JPWO2019065001A1 - Photosensitive coloring composition, cured film, pattern forming method, color filter, solid-state image sensor and image display device - Google Patents

Abstract

Provided is a photosensitive coloring composition capable of forming a cured film having excellent color loss resistance to a developing solution. In addition, a cured film, a pattern forming method, a color filter, a solid-state image sensor, and an image display device are provided. The photosensitive coloring composition comprises a photopolymerization initiator a having an extinction coefficient of light having a wavelength of 365 nm in methanol exceeding 1.0 × 102 mL / gcm and an extinction coefficient of light having a wavelength of 365 nm in methanol being 1.0. It contains a photopolymerization initiator b having an extinction coefficient of light of × 102 mL / gcm or less and a wavelength of 254 nm of 1.0 × 103 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% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more.

Description

The present invention relates to a photosensitive coloring composition. More specifically, the present invention relates to a photosensitive coloring composition used for forming colored pixels of a color filter and the like. The present invention also relates to a cured film using a photosensitive coloring composition, a pattern forming method, a color filter, a solid-state image sensor, and an image display device.

In recent years, with the spread of digital cameras, camera-equipped mobile phones, and the like, demand for solid-state image sensors such as charge-coupling elements (CCD) image sensors has increased significantly. Color filters are used as key devices for displays and optical elements.

In the color filter, a colored photosensitive composition for forming pixels of each color is applied onto a support, prebaked at about 100 ° C., then exposed and developed to form a pattern, and then post-baked. Manufactured. Post-baking is a heat treatment for accelerating the curing of the film after development, and is performed at a relatively high temperature. For example, in Patent Document 1, post-baking is performed on the developed film at a temperature of 200 ° C. or higher.

Further, in recent years, the use of organic electroluminescence (organic EL) as a light emitting light source in an image display device and the use of an organic material for a photoelectric conversion film in an image sensor have been studied. Many of these members have low heat resistance. Therefore, it is considered to manufacture a color filter at a low temperature. For example, Patent Document 2 describes (i) a step of forming a layer on a substrate using a photosensitive coloring composition, and (ii) a step of exposing the photosensitive coloring composition layer with light having a wavelength of more than 350 nm and 380 nm or less. , (Iii) The step of alkaline-developing the photosensitive coloring composition layer and (iv) the step of exposing the photosensitive coloring composition layer with light having a wavelength of 254 to 350 nm are provided in this order. a) A polymerization initiator in which the absorption coefficient of light having a wavelength of 365 nm in methanol is 1.0 × 10 ³ mL / gcm or more, (b) The absorption coefficient of light having a wavelength of 365 nm in methanol is 1.0 × 10 × A polymerization initiator having a light absorption coefficient of 10 ² mL / g cm or less and a wavelength of 254 nm of 1.0 × 10 ³ mL / g cm or more, (c) a compound having an unsaturated double bond, and (d) alkali-soluble. The content of (a) the polymerization initiator in the total solid content of the photosensitive coloring composition containing the resin and (e) the coloring material is 1.5 to 10% by mass, and (b) the polymerization initiator. A method for producing a color filter using a photosensitive coloring composition having a content of 1.5 to 7.5% by mass is described.

JP-A-2015-143330 JP-A-2015-41058

As described above, in recent years, it has been studied to manufacture a color filter at a lower temperature.
On the other hand, when the present inventor has proceeded with a study on a photosensitive coloring composition containing a coloring material and an alkali-soluble resin, when such a photosensitive coloring composition is cured at a low temperature to form a cured film, It was found that the obtained cured film tended to have low color loss resistance to the developing solution.

Therefore, an object of the present invention is to provide a photosensitive coloring composition capable of forming a cured film having excellent color loss resistance to a developing solution. Another object of the present invention is to provide a cured film, a pattern forming method, a color filter, a solid-state image sensor, and an image display device.

As a result of diligent studies by the present inventor, the photosensitive coloring composition containing a specific photopolymerization initiator described later and a coloring material having a polymerizable group has color loss resistance to a developing solution even when cured at a low temperature. We have found that an excellent cured film can be formed, and have completed the present invention. That is, the present invention is as follows.
<1> Photopolymerization initiator a having an extinction coefficient of light having a wavelength of 365 nm in methanol exceeding 1.0 × 10 ² mL / gcm, and
Photopolymerization initiator b in which the extinction coefficient of light having a wavelength of 365 nm in methanol is 1.0 × 10 ² mL / gcm or less and the extinction coefficient of light having a wavelength of 254 nm is 1.0 × 10 ³ mL / gcm or more. When,
Alkali-soluble resin and
A photosensitive coloring composition containing a coloring material having a polymerizable group.
Photosensitivity coloring in which 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. Composition.
<2> The photosensitive coloring composition according to <1>, wherein the photopolymerization initiator a has an extinction coefficient of light having a wavelength of 365 nm in methanol of 1.0 × 10 ³ mL / gcm or more.
<3> The photosensitive coloring composition according to <1> or <2>, wherein the photopolymerization initiator a is an oxime compound.
<4> The photosensitive coloring composition according to any one of <1> to <3>, wherein the photopolymerization initiator b is a hydroxyacetophenone compound.
<5> The photosensitive coloring composition according to any one of <1> to <4>, which contains 50 to 500 parts by mass of the photopolymerization initiator a with respect to 100 parts by mass of the photopolymerization initiator b.
<6> Any 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. The photosensitive coloring composition according to.
<7> The photosensitive coloring composition according to any one of <1> to <6>, wherein the coloring material is a dye multimer.
<8> A cured film obtained by curing the photosensitive coloring composition according to any one of <1> to <7>.
<9> A step of forming a photosensitive coloring composition layer on a support using the photosensitive coloring composition according to any one of <1> to <7>.
A step of irradiating the photosensitive coloring composition layer with light having a wavelength of more than 350 nm and 380 nm or less to expose the photosensitive coloring composition layer in a pattern.
The process of alkaline developing the photosensitive coloring composition layer after exposure,
A method for forming a pattern, which comprises a step of irradiating and exposing a photosensitive coloring composition layer after development with light having a wavelength of 254 to 350 nm.
<10> A color filter having the cured film according to <8>.
<11> A solid-state image sensor having the cured film according to <8>.
<12> An image display device having the cured film according to <8>.

According to the present invention, it is possible to provide a photosensitive coloring composition capable of forming a cured film having excellent color loss resistance to a developing solution. Further, a cured film, a pattern forming method, a color filter, and a solid-state image sensor can be provided.

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

<Photosensitive coloring composition>
The photosensitive coloring composition of the present invention is
Photopolymerization initiator a having an extinction coefficient of light having a wavelength of 365 nm in methanol exceeding 1.0 × 10 ² mL / gcm, and
Photopolymerization initiator b in which the extinction coefficient of light having a wavelength of 365 nm in methanol is 1.0 × 10 ² mL / gcm or less and the extinction coefficient of light having a wavelength of 254 nm is 1.0 × 10 ³ mL / gcm or more. When,
Alkali-soluble resin and
A photosensitive coloring composition containing a coloring material having a polymerizable group.
The feature is that 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. To do.

Since the photosensitive coloring composition of the present invention contains the photopolymerization initiator a and the photopolymerization initiator b as the photopolymerization initiator in the above-mentioned predetermined ratios, it is possible to firmly cure the cured film to the deep part by exposure. it can. Since a coloring material having a polymerizable group is used in the present invention, the polymerizable group of the coloring material reacts with components other than the coloring material of the photosensitive coloring composition when the photosensitive coloring composition is cured. The coloring material is easily incorporated into the cured film, and a cured film having excellent color loss resistance to the developing solution can be formed. Therefore, color loss after development can be effectively suppressed. For example, in the case of producing a color filter having pixels of a plurality of colors by sequentially forming patterns (pixels) of cured films of each color using a photosensitive coloring composition of a plurality of colors, when forming pixels of the second and subsequent colors, it is performed. Pixels formed in the previous step are also exposed to the developing solution, but by using the photosensitive coloring composition of the present invention, a cured film having excellent color loss resistance to the developing solution can be formed. When the second and subsequent pixels are formed, it is possible to suppress color loss from the pixels formed before that.
Further, according to the photosensitive coloring composition of the present invention, the photosensitive coloring composition can be appropriately cured in the first exposure (exposure before development). Therefore, a pattern having good rectangularity can be formed. Then, the entire photosensitive coloring composition can be substantially cured by the next exposure (exposure after development). Therefore, it is possible to form a pattern having excellent color loss resistance to a developing solution while having excellent pattern forming properties.
In addition, the photosensitive coloring composition of the present invention has a particularly remarkable effect when a dye having a polymerizable group is used as the coloring material having a polymerizable group. When a dye is used as the coloring material, it tends to have a high affinity for the developing solution and tends to cause color loss with respect to the developing solution. Therefore, in the conventional photosensitive coloring composition, it is necessary to perform heat treatment at a high temperature to sufficiently cure the film. However, according to the photosensitive coloring composition of the present invention, by using a dye having a polymerizable group, it is possible to form a cured film having excellent color loss resistance to a developing solution even if it is cured at a low temperature. In particular, the effect of the present invention is remarkable. Further, by using a dye, a cured film having a clearer color and a higher 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 hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole compounds, and oxime derivatives. Oxime compounds such as, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketooxime ether compounds, aminoacetophenone compounds, hydroxyacetophenone compounds, phenylglioxylate compounds and the like can be mentioned. As a specific example of the photopolymerization initiator, for example, the description in paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.

In the present invention, a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator. Specific examples of such a photopolymerization initiator include paragraphs 0417 to 0421 of JP-A-2010-527339, JP-A-2011-524436, WO2015 / 004565, and JP-A-2016-532675. , International Publication WO2017 / 033680, paragraph numbers 0039 to 0055, dimers of oxime compounds, and compounds (E) and compounds (G) described in JP2013-522445, International. Examples thereof include Cmpd1 to 7 described in Japanese Publication No. WO2016 / 034963.

Examples of the phenylglycolate compound include phenylglycoxylic acid methyl ester. Examples of commercially available products include DAROCUR-MBF (manufactured by BASF).

Examples of the aminoacetophenone compound include the aminoacetophenone compound described in JP-A-10-291969. Further, as the aminoacetophenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF) can also be used.

Examples of the acylphosphine compound include the acylphosphine compound described in Japanese Patent No. 4225898. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide. As the acylphosphine compound, IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF) can also be used.

Examples of the hydroxyacetophenone compound include a compound represented by the following formula (V).
Equation (V)

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent, and Rv ² and Rv ³ may be bonded to each other to form a ring. m represents an integer from 0 to 4.

Examples of the substituent represented by Rv ¹ include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms). The alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear. The alkyl group and alkoxy group represented by Rv ¹ may be unsubstituted or have a substituent. Examples of the substituent include a hydroxyl group and a group having a hydroxyacetophenone structure. Examples of the group having a hydroxyacetophenone structure include a benzene ring to which Rv ¹ is bonded in the formula (V) or a group having a structure in which one hydrogen atom is removed from Rv ¹ .

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

Specific examples of the compound represented by the formula (V) include the following compounds.

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

As the oxime compound, for example, the compound described in JP-A-2001-233842, the compound described in JP-A-2000-80068, and the compound described in JP-A-2006-342166 can be used. In addition, as an oxime compound, J. C. S. Perkin II (1979) pp. 1653-1660, J. Mol. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995, pp.202-232), JP-A-2000-66385, JP-A-2000-80068, JP-A-2004-534977, JP-A-2006-342166 The compounds described in Japanese Patent Publication No. can also be used. Specific examples of the oxime compound include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], etanone, 1- [9-ethyl-6- (2-methyl). Benzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) and the like can be mentioned. As 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 Powerful Electronics New Materials Co., Ltd. , ADEKA PUTMER N-1919 (Photopolymerization Initiator 2 of JP2012-14052A) (all manufactured by ADEKA Corporation) can be used.

Examples of the oxime compound include the compound described in JP-A-2009-5199004 in which an oxime is linked to the N-position of the carbazole ring, and the compound described in US Pat. No. 7,626,957 in which a heterosubstituted group is introduced at the benzophenone moiety. Compounds described in JP-A-2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into a dye site, ketooxime compounds described in International Publication WO2009 / 131189, triazine skeleton and oxime skeleton having the same molecule. Even if the compound described in US Pat. No. 7,556,910, the compound described in JP-A-2009-221114, which has a maximum absorption at 405 nm and has good sensitivity to a g-ray light source, is used. Good. Preferably, for example, paragraph numbers 0274 to 0306 of JP2013-29760A can be referred to, the contents of which are incorporated herein.

Further, 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 the compounds described in JP-A-2014-137466. This content is incorporated herein.

Further, as the oxime compound, an oxime compound having a benzofuran skeleton can also be used. Specific examples thereof include compounds OE-01 to OE-75 described in International Publication WO2015 / 036910.

Further, as the oxime compound, an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used. Specific examples of such an oxime compound include the compounds described in WO2013 / 083505.

Further, as the photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471. Compound (C-3) and the like. This content is incorporated herein.

Further, as the oxime compound, an oxime compound having a nitro group can be used. The oxime compound having a nitro group is also preferably a dimer. Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A, paragraphs 0008 to 0012 and 0070 to 0079 of JP2014-137466, and Patents 4223071. Examples thereof include the compounds described in paragraphs 0007 to 0025 of the publication, ADEKA ARKULS NCI-831 (manufactured by ADEKA Corporation) and the like.

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

In the present invention, as the photopolymerization initiator, the photopolymerization initiator a (hereinafter, also referred to as photopolymerization initiator a) having an extinction coefficient of light having a wavelength of 365 nm in methanol exceeding 1.0 × 10 ² mL / gcm is used. ,
Photopolymerization initiator b in which the extinction coefficient of light having a wavelength of 365 nm in methanol is 1.0 × 10 ² mL / gcm or less and the extinction coefficient of light having a wavelength of 254 nm is 1.0 × 10 ³ mL / gcm or more. (Hereinafter, also referred to as photopolymerization initiator b) is used in combination. As the photopolymerization initiator a and the photopolymerization initiator b, a compound having the above extinction coefficient can be selected and used from the above-mentioned compounds.

In the present invention, the extinction coefficient of the photopolymerization initiator at the above wavelength is a value measured as follows. That is, it was calculated by dissolving the photopolymerization initiator in methanol to prepare a measurement solution, and measuring the absorbance of the above-mentioned measurement solution. Specifically, the above-mentioned measurement solution is placed in a glass cell having a width of 1 cm, the absorbance is measured using a UV-Vis-NIR spectrum meter (Cary5000) manufactured by Agilent Technologies, and the wavelength is 365 nm and the wavelength is applied to the following formula. The absorbance coefficient (mL / gcm) at 254 nm was calculated.

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

The absorption coefficient of the photopolymerization initiator a at a wavelength of 365 nm in methanol is a value exceeding 1.0 × 10 ² mL / gcm, preferably 1.0 × 10 ³ mL / gcm or more. It is 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 3.0 × 10 It is particularly preferably 10 ^{3 to} 8.0 × 10 ³ mL / gcm.
The extinction coefficient of light of the photopolymerization initiator a at a wavelength of 254 nm in methanol is preferably 1.0 × 10 ^{4 to} 1.0 × 10 ⁵ mL / gcm, preferably 1.5 × 10 ⁴ to 1.5 It is more preferably 9.5 × 10 ⁴ mL / gcm, and even more preferably 3.0 × 10 ^{4 to} 8.0 × 10 ⁴ mL / gcm.

As the photopolymerization initiator a, an oxime compound, an aminoacetophenone compound, and an acylphosphine compound are preferable, an oxime compound and an acylphosphine compound are more preferable, and an oxime compound is further preferable. Specific examples of the photopolymerization initiator a include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (commercially available products include, for example, IRGACURE-OXE01, BASF. , Etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime) (commercially available, for example, IRGACURE- OXE02, manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (commercially available, for example, IRGACURE-819, manufactured by BASF), and specific examples of the above oxime compounds are shown ( Examples thereof include the compound of C-13).

Extinction coefficient of light of wavelength 365nm in methanol of the photoinitiator b is at 1.0 × ¹⁰ 2 mL / gcm or less, is preferably ^{10~1.0 × 10 2 mL / gcm,} 20 More preferably, it is ~ 1.0 × 10 ² mL / gcm. The difference between the extinction coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator a and the extinction coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator b is 9.0 × 10 ² mL. It is preferably 9.0 × 10 ^{2 to} 1.0 × 10 ⁵ mL / gcm, more preferably 9.0 × 10 ^{2 to} 1.0 × 10 ⁴ mL / gcm. Is even more preferable. The absorption coefficient of the photopolymerization initiator b at a wavelength of 254 nm in methanol is 1.0 × 10 ³ mL / gcm or more, and 1.0 × 10 ^{3 to} 1.0 × 10 ⁶ mL / gcm. It is preferably 5.0 × 10 ^{3 to} 1.0 × 10 ⁵ mL / gcm, and more preferably 1.0 × 10 ^{4 to} 5.0 × 10 ⁵ mL / gcm.

As the photopolymerization initiator b, a hydroxyacetophenone compound, a phenylglycophenone compound, an aminoacetophenone compound, and an acylphosphine compound are preferable, a hydroxyacetophenone compound and a phenylglioxylate compound are more preferable, and a hydroxyacetophenone compound is further preferable. Further, as the hydroxyacetophenone compound, the compound represented by the above-mentioned formula (V) is preferable. Specific examples of the photopolymerization initiator b include 1-hydroxy-cyclohexyl-phenyl-ketone (commercially available products include IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl). ] -2-Hydroxy-2-methyl-1-propane-1-one (commercially available products include, for example, IRGACURE-2959, manufactured by BASF) and the like.

As a combination of the photopolymerization initiator a and the photopolymerization initiator b, the absorption coefficient of light having a wavelength of more than 350 nm and 380 nm or less and the absorption coefficient of light having a wavelength of 254 nm or more and 350 nm or less can be increased. A combination in which the photopolymerization initiator a is an oxime compound and the photopolymerization initiator b is a hydroxyacetophenone compound is preferable, the photopolymerization initiator a is an oxime compound, and the photopolymerization initiator b is the above-mentioned formula (V). Combinations that are the represented compounds are more preferred.

The content of the photopolymerization initiator a is 1.5% by mass or more, preferably 1.5 to 15% by mass, based on the total solid content of the photosensitive coloring composition of the present invention. From the viewpoint of adhesion of the cured film (pattern) after development to the support, the lower limit of the content of the photopolymerization initiator a is preferably 2% by mass or more, more preferably 3% by mass or more. It is more preferably 5% by mass or more. From the viewpoint of miniaturization of the development pattern, the upper limit of the content of the photopolymerization initiator a is preferably 14.5% by mass or less, more preferably 12.5% by mass or less, and 9% by mass or less. It is more preferable to have. The photopolymerization initiator a may contain only one type, or may contain two or more types. When two or more kinds of photopolymerization initiators a are contained, the total of them is preferably in the above range.

The content of the photopolymerization initiator b is 1.5% by mass or more, preferably 1.5 to 10% by mass, based on the total solid content of the photosensitive coloring composition of the present invention. From the viewpoint of color loss 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 3% by mass. The above is more preferable. From the viewpoint of miniaturization of the development 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 5% by mass or less. It is more preferable to have. The photopolymerization initiator b may contain only one type, or may contain two or more types. When two or more kinds of photopolymerization initiators b are contained, the total of them is preferably in the above range.

The photosensitive coloring composition of the present invention preferably contains 50 to 500 parts by mass of the photopolymerization initiator a with respect to 100 parts by mass of the photopolymerization initiator b. The upper limit is preferably 400 parts by mass or less, and more preferably 350 parts by mass or less because it is easy to form a cured film having excellent color loss resistance. Further, the lower limit is preferably 100 parts by mass or more, preferably 150 parts by mass or more, because the residual film ratio after development is high and it is easy to form a cured film having excellent adhesion to the support. More preferred.

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 viewpoint of the stability of the composition over time, the lower limit is preferably 3.2% by mass or more, more preferably 3.5% by mass or more, and further preferably 4.5% by mass or more. From the viewpoint of miniaturization of the development pattern, the upper limit is preferably 16% by mass or less, more preferably 15% by mass or less, and further preferably 14% by mass or less.

The photosensitive coloring composition of the present invention may also contain a photopolymerization initiator (hereinafter, also referred to as another photopolymerization initiator) other than the photopolymerization initiator a and the photopolymerization initiator b as the photopolymerization initiator. However, it is preferable that the other photopolymerization initiator is substantially not contained. When the content of the other photopolymerization initiator is substantially not contained, the content of the other photopolymerization initiator is 1 part by mass with respect to 100 parts by mass in total of the photopolymerization initiator a and the photopolymerization initiator b. It is preferably less than or equal to, more preferably 0.5 parts by mass or less, further preferably 0.1 parts by mass or less, and further preferably not containing another photopolymerization initiator.

<< Coloring material with polymerizable group >>
The photosensitive coloring composition of the present invention contains a coloring material having a polymerizable group. The coloring material having a polymerizable group may be a pigment or a dye, but is preferably a dye. That is, the coloring material having a polymerizable group is preferably a dye having a polymerizable group. A cured film obtained by using a photosensitive coloring composition containing a dye as a coloring material tends to cause color loss depending on a developing solution, but by using a dye having a polymerizable group, it is cured at a low temperature. Even so, a cured film having excellent color loss resistance to a developing solution can be formed. Therefore, the effect of the present invention is more remarkable.
In the present specification, the dye refers to a dye compound that dissolves in water or an organic solvent. For example, a dye compound that dissolves 0.1% by mass or more in cyclohexanone or propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. is preferable.

Coloring materials having a polymerizable group include triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, and pyrazolo. Triazole pigment structure, dipyrromethene pigment structure, isoindolin pigment structure, thiazole pigment structure, benzimidazolone pigment structure, perinone pigment structure, pyrolopyrrolop pigment structure, diketopyrrolopyrrole pigment structure, diimmonium pigment structure, naphthalocyanine pigment structure, lilene It is preferable that the compound has a dye structure selected from a dye structure, a dibenzofuranone dye structure, a merocyanine dye structure, a croconium dye structure and an oxonol dye structure, and is preferably a triarylmethane dye structure, a xanthene dye structure, an anthraquinone dye structure and a cyanine dye structure. , Squalylium pigment structure, quinophthalone pigment structure, phthalocyanine pigment structure, subphthalocyanine pigment structure, azo pigment structure, thiazole pigment structure, pyrazolotriazole pigment structure and dipyromethene pigment structure are more preferable. A compound having a dye structure selected from a triarylmethane dye structure, a xanthene dye structure and a dipyromethene dye structure is more preferable, and a compound having a triarylmethane dye structure or a xanthene dye structure is particularly preferable.

(Compound with triarylmethane dye structure)
Examples of the compound having a triarylmethane dye structure include a compound represented by the following formula (TP).

Equation (TP)

In formula (TP), Rtp ^{1 to} Rtp ⁴ 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 an 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 substituents. a, b and c represent integers from 0 to 4. a, when b and c is 2 or more, Rtp ⁶ together, Rtp ⁷ together and Rtp ⁸ each other, may be coupled to each other to form a ring. X represents an anion. In the absence of X, at least one of Rtp ^{1 through} 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 a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group. As Rtp ⁵ , a hydrogen atom or NRtp ⁹ Rtp ¹⁰ is preferable, and NRtp ⁹ Rtp ¹⁰ is particularly preferable. Rtp ⁹ and Rtp ¹⁰ are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group. Examples of the substituent represented by Rtp ⁶ , Rtp ⁷ and Rtp ⁸ include the groups listed in the substituent T group described later and the polymerizable group.

In formula (TP), X represents a counter anion. In the absence of X, at least one of Rtp ^{1 through} Rtp ⁸ contains an anion. The counter anion is not particularly limited. It may be an organic anion or an inorganic anion. The counter anion is preferably an organic anion. Examples of the counter anion include a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, and a non-nucleophilic anion. From the viewpoint of heat resistance, it is preferably a non-nucleophilic anion. Examples of counter anions include known non-nucleophilic anions described in paragraph number 0075 of JP-A-2007-310315, the contents of which are incorporated herein. Here, the non-nucleophilic property means a property that does not nucleophilically attack the pigment by heating.

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

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

In formula ^(TP), if it contains at least one anion of Rtp 1 ~Rtp ^7, as the _{^{anion, -SO 3 -, -COO -,}} -PO 4 -, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion And tetraarylborate anions are preferred, bis (sulfonyl) imide anions, tris (sulfonyl) methide anions and tetraarylborate anions are more preferred, and bis (sulfonyl) imide anions and tris (sulfonyl) methide anions are even more preferred. Specifically, a structure in which at least one of Rtp ^{1 to} Rtp ⁷ is replaced by the formula (P) can be mentioned.
Equation (P)

In formula (P), L represents a single bond or a divalent linking group, and X ¹ represents an anion.

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

Wherein (P), ^{X 1} represents an _{^{anion, -SO 3 -, -COO -,}} -PO 4 -, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion, and one selected from the tetraarylborate anion Is preferable, one selected from bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraarylborate anion is more preferable, and bis (sulfonyl) imide anion or tris (sulfonyl) methide anion is further preferable.

When at least one of Rtp ^{1 to} Rtp ⁸ contains an anion, a structure in which at least one of Rtp ^{1 to} Rtp ⁸ is substituted by the formula (P-1) is also preferable.
Equation (P-1)

In the formula (P-1), L ¹ represents a single bond or a divalent linking group, and is preferably a single bond. Examples of the divalent linking group represented by L ¹ 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 a combination thereof. L ² represents −SO _2- or −CO−. G represents a carbon atom or a nitrogen atom. n1 represents 2 when G is a carbon atom and represents 1 when G is a nitrogen atom. R ⁶ represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. If n1 is 2, the two R ⁶ may each be the same or different. The number of carbon atoms of the alkyl group containing a fluorine atom represented by R ⁶ is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3. The number of carbon atoms 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 with xanthene dye structure)
Examples of the compound having a xanthene dye structure include a compound represented by the following formula (J).

(Formula J)

In formula (J), R ⁸¹ , R ⁸² , R ⁸³ and R ⁸⁴ each independently represent a hydrogen atom or a monovalent substituent, and R ⁸⁵ each independently represents a monovalent substituent, m. Represents an integer from 0 to 5. X represents a counter anion. In the absence of X, at least one of R ^81- R ⁸⁵ contains anions. At least one of R ^{81 to} R ⁸⁵ contains a polymerizable group.

Examples of the substituents that R ^{81 to} R ⁸⁵ in the formula (J) can take include the group mentioned in the substituent T described later and the polymerizable group. R ⁸¹ and R ⁸² , R ⁸³ and R ⁸⁴ in formula (J), and R ⁸⁵ when m is 2 or more are independently coupled to each other and are 5-membered, 6-membered, or 7-membered saturated rings. , Or a 5-membered, 6-membered or 7-membered unsaturated ring may be formed. Examples of the ring to be formed include a pyrrole ring, a furan ring, a thiophene ring, a pyrazole ring, an imidazole ring, a triazole ring, an oxazole ring, a thiazole ring, a pyrrolidine ring, a piperidine ring, a cyclopentene ring, a cyclohexene ring, a benzene ring, and a pyridine ring. Examples thereof include a pyrazine ring and a pyridazine ring, and preferably, a benzene ring and a pyridine ring are used.
If the ring to be formed is a further substitutable group, it may be substituted with the substituents described in R ^{81 to} R ⁸⁵ , and if it is substituted with two or more substituents, it may be substituted. The substituents may be the same or different.

In formula (J), X represents a counter anion. Examples of the counter anion include the counter anion described by the above formula (TP). In the absence of X, at least one of R ^81- R ⁸⁵ contains anions. Further, in the formula (J), when at least one of R ^{81 to} R ⁸⁵ contains an anion, the anion includes the anion described in the above formula (TP).

(Compound having dipyrromethene dye structure)
As the compound having a dipyrromethene dye structure, a dipyrromethene compound and a dipyrromethene metal complex compound obtained from the dipyrromethene compound and a metal or a metal compound are preferable. For example, a dipyrromethene dye represented by the formula (PM) is preferable.
Equation (PM)

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a substituent, and R ⁷ is a hydrogen atom, a halogen atom, an alkyl group or an aryl group. , Or a heterocyclic group. Examples of these substituents include a substituent T group described later. At least one of R ^{1 to} R ⁷ contains a polymerizable group.

The metal or metal compound forming the dipyrromethene metal complex compound will be described. The metal or metal compound may be any metal atom or metal compound capable of forming a complex, and may be a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or 2 Valuable metal chlorides are included. For example, in addition to Zn, Mg, Si, Sn, Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, B, etc., AlCl, InCl, FeCl, TiCl ₂ , SnCl, SiCl ₂ , etc. It also contains metal chlorides such as GeCl ₂ , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) ₂ . Among these, from the viewpoints of complex stability, spectral characteristics, heat resistance, light resistance, production suitability, etc., Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B , Or VO is preferable, Fe, Zn, Mg, Si, Pt, Pd, Cu, Ni, Co, B, or VO is more preferable, and Fe, Zn, Cu, Co, B, or VO (V = O) is preferable. Most preferred. Among these, Zn is particularly preferable.

For details of the dipyrromethene dye structure, the description of paragraphs 0045 to 0095 of JP2014-132348 and the description of paragraphs 0033 to 0136 of JP2011-95732 can be referred to, and the contents thereof are described in the present specification. Be incorporated.

(Substituent T group)
Examples of the substituent T group include the following groups. Alkyl group (preferably an alkyl group having 1 to 30 carbon atoms), alkenyl group (preferably an alkenyl group having 2 to 30 carbon atoms), alkynyl group (preferably an alkynyl group having 2 to 30 carbon atoms), aryl group (preferably an aryl group having 2 to 30 carbon atoms). Aryl groups with 6 to 30 carbon atoms), amino groups (preferably amino groups with 0 to 30 carbon atoms), alkoxy groups (preferably alkoxy groups with 1 to 30 carbon atoms), aryloxy groups (preferably 6 to 30 carbon atoms). 30 aryloxy groups), heteroaryloxy groups, acyl groups (preferably acyl groups having 1 to 30 carbon atoms), alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 30 carbon atoms), aryloxycarbonyl groups (preferably aryloxycarbonyl groups). Is an aryloxycarbonyl group having 7 to 30 carbon atoms), an acyloxy group (preferably an acyloxy group having 2 to 30 carbon atoms), an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), and an alkoxycarbonylamino group (preferably). An alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 30 carbon atoms), a sulfamoyl group (preferably a sulfamoyl group having 0 to 30 carbon atoms), a carbamoyl group. (Preferably a carbamoyl 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 heteroarylthio group). 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 6 to 30 carbon atoms), heteroarylsulfonyl group (preferably 1 to 30 carbon atoms), alkylsulfinyl group (Preferably 1 to 30 carbon atoms), arylsulfinyl group (preferably 6 to 30 carbon atoms), heteroarylsulfinyl group (preferably 1 to 30 carbon atoms), ureido group (preferably 1 to 30 carbon atoms), hydroxyl Group, carboxyl group, sulfo group, phosphoric acid group, carboxylic acid amide group, sulfonic acid amide group, imide acid group, mercapto group, halogen atom, cyano group, alkylsulfino group, arylsulfino group, hydradino group, imino group , Heteroaryl group (preferably 1 to 30 carbon atoms). These groups may have additional substituents if they are further substitutable groups. Examples of the substituent include the group described in the above-mentioned Substituent T.

Examples of the polymerizable group contained in the coloring material include an ethylenically unsaturated group such as a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.

The coloring material having a polymerizable group is preferably a dye multimer because it is easy to form a cured film having excellent color loss resistance to a developing solution. The dye multimer is a dye compound having two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less. The dye structure contained in one molecule may be the same dye structure or may be a different dye structure. In the present invention, the different dye structures include not only dye structures having different dye skeletons but also dye structures having the same dye skeleton and different types of substituents bonded to the dye skeleton. And.

The dye multimer includes at least one of a repeating unit represented by the formula (A), a repeating unit represented by the formula (B), and a repeating unit represented by the formula (C), which will be described later. A body or a dye multimer represented by the formula (D) described later is preferable. That is, the dye multimer is a dye multimer having a repeating unit represented by the formula (A) (also referred to as a dye multimer (A)) and a dye multimer having a repeating unit represented by the formula (B) (dye). A dye multimer (also referred to as a multimer (B)), a dye multimer having a repeating unit represented by the formula (C) (also referred to as a dye multimer (C)), and a dye multimer (dye) represented by the formula (D). The multimer (D) is preferable, and the dye multimer (A) or the dye multimer (D) is more preferable.

(Dye multimer (A))
The dye multimer (A) preferably contains a repeating unit represented by the formula (A). The ratio of the repeating unit represented by the formula (A) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more of all the repeating units constituting the dye multimer (A). 50% by mass or more is particularly preferable. The upper limit may be 100% by mass or less, or 95% by mass or less.

In formula (A), X ¹ represents the backbone of the repeating unit, L ¹ represents a single bond or a divalent linking group, and D ¹ represents the dye structure.

In formula (A), X ¹ represents the backbone of the repeating unit. Examples of X ¹ include a linking group formed by a polymerization reaction, and a main chain derived from a compound having a (meth) acrylic group, a styrene group, a vinyl group and an ether group is preferable. It is also preferable that the main chain has a cyclic alkylene group. X ¹ is not particularly limited as long as it is a linking group formed from a known polymerizable monomer. The linking groups represented by the following (XX-1) to (XX-25) are preferable, and (XX-1), (XX-2), (XX-10) to (XX-17), (XX-18). , (XX-19), (XX-24) and (XX-25), more preferably selected from (XX-1), (XX-2), (XX-10) to (XX-17). , (XX-24) and (XX-25) are more preferred.

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

L ¹ represents a single bond or a divalent linking group. The divalent linking group includes 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-, and -C (= O). )-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO _2-, and a linking group formed by linking two or more of these. Here, R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

The alkylene group preferably has 1 to 30 carbon atoms. The upper limit is more preferably 25 or less, and even more preferably 20 or less. The lower limit is more preferably 2 or more, and even more preferably 3 or more. The alkylene group may be linear, branched or cyclic. The alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent T group.
The arylene group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms. The arylene group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent T group.
The heterocyclic linking group is preferably a 5-membered ring or a 6-membered ring. The hetero atom contained in the heterocyclic linking group is preferably an oxygen atom, a nitrogen atom and a sulfur atom. The number of heteroatoms contained in the heterocyclic linking group is preferably 1 to 3. The heterocyclic linking group may have a substituent or may be unsubstituted. Examples of the substituent include the groups described in the substituent T group.

D ¹ represents the dye structure. The type of dye structure represented by D ¹ is not particularly limited. Triarylmethane pigment structure, xanthene pigment structure, anthraquinone pigment structure, cyanine pigment structure, squarylium pigment structure, quinophthalocyanine pigment structure, phthalocyanine pigment structure, subphthalocyanine pigment structure, azo pigment structure, pyrazolotriazole pigment structure, dipyromethene pigment structure, iso Indoline pigment structure, thiazole pigment structure, benzimidazolone pigment structure, perinone pigment structure, pyrolopyrrolop pigment structure, diketopyrrolopyrrole pigment structure, diimmonium pigment structure, naphthalocyanine pigment structure, lilene pigment structure, dibenzofuranone pigment structure, merocyanine Examples thereof include a pigment structure, a croconium pigment structure, and an oxonol pigment structure. The dye structure represented by D ¹ may contain a polymerizable group.

The dye multimer (A) preferably has a repeating unit having a polymerizable group in addition to the repeating unit represented by the formula (A). When the dye structure represented by D ^{1 of} the above formula (A) does not have a polymerizable group, the dye multimer (A) has a repeating unit having a polymerizable group.

The dye multimer (A) may contain other repeating units in addition to the repeating unit represented by the formula (A). The other repeating unit may contain a functional group such as a polymerizable group or an acid group. It does not have to contain a functional group. When the dye structure represented by D ^{1 of} the above formula (A) does not have a polymerizable group, the dye multimer (A) has a repeating unit having a polymerizable group.

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

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

Other functional groups include groups consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, development promoting groups such as lactones, acid anhydrides, amides and cyano groups, long chain and cyclic alkyl groups, aralkyl groups and aryls. Examples thereof include a hydrophobicity adjusting group such as a group, a polyalkylene oxide group, a hydroxyl group, a maleimide group and an amino group, which can be appropriately introduced. In a group consisting of 2 to 20 unsubstituted alkyleneoxy chain repeats, the number of alkyleneoxy chain repeats is preferably 2 to 15 and even more preferably 2 to 10. One alkyleneoxy chain is represented by − (CH ₂ ) _n O−, where n is an integer, where n is preferably 1-10, more preferably 1-5, even 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.

(Dye multimer (B))
The dye multimer (B) contains a repeating unit represented by the formula (B). The ratio of the repeating unit represented by the formula (B) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more of all the repeating units constituting the dye multimer (B). 50% by mass or more is particularly preferable. The upper limit may be 100% by mass or less, or 95% by mass or less.

In formula (B), X ² represents the main chain of the repeating unit, L ² represents a single bond or a divalent linking group, and D ² is a dye structure having an ionic bond or a coordinate bond group with Y ^2. And Y ² represents a group that can be ionic or coordinated with D ² ;

X ² is synonymous with X ¹ of the formula (A), and the preferred range is also the same.
L ² represents a single bond or a divalent linking group. The divalent linking group includes 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-, and -C (= O). )-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO _2-, and a linking group formed by linking two or more of these. Here, 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 L ¹ of the formula (A). L ² is preferably a single bond or a divalent linking group consisting of an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, or a combination thereof.

Y ² may be a group capable of ionic bond or coordinate bond with D ² . For example, an anionic group, a cationic group and the like can be mentioned. Examples of the anionic _{^{group, -SO 3 -, -COO -,}} -PO 4 -, -PO 4 H -, bis (sulfonyl) imide anion, and tris (sulfonyl) methide anion and tetraarylborate anions. Examples of the cationic group include substituted or unsubstituted onium cations (for example, ammonium, pyridinium, imidazolium and phosphonium), and ammonium cations are particularly preferable. The ammonium cation, -N _(R) ^{3 +} and the like. R each independently represents a hydrogen atom or an alkyl group, and at least one of R represents an alkyl group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. The alkyl group may be linear, branched or cyclic, but linear is preferred.

D ² represents a dye structure having a group capable of ionic or coordinate bond with Y ² . The type of dye structures, particularly limited include kinds of dyes structure described in no D ^1. Examples of the group of D ² capable of ionic bond or coordinate bond with Y ² include the anionic group and the cationic group described in Y ² . Also, if the balance of charge D ² is biased to one of the cation and anion, the cation portion or the anion portion of the D ^2, can also be combined with Y ^2. The dye structure represented by D ² may have a polymerizable group.

The dye multimer (B) may contain other repeating units described in the dye multimer (A) in addition to the repeating unit represented by the formula (B). Further, the repeating unit represented by the above-mentioned formula (A) and the repeating unit represented by the formula (C) described later may be further included. When the dye structure represented by D ^{2 of} the above formula (B) does not have a polymerizable group, the dye multimer (B) has a repeating unit having a polymerizable group.

(Dye multimer (C))
The dye multimer (C) preferably contains a repeating unit represented by the formula (C). The ratio of the repeating unit represented by the formula (C) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more of all the repeating units constituting the dye multimer (C). 50% by mass or more is particularly preferable. The upper limit may be 100% by mass or less, or 95% by mass or less.

In formula (C), L ³ represents a single bond or a divalent linking group, D ³ represents a dye structure, and m represents 0 or 1.

In formula (C), L ³ represents a single bond or a divalent linking group. The divalent linking group includes 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-, and -C (= O). )-, -COO-, -NR-, -CONR-, -OCO-, -SO-, -SO _2-, and a linking group formed by linking two or more of these. Here, R independently represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

The alkyl group and the alkylene group preferably have 1 to 30 carbon atoms. The upper limit is more preferably 25 or less, and even more preferably 20 or less. The lower limit is more preferably 2 or more, and even more preferably 3 or more. The alkyl group and the alkylene group may be linear, branched or cyclic.
The aryl group and arylene group preferably have 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
The heterocyclic linking group and the heterocyclic group are preferably a 5-membered ring or a 6-membered ring. The heterocyclic linking group and the heteroatom contained in the heterocyclic group are preferably an oxygen atom, a nitrogen atom and a sulfur atom. The number of heteroatoms contained in the heterocyclic linking 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 have a substituent. Examples of the substituent include a polymerizable group and an acid group. Further, a group consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, a development promoting group such as a lactone, an acid anhydride, an amide and a cyano group, a long chain and a cyclic alkyl group, an aralkyl group, an aryl group and a polyalkylene It may have a prohydrophobicity adjusting group such as an oxide group, a hydroxyl group, a maleimide group and an amino group as a substituent.

L ³ is preferably an alkylene group, an arylene group, -NH-, -CO-, -O-, -COO-, -OCO-, -S-, or a linking group in which two or more of these are combined.
D ³ represents the dye structure. The type of dye structures, particularly limited include kinds of dyes structure described in no D ^1. The dye structure represented by D ³ may have a polymerizable group.
m represents 0 or 1, and 1 is preferable.

The dye multimer (C) may contain other repeating units described in the dye multimer (A) in addition to the repeating unit represented by the general formula (C).

(Dye multimer (D))
The dye multimer (D) is preferably represented by the formula (D).

In formula (D), L ⁴ represents a (n + k) -valent linking group, L ⁴¹ and L ⁴² independently represent a single bond or a divalent linking group, D ⁴ represents a dye structure, P. ⁴ represents a substituent; n represents 2 to 15, k represents 0 to 13, and n + k represents 2 to 15. n-number of D ⁴ may be different from each other, it may be identical. when k is 2 or more, a plurality of P ⁴ may be different from each other, it may be identical.

n is preferably 2 to 14, more preferably 2 to 8, particularly preferably 2 to 7, and even more preferably 2 to 6. k is preferably 1 to 13, more preferably 1 to 10, even more preferably 1 to 8, particularly preferably 1 to 7, and even more 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 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 atoms. It contains a group consisting of up to 20 sulfur atoms and may be unsubstituted or have additional substituents. As a specific example, the divalent linking group may be a group composed of the following structural units or a combination of two or more of the following structural units.

The (n + k) valence linking group represented by L ⁴ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 carbon atoms. It contains a group consisting of a hydrogen atom and 0 to 20 sulfur atoms. Examples of the (n + k) valent linking group include a group composed of the following structural units or a combination of two or more of the following structural units (which may form a ring structure).

Specific examples of the (n + k) -valent linking group include the linking group described in paragraphs 0071 to 0072 of JP-A-2008-222950 and the linking group described in paragraph number 0176 of JP2013-209760A. Can be mentioned.

In the general formula (D), D ⁴ represents a dye structure. The type of dye structures, particularly limited include kinds of dyes structure described in no D ^1. The dye structure represented by D ⁴ may contain a polymerizable group.

In the formula (D), examples of the substituent represented by P ⁴ include an acid group and a polymerizable group. Further, the substituent represented by P ⁴ may 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. If k is 2 or more, k number of P ⁴ may be the same, may be different. If the dye structure represented by D ⁴ do not contain a polymerizable group, one or more of the k P ⁴ represents a polymerizable group.

The dye multimer represented by the formula (D) preferably has a structure represented by the formula (D-1).

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 dye structure and P ⁴ represents a substituent. B ⁴¹ and ^{B 42} are each independently a single bond, -O -, - S -, - CO -, - NR -, - O 2 C -, - CO 2 -, - NROC-, or, -CONR- Represents. 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-number of D ⁴ may be different from each other, it may be identical. when k is 2 or more, a plurality of P ⁴ may be different from each other, it may be identical. n + k is 2 to 15.

^L 4, ^{D 4} and ^{P 4} of formula (D-1) has the same meaning as ^L 4, ^{D 4} and ^{P 4} of the formula (D).
^{B 41} and ^{B 42} of formula (D-1) is 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- are more preferred. R represents a hydrogen atom, an alkyl group or an aryl group.

As the divalent linking group represented by C ⁴¹ and C ⁴² of the formula (D-1), an alkylene group, an arylene group and a group combining these are preferable. The alkylene group preferably has 1 to 30 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkylene group may be linear, branched or cyclic. The arylene group preferably has 6 to 30 carbon atoms, more preferably 6 to 12 carbon atoms.

The weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000. The lower limit is more preferably 3000 or more, and even more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. By satisfying the above range, it is easy to produce a cured film having excellent color loss resistance.

The content of the coloring material having a polymerizable group is preferably 5 to 40% by mass based on the total solid content of the photosensitive coloring composition. The lower limit is more preferably 6% by mass or more, further preferably 10% by mass or more. The upper limit is more preferably 35% by mass or less, and further preferably 30% by mass or less.
The content of the coloring material having a polymerizable group is preferably 25 to 500 parts by mass with respect to 100 parts by mass in total of the photopolymerization initiator a and the photopolymerization initiator b. The lower limit is more preferably 30 parts by mass or more, further preferably 50 parts by mass or more, and particularly preferably 100 parts by mass or more. The upper limit is more preferably 450 parts by mass or less, further preferably 400 parts by mass or less, and particularly preferably 350 parts by mass or less. Within this range, it is easy to obtain a cured film having more excellent color loss resistance to the developing solution.

<< Other color materials >>
The photosensitive coloring composition of the present invention can further contain a coloring material having no polymerizable group (hereinafter, also referred to as another coloring material). The other coloring material may be either a pigment or a dye. Examples of the pigment include inorganic pigments and organic pigments, and organic pigments are preferable. The average particle size of the pigment is preferably 20 to 300 nm, more preferably 25 to 250 nm, and even more preferably 30 to 200 nm. The "average particle size" here means the average particle size of the secondary particles in which the primary particles of the pigment are aggregated. Further, the particle size distribution of the secondary particles of the pigment (hereinafter, also simply referred to as “particle size distribution”) is such that the secondary particles in (average particle size ± 100) nm are 70% by mass or more, preferably 80. It is preferably mass% or more. The particle size distribution of the secondary particles can be measured using the scattering intensity distribution. The average particle size of the primary particles is observed with a scanning electron microscope (SEM) or a transmission electron microscope (TEM), and 100 particle sizes are measured at the portion where the particles are not aggregated to calculate the average value. It can be obtained by.

Examples of the organic pigment include those shown below.
Color Index (CI) 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. (above, yellow pigment),
C. I. Pigment Orange 2,5,13,16,17: 1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73, etc. (The above is orange pigment),
C. I. Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48: 1,48: 2,48: 3,48: 4, 49,49: 1,49: 2,52: 1,52: 2,53: 1,57: 1,60: 1,63: 1,66,67,81: 1,81: 2,81: 3, 83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279 etc. , Red pigment),
C. I. Pigment Green 7, 10, 36, 37, 58, 59, etc. (above, green pigment),
C. I. Pigment Violet 1,19,23,27,32,37,42, etc. (above, purple pigment),
C. I. Pigment Blue 1,2,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,22,60,64,66,79,80 etc. (above, blue pigment).

Further, as the green pigment, a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms is used. You can also do it. Specific examples include the compounds described in International Publication WO2015 / 118720.
Further, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP2012-247591A and paragraphs 0047 of JP2011-157478A.

The dye is not particularly limited, and a known dye can be used. The chemical structures include pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, and pyrrolopyrazole azomethine. Dyes such as xanthene, phthalocyanine, benzopyran, indigo, and pyrromethene can be used. Further, the thiazole compound described in JP2012-158649, the azo compound described in JP2011-184493, and the azo compound described in JP2011-145540 can also be preferably used. Further, as the yellow dye, the quinophthalone compounds described in paragraphs 0011 to 0034 of JP2013-54339A, the quinophthalone compounds described in paragraphs 0013 to 0058 of JP2014-262228, and the like can also be used.

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

<< Resin >>
The photosensitive coloring composition of the present invention contains a resin. Examples of the resin include alkali-soluble resins. The resin is blended, for example, for the purpose of dispersing particles such as pigments in the composition and for the purpose of a binder. A resin mainly used for dispersing particles such as pigments is also referred to as a dispersant. However, such an application of the resin is an example, and the resin can be used for a purpose other than such an application.

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

(Alkali-soluble resin)
The photosensitive coloring composition of the present invention contains 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 sulfo group, a phenolic hydroxyl group, and the like, and a carboxyl group is preferable. The type of acid group contained in the alkali-soluble resin may be only one type or 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 further preferably 40 mgKOH / g or more. The upper limit is more preferably 150 mgKOH / g or less, further preferably 120 mgKOH / g or less, and particularly preferably 100 mgKOH / g or less.

As the alkali-soluble resin, a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, and an acrylic / acrylamide copolymer resin are preferable from the viewpoint of heat resistance. From the viewpoint of controllability of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.

As the alkali-soluble resin, a polymer having a carboxyl group in the side chain is preferable. For example, polymers having repeating units derived from monomers such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinyl benzoic acid, partially esterified maleic acid, etc. Examples thereof include alkali-soluble phenolic resins such as novolak-type resins, acidic cellulose derivatives having a carboxyl group in the side chain, and polymers in which an acid anhydride is added to a polymer having a hydroxyl group. In particular, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like. Examples of alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, trill (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Can be mentioned. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like. The other monomers copolymerizable with these (meth) acrylic acids may be only one kind or two or more kinds.

The alkali-soluble resin may have repeating units derived from the maleimide compound. Examples of the maleimide compound include N-alkylmaleimide and N-arylmaleimide. Examples of the repeating unit derived from the maleimide compound include a repeating unit represented by the formula (C-mi).

In formula (C-mi), Rmi represents an alkyl or 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.

Examples of the alkali-soluble resin include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate. A multi-polymer copolymer composed of / (meth) acrylic acid / other monomer can be preferably used. Further, a copolymer obtained by copolymerizing 2-hydroxyethyl (meth) acrylate with another monomer, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / described in JP-A-7-140654. Methacrylate copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethylmethacrylate macromonomer / benzylmethacrylate / methacrylic acid copolymer, 2-hydroxyethylmethacrylate / polystyrene macromonomer / methylmethacrylate / methacrylic acid copolymer, 2-Hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used.

As the alkali-soluble resin, an alkali-soluble resin having a polymerizable group can also be used. Examples of the polymerizable group include a (meth) allyl group and a (meth) acryloyl group. As the alkali-soluble resin having a polymerizable group, an alkali-soluble resin or the like having a polymerizable group in the side chain is useful. Commercially available products of alkali-soluble resins having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamlock Co., Ltd.), and Viscort R-264. , KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Praxel CF200 series (all manufactured by Daicel Co., Ltd.), Ebeclyl3800 (manufactured by Daicel UCB Co., Ltd.), Examples thereof include acrylic cure RD-F8 (manufactured by Nippon Catalyst Co., Ltd.) and DP-1305 (manufactured by Fujifilm Fine Chemicals Co., Ltd.).

As the alkali-soluble resin, an alkali-soluble resin containing a repeating unit having a hydroxyl group is preferable. According to this aspect, the affinity with the developing solution is improved, and it is easy to form a pattern having excellent rectangularity. In the alkali-soluble resin containing a repeating unit having a hydroxyl group, the hydroxyl group value of the alkali-soluble resin is preferably 30 to 100 mgKOH / g. The lower limit is more preferably 35 mgKOH / g or more, and further preferably 40 mgKOH / g or more. The upper limit is more preferably 80 mgKOH / g or less. When the hydroxyl group value of the alkali-soluble resin is within the above range, it is easy to form a pattern having excellent rectangularity. Examples of the alkali-soluble resin containing a repeating unit having a hydroxyl group include a resin having the following structure.

The alkali-soluble resin is at least one compound selected from the compound represented by the following formula (ED1) and the compound represented by the formula (1) of JP2010-168539 (hereinafter, these compounds are referred to as "ether dimer". It is also preferable to include a polymer obtained by polymerizing a monomer component containing ().

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

As a specific example of the ether dimer, for example, paragraph number 0317 of JP2013-29760A can be referred to, and the content thereof is incorporated in the present specification. The ether dimer may be only one type or two or more types.

Examples of the polymer obtained by polymerizing a monomer component containing an ether dimer include a polymer having the following structure.

The alkali-soluble resin may contain a repeating unit derived from the compound represented by the following formula (X).

In formula (X), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents an alkylene group having 2 to 10 carbon atoms, and R ₃ represents a hydrogen atom or a benzene ring having 1 to 20 carbon atoms. Represents the alkyl group of. n represents an integer of 1 to 15.

For the alkali-soluble resin, the description in paragraphs 0558 to 0571 of JP2012-208494A (paragraph numbers 0685 to 0700 of the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof are described in the present specification. Incorporated into the book. Further, the copolymer (B) described in paragraphs 0029 to 0063 of JP-A-2012-32767 and the alkali-soluble resin used in Examples, and paragraph numbers 0088 to 098 of JP-A-2012-208474. The binder resin described and the binder resin used in Examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A, and the binder resin used in Examples, JP2013-024934. Binder resins described in paragraphs 0132 to 0143 of Japanese Patent Application Laid-Open No. 0132 to 0143 and binder resins used in Examples, paragraph numbers 0092 to 0098 of Japanese Patent Application Laid-Open No. 2011-242752 and binder resins used in Examples of Japanese Patent Application Laid-Open No. 2012 It is also possible to use the binder resin described in paragraphs 0030 to 0072 of JP-A-032770. These contents are incorporated in the present specification.

The content of the alkali-soluble resin is preferably 1 to 50% by mass based on the total solid content of the photosensitive coloring composition. The lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more. The upper limit is more preferably 40% by mass or less, and further preferably 35% by mass or less. The photosensitive coloring composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types of alkali-soluble resin. When two or more types are included, the total is preferably in the above range.

(Dispersant)
The photosensitive coloring composition of the present invention can contain a resin as a dispersant. Examples of the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).

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

Examples of the dispersant include polymer dispersants [for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth). Acrylic copolymer, naphthalene sulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, alkanol amine and the like. Polymer dispersants can be further classified into linear polymers, terminally modified polymers, graft-type polymers, and block-type polymers based on their structures. The polymer dispersant acts on the surface of the pigment to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site on the pigment surface can be mentioned as preferable structures. Further, the dispersant described in paragraphs 0028 to 0124 of JP2011-070156 and the dispersant described in JP2007-277514 are also preferably used. These contents are incorporated in the present specification.

In the present invention, a graft copolymer can also be used as the dispersant. For details of the graft copolymer, the description in paragraphs 0131 to 0160 of JP2012-137564A can be referred to, and the contents thereof are incorporated in the present specification. Further, in the present invention, as the dispersant, a resin containing a nitrogen atom in the main chain can also be used. Resins containing a nitrogen atom in the main chain (hereinafter, also referred to as oligoimine-based resin) are poly (lower alkyleneimine) -based repeating units, polyallylamine-based repeating units, polydialylamine-based repeating units, and metaxylene diamine-epicrolhydrin polycondensate-based. It is preferable to contain at least one repeating unit having a nitrogen atom selected from the repeating unit and the polyvinylamine-based repeating unit. Regarding the oligoimine-based resin, the description in paragraphs 0102 to 0174 of JP2012-255128A can be referred to, and this content is incorporated in the present specification.

Commercially available products can also be used as the dispersant. For example, the product described in paragraph No. 0129 of JP2012-137564A can also be used as a dispersant. For example, the DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-161) and the like can be mentioned. The resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.

The content of the dispersant is preferably 1 to 200 parts by mass with respect 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 can contain a resin other than the above-mentioned dispersant and alkali-soluble resin (also referred to as other resin) as the resin. Examples of other resins include (meth) acrylic resin, (meth) acrylamide resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene ether. Examples thereof include phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and siloxane resin. As for other resins, one kind of these resins may be used alone, or two or more kinds may be mixed and used.

<< Polymerizable compound >>
The photosensitive coloring composition of the present invention preferably further contains a polymerizable compound in addition to the coloring material having a polymerizable group. Examples of the polymerizable compound include compounds having an ethylenically unsaturated group. Examples of the ethylenically unsaturated group include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group. The polymerizable compound is preferably a compound that can be polymerized by radicals (radical polymerizable compound). In the present specification, the polymerizable compound is a compound different from the coloring material having a polymerizable group. The polymerizable compound is preferably a compound having no dye structure.

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

The polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and 3 to 6 ethylenically unsaturated groups. It is more preferable that the compound contains two compounds. Further, the radically polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities. Specific examples of the radically polymerizable compound are described in paragraphs 0905 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-29760, and paragraphs 0254 to 0257 of JP2008-292970. Compounds are mentioned, the contents of which are incorporated herein by reference.

The polymerizable compounds are dipentaerythritol triacrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetraacrylate (commercially available KAYARAD D-320; Nippon Kayaku Co., Ltd.). , Dipentaerythritol penta (meth) acrylate (commercially available KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (commercially available KAYARAD DPHA; NK ester A-DPH-12E manufactured by Shin-Nakamura Chemical Industry Co., Ltd., and compounds having a structure in which these (meth) acryloyl groups are bonded via ethylene glycol and / or propylene glycol residues. (For example, SR454 and SR499 commercially available from Sartmer) are preferable. These oligomer types can also be used. Further, as the radically polymerizable compound, NK ester A-TMMT (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), KAYARAD RP-1040, DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.) can also be used. Further, as the radically polymerizable compound, trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanurate ethyleneoxy-modified tri (meth) It is also preferable to use a trifunctional (meth) acrylate compound such as acrylate or pentaerythritol trimethylolpropane (meth) acrylate. Commercially available products of trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306 and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.

The polymerizable compound may have an acid group. Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable. Examples of commercially available products of the radically polymerizable compound having an acid group include Aronix M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like.

The preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. When the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling.

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

The polymerizable compound is also preferably a compound having an alkyleneoxy group. The polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups. More preferably, it is a 3-6 functional (meth) acrylate compound. Commercially available products of the polymerizable compound having an alkyleneoxy group include SR-494, which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, and a trifunctional (meth) having three isobutyleneoxy groups. Examples thereof include KAYARAD TPA-330, which is an acrylate.

Examples of the polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-41708, Japanese Patent Application Laid-Open No. 51-37193, Japanese Patent Application Laid-Open No. 2-32293, and Japanese Patent Application Laid-Open No. 2-16765. Urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-49860, Japanese Patent Publication No. 56-17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Further, it is also preferable to use a polymerizable compound having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Commercially available products include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T- Examples include 600 and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.).
Further, as the polymerizable compound, it is also preferable to use 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), light acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
Further, as the polymerizable compound, the compounds described in Japanese Patent Application Laid-Open No. 2017-48637, Japanese Patent No. 6057891, and Japanese Patent No. 6031807 can also be used.

The content of the polymerizable compound is preferably 0.1 to 50% by mass based on the total solid content of the photosensitive coloring composition. The lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and further preferably 40% by mass or less.
The content of the polymerizable compound is preferably 25 to 500 parts by mass with respect to 100 parts by mass of the coloring material having a polymerizable group. The lower limit is more preferably 30 parts by mass or more, and further preferably 50 parts by mass or more. The upper limit is more preferably 450 parts by mass or less, and further preferably 300 parts by mass or less. If the content of the polymerizable compound is within the above range, further miniaturization of the development pattern can be expected.
The total amount of the polymerizable compound and the coloring material having a polymerizable group is preferably 20 to 80% by mass based on the total solid content of the photosensitive coloring composition. The lower limit is more preferably 25% by mass or more, further preferably 40% by mass or more. The upper limit is more preferably 75% by mass or less, and further preferably 60% by mass or less. When the above-mentioned total amount is in the above-mentioned range, a cured film having better adhesion to the support can be easily obtained.
The total amount of the polymerizable compound and the coloring material having a polymerizable group is preferably 25 to 500 parts by mass with respect to 100 parts by mass of the total of the photopolymerization initiator a and the photopolymerization initiator b. The lower limit is more preferably 30 parts by mass or more, and further preferably 50 parts by mass or more. The upper limit is more preferably 450 parts by mass or less, and further preferably 300 parts by mass or less. Within this range, it is easy to obtain a cured film having more excellent color loss resistance to the developing solution and adhesion to the support.

<< Compound with epoxy group >>
The photosensitive coloring composition of the present invention preferably further contains a compound having an epoxy group. According to this aspect, 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 preferable. It is preferable to have 2 to 100 epoxy groups in one molecule. The upper limit may be, for example, 10 or less, or 5 or less.

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

The compound having an epoxy group may be either a low molecular weight compound (for example, a molecular weight of less than 1000) or a high molecular weight compound (macromethylule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). .. The molecular weight of the compound having an epoxy group (in the case of a polymer, the weight average molecular weight) is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the molecular weight (in the case of a polymer, the weight average molecular weight) is preferably 3000 or less, more preferably 2000 or less, still more preferably 1500 or less.

Examples of the compound having an epoxy group include paragraph numbers 0034 to 0036 of JP2013-011869A, paragraph numbers 0147 to 0156 of JP2014-043556, and paragraph numbers 0085-0092 of JP2014-089408. The described compounds can also be used. These contents are incorporated in the present 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 is preferably 0.1 to 40% by mass based on the total solid content of the photosensitive coloring composition. The lower limit is, for example, more preferably 0.5% by mass or more, further preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, further preferably 20% by mass or less. The compound having an epoxy group may be used alone or in combination of two or more. When two or more types are used in combination, the total amount is preferably in the above range. The content of the compound having an epoxy group is preferably 1 to 400 parts by mass, more preferably 1 to 100 parts by mass, and 1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound. Is more preferable.

<< 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 coatability of the photosensitive coloring composition.

Examples of the organic solvent include the following organic solvents. 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, alkyloxyoxyacetate. (For example, methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (eg, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate) (Ethyl, etc.)), 2-alkyloxypropionate alkyl esters (eg, methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (eg, methyl 2-methoxypropionate)) , 2-Methyl propionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), 2-alkyloxy-2-methylpropionate methyl and 2-alkyloxy-2- Ethyl methyl propionate (eg, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate , 2-oxobutanoate methyl, 2-oxobutanoate ethyl and the like. Examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and propylene glycol. Examples thereof include monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate. Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like. Preferred examples of aromatic hydrocarbons include toluene and xylene. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may need to be reduced for environmental reasons (for example, 50 mass ppm (parts per) with respect to the total amount of the organic solvent. Million) or less, 10 mass ppm or less, or 1 mass ppm or less).

The organic solvent may be used alone or in combination of two or more. When two or more kinds of organic solvents are used in combination, the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate are particularly preferable. , 2-Heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, which is a mixed solution composed of two or more kinds.

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

The content of the solvent is preferably an amount such that the total solid content of the photosensitive coloring composition is 5 to 80% by mass. 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.

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

(In the formula (T1), n represents an integer of 2 to 4 and L represents a linking group of 2 to 4 valences.)

In the formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and the compound represented by the formula (T2) is particularly preferable. These polyfunctional thiol compounds can be used alone or in combination of two or more.

Further, the curing accelerator is a methylol compound (for example, a compound exemplified as a cross-linking agent in paragraph No. 0246 of JP-A-2015-34963), amines, phosphonium salt, amidin salt, amide compound (for example, above, for example. Hardeners described in paragraph No. 0186 of JP2013-41165A, base generators (eg, ionic compounds described in JP2014-55114), cyanate compounds (eg, JP2012-150180). A compound described in paragraph No. 0071 of Japanese Patent Application Laid-Open No. 0071), an alkoxysilane compound (for example, an alkoxysilane compound having an epoxy group described in JP-A-2011-253504), and an onium salt compound (for example, JP-A-2015-34963). Compounds exemplified as acid generators in paragraph No. 0216, compounds described in JP-A-2009-180949) and the like can also be used.

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

<< Surfactant >>
The photosensitive coloring composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.

By containing a fluorine-based surfactant in the photosensitive coloring composition of the present invention, the liquid characteristics (particularly, fluidity) when prepared as a coating liquid are improved, and the uniformity of the coating thickness and the liquid saving property are further improved. Can be improved. That is, when a film is formed by using a coating liquid to which a photosensitive coloring composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the coating liquid is applied to the surface to be coated. Wetability is improved, and coatability to the surface to be coated is improved. Therefore, it is possible to more preferably form a film having a uniform thickness with small thickness unevenness.

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

Examples of the fluorine-based surfactant include Megafuck F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (above, DIC Corporation). , Florard FC430, FC431, FC171 (all manufactured by Sumitomo 3M Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393, KH-40 (all manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (all manufactured by OMNOVA) and the like. As the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP2015-117327 and the compounds described in paragraphs 0117 to 0132 of JP2011-132503 can also be used.

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

As the fluorine-based surfactant, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound. For such a fluorine-based surfactant, the description in JP-A-2016-216602 can be referred to, and the content thereof is incorporated in the present specification.

As the fluorine-based surfactant, a block polymer can also be used. For example, the compounds described in JP-A-2011-89090 can be mentioned. The fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth). A fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used. The following compounds are also exemplified as the fluorine-based surfactant used in the present invention. In the formula below,% indicating the ratio of the repeating unit is mol%.

The weight average molecular weight of the above compounds is preferably 3,000 to 50,000, for example 14,000.

As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965. Examples of commercially available products include Megafvck RS-101, RS-102, RS-718-K, RS-72-K manufactured by DIC Corporation.

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

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

Examples of the anionic surfactant include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Industries, Ltd.) and the like.

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

The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the photosensitive coloring composition. Only one type of surfactant may be used, or two or more types may be combined. When two or more types are included, the total amount is preferably in 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 kinds of functional groups having different reactivity in one molecule is preferable. The silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group. A silane compound having and is preferable. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., KBM-602) and N-β-aminoethyl-γ-aminopropyltri. Methoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., KBM-603), N-β-aminoethyl-γ-aminopropyltriethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., KBE-602), γ-aminopropyltrimethoxysilane (Shinetsu Chemical Co., Ltd.) Kogyo Co., Ltd., KBM-903), γ-aminopropyltriethoxysilane (Shinetsu Chemical Industry Co., Ltd., KBE-903), 3-methacryloxypropyltrimethoxysilane (Shinetsu Chemical Industry Co., Ltd., KBM-503), 3- Examples thereof include glycidoxypropyltrimethoxysilane (manufactured by Shinetsu Chemical Industry Co., Ltd., KBM-403). For details of the silane coupling agent, the description in paragraphs 0155 to 0158 of JP2013-254847A can be referred to, and the contents thereof are incorporated in the present specification.

When the photosensitive coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent is preferably 0.001 to 20% by mass, preferably 0.01 to 20% by mass, based on the total solid content of the photosensitive coloring composition. 10% by mass is more preferable, and 0.1% by mass to 5% by mass is particularly preferable. The photosensitive coloring composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types of silane coupling agent. When two or more types are included, it is preferable that the total amount thereof is 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-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), and the like. Examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, 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 based on the total solid content of the photosensitive coloring composition. The photosensitive coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types of polymerization inhibitors. When two or more types are included, the total amount is preferably in the above range.

<< UV absorber >>
The photosensitive coloring composition of the present invention can 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 and the like can be used. For details thereof, the description of paragraphs 0052 to 0072 of JP2012-208374A and paragraphs 0317 to 0334 of JP2013-68814 can be referred to, and these contents are incorporated in the present specification. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.). Further, as the benzotriazole compound, the MYUA series (The Chemical Daily, February 1, 2016) manufactured by Miyoshi Oil & Fat may be used.

When the photosensitive coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber is preferably 0.1 to 10% by mass, preferably 0.1 to 5% by mass, based on the total solid content of the photosensitive coloring composition. By mass% is more preferable, and 0.1 to 3% by mass is particularly preferable. Further, as the ultraviolet absorber, only one kind may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.

<< Other additives >>
Various additives such as a filler, an adhesion accelerator, an antioxidant, an antioxidant, and the like can be added to the photosensitive coloring composition of the present invention, if necessary. Examples of these additives include the additives described in paragraphs 0155 to 0156 of JP-A-2004-295116, the contents of which are incorporated in the present specification. Further, as the antioxidant, for example, a phenol compound, a phosphorus-based compound (for example, the compound described in paragraph No. 0042 of JP-A-2011-090147), a thioether compound and the like can be used. Commercially available products include, for example, the ADEKA stub series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-" manufactured by ADEKA Corporation. 330, etc.). Only one type of antioxidant may be used, or two or more types may be used. The coloring composition of the present invention can contain a sensitizer and a light stabilizer described in paragraph No. 0078 of JP-A-2004-295116, and a thermal polymerization inhibitor described in paragraph No. 1981 of the same publication.

Metallic elements may be contained in the photosensitive coloring composition depending on the raw materials used, etc., but from the viewpoint of suppressing the occurrence of defects, the content of Group 2 elements (calcium, magnesium, etc.) in the coloring composition is 50 parts by mass. It is preferably ppm or less, and more preferably 0.01 to 10 mass ppm. The total amount of the inorganic metal salt in the photosensitive coloring composition is preferably 100 mass ppm or less, more preferably 0.5 to 50 mass ppm.

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 by adjusting the viscosity for the purpose of adjusting the film surface (flatness, etc.), adjusting the film thickness, and the like. The value of the viscosity can be appropriately selected as needed, but for example, at 25 ° C., 0.3 mPa · s to 50 mPa · s is preferable, and 0.5 mPa · s to 20 mPa · s is more preferable. As a method for measuring the viscosity, for example, a viscometer RE85L (rotor: 1 ° 34'× R24, measuring range 0.6 to 1200 mPa · s) manufactured by Toki Sangyo Co., Ltd. is used, and the temperature is adjusted to 25 ° C. Can be measured.

The storage container for the photosensitive coloring composition of the present invention is not particularly limited, and a known storage container can be used. In addition, as a storage container, for the purpose of suppressing impurities from being mixed into raw materials and compositions, a multi-layer bottle in which the inner wall of the container is composed of 6 types and 6 layers of resin and a bottle in which 6 types of resin are composed of 7 layers are used. It is also preferable to use it. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.

The photosensitive coloring composition of the present invention can be preferably used as a photosensitive coloring composition for forming colored pixels in a color filter. Examples of the colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. Further, since many of the coloring materials contained in the blue pixels have absorption for i-rays, the conventional photosensitive coloring composition tends to be insufficiently cured by exposure. For this reason, conventionally, post-baking at a high temperature has been required for forming blue pixels. However, according to the present invention, blue pixels (cured film) having excellent color loss resistance to a developing solution can be formed by curing at a low temperature, and the effect of the present invention is more remarkably exhibited.

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 provided with the color filter is preferably 70% or more, preferably 90% or more. More preferred. Known means for obtaining a high voltage retention rate can be appropriately incorporated, and typical means are the use of a high-purity material (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition. Can be mentioned. The voltage holding ratio can be measured by the methods described in paragraphs 0243 of JP2011-008004A and paragraphs 0123 to 0129 of JP2012-224847A.

<Method for preparing photosensitive coloring composition>
The photosensitive coloring composition of the present invention can be prepared by mixing the above-mentioned components. In preparing the photosensitive coloring composition, all the components may be simultaneously dissolved and / or dispersed in a solvent to prepare a photosensitive coloring composition, or if necessary, each component may be appropriately added to two or more solutions. Alternatively, they may be left as a dispersion and mixed at the time of use (at the time of application) to prepare a photosensitive coloring composition.

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

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

The pore size of the filter is preferably 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.

Further, as the filter, it is also preferable to use a filter using a fibrous filter medium. Examples of the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specific examples of the filter using the fibrous filter medium include filter cartridges of SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd. ..

When using filters, different filters may be combined. At that time, the filtration with each filter may be performed only once or twice or more.
For example, filters having different pore diameters within the above range may be combined. For the hole diameter here, the nominal value of the filter manufacturer can be referred to. As a commercially available filter, for example, select from various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd. can do.
Further, the filtration with the first filter may be performed only with the dispersion liquid, and after mixing the other components, the filtration with the second filter may be performed. As the second filter, a filter made 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 colored pixels of a color filter. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, and a yellow color pixel. The film thickness of the cured film can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more.

<Pattern formation method>
The pattern forming method of the present invention includes a step of forming a photosensitive coloring composition layer on a support using the above-mentioned photosensitive coloring composition of the present invention.
A step of irradiating the photosensitive coloring composition layer with light having a wavelength of more than 350 nm and 380 nm or less to expose the photosensitive coloring composition layer in a pattern.
The process of alkaline developing the photosensitive coloring composition layer after exposure,
The present invention comprises a step of irradiating a photosensitive coloring composition layer after alkaline development with light having a wavelength of 254 to 350 nm to expose the layer. Further, if necessary, a step of baking the photosensitive coloring composition layer after forming the photosensitive coloring composition layer on the support and before the exposure (pre-baking step), and a step of baking the alkali-developed pattern (post-baking). Step) may be provided. Hereinafter, each step will be described.

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

The support is not particularly limited and may be appropriately selected depending on the intended use. For example, a glass substrate, a substrate for a solid-state image sensor provided with a solid-state image sensor (light receiving element), a silicon substrate, and the like can be mentioned. Further, if necessary, an undercoat layer may be provided on these substrates 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 on the support, various methods such as slit coating, inkjet method, rotary coating, cast coating, roll coating, screen printing and the like can be used.

The photosensitive coloring composition layer formed on the support may be dried (prebaked). Prebaking may not be required if the pattern is formed by a low temperature process. When prebaking is performed, the prebaking temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, and even more preferably 105 ° C. or lower. The lower limit can be, for example, 50 ° C. or higher, or 80 ° C. or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Pre-baking can be performed on a hot plate, an oven, or the like.

Next, the photosensitive coloring composition layer is irradiated with light having a wavelength of more than 350 nm and 380 nm or less to expose it in a pattern. For example, the photosensitive coloring composition layer can be exposed in a pattern by exposing the photosensitive coloring composition layer through a mask having a predetermined mask pattern using an exposure device such as a stepper. As a result, the exposed portion of the photosensitive coloring composition layer can be cured. The radiation (light) that can be used for exposure is light having a wavelength of more than 350 nm and 380 nm or less, preferably light having a wavelength of 355 to 370 nm, and more preferably i-line. As the irradiation amount (exposure amount), for example, 30 to 1500 mJ / cm ² is preferable, and 50 to 1000 mJ / cm ² is more preferable. The oxygen concentration at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially anoxic). ), Or in a high oxygen atmosphere where the oxygen concentration exceeds 21% by volume (for example, 22% by volume, 30% by volume, 50% by volume). The exposure intensity is can be set appropriately, usually ^{1000W / m 2 ~100000W / m 2} ( ^{e.g., 5000W / m 2, 15000W /} m 2, 35000W / m 2) can be selected from the range of .. Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / ^{m 2} at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / ^{m 2.}

The reaction rate of the polymerizable compound in the photosensitive coloring composition layer after exposure is preferably more than 30% and less than 60%. By setting the reaction rate to such a level, the polymerizable compound can be appropriately cured. Here, the reaction rate of the polymerizable compound means the ratio of the reacted ethylenically unsaturated groups to the total ethylenically unsaturated groups contained in the polymerizable compound.

Next, the photosensitive coloring composition layer after exposure is alkaline-developed. That is, the photosensitive coloring composition layer in the unexposed portion is removed with an alkaline developer to form a pattern. The temperature of the alkaline developer is preferably 20 to 30 ° C., for example. The development time is preferably 20 to 300 seconds.

As the alkaline developer, an alkaline aqueous solution obtained by diluting an alkaline agent with pure water is preferably used. Examples of the alkaline agent include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. Do, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene and other organic alkaline compounds, and water. Examples thereof include inorganic alkaline compounds such as sodium oxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate. The concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. Further, the alkaline developer may further contain a surfactant. Examples of the surfactant include the above-mentioned surfactants, and nonionic surfactants are preferable. The alkaline developer may be once produced as a concentrated solution and diluted to a concentration required for use from the viewpoint of convenience of transfer and storage. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. Further, it is preferable to wash (rinse) with pure water after development. When a developer composed of such an alkaline aqueous solution is used, it is preferable to wash (rinse) with pure water after development.

Next, the photosensitive coloring composition layer after alkaline development is exposed to light having 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 for the post-exposure, ultraviolet rays having a wavelength of 254 to 300 nm are preferable, and ultraviolet rays having a wavelength of 254 nm are more preferable. The post-exposure can be performed using, for example, an ultraviolet photoresist curing apparatus. The ultraviolet photoresist curing apparatus may irradiate light having a wavelength of 254 to 350 nm and other light (for example, i-line).

The difference between the wavelength of light used in the above-mentioned exposure before alkaline development and the wavelength of light used in the exposure (post-exposure) after alkaline development is preferably 200 nm or less, and more preferably 100 to 150 nm. preferable. Irradiation dose (exposure dose) is preferably ^{30~4000mJ / cm 2, 50~3500mJ / cm} 2 is more preferable. The oxygen concentration at the time of exposure can be appropriately selected. Examples thereof include the conditions described in the exposure step before alkaline development described above.

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 100% or less, or 90% or less. By setting such a reaction rate, the cured state of the photosensitive coloring composition layer after exposure can be improved.

In the present invention, by exposing the photosensitive coloring composition layer in two stages, before alkaline development and after alkaline development, the photosensitive coloring composition can be appropriately cured by the first exposure (exposure before alkaline development). It is possible to cure the entire photosensitive coloring composition almost completely at the next exposure (exposure after development). As a result, the photosensitive coloring composition can be sufficiently cured even under low temperature conditions, and a pattern (cured film) having excellent color loss resistance to the developing solution can be formed.

In the pattern formation of the present invention, post-baking may be further performed after post-exposure. When post-baking is performed, when an organic electroluminescence element is used as the light source of the image display device, or when the photoelectric conversion film of the image sensor is made of an organic material, the temperature is 50 to 120 ° C (more preferably 80 to 100). It is preferable to perform the heat treatment (post-baking) at ° C., more preferably 80 to 90 ° C.). Post-baking can be performed continuously or in batch by using a heating means such as a hot plate, a convection oven (hot air circulation dryer), or a high frequency heater. Further, when the pattern is formed by the low temperature process, post-baking may not be performed.

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

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

Pixels preferably have high flatness. Specifically, the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less. The lower limit is not specified, but it is preferably 0.1 nm or more, for example. The surface roughness can be measured by using, for example, AFM (Atomic Force Microscope) Dimension 3100 manufactured by Veeco.
Further, the contact angle of water on the pixel can be appropriately set to a preferable value, but is 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 value of the pixel is high. Specifically, it is preferred that the volume resistivity value of the pixel is 10 ⁹ Ω · cm or more, and more preferably 10 ¹¹ Ω · cm or more. The upper limit is not specified, but it is preferably 10 ¹⁴ Ω · cm or less, for example. The volume resistance value of the pixel can be measured using, for example, an ultra-high resistance meter 5410 (manufactured by Advantest).

<Color filter>
Next, the color filter of the present invention will be described. The color filter of the present invention has the cured film of the present invention described above. In the color filter of the present invention, the film thickness of the cured film can be appropriately adjusted according to the intended purpose. The film thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and further preferably 0.3 μm or more. The color filter of the present invention can be used for a solid-state image sensor such as a CCD (charge coupling element) or CMOS (complementary metal oxide semiconductor), an image display device, or the like.

<Solid image sensor>
The solid-state imaging device of the present invention has the cured film of the present invention described above. The configuration of the solid-state image sensor of the present invention is not particularly limited as long as it includes the cured film of the present invention and functions as a solid-state image sensor, and examples thereof include the following configurations.

On the substrate, there are a plurality of photodiodes constituting the light receiving area of a solid-state image sensor (CCD (charge coupling element) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like. A device protective film made of silicon nitride or the like formed on the photodiode and the transfer electrode so as to have a light-shielding film in which only the light-receiving part of the photodiode is opened, and to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. The configuration has a color filter on the device protective film. Further, a configuration having a condensing means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the color filter (near the substrate), a configuration having a condensing means on the color filter, and the like. There may be. Further, the color filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. In this case, the partition wall preferably has a low refractive index for each colored pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478 and JP-A-2014-179757. The image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones and the like), but also for in-vehicle cameras and surveillance cameras.

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

The present invention will be specifically described below with reference to examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

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

Dispersant 1: Resin having the following structure (the numerical value added to the main chain is the molar ratio, Mw = 11000)

(Pigment dispersion P2)
A pigment dispersion P2 was obtained in the same manner as the pigment dispersion P1 except that the dispersion resin A described in paragraph No. 0577 of JP2013-195854A was used instead of the dispersant 1.

<Preparation of photosensitive coloring composition>
(Example 1)
The raw materials shown below were mixed, stirred, and then filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 μm to prepare a 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 ・Alkaline-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 Co., Ltd.) ・ ・ ・ 0.66 parts by mass ・ Polymerization inhibitor (p-methoxyphenol) ・ ・ ・ 0.0007 parts by mass ・ Surface active agent (Compound with the following structure (Mw = 14000, ratio of repeating units) 1% by mass of cyclohexanone solution) ・ ・ ・ 2.50 parts by mass

・ Cyclohexanone ・ ・ ・ 7.74 parts by mass

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

(Examples 19 to 22)
A photosensitive coloring composition was prepared in the same manner as in Example 1 except that the content of the dye (V1) was changed as described in the table below. The table below also shows the mass ratio of the colorant having a polymerizable group and the photopolymerization initiator (total amount of the initiator 1 and the initiator 4).

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

(Photopolymerization initiator)
Initiator 1: IRGACURE-OXE01 (manufactured by BASF, the extinction coefficient of light at a wavelength of 365 nm in methanol is 6696 mL / gcm)
Initiator 2: IRGACURE-OXE02 (manufactured by BASF, the extinction coefficient of light at a wavelength of 365 nm in methanol is 7749 mL / gcm)
Initiator 3: A compound having the following structure (the extinction coefficient of light at a wavelength of 365 nm in methanol is 18900 mL / gcm).

Initiator 4: IRGACURE 2959 (manufactured by BASF, the extinction coefficient of light at a wavelength of 365 nm in methanol is 48.93 mL / gcm, and the extinction coefficient of light at a wavelength of 254 nm is 3.0 × 10 ⁴ mL / gcm. .)
Initiator 5: IRGACURE 184 (manufactured by BASF, the extinction coefficient of light at a wavelength of 365 nm in methanol is 88.64 mL / gcm, and the extinction coefficient of light at a wavelength of 254 nm is 3.3 × 10 ⁴ mL / gcm. .)

(Alkali-soluble resin)
Resin A: Resin having the following structure (Mw = 11000, acid value = 31.5 mgKOH / g, the numerical value added to the main chain is the molar ratio).

Resin B: Resin having the following structure (Mw = 30,000, acid value = 112.8 mgKOH / g, the numerical value added to the main chain is the molar ratio).

Resin C: Alkali-soluble resin J5 described in paragraph No. 0573 of JP2013-225112A.
Resin D: Resin B-1 described in paragraph No. 0150 of JP2010-049161A.

(dye)
Dye V1: A cyclohexanone solution of 20% by mass of a dye multimer (dye having a polymerizable group) having the following structure.

Dye V2: A cyclohexanone solution of 20% by mass of a dye multimer having the following structure (dye having a polymerizable group, the numerical value added to the main chain is a molar ratio, Mw = 13000).

Dye V3: A cyclohexanone solution of 20% by mass of a dye multimer having the following structure (dye having no polymerizable group, the numerical value added to the main chain is the molar ratio, Mw = 12000).

Dye V4: A cyclohexanone solution of 20% by mass of a dye compound (dye having a polymerizable group) having the following structure.

(Polymerizable compound)
M1: Mixture of compounds with the following structure (left compound: right compound = 7: 3 (molar ratio))

M2: Compound with the following structure

<Evaluation>
(Color loss resistance)
Each photosensitive coloring composition is applied onto a glass substrate using a spin coater so that the film thickness after prebaking is 1.6 μm, and heat treatment (prebaking) is performed for 120 seconds using a hot plate at 100 ° C. It was.
Next, an ultraviolet photoresist curing apparatus (UMA-802-HC-552; manufactured by Ushio Denki Co., Ltd.) was used to perform exposure at an exposure amount of 3000 mJ / cm ² , and a cured film was prepared.
With respect to the obtained cured film, the transmittance of light in the wavelength range of 300 to 800 nm was measured using a spectrophotometer (reference: glass substrate) of an ultraviolet-visible near-infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation). In addition, a differential interference contrast image was observed by reflection observation (magnification 50 times) using an optical microscope BX60 manufactured by OLYMPUS.
Next, the cured film was immersed in an alkaline developer (FHD-5, manufactured by FUJIFILM Electronics Materials Co., Ltd.) at 25 ° C. for 5 minutes, dried, and then spectroscopic measurement was performed again to immerse the cured film in the alkaline developer. The change in transmittance before and after was calculated, and the color loss resistance was evaluated according to the following criteria.
Transmittance fluctuation = | 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 fluctuation in the entire wavelength range of 300 to 800 nm is less than 2%.
A: The transmittance fluctuation in the entire range of the wavelength of 300 to 800 nm is less than 5%, and the transmittance fluctuation is 2% or more and less than 5% in a part range.
B: The transmittance fluctuation in the entire range of the wavelength of 300 to 800 nm is less than 7.5%, and the transmittance fluctuation is 5% or more and less than 7.5% in a part range.
C: The transmittance fluctuation in the entire range of the wavelength of 300 to 800 nm is less than 10%, and the transmittance fluctuation is 7.5% or more and less than 10% in a part range.
D: The transmittance fluctuation is 10% or more in at least a part of the wavelength range of 300 to 800 nm.

(Evaluation of residual film ratio and adhesion)
On an 8-inch (20.32 cm) glass substrate sprayed with hexamethyldisilazane, each photosensitive coloring composition was applied using a spin coater so that the film thickness after prebaking was 1.6 μm, and 100 Heat treatment (pre-baking) was performed for 120 seconds using a hot plate at ° C.
Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), irradiation was performed at a wavelength of 365 nm through a 3.0 μm square island pattern mask at 300 mJ / cm ² (3.0 μm line width). Is the amount of exposure required to obtain).
Next, the glass substrate on which the coating film after exposure was formed was placed on a horizontal rotary table of a spin shower developer (DW-30 type; manufactured by Chemitronics Co., Ltd.), and a developer (CD-2000 (CD-2000) Paddle development was performed at 23 ° C. for 180 seconds using a 40% diluted solution manufactured by FUJIFILM Electronics Materials Co., Ltd. to form colored patterns (pixels) on a glass substrate. The glass substrate on which this colored pattern (pixels) is formed is fixed to a horizontal rotary table by a vacuum chuck method, and while the glass substrate is rotated at a rotation speed of 50 rpm by a rotating device, pure water is ejected from above the center of rotation from the nozzle. It was supplied in a shower shape and rinsed, and then spin-dried to form a colored pattern (pixels).

The residual film ratio was measured by measuring the thickness of the film before and after development using a scanning electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation). The higher the value, the more preferable the residual film ratio, and more preferably 80% or more.
Residual film ratio (%) = (thickness before development / thickness after development) x 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 80 %Less than

The adhesion was evaluated by observing the coloring pattern formed on the glass substrate with an optical microscope and using the following criteria.
AA: There is no peeling of the coloring pattern.
A: Colored pattern peeling exists in 1 to 5 pixels out of 100 pixels B: Colored pattern peeling exists in 6 to 15 pixels in 100 pixels C: Colored pattern peeling exists in 16 pixels or more out of 100 pixels

As shown in the above table, the examples were excellent in color loss resistance. On the other hand, Comparative Example 1 in which a coloring material having a polymerizable group was not used, Comparative Examples 2 and 3 containing only one of the photopolymerization initiator a and the photopolymerization initiator b, the photopolymerization initiator a and photopolymerization. Comparative Example 4 containing the initiator b and having a content of less than 1.5% by mass was inferior in color loss resistance to that of Example.

Claims (12)

Photopolymerization initiator a having an extinction coefficient of light having a wavelength of 365 nm in methanol exceeding 1.0 × 10 ² mL / gcm, and
Photopolymerization initiator b in which the extinction coefficient of light having a wavelength of 365 nm in methanol is 1.0 × 10 ² mL / gcm or less and the extinction coefficient of light having a wavelength of 254 nm is 1.0 × 10 ³ mL / gcm or more. When,
Alkali-soluble resin and
A photosensitive coloring composition containing 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% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more. Photosensitive coloring composition. The photosensitive coloring composition according to claim 1, wherein the photopolymerization initiator a has an extinction coefficient of light having a wavelength of 365 nm in methanol of 1.0 × 10 ³ mL / g cm or more. The photosensitive coloring composition according to claim 1 or 2, wherein the photopolymerization initiator a is an oxime compound. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the photopolymerization initiator b is a hydroxyacetophenone compound. The photosensitive coloring composition according to any one of claims 1 to 4, which contains 50 to 500 parts by mass of the photopolymerization initiator a with respect to 100 parts by mass of the photopolymerization initiator b. Any one of claims 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. The photosensitive coloring composition according to. The photosensitive coloring composition according to any one of claims 1 to 6, wherein the coloring material is a dye multimer. A cured film obtained by curing the photosensitive coloring composition according to any one of claims 1 to 7. A step of forming a photosensitive coloring composition layer on a support using the photosensitive coloring composition according to any one of claims 1 to 7.
A step of irradiating the photosensitive coloring composition layer with light having a wavelength of more than 350 nm and 380 nm or less to expose the photosensitive coloring composition layer in a pattern.
The step of alkaline-developing the photosensitive coloring composition layer after the exposure, and
A method for forming a pattern, comprising a step of irradiating the developed photosensitive coloring composition layer with light having a wavelength of 254 to 350 nm to expose the layer. The color filter having the cured film according to claim 8. The solid-state imaging device having the cured film according to claim 8. An image display device having the cured film according to claim 8.