 2015-034963, the compounds described in Japanese Patent Publication No. 2009-180949), etc.

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

<<Surfactant>> From the viewpoint of further improving coating properties, the photosensitive coloring composition of the present invention may also contain various surfactants. As the surfactant, various surfactants such as fluorine-based surfactants, non-ionic surfactants, cationic surfactants, anionic surfactants, silicone-based surfactants, etc. can be used.

By including a fluorine-based surfactant in the photosensitive coloring composition of the present invention, the liquid properties (especially fluidity) when prepared as a coating liquid can be improved, and the uniformity of coating thickness and liquid saving can be further improved. That is, when a film is formed using a coating liquid using a photosensitive coloring composition containing a fluorine-based surfactant, the interfacial tension between the coated surface and the coating liquid is reduced, the wettability to the coated surface is improved, and the coating property to the coated surface is improved. Therefore, a uniform film with less uneven thickness can be formed more appropriately.

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

Examples of fluorine-based surfactants include Magaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (all manufactured by DIC CORPORATION), Fluorad FC430, FC431, and FC171 (all manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA SOLUTIONS INC.), etc. The fluorine-based surfactant may also include compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 and compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503.

Fluorine-based surfactants can also preferably use acrylic compounds having a molecular structure with a functional group containing a fluorine atom, and part of the functional group containing a fluorine atom is broken when heated to volatilize the fluorine atom. Examples of such fluorine-based surfactants include the Magaface DS series manufactured by DIC CORPORATION (Chemical Industry Daily, February 22, 2016) (Nikkei Industrial News, February 23, 2016), such as Magaface DS-21.

The fluorine-based surfactant is preferably a polymer of a fluorine-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. The fluorine-based surfactant can be described in Japanese Patent Application Publication No. 2016-216602, and the content is incorporated into this specification.

Fluorine-based surfactants can also use block polymers. For example, the compounds described in Japanese Patent Publication No. 2011-089090 can be cited. Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds, which contain: repeating units derived from (meth)acrylate compounds having fluorine atoms; and repeating units derived from (meth)acrylate compounds having 2 or more (preferably 5 or more) alkoxy groups (preferably ethoxy and propoxy groups). As fluorine-based surfactants used in the present invention, the following compounds are also exemplified. In the following formula, the % representing the proportion of repeating units is molar %. [Chemical Formula 27] The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000.

As a fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. As specific examples, the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of Japanese Patent Publication No. 2010-164965 can be cited. As commercially available products, for example, Magaface RS-101, RS-102, RS-718-K, RS-72-K, etc. manufactured by DIC CORPORATION can be cited.

Examples of the nonionic surfactant include glycerin, trihydroxymethylpropane, trihydroxymethylethane, and ethoxylates and propoxylates thereof (e.g., glycerin propoxylate, glycerin 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 esters, PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), SOLSPERSE 20000 (Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by Wako Pure Corporation), PIONIN D-6112, D-6112-W, D-6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Examples of cationic surfactants include organosiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth)acrylic (co)polymers Polyflow No.75, No.90, No.95 (manufactured by Kyoeisha Chemical Co., Ltd.), and W001 (manufactured by Yusho Co., Ltd.).

Examples of the anionic surfactant include W004, W005, and W017 (manufactured by Yusho Co., Ltd.), and SANDET BL (manufactured by Sanyo Kasei Co., Ltd.).

Examples of the silicone surfactant include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, and Toray Silicone SH8400 (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive performance Materials Inc.), KP341, KF-6001, and KF-6002 (all manufactured by Shin-Etsu Chemical Co., Ltd.), and BYK-307, BYK-323, and BYK-330 (all manufactured by BYK Chemie GmbH).

The content of the surfactant is preferably 0.001 to 2.0 mass % in the total solid content of the photosensitive coloring composition, and more preferably 0.005 to 1.0 mass %. The surfactant may be used alone or in combination of two or more. When two or more surfactants are included, the total amount is preferably within the above range.

＜＜Silane coupling agent＞＞ The photosensitive coloring composition of the present invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two functional groups with different reactivities in one molecule is preferred. The silane coupling agent is preferably a silane compound having at least one group selected from vinyl, epoxy, styryl, methacryl, amino, isocyanurate, urea, butyl, thioether and isocyanate groups and having an alkoxy group or the like. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903), and 3-methacryloyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903). Ltd., KBM-503), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-403), etc. For details of the silane coupling agent, reference can be made to paragraphs 0155 to 0158 of JP-A-2013-254047, which is incorporated herein by reference.

When the photosensitive coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent in the total solid content of the photosensitive coloring composition is preferably 0.001 to 20 mass %, more preferably 0.01 to 10 mass %, and particularly preferably 0.1 to 5 mass %. The photosensitive coloring composition of the present invention may contain only one or more silane coupling agents. When containing more than two silane coupling agents, the total amount is preferably within the above range.

＜＜Polymerization Inhibitor＞＞ The photosensitive coloring composition of the present invention preferably contains a polymerization inhibitor. Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butyl-pyrogallol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenolaldehyde), N-nitrosobishydroxylamine salts (ammonium salts, first phosphonium salts, etc.). When the photosensitive coloring composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 5% by mass in the total solid content of the photosensitive coloring composition. The photosensitive coloring composition of the present invention may contain only one or two or more polymerization inhibitors. When two or more polymerization inhibitors are contained, the total amount thereof is preferably within the above range.

<<Ultraviolet absorber>> The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. As the ultraviolet absorber, a conjugated diene compound, an aminobutadiene compound, a methyldibenzoyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, etc. can be used. For details of the above, reference can be made to paragraphs 0052 to 0072 of Japanese Patent Application Publication No. 2012-208374 and paragraphs 0317 to 0334 of Japanese Patent Application Publication No. 2013-068814, and the contents are incorporated into this specification. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by DAITO CHEMICAL CO., LTD.) and the like. In addition, as benzotriazole compounds, the MYUA series manufactured by MIYOSHI OIL & FAT CO., LTD. (Chemical Industry Daily, February 1, 2016) can also be used.

When the photosensitive coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the photosensitive coloring composition is preferably 0.1 to 10 mass %, more preferably 0.1 to 5 mass %, and particularly preferably 0.1 to 3 mass %. In addition, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

<<Other additives>> The photosensitive coloring composition of the present invention can be blended with various additives as needed, such as fillers, adhesion promoters, antioxidants, anti-agglomeration agents, etc. As such additives, the additives described in paragraphs 0155 to 0156 of Japanese Patent Publication No. 2004-295116 can be cited, and the contents are incorporated into this specification. In addition, as antioxidants, for example, phenolic compounds, phosphorus compounds (for example, compounds described in paragraph 0042 of Japanese Patent Publication No. 2011-090147), thioether compounds, etc. can be used. As commercially available products, for example, the Adekastab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330, etc.) manufactured by ADEKA CORPORATION can be listed. The antioxidant may be used alone or in combination. The coloring composition of the present invention may contain a sensitizer or a light stabilizer described in paragraph 0078 of Japanese Unexamined Patent Publication No. 2004-295116, or a thermal polymerization inhibitor described in paragraph 0081 of Japanese Unexamined Patent Publication No. 2004-295116.

Sometimes, the photosensitive coloring composition contains metal elements due to the raw materials used, but from the viewpoint of suppressing the generation of defects, the content of Group 2 elements (calcium, magnesium, etc.) in the photosensitive coloring composition is preferably 50 mass ppm or less, and 0.01 to 10 mass ppm is more preferably. In addition, the total amount of inorganic metal salts in the photosensitive coloring composition is preferably 100 mass ppm or less, and 0.5 to 50 mass ppm is more preferably.

The water content of the photosensitive coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

The photosensitive coloring composition of the present invention can be used to adjust the viscosity for the purpose of adjusting the film surface shape (flatness, etc.), adjusting the film thickness, etc. The viscosity value can be appropriately selected as needed, for example, 0.3mPa･s to 50mPa･s is preferred at 25°C, and 0.5mPa･s to 20mPa･s is more preferred. As a method for measuring the viscosity, for example, a viscometer RE85L manufactured by TOKI SANGYO CO., LTD. (rotor: 1°34'×R24, measuring range 0.6 to 1200mPa･s) can be used and the temperature can be adjusted at 25°C for measurement.

The storage container of the photosensitive coloring composition of the present invention is not particularly limited, and a known storage container can be used. In addition, as the storage container, in order to suppress the mixing of impurities into the raw materials or the composition, it is also preferable to use a multi-layer bottle with six layers of six types of resins as the inner wall of the container or a bottle with six types of resins as a seven-layer structure. As such a container, for example, the container described in Japanese Patent Publication No. 2015-123351 can be cited.

The photosensitive coloring composition of the present invention can be preferably used as a photosensitive coloring composition for forming coloring pixels in a color filter. Examples of coloring pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. In addition, the coloring materials contained in cyan pixels are mostly absorbers of radiation, and therefore, conventional photosensitive coloring compositions tend to be insufficiently cured during exposure. Therefore, in the past, post-baking at high temperatures was required to form cyan pixels. However, the present invention can more significantly exert the effect of the present invention by forming blue pixels (cured films) that are excellent in resistance to discoloration of developer solutions through curing at low temperatures.

When the photosensitive coloring composition of the present invention is used as a color filter for a liquid crystal display device, the voltage retention rate of the liquid crystal display element equipped with the color filter is preferably 70% or more, and more preferably 90% or more. Known means for obtaining a higher voltage retention rate can be appropriately combined. As typical means, the use of raw materials with higher purity (for example, the reduction of ionic impurities) and the control of the amount of acidic functional groups in the composition can be listed. The voltage retention rate can be measured, for example, by the method described in paragraph 0243 of Japanese Patent Publication No. 2011-008004 and paragraphs 0123 to 0129 of Japanese Patent Publication No. 2012-224847.

<Preparation method of photosensitive coloring composition> The photosensitive coloring composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the photosensitive coloring composition, all the components can be dissolved and/or dispersed in a solvent at the same time to prepare the photosensitive coloring composition, or the components can be appropriately prepared as two or more solutions or dispersions as needed, and these can be mixed when using (when applying) to prepare the photosensitive coloring composition.

Furthermore, in the case of preparing a photosensitive coloring composition containing a pigment, it is also preferred to include a step of dispersing the pigment when preparing the photosensitive coloring composition. In the step of dispersing the pigment, as mechanical forces used for dispersing the pigment, compression, pressing, impact, shearing, erosion, etc. can be listed. As specific examples of such steps, bead mill, sand mill, roller mill, ball mill, paint agitator (pain shaker), microfluidizer (microfluidizer), high-speed impeller, sand mill, flow jet mixer (flowjet mixer), high-pressure wet micronization, ultrasonic dispersion, etc. can be listed. In addition, in the pulverization of the pigment in the sand mixer (bead mill), it is preferred to perform the treatment under the condition that the pulverization efficiency is improved by using beads with a small diameter and increasing the filling rate of the beads. In addition, after the pulverization treatment, it is preferred to remove the coarse particles by filtering, centrifugal separation, etc. In addition, the steps and dispersing machines described in paragraph 0022 of "Dispersion Technology Encyclopedia, JOHOKIKO CO., LTD., July 15, 2005" or "Practical Comprehensive Data Collection of Dispersion Technology and Industrial Applications Centered on Suspension (Solid/Liquid Dispersion System), Business Development Center Publishing Department, October 10, 1978", and Japanese Patent Publication No. 2015-157893 can be preferably used for the steps and dispersing machines described in paragraph 0022. In the step of dispersing the pigment, the particles may be finely divided by a salt milling step. The materials, machines, and processing conditions used in the salt milling step can be found in, for example, Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629.

When preparing a photosensitive coloring composition, it is preferred to filter the composition using a filter for the purpose of removing foreign matter and reducing defects. As a filter, any filter that has been used for filtering purposes can be used without particular limitation. For example, filters using raw materials such as fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g., nylon-6, nylon-6,6), polyethylene, polypropylene (PP) and other polyolefin resins (including high-density and/or ultra-high molecular weight polyolefin resins) can be cited. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is appropriately about 0.01 to 7.0 μm, preferably about 0.01 to 3.0 μm, and more preferably about 0.05 to 0.5 μm.

Furthermore, it is also preferable to use a filter using a fibrous filter material as the filter. Examples of the fibrous filter material include polypropylene fiber, nylon fiber, and glass fiber. Specifically, examples of the filter using a fibrous filter material include filter elements of the SBP series (SBP008, etc.), TPR series (TPR002, TPR005, etc.), and SHPX series (SHPX003, etc.) manufactured by ROKI GROUP CO., Ltd.

When using filters, different filters can also be combined. In this case, the filtration in each filter can be only once or twice or more. For example, filters with different pore sizes can be combined within the above range. The pore size can refer to the nominal value of the filter manufacturer. As commercially available filters, for example, it can be selected from various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon Mykrolis Corporation) or KITZ MICROFILTER CORPORATION. In addition, the filtration in the first filter is only performed by the dispersion, and the second filter can also be used for filtering after mixing other components. As the second filter, a filter formed of the same material as the first filter can be used.

<Cured film> The cured film of the present invention is a cured film obtained from the above-mentioned photosensitive coloring composition of the present invention. The cured film of the present invention can be preferably used as a colored pixel of a color filter. As colored pixels, red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. can be listed. The film thickness of the cured film can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20μm or less, 10μm or less is more preferably, and 5μm or less is further preferably. The lower limit of the film thickness is preferably 0.1μm or more, 0.2μm or more is more preferably, and 0.3μm or more is further preferably.

<Method for forming a pattern> The method for forming a pattern of the present invention comprises: a step of forming a photosensitive coloring composition layer on a support using the photosensitive coloring composition of the present invention; a step of irradiating the photosensitive coloring composition layer with light having a wavelength greater than 350 nm and less than 380 nm and exposing it in a pattern; a step of alkaline developing the exposed photosensitive coloring composition layer; a step of irradiating the alkaline developed photosensitive coloring composition layer with light having a wavelength of 254 to 350 nm and exposing it. In addition, as required, a step of baking the photosensitive coloring composition layer after forming it on the support and before exposure (pre-baking step) and a step of baking the alkaline developed pattern (post-baking step) may also be provided. Each step is described below.

In the step of forming a photosensitive coloring composition layer, a photosensitive coloring composition is used to form a photosensitive coloring composition layer on a support.

The support is not particularly limited and can be appropriately selected according to the application. For example, a glass substrate, a solid-state imaging element substrate provided with a solid-state imaging element (light-receiving element), a silicon substrate, etc. are listed. In addition, a base coating layer is provided on these substrates as needed in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

As a method of applying the photosensitive coloring composition to the support, various methods such as slit coating, inkjet coating, spin coating, cast coating, roll coating, screen printing, etc. can be used.

The photosensitive coloring composition layer formed on the support can be dried (pre-baked). When the pattern is formed by a low-temperature process, pre-baking is not required. When pre-baking is performed, the pre-baking temperature is preferably below 120°C, more preferably below 110°C, and further preferably below 105°C. The lower limit can be set to, for example, above 50°C, and can also be set to above 80°C. The pre-baking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Pre-baking can be performed by a heating plate, an oven, etc.

Next, the photosensitive coloring composition layer is exposed in a pattern by irradiating light having a wavelength greater than 350nm and less than 380nm. For example, the photosensitive coloring composition layer can be exposed in a pattern by using an exposure device such as a stepper through a mask having a prescribed mask pattern. In this way, the exposed portion of the photosensitive coloring composition layer can be hardened. The radiation (light) that can be used for exposure is light having a wavelength greater than 350nm and less than 380nm, preferably light having a wavelength of 355 to 370nm, and more preferably i-rays. As the irradiation amount (exposure amount), for example, 30 to 1500mJ/ ^cm2 is preferred, and 50 to 1000mJ/ ^cm2 is more preferred. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in the atmosphere, exposure can also be performed in a low oxygen environment with an oxygen concentration of 19 volume % or less (e.g., 15 volume %, 5 volume %, substantially oxygen-free), or in a high oxygen environment with an oxygen concentration greater than 21 volume % (e.g., 22 volume %, 30 volume %, 50 volume %). In addition, the exposure illuminance can be appropriately set, and can generally be selected from a range of 1000 W/m ² to 100000 W/m ² (e.g., 5000 W/m ² , 15000 W/m ² , 35000 W/m ² ). Oxygen concentration and exposure illuminance can be combined with appropriate conditions. For example, the illuminance can be set to 10000 W/m ² at an oxygen concentration of 10 volume %, and the illuminance can be set to 20000 W/m ² at an oxygen concentration of 35 volume %.

The reaction rate of the polymerizable compound in the photosensitive coloring composition layer after exposure is preferably greater than 30% and less than 60%. By setting such a reaction rate, the polymerizable compound can be set to a state where it can be properly cured. Here, the reaction rate of the polymerizable compound refers to the proportion of the ethylenically unsaturated groups that react among all the ethylenically unsaturated groups in the polymerizable compound.

Next, the exposed photosensitive coloring composition layer is subjected to alkaline development. That is, the unexposed portion of the photosensitive coloring composition layer is removed using an alkaline developer to form a pattern. The temperature of the alkaline developer is preferably 20 to 30° C. The development time is preferably 20 to 300 seconds.

As the alkaline developer, it is preferable to use an alkaline aqueous solution obtained by diluting an alkali agent with pure water. Examples of the alkali include organic alkaline compounds such as ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene; and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10 mass %, and more preferably 0.01 to 1 mass %. In addition, the alkaline developer may further contain a surfactant. As examples of surfactants, the above-mentioned surfactants can be listed, and non-ionic surfactants are preferred. From the perspective of convenience in transportation and storage, the alkaline developer is temporarily made into a concentrated solution, and can also be diluted to the concentration required for use. There is no particular limitation on the dilution ratio, but for example, it can be set in the range of 1.5 to 100 times. In addition, it is preferred to use pure water for cleaning (rinsing) after development. In addition, when using a developer including such an alkaline aqueous solution, it is preferably washed (rinsed) with pure water after development.

Next, the photosensitive coloring composition layer after alkaline development is exposed by irradiating light with a wavelength of 254 to 350 nm. Hereinafter, the exposure after alkaline development is also referred to as post-exposure. As the radiation (light) that can be used in the post-exposure, ultraviolet light with a wavelength of 254 to 300 nm is preferred, and ultraviolet light with a wavelength of 254 nm is more preferred. Post-exposure can be performed using, for example, an ultraviolet photoresist curing device. It is also possible to irradiate other light (for example, i-rays) from the ultraviolet photoresist curing device together with light with a wavelength of 254 to 350 nm.

The difference between the wavelength of the light used in the exposure before the alkaline development and the wavelength of the light used in the exposure after the alkaline development (post-exposure) is preferably 200nm or less, and more preferably 100 to 150nm. The irradiation amount (exposure amount) is preferably 30 to 4000mJ/ ^cm2 , and more preferably 50 to 3500mJ/ ^cm2 . The oxygen concentration during exposure can be appropriately selected. The conditions described in the exposure step before the alkaline development can be listed.

The reaction rate of the polymerizable compound in the photosensitive coloring composition layer after post-exposure is preferably 60% or more. The upper limit can be set to 100% or less, and can also be set to 90% or less. By setting such a reaction rate, the cured state of the photosensitive coloring composition layer after exposure can be set more favorably.

In the present invention, by exposing the photosensitive coloring composition layer in two stages, before and after alkaline development, the photosensitive coloring composition can be properly cured in the first exposure (exposure before alkaline development), and the entire photosensitive coloring composition can be almost completely cured in the next exposure (exposure after development). As a result, the photosensitive coloring composition can be fully cured under low temperature conditions, and a pattern (cured film) with excellent resistance to discoloration by a developer can be formed.

In the pattern formation of the present invention, post-baking can also be performed after post-exposure. When post-baking is performed, when an organic electroluminescent layer element is used as the light source of the image display device or when a photoelectric conversion film of an image sensor is composed of organic materials, it is better to perform heat treatment (post-baking) at 50-120°C (80-100°C is better, 80-90°C is even better). Post-baking can be performed continuously or intermittently using a heating mechanism such as a heating plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. In addition, when the pattern is formed by a low-temperature process, post-baking may not be performed.

The thickness of the pattern (hereinafter also referred to as pixel) after post-exposure (after post-baking in the case of post-exposure), is preferably 0.1 to 2.0 μm. The lower limit is preferably 0.2 μm or more, more preferably 0.3 μm or more. The upper limit is preferably 1.7 μm or less, more preferably 1.5 μm or less.

The pixel width is preferably 0.5 to 20.0 μm, with a lower limit of preferably 1.0 μm or more, more preferably 2.0 μm or more, and an upper limit of preferably 15.0 μm or less, more preferably 10.0 μm or less.

The Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.

It is better for the pixel to have higher flatness. Specifically, the surface roughness Ra of the pixel is preferably less than 100nm, more preferably less than 40nm, and further preferably less than 15nm. There is no regulation on the lower limit, for example, 0.1nm or more is better. The surface roughness can be measured using, for example, AFM (atomic force microscope) Dimension 3100 manufactured by Veeco. In addition, the contact angle of water on the pixel can be set to an appropriate and optimal value, typically in the range of 50 to 110°. The contact angle can be measured using, for example, a contact angle meter CV-DT A type (manufactured by Kyowa Interface Science Co., LTD.).

It is desirable that the volume resistance of the pixel is high. Specifically, the volume resistance of the pixel is preferably 10 ⁹ Ω·cm or more, and more preferably 10 ¹¹ Ω·cm or more. There is no upper limit, and for example, 10 ¹⁴ Ω·cm or less is preferred. The volume resistance of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest Corporation).

<Color filter> Next, the color filter of the present invention is described. The color filter of the present invention has the cured film of the present invention mentioned above. In the color filter of the present invention, the film thickness of the cured film can be appropriately adjusted according to the purpose. The film thickness is preferably 20μm or less, 10μm or less is more preferably, and 5μm or less is further preferably. The lower limit of the film thickness is preferably 0.1μm or more, 0.2μm or more is more preferably, and 0.3μm or more is further preferably. The color filter of the present invention can be used in solid-state imaging elements such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor) and image display devices, etc.

<Solid State Imaging Device> The solid state imaging device of the present invention has the cured film of the present invention. The structure of the solid state imaging device of the present invention is not particularly limited as long as it has the cured film of the present invention and functions as a solid state imaging device, and examples thereof include the following structures.

The following structure is formed on the substrate: a plurality of diodes and transmission electrodes such as polysilicon that constitute a light-receiving area of a solid-state imaging element (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.), a shielding film having only a light-receiving portion of the diode open on the diode and the transmission electrode, an element protection film including silicon nitride formed in a manner covering the entire surface of the shielding film and the light-receiving portion of the diode, and a color filter on the element protection film. In addition, it can also be a structure having a focusing mechanism (for example, a microlens, etc., the same below) on the element protection film and below the color filter (close to the substrate side) or a structure having a focusing mechanism on the color filter. In addition, the color filter has a structure in which a cured film forming each colored pixel is embedded in a space divided into a grid shape by a partition wall. In this case, the partition wall preferably has a lower refractive index than each colored pixel. As examples of imaging devices having such structures, the devices described in Japanese Patent Publication No. 2012-227478 and Japanese Patent Publication No. 2014-179577 can be cited. An imaging device equipped with the solid-state imaging element of the present invention can be used as a car camera or a surveillance camera in addition to a digital camera or an electronic device with a camera function (such as a mobile phone).

<Image display device> The cured film of the present invention can be used for image display devices such as liquid crystal display devices and organic electroluminescent layer display devices. The definition of display devices and the details of each image display device are described in, for example, "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo-Tosho Publishing Co., Ltd. in 1989)". In addition, regarding liquid crystal display devices, for example, it is described in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd. in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied. For example, the present invention can be applied to various liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology". [Example]

The present invention is specifically described below with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing sequences, etc. shown in the following examples can be appropriately changed without departing from the purpose of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, unless otherwise specified, "parts" and "%" are mass standards.

<Preparation of pigment dispersion composition> (Pigment dispersion P1) A mixture of 20.0 parts by mass (average primary particle size 55 nm) of CI Pigment Blue 15:6, 2.40 parts by mass of pigment dispersant (DISPERBYK-161, manufactured by BYK Chemie GmbH), 2.40 parts by mass of dispersant 1, and 175.2 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was mixed and dispersed for 3 hours using a bead mill (zirconia microbeads with a diameter of 0.3 mm). Then, a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a pressure reducing mechanism was used to further disperse the mixture at a flow rate of 500 g/min at a pressure of 2000 kg/cm ³ . This dispersion treatment was repeated 10 times to obtain a pigment dispersion P1. The average primary particle size of the pigment in the obtained pigment dispersion P1 was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.) and was found to be 24 nm.

･Dispersant 1: Resin with the following structure (the values in the main chain are molar ratios, Mw=11000) [Chemical formula 28] (Pigment Dispersion Liquid P2) Pigment Dispersion Liquid P2 was obtained in the same manner as Pigment Dispersion Liquid P1 except that the dispersing resin A described in paragraph 0577 of JP-A-2013-195854 was used instead of the dispersant 1.

<Preparation of Photosensitive Coloring Composition> (Example 1) The raw materials shown below were mixed and stirred, and then filtered using a nylon filter with a pore size of 0.45 μm (manufactured by NIHON PALL LTD.) to prepare a photosensitive coloring composition. ･Pigment dispersion P1……60.0 parts by mass･Photopolymerization initiator (Initiator 1)……1.68 parts by mass･Photopolymerization initiator (Initiator 4)……0.63 parts by mass･Alkali-soluble resin (Resin A)……0.60 parts by mass･Polymerizable compound (M1)……6.00 parts by mass･Dye (V1)……20.0 parts by mass･Epoxy compound (EHPE 3150, manufactured by Daicel Chemical Industries Ltd.)……0.66 parts by mass･Polymerization inhibitor (p-methoxyphenol)……0.0007 parts by mass･Surfactant (1% by mass solution of a compound having the following structure (Mw=14000, % values indicating the ratio of repeating units are molar %) in cyclohexanone)……2.50 parts by mass [Chemical formula 29] ･Cyclohexanone……7.74 parts by mass

(Examples 2 to 18, Comparative Examples 1 to 4) A photosensitive coloring composition was prepared in the same manner as in Example 1 except that the type of pigment dispersion, the type and content of photopolymerization initiator, the type of alkali-soluble resin, the type of dye, and the type of polymerizable compound were changed as shown in the following table. The numerical value of the content described in the column of photopolymerization initiator in the following table is the content in the total solid content of the photosensitive coloring composition.

[Table 1]

(Examples 19 to 22) Photosensitive coloring compositions were prepared in the same manner as in Example 1 except that the content of the dye (V1) was changed as shown in the following table. The mass ratio of the color material having a polymerizable group and the photopolymerization initiator (the total amount of initiator 1 and initiator 4) is also shown in the following table.

[Table 2]

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

(Photopolymerization initiator) Initiator 1: IRGACURE-OXE01 (manufactured by BASF, the absorbance coefficient of light with a wavelength of 365 nm in methanol is 6969 mL/gcm) Initiator 2: IRGACURE-OXE02 (manufactured by BASF, the absorbance coefficient of light with a wavelength of 365 nm in methanol is 7749 mL/gcm) Initiator 3: The compound with the following structure (the absorbance coefficient of light with a wavelength of 365 nm in methanol is 18900 mL/gcm) [Chemical formula 30] Initiator 4: IRGACURE 2959 (manufactured by BASF, the absorbance coefficient of light at a wavelength of 365 nm in methanol is 48.93 mL/gcm, and the absorbance coefficient of light at a wavelength of 254 nm is 3.0×10 ⁴ mL/gcm.) Initiator 5: IRGACURE 184 (manufactured by BASF, the absorbance coefficient of light at a wavelength of 365 nm in methanol is 88.64 mL/gcm, and the absorbance coefficient of light at a wavelength of 254 nm is 3.3×10 ⁴ mL/gcm.)

(Alkali-soluble resin) ･Resin A: Resin with the following structure (Mw = 11000, acid value = 31.5 mgKOH/g, the values attached to the main chain are molar ratios.) [Chemical formula 31] ･Resin B: Resin with the following structure (Mw = 30000, acid value = 112.8 mgKOH/g, the values attached to the main chain are molar ratios.) [Chemical formula 32] Resin C: Alkali-soluble resin J5 described in paragraph 0573 of Japanese Patent Application Publication No. 2013-225112 Resin D: Resin B-1 described in paragraph 0150 of Japanese Patent Application Publication No. 2010-049161

(Dye) Dye V1: A 20 mass% cyclohexanone solution of a dye polymer (dye with a polymerizable group) having the following structure [Chemical Formula 33] Dye V2: A 20% by mass solution of a dye polymer of the following structure (a dye having a polymerizable group, the value attached to the main chain is the molar ratio, Mw = 13000) in cyclohexanone [chemical formula 34] Dye V3: A 20% by mass solution of a dye polymer of the following structure (a dye without a polymerizable group, the value attached to the main chain is a molar ratio, Mw = 12000) in cyclohexanone [chemical formula 35] Dye V4: A 20 mass% cyclohexanone solution of a pigment compound (a dye having a polymerizable group) having the following structure [Chemical Formula 36]

(Polymerizable compound) M1: A mixture of compounds having the following structure (left-hand compound: right-hand compound = 7:3 (molar ratio)) [Chemical formula 37] M2: Compound with the following structure [Chemical Formula 38]

<Evaluation> (Fading resistance) Each photosensitive coloring composition was applied to a glass substrate using a spin coater so that the film thickness after pre-baking was 1.6 μm, and then heat-treated (pre-baked) for 120 seconds using a 100°C hot plate. Next, a UV photoresist curing device (UMA-802-HC-552; manufactured by USHIO INC.) was used to expose the film at an exposure dose of 3000 mJ/cm ² to produce a cured film. The transmittance of the cured film obtained was measured using a spectrophotometer (reference: glass substrate) of an ultraviolet-visible near-infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation) in the range of 300 to 800 nm. In addition, the differential interference pattern was observed under reflection observation (magnification 50 times) using an OLYMPUS optical microscope BX60. Next, the cured film was immersed in an alkaline developer (FHD-5, manufactured by FUJIFILM Electronic Materials Co., Ltd.) at 25°C for 5 minutes, and after drying, the spectrum was measured again. The transmittance change before and after immersion in the alkaline developer was calculated and the discoloration resistance was evaluated according to the following criteria. Transmittance change = |T0-T1| T0 is the transmittance of the cured film before immersion in the alkaline developer, and T1 is the transmittance of the cured film after immersion in the alkaline developer. AA: The transmittance change in the entire wavelength range of 300 to 800 nm is less than 2%. A: The transmittance variation is less than 5% in the entire wavelength range of 300-800nm, and the transmittance variation is 2% or more and less than 5% in a part of the range. B: The transmittance variation is less than 7.5% in the entire wavelength range of 300-800nm, and the transmittance variation is 5% or more and less than 7.5% in a part of the range. C: The transmittance variation is less than 10% in the entire wavelength range of 300-800nm, and the transmittance variation is 7.5% or more and less than 10% in a part of the range. D: The transmittance variation is 10% or more in at least a part of the wavelength range of 300-800nm.

(Evaluation of residual film rate and adhesion) Each photosensitive coloring composition was applied to an 8-inch (20.32 cm) glass substrate sprayed with hexamethyldisilazane using a spin coater so that the film thickness after pre-baking was 1.6 μm, and then heated for 120 seconds using a 100°C heating plate (pre-baking). Then, an i-ray stepper exposure device FPA-3000i5+ (manufactured by Canon Co., Ltd.) was used to irradiate at a wavelength of 365 nm through a 3.0 μm square island pattern mask at 300 mJ/cm ² (exposure required to obtain a line width of 3.0 μm). Next, the glass substrate with the coating film formed after exposure was placed on a horizontal rotating table of a rotary spray developer (DW-30 model; manufactured by CHEMITRONICS CO., LTD.), and flood development was performed at 23°C for 180 seconds using a developer (CD-2000 (40% dilution manufactured by FUJIFILM Electronic Materials Co., Ltd.) to form a colored pattern (pixel) on the glass substrate. The glass substrate with the colored pattern (pixel) formed was fixed to the horizontal rotating table by a vacuum chuck, and while the glass substrate was rotated at a speed of 50 rpm by a rotating device, pure water was supplied from a spray nozzle from above the rotation center to perform a rinsing process, and then spray-dried to form a colored pattern (pixel).

Regarding the residual film rate, the film thickness before and after development was measured using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation). The higher the value, the better the residual film rate, and 80% or more is more preferable. Residual film rate (%) = (thickness before development / thickness after development) × 100 AA: Residual film rate is 87.5% or more A: Residual film rate is 82.5% or more and less than 87.5% B: Residual film rate is 80% or more and less than 82.5% C: Residual film rate is less than 80%

Regarding adhesion, the colored pattern formed on the glass substrate was observed using an optical microscope and evaluated according to the following criteria. AA: No peeling of the colored pattern. A: Peeling of the colored pattern occurs in 1 to 5 pixels out of 100 pixels. B: Peeling of the colored pattern occurs in 6 to 15 pixels out of 100 pixels. C: Peeling of the colored pattern occurs in 16 or more pixels out of 100 pixels.

[table 3]

As shown in the above table, the discoloration resistance of the embodiment is excellent. In contrast, the comparative example 1 which does not use a color material having a polymerizable group, the comparative examples 2 and 3 which contain only one of the photopolymerization initiator a and the photopolymerization initiator b, and the comparative example 4 which contains the photopolymerization initiator a and the photopolymerization initiator b and the content thereof is less than 1.5 mass % are inferior to the embodiment in discoloration resistance.

without

Claims (16)

A photosensitive coloring composition comprising: a photopolymerization initiator a, the light absorption coefficient of light with a wavelength of 365 nm in methanol exceeds 1.0×10 ² mL/gcm, and the light absorption coefficient of light with a wavelength of 254 nm is 1.0×10 ⁴ to 1.0×10 ⁵ mL/gcm; a photopolymerization initiator b, the light absorption coefficient of light with a wavelength of 365 nm in methanol is less than 1.0×10 ² mL/gcm, and the light absorption coefficient of light with a wavelength of 254 nm is 1.0×10 ³ mL/gcm or more; an alkali-soluble resin; and a colorant having a polymerizable group, wherein the content of the photopolymerization initiator a in the total solid components of the photosensitive coloring composition is 1.5 mass % or more, and the content of the photopolymerization initiator b is 1.5 mass % or more, wherein the content of the colorant is 30 mass parts or more and 400 mass parts or less relative to the total of 100 mass parts of the photopolymerization initiator a and the photopolymerization initiator b. The photosensitive coloring composition as described in item 1 of the patent application, wherein the absorption coefficient of the photopolymerization initiator a in methanol for light with a wavelength of 365 nm is 1.0×10 ³ mL/gcm or more. The photosensitive coloring composition as described in item 1 of the patent application, wherein the photopolymerization initiator a is an oxime compound. The photosensitive coloring composition as described in item 2 of the patent application scope, wherein the photopolymerization initiator a is an oxime compound. The photosensitive coloring composition as described in item 1 of the patent application, wherein the photopolymerization initiator b is a hydroxyacetophenone compound. The photosensitive coloring composition as described in item 2 of the patent application scope, wherein the photopolymerization initiator b is a hydroxyacetophenone compound. The photosensitive coloring composition as described in item 3 of the patent application, wherein the photopolymerization initiator b is a hydroxyacetophenone compound. The photosensitive coloring composition described in any one of items 1 to 7 of the patent application scope contains 50 to 500 parts by mass of the photopolymerization initiator a relative to 100 parts by mass of the photopolymerization initiator b. A photosensitive coloring composition as described in any one of items 1 to 7 of the patent application scope, wherein the total content of the photopolymerization initiator a and the photopolymerization initiator b in the total solid components of the photosensitive coloring composition is 3 mass% to 17 mass%. A photosensitive coloring composition as described in any one of items 1 to 7 of the patent application scope, wherein the coloring material is a pigment polymer. The photosensitive coloring composition as described in item 1 of the patent application further contains a polymerizable compound and a compound having an epoxy group, wherein the content of the compound having an epoxy group is 1 to 50 parts by mass relative to 100 parts by mass of the polymerizable compound. A cured film obtained by curing the photosensitive coloring composition described in any one of items 1 to 11 of the patent application scope. A method for forming a pattern, comprising: forming a photosensitive coloring composition layer on a support using a photosensitive coloring composition described in any one of items 1 to 11 of the patent application; irradiating the photosensitive coloring composition layer with light having a wavelength greater than 350nm and less than 380nm and exposing it in a pattern; performing alkaline development on the exposed photosensitive coloring composition layer; and irradiating the developed photosensitive coloring composition layer with light having a wavelength of 254nm to 350nm and exposing it. A color filter having a hardened film as described in item 12 of the patent application scope. A solid-state imaging element having a hardened film as described in item 12 of the patent application scope. An image display device having the hardened film described in claim 12.