Colored photosensitive composition, cured film, pattern forming method, infrared light cutoff filter, and solid imaging element

Abstract

The present invention provides a colored photosensitive composition, which can form a film with low transmittance to light of wavelength 365nm with good adhesion. In addition, a cured film, a pattern forming method, an infrared light cutoff filter with a light-shielding film, a solid imaging element, an image display device and an infrared sensor using the colored photosensitive composition are provided. The colored photosensitive composition comprises an oxime ester-based photopolymerization initiator containing fluorine atoms, a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a colorant, wherein when the colored photosensitive composition is used to form a film with a film thickness of 2.0μm after drying, the optical density of the film at a wavelength of 365nm is greater than 1.5.

Description

[0001] This application is a divisional application of an application having a PCT international application date of February 25, 2016, a PCT international application number of PCT / JP2016 / 055661, a national application number of 201680017381.1, and an invention name of "Colored photosensitive composition, cured film, pattern forming method, infrared light cutoff filter with light-shielding film, solid imaging element, image display device and infrared sensor". Technical Field

[0002] The present invention relates to a colored photosensitive composition, a cured film, a pattern forming method, an infrared light cutoff color filter with a light-shielding film, a solid imaging element, an image display device and an infrared sensor. Background Art

[0003] Color filters are indispensable components of solid-state imaging devices and image display devices.

[0004] Solid-state imaging devices and image display devices may generate noise due to reflection of visible light. Therefore, a light shielding film is provided in the solid-state imaging device and the image display device to suppress the generation of noise.

[0005] As a method for producing such a color filter and a light-shielding film, there is known a method of forming a colored composition layer using a colored photosensitive composition containing a colorant, a polymerizable compound, a photopolymerization initiator, and an alkali-soluble resin, and exposing and developing the colored composition layer to form a pattern.

[0006] As the photopolymerization initiator, fluorine-containing oxime ester-based photopolymerization initiators are known (see Patent Documents 1 to 3).

[0007] Previous technical literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Publication No. 2014-500852

[0010] Patent Document 2: Japanese Patent Application Publication No. 2010-262028

[0011] Patent Document 3: Japanese Patent Application Publication No. 2013-164471 Summary of the invention

[0012] Technical issues to be solved by the invention

[0013] According to the research conducted by the present inventors, it was found that after forming a pattern by exposure and development using a colored photosensitive composition for forming a cured film having a low transmittance to light at 365 nm, the obtained pattern has insufficient adhesion to a support or the like.

[0014] In addition, Patent Documents 1 to 3 disclose a fluorine-containing oxime ester photopolymerization initiator. However, Patent Documents 1 to 3 do not disclose or suggest that a film having good adhesion and low transmittance to light of a wavelength of 365 nm can be formed using a colored photosensitive composition containing a fluorine-containing oxime ester photopolymerization initiator.

[0015] Therefore, the object of the present invention is to provide a colored photosensitive composition that can form a film with a low transmittance to light of a wavelength of 365 nm with good adhesion, and to provide a cured film using the colored photosensitive composition, a pattern forming method, an infrared light cutoff filter with a light-shielding film, a solid imaging element, an image display device, and an infrared sensor.

[0016] Means for solving technical problems

[0017] The inventors of the present invention have conducted detailed studies and found that the above-mentioned object can be achieved by including a fluorine-containing oxime ester-based photopolymerization initiator in a colored photosensitive composition having an optical density of 1.5 or more at a wavelength of 365 nm when the film thickness after drying is 2.0 μm, thereby completing the present invention. That is, the present invention is as follows.

[0018] <1> A colored photosensitive composition comprising a fluorine-containing oxime ester photopolymerization initiator, a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a colorant, wherein when the colored photosensitive composition is used to form a film having a thickness of 2.0 μm after drying, the optical density of the film at a wavelength of 365 nm is 1.5 or more.

[0019] <2> like <1> In the colored photosensitive composition, the fluorine-containing oxime ester photopolymerization initiator is at least one selected from an alkyl group having a fluorine atom and a group containing an alkyl group having a fluorine atom.

[0020] <3> like <1> or <2> In the colored photosensitive composition, the fluorine-containing oxime ester photopolymerization initiator includes a compound represented by the following formula (1a).

[0021] [Chemical formula 1]

[0022]

[0023] In the general formula (1a), A 1 and A 2 Each independently represents an alkyl group, an acyl group, an aryl group or a heterocyclic group, and A 3 represents an alkyl group, an aryl group or a heterocyclic group, wherein A 1 ~A 3 At least one of them contains a fluorine atom.

[0024] <4> like <1> or <2> In the colored photosensitive composition, the fluorine-containing oxime ester photopolymerization initiator comprises a compound represented by the following formula (1).

[0025] [Chemical formula 2]

[0026]

[0027] In formula (1), Ar 1 and Ar 2 Each independently represents an aromatic hydrocarbon ring which may have a substituent,

[0028] R 1 represents an aryl group having a fluorine atom-containing group,

[0029] R 2 and R 3 Each independently represents an alkyl group or an aryl group.

[0030] <5> like <1> ~ <4> The colored photosensitive composition according to any one of the preceding claims, further comprising an organic pigment, wherein the ratio A / B of the minimum absorbance value A in the range of wavelength 400 nm to less than 580 nm to the minimum absorbance value B in the range of wavelength 580 nm to 750 nm is 0.3 to 3, and the ratio C / D of the minimum absorbance value C in the range of wavelength 400 nm to 750 nm to the maximum absorbance value D in the range of wavelength 1000 nm to 1300 nm is 5 or more.

[0031] <6> like <1> ~ <4> The colored photosensitive composition described in any one of the above aspects further comprises a curable compound having a fluorine atom and a curable functional group.

[0032] <7> like <6> The colored photosensitive composition further comprises a black pigment.

[0033] <8> like <1> ~ <7> The colored photosensitive composition described in any one of the above claims further comprises an α-aminoketone photopolymerization initiator, wherein the mass ratio of the fluorine-containing oxime ester photopolymerization initiator to the α-aminoketone photopolymerization initiator is 1:1.5 to 1:10.

[0034] <9> like <1> ~ <8> The colored photosensitive composition described in any one of the above further contains an oxime-based photopolymerization initiator other than the fluorine-containing oxime ester-based photopolymerization initiator.

[0035] <10> like <1> ~ <9> The colored photosensitive composition according to any one of the preceding claims, wherein the total mass of monochlorobenzene and methyl tert-butyl ether is 2 ppm or less relative to the total mass of the colored photosensitive composition.

[0036] <11> like <1> ~ <10> The colored photosensitive composition described in any one of the above is used for i-ray exposure.

[0037] <12> A use such as <1> ~ <11> A cured film of any one of the colored photosensitive compositions.

[0038] <13> like <12> The cured film is a color filter or a light-shielding film.

[0039] <14> A method for forming a pattern, comprising: using <1> ~ <11> The step of forming a colored composition layer on a support using the colored photosensitive composition described in any one of the preceding claims, exposing the colored composition layer in a pattern, and developing and removing unexposed portions of the colored composition layer to form a colored pattern.

[0040] <15> like <14> The pattern forming method uses i-rays for exposure.

[0041] <16> An infrared light cutoff color filter with a light shielding film comprises an infrared light cutoff color filter, and a curing <7> A light-shielding film formed by the colored photosensitive composition.

[0042] <17> A kind of <12> The solid imaging element of the cured film.

[0043] <18> A kind of <12> An image display device of the cured film.

[0044] <19> A kind of <12> An infrared sensor for the cured film.

[0045] Effects of the Invention

[0046] The present invention can provide a colored photosensitive composition that can form a film with low transmittance to light of wavelength 365 nm with good adhesion. In addition, a cured film using the colored photosensitive composition, a pattern forming method, an infrared light cutoff filter with a light-shielding film, a solid imaging element, an image display device, and an infrared sensor can be provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0047] Figure 1 This is a schematic diagram showing a cured film obtained by using a colored photosensitive composition containing a curable compound having a fluorine atom and a curable functional group.

[0048] Figure 2 It is a schematic cross-sectional view showing the structure of an infrared sensor. DETAILED DESCRIPTION

[0049] Hereinafter, the contents of the present invention will be described in detail.

[0050] In the marking of groups (atomic groups) in this specification, the marking without substitution and unsubstituted refers to groups with no substitution and groups with substitution. For example, "alkyl" includes not only alkyl groups with no substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0051] In this specification, light refers to active light or radiation. Furthermore, the term "active light" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, electron beams, and the like.

[0052] In this specification, unless otherwise specified, "exposure" refers not only to exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet light represented by an excimer laser, X-rays, EUV light, etc., but also includes drawing using particle beams such as electron beams and ion beams.

[0053] In the present specification, a numerical range expressed by "to" means a range including the numerical values ​​described before and after "to" as the lower limit and the upper limit.

[0054] In this specification, the total solid content refers to the total mass of the components after removing the solvent from the overall composition of the composition.

[0055] In the present specification, "(meth)acrylate" means both or either acrylate and methyl acrylate, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid, "(meth)allyl" means both or either allyl and methallyl, and "(meth)acryloyl" means both or either acryloyl and methacryloyl.

[0056] In the present specification, the term "step" includes not only an independent step but also a step that cannot be clearly distinguished from other steps as long as the expected effect of the step can be achieved.

[0057] In this specification, the weight average molecular weight and the number average molecular weight are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC).

[0058] <Coloring Photosensitive Composition>

[0059] The colored photosensitive composition of the present invention (hereinafter also referred to as a colored composition) comprises an oxime ester-based photopolymerization initiator containing a fluorine atom, a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a colorant. When the colored composition is used to form a film having a film thickness of 2.0 μm after drying, the optical density of the film at a wavelength of 365 nm is 1.5 or more.

[0060] By using the coloring composition of the present invention, a film having a low transmittance to light of a wavelength of 365 nm can be formed with good adhesion to a support, etc. The mechanism for obtaining the above effect is not clear, but it is presumed that it is obtained by including a fluorine-containing oxime ester-based photopolymerization initiator in the coloring composition.

[0061] In the coloring composition of the present invention, when the coloring composition is used to make a film with a film thickness of 2.0 μm after drying, the optical concentration of the film at a wavelength of 365 nm is preferably 1.5 or more, more preferably 1.8 or more, and further preferably 2.1 or more. The upper limit is not particularly limited and can be set to 5.0 or less. The higher the optical concentration at a wavelength of 365 nm, the more difficult it is to form a film with good adhesion to the support body in the past, but according to the coloring composition of the present invention, a film with a high optical concentration at a wavelength of 365 nm can be formed with good adhesion to the support body. Thus, the higher the above optical concentration, the more significant the effect of the present invention. In addition, the coloring composition of the present invention is particularly suitable as a coloring composition for i-ray exposure.

[0062] In addition, the optical density (OD) is a value expressing the degree of absorption in logarithm, and the value is defined by the following formula.

[0063] OD(λ)=Log 10 [T(λ) / I(λ)]

[0064] λ represents wavelength, T(λ) represents the amount of transmitted light at wavelength λ, and I(λ) represents the amount of incident light at wavelength λ.

[0065] When a film having a thickness of 2.0 μm after drying is prepared, the optical density of the film at a wavelength of 365 nm can be made to be 1.5 or more, which can be achieved by, for example, making it contain a colorant that absorbs light at a wavelength of 365 nm or appropriately adjusting the content of the colorant in the total solid content.

[0066] In the present invention, the optical density of a film is a value of transmittance measured by using a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation when light of a wavelength of 365 nm is incident.

[0067] The coloring composition of the present invention can be preferably used in the manufacture of color filters and light-shielding films. In addition, in the present invention, the so-called color filter refers to a color filter that allows light of a specific wavelength range among light of wavelengths in the visible light range to pass, blocks light of a specific wavelength range, and blocks light of wavelengths in the visible light range and transmits light of a specific wavelength in the infrared range (infrared rays). A color filter that blocks light of wavelengths in the visible light range and transmits light of a specific wavelength in the infrared range (infrared rays) is also called an infrared transmission filter.

[0068] For example, the coloring composition of the present invention contains an organic pigment, and the coloring composition has a ratio A / B of 0.3 to 3 between the minimum value A of the absorbance in the range of wavelengths of 400 nm to less than 580 nm and the minimum value B of the absorbance in the range of wavelengths of 580 nm to 750 nm, and a ratio C / D of 5 or more between the minimum value C of the absorbance in the range of wavelengths of 400 nm to 750 nm and the maximum value D of the absorbance in the range of wavelengths of 1000 nm to 1300 nm. A cured film such as a color filter (infrared transmission filter) that blocks visible light (preferably light of 400 to 700 nm) and transmits infrared light (for example, light of 850 ohms or more) can be formed. The cured film has good adhesion to the support, and is excellent in sensitivity and rectangularity.

[0069] Furthermore, when the colored composition of the present invention contains a curable compound having a fluorine atom and a curable functional group, it is possible to form a cured film having high adhesion to a support and low reflectivity.

[0070] The mechanism for forming a cured film with low reflectivity can be inferred as follows. The curable compound having fluorine atoms and curable functional groups (hereinafter also referred to as fluorine-containing curable compound) has low surface free energy. Therefore, in a coating formed by applying a coloring composition on a support such as a substrate, the fluorine-containing curable compound tends to be concentrated near the coating surface on the opposite side of the support. As a result, Figure 1 As shown in the figure, the cured film 200 on the substrate 201 obtained by curing the coating film has a two-layer structure of a coloring layer (lower layer) 202 containing a colorant and a coating layer (upper layer) 203 formed of a fluorine-containing curable compound. When such a two-layer structure is formed, it is considered that low reflectivity can be achieved by interference and cancellation of light reflected on the surface of the coating layer and light reflected at the interface between the coating layer and the coloring layer.

[0071] Furthermore, due to the presence of the curable functional group derived from the fluorine-containing curable compound, when a patterned cured film is produced, undercut is suppressed, and defect of the cured film is suppressed, while the linearity of the pattern is improved.

[0072] In one embodiment including a fluorine-containing curable compound, when a black pigment is further included, a cured film having good light-shielding property and low reflectivity can be formed, and the obtained cured film is particularly suitable as a light-shielding film.

[0073] In addition, the coloring composition of the present invention further contains an α-aminoketone-based photopolymerization initiator as a photopolymerization initiator. When the mass ratio of the fluorine-containing oxime ester-based photopolymerization initiator to the α-aminoketone-based photopolymerization initiator is 1:1.5 to 1:10, a cured film such as a color filter having good adhesion and rectangularity can be formed.

[0074] When the colored composition of the present invention further contains an oxime photopolymerization initiator other than the fluorine-containing oxime ester photopolymerization initiator (other oxime photopolymerization initiator) as a photopolymerization initiator, it is easy to produce a cured film having good sensitivity and adhesion and suppressed fading.

[0075] Hereinafter, each structure of the present invention will be described in detail.

[0076] 《Fluorine-containing oxime ester photopolymerization initiators》

[0077] The coloring composition of the present invention contains a fluorine-containing oxime ester photopolymerization initiator (hereinafter also referred to as a fluorine-containing oxime ester photopolymerization initiator).

[0078] In the present invention, the fluorine-containing oxime ester photopolymerization initiator is preferably a compound having a maximum absorption wavelength in the wavelength region of 350 to 500 nm, more preferably a compound having an absorption wavelength in the wavelength region of 360 to 480 nm, and particularly preferably a compound having a high absorbance at 365 nm.

[0079] The molar absorption coefficient of the fluorine-containing oxime ester photopolymerization initiator at 365 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and particularly preferably 5,000 to 200,000 from the viewpoint of sensitivity.

[0080] The molar absorption coefficient of a compound can be measured using a known method, but is preferably measured, for example, using an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.

[0081] In the present invention, the fluorine-containing oxime ester photopolymerization initiator preferably has a fluorine-containing group. The fluorine-containing group is preferably an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing alkyl group) and / or a group containing an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing group).

[0082] As the fluorine-containing group, it is preferably selected from -ORX11 、-SR X11 、-COR X11 、-COOR X11 、-OCOR X11 、-NR X11 R X12 、-NHCOR X11 、-CONR X11 R X12 、-NHCONR X11 R X12 、-NHCOOR X11 、-SO 2 R X11 、-SO 2 OR X11 and-NHSO 2 R X11 At least one group of X11 represents a fluorinated alkyl group, R X12 represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, an aryl group or a heterocyclic group. The fluorinated group is more preferably -OR X11 .

[0083] The fluorine-containing group is preferably a fluorine-containing alkyl group, and / or -OR X11 .

[0084] The fluorine atom-containing group preferably has a terminal structure represented by the following formula (1) or (2): wherein * represents a connecting bond.

[0085] *-CHF 2 (1)

[0086] *-CF 3 (2)

[0087] The number of perfluorinated atoms in the compound containing the fluorine oxime ester-based photopolymerization initiator is preferably 3 or more, more preferably 4 to 10.

[0088] The number of carbon atoms in the alkyl group and the fluorinated alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group and the fluorinated alkyl group may be linear, branched, or cyclic, and are preferably linear or branched.

[0089] The fluorine atom substitution rate of the fluorine-containing alkyl group is preferably 40 to 100%, more preferably 50 to 100%, and further preferably 60 to 100%. In addition, the fluorine atom substitution rate refers to the ratio (%) of the number of hydrogen atoms in the alkyl group to the number of fluorine atoms.

[0090] The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

[0091] The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of condensed rings is preferably 2 to 8, more preferably 2 to 6, further preferably 3 to 5, and particularly preferably 3 to 4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and further preferably 3 to 20. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heteroatom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.

[0092] In the present invention, examples of the fluorine-containing oxime ester-based photopolymerization initiator include compounds represented by the following formula (1a).

[0093] [Chemical formula 3]

[0094]

[0095] In the general formula (1a), A 1 and A 2 Each independently represents an alkyl group, an acyl group, an aryl group or a heterocyclic group, and A 3 represents an alkyl group, an aryl group or a heterocyclic group, wherein A 1 ~A 3 At least one of them contains a fluorine atom.

[0096] A 1 It represents an alkyl group, an acyl group, an aryl group or a heterocyclic group, preferably an aryl group or a heterocyclic group, and more preferably a heterocyclic group.

[0097] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0098] The number of carbon atoms in the acyl group is preferably 2 to 20, more preferably 2 to 15. Examples of the acyl group include acetyl and benzoyl.

[0099] The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

[0100] The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of condensed rings is preferably 2 to 8, more preferably 2 to 6, further preferably 3 to 5, and particularly preferably 3 to 4. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 40, more preferably 3 to 30, and further preferably 3 to 20. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heteroatom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.

[0101] A 1The above-mentioned groups may be unsubstituted or may have a substituent. Examples of the substituent include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR X1 、-SR X1 、-COR X1 、-COOR X1 、-OCOR X1 、-NR X1 R X2 、-NHCOR X1 、-CONR X1 R X2 、-NHCONR X1 R X2 、-NHCOOR X1 、-SO 2 R X1 、-SO 2 OR X1 、-NHSO 2 R X1 Etc. R X1 and R X2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.

[0102] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is more preferred.

[0103] Alkyl as a substituent and R X1 and R X2 The number of carbon atoms of the alkyl group represented is preferably 1 to 20. The alkyl group may be any of a straight chain, a branched chain, or a cyclic chain, preferably a straight chain or a branched chain. The alkyl group may also be a group in which some or all of the hydrogen atoms are substituted by halogen atoms (preferably fluorine atoms). Furthermore, the alkyl group may be a group in which some or all of the hydrogen atoms are substituted by the above-mentioned substituents.

[0104] Aryl and R as substituents X1 and R X2 The number of carbon atoms of the aryl group represented is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring. In addition, the hydrogen atoms of the aryl group may be partially or entirely substituted with the above-mentioned substituents.

[0105] The heterocyclic group and R as a substituent X1 and R X2The heterocyclic group represented is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and further preferably 3 to 12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heteroatom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In addition, the heterocyclic group may be partially or completely substituted with the above-mentioned substituents for the hydrogen atoms.

[0106] A 2 represents an alkyl group, an acyl group, an aryl group or a heterocyclic group, preferably an alkyl group or an aryl group, and particularly preferably an aryl group. 1 The meanings of the ranges described in are the same as those in the above. These groups may be unsubstituted or may have a substituent. Preferably, they have a substituent.

[0107] As the substituent, A 1 The substituent described in is preferably an alkyl group, -OR X1 and halogen atoms. X1 represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group, and is preferably an alkyl group. X1 The alkyl group represented is preferably one in which a part or all of the hydrogen atoms are substituted with fluorine atoms.

[0108] A 3 represents an alkyl group, an aryl group or a heterocyclic group, preferably an alkyl group or an aryl group. These groups may be unsubstituted or may have a substituent. Examples of the substituent include A 1 The substituents described in .

[0109] In the present invention, the fluorine-containing oxime ester-based photopolymerization initiator is preferably a compound represented by the following formula (1).

[0110] [Chemical formula 4]

[0111]

[0112] In formula (1), Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon ring which may have a substituent, R 1 represents an aryl group having a fluorine atom-containing group, R 2 and R 3 Each independently represents an alkyl group or an aryl group.

[0113] Ar 1 and Ar 2 Each independently represents an aromatic hydrocarbon ring which may have a substituent.

[0114] The aromatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms constituting the aromatic hydrocarbon ring is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10. The aromatic hydrocarbon ring is preferably a benzene ring or a naphthalene ring. 1 and Ar 2 At least one of them is preferably a benzene ring, Ar 1 More preferably, it is a benzene ring. 1 Preferably it is a benzene ring or a naphthalene ring, more preferably a naphthalene ring

[0115] As can also have Ar 1 and Ar 2 The substituents of 1 The substituents described in .

[0116] Ar 1 Preferably, it is unsubstituted. 1 It may be unsubstituted or may have a substituent. A preferred substituent is -COR X1 . R X1 An alkyl group, an aryl group or a heterocyclic group is preferred, and an aryl group is more preferred. The aryl group may have a substituent or may not have a substituent. Examples of the substituent include an alkyl group having 1 to 10 carbon atoms.

[0117] R 1 It represents an aryl group having a fluorine atom-containing group.

[0118] The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

[0119] The group containing a fluorine atom is preferably a group having an alkyl group containing a fluorine atom (fluorine-containing alkyl group) and / or a group containing an alkyl group containing a fluorine atom (fluorine-containing group).

[0120] The fluorine-containing group is preferably selected from -OR X11 、-SR X11 、-COR X11 、-COOR X11 、-OCOR X11 、-NR X11 R X12 、-NHCOR X11 、-CONR X11 R X12 、-NHCONR X11 R X12 、-NHCOOR X11 、-SO 2 R X11 、-SO 2 OR X11 and-NHSO 2 RX11 At least one of the groups, more preferably -OR X11 . R X11 represents a fluorinated alkyl group, R X12 represents a hydrogen atom, an alkyl group, a fluorinated alkyl group, an aryl group or a heterocyclic group.

[0121] The fluorine-containing group is preferably a fluorine-containing alkyl group, and / or -OR X11 .

[0122] The number of carbon atoms in the fluorinated alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The fluorinated alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0123] The substitution rate of fluorine atoms in the fluorine-containing alkyl group is preferably 40 to 100%, more preferably 50 to 100%, further preferably 60 to 100%.

[0124] R X12 The alkyl, aryl and heterocyclic groups represented by A 1 R X1 and R X2 The meanings of the ranges described for the alkyl group, aryl group, and heterocyclic group are the same as those of the ranges described above.

[0125] R 2 represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned A 1 The substituents described in .

[0126] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, further preferably 1 to 10, and particularly preferably 1 to 4. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0127] The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

[0128] R 3 represents an alkyl group or an aryl group, preferably an alkyl group. The alkyl group and the aryl group may be unsubstituted or may have a substituent. Examples of the substituent include the above-mentioned A 1 The substituents described in .

[0129] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0130] The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring.

[0131] Specific examples of the compound represented by formula (1) include the following compounds.

[0132] [Chemical formula 5]

[0133]

[0134] In the present invention, the following compounds may be used as the fluorine-containing oxime ester-based photopolymerization initiator. In addition, compounds described in JP-A-2010-262028 and compounds (C-3) described in JP-A-2013-164471 may be used. These contents are incorporated into the present specification.

[0135] [Chemical formula 6]

[0136]

[0137] The content of the fluorine-containing oxime ester photopolymerization initiator is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and further preferably 1 to 20% by mass relative to the total solid content of the coloring composition. By setting it to this range, a pattern with good adhesion can be obtained. The coloring composition of the present invention may contain only one fluorine-containing oxime ester photopolymerization initiator, or may contain two or more. When containing two or more, the total amount is preferably set to the above range.

[0138] 《α-Aminoketone-based photopolymerization initiator》

[0139] The colored composition of the present invention may further contain an α-aminoketone-based photopolymerization initiator. By containing an α-aminoketone-based photopolymerization initiator, a pattern having good rectangularity can be formed.

[0140] Examples of the α-aminoketone-based photopolymerization initiator include compounds represented by the following formula (AK-1).

[0141] [Chemical formula 7]

[0142]

[0143] In the formula, Ar represents -SR 13 or -N(R 7E )(R 8E ) substituted phenyl, R 13 represents a hydrogen atom or an alkyl group.

[0144] R 1D and R 2D R each independently represents an alkyl group having 1 to 8 carbon atoms.1D With R 2D They may be bonded to each other to form an alkylene group having 2 to 9 carbon atoms.

[0145] R 1D and R 2D The alkyl group represented may be any of linear, branched, and cyclic, and is preferably linear or branched.

[0146] R 1D and R 2D The alkyl group represented may be unsubstituted or may have a substituent. Examples of the substituent include an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, -OR Y1 、-SR Y1 、-COR Y1 、-COOR Y1 、-OCOR Y1 、-NR Y1 R Y2 、-NHCOR Y1 、-CONR Y1 R Y2 、-NHCONR Y1 R Y2 、-NHCOOR Y1 、-SO 2 R Y1 、-SO 2 OR Y1 、-NHSO 2 R Y1 Etc. R Y1 and R Y2 Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group. The substituent is preferably an aryl group. 1D and R 2D One of them is an unsubstituted alkyl group, and the other is an alkyl group substituted with an aryl group.

[0147] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0148] R Y1 and R Y2 The number of carbon atoms of the alkyl group represented is preferably 1 to 20. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched.

[0149] Aryl and R as substituents Y1 and R Y2 The number of carbon atoms of the aryl group represented is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. The aryl group may be a monocyclic ring or a condensed ring. In addition, the aryl group may have some or all of the hydrogen atoms substituted by an alkyl group having 1 to 8 carbon atoms.

[0150] R Y1 and R Y2 The heterocyclic group represented is preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number of carbon atoms constituting the heterocyclic group is preferably 3 to 30, more preferably 3 to 18, and further preferably 3 to 12. The number of heteroatoms constituting the heterocyclic group is preferably 1 to 3. The heteroatom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.

[0151] R 3D and R 4D R each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms. 3D With R 4D They may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group may contain -O- or -N(R 12 )-. 12 It represents an alkyl group having 1 to 4 carbon atoms.

[0152] R 7E and R 8E R each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 2 to 4 carbon atoms substituted with an alkoxy group having 1 to 4 carbon atoms, or an alkenyl group having 3 to 5 carbon atoms. 7E With R 8E They may be bonded to each other to form an alkylene group having 3 to 7 carbon atoms, and the alkylene group may contain -O- or -N(R 12 )-. 12 The meanings are the same as those of the above groups.

[0153] Examples of the compound represented by formula (AK-1) include 2-methyl-1-phenyl-2-morpholin-1-one, 2-methyl-1-[4-(hexyl)phenyl]-2-morpholin-1-one, 2-ethyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone.

[0154] Examples of commercially available α-aminoketone-based photopolymerization initiators include Irgacure 907, Irgacure 369, and Irgacure 379 (trade names: all manufactured by BASF Corporation).

[0155] When the coloring composition of the present invention contains an α-aminoketone photopolymerization initiator, the mass ratio of the fluorine-containing oxime ester photopolymerization initiator to the α-aminoketone photopolymerization initiator is preferably 1:1.5 to 1:10, more preferably 1:1.5 to 1:8, further preferably 1:1.5 to 1:5, and particularly preferably 1:1.5 to 1:4. In addition, the content of the α-aminoketone photopolymerization initiator is preferably 0.1 to 10% by mass in the total solid content of the coloring composition of the present invention. The lower limit is preferably 0.2% by mass or more, and more preferably 0.5% by mass or more. The upper limit is more preferably 8% by mass or less, and more preferably 5% by mass or less. When the content of the α-aminoketone photopolymerization initiator is within the above range, a pattern with good rectangularity is easily formed.

[0156] The total amount of the fluorine-containing oxime ester photopolymerization initiator and the α-aminoketone photopolymerization initiator is preferably 50% by mass or more, more preferably 75% by mass or more, and particularly preferably 90% by mass or more, based on the total mass of all photopolymerization initiators.

[0157] 《Other photopolymerization initiators》

[0158] The colored composition of the present invention may further contain a photopolymerization initiator (other photopolymerization initiator) other than the fluorine-containing oxime ester-based photopolymerization initiator and the α-aminoketone-based photopolymerization initiator.

[0159] As other photopolymerization initiators, for example, halogenated hydrocarbon derivatives (for example, derivatives having a triazine skeleton, derivatives having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxides, hexaarylbiimidazoles, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketone oxime ethers, aminoacetophenone compounds, hydroxyacetophenone, etc. can be cited. As the halogenated hydrocarbon compound having a triazine skeleton, for example, there can be mentioned the compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), the compounds described in the specification of British Patent No. 1388492, the compounds described in Japanese Unexamined Patent Publication No. 53-133428, the compounds described in German Patent No. 3337024, the compounds described in J. Org. Chem. 29, 1527 (1964) by FC Schaefer et al., the compounds described in Japanese Unexamined Patent Publication No. 62-58241, the compounds described in Japanese Unexamined Patent Publication No. 5-281728, the compounds described in Japanese Unexamined Patent Publication No. 5-34920, the compounds described in the specification of U.S. Patent No. 4212976, etc. Among these, compounds other than fluorine-containing oxime ester photopolymerization initiators and α-aminoketone photopolymerization initiators can be used.

[0160] From the viewpoint of exposure sensitivity, other photopolymerization initiators are preferably selected from the group consisting of trihalomethyl triazine compounds, benzyl dimethyl ketal compounds, α-hydroxy ketone compounds, acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and 3-aryl substituted coumarin compounds.

[0161] More preferred are trihalomethyl triazine compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds, and particularly preferred is at least one compound selected from the group consisting of trihalomethyl triazine compounds, oxime compounds, triallylimidazole dimers, and benzophenone compounds.

[0162] As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP-A-2013-29760 can be referred to, the contents of which are incorporated herein by reference.

[0163] As other photopolymerization initiators, hydroxyacetophenone compounds and acylphosphine compounds can also be used appropriately. More specifically, acylphosphine-based initiators described in Japanese Patent No. 4225898 can also be used.

[0164] As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.

[0165] As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF Corporation) can be used.

[0166] As other photopolymerization initiators, oxime compounds can be mentioned.

[0167] As specific examples of the oxime compound, compounds described in JP-A-2001-233842, compounds described in JP-A-2000-80068, and compounds described in JP-A-2006-342166 can be used.

[0168] Specific examples of oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutane-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

[0169] In addition, compounds described in JCS Perkin II (1979) pp. 1653-1660, JCS Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, Japanese Patent Application Publication No. 2000-66385, Japanese Patent Application Publication No. 2000-80068, Japanese Patent Publication No. 2004-534797, Japanese Patent Application Publication No. 2006-342166, and the like can be cited.

[0170] Among commercially available products, IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) can also be suitably used. In addition, TR-PBG-304 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA Corporation) can also be used.

[0171] In addition, as oxime compounds other than those described above, compounds described in Japanese Patent Publication No. 2009-519904 in which oxime is linked to the N-position of carbazole, compounds described in U.S. Patent No. 7626957 in which a hetero substituent is introduced at the benzophenone site, compounds described in Japanese Patent Publication No. 2010-15025 and U.S. Patent Publication No. 2009-292039 in which a nitro group is introduced at the pigment site, ketone oxime compounds described in International Patent Publication No. 2009-131189, compounds described in U.S. Patent No. 7556910 containing a triazine skeleton and an oxime skeleton in the same molecule, compounds described in Japanese Patent Publication No. 2009-221114 having maximum absorption at 405 nm and good sensitivity to a g-line light source, etc. can also be used.

[0172] For example, it is preferable to refer to paragraphs 0274 to 0275 of Japanese Patent Application Laid-Open No. 2013-29760, and the contents are incorporated into the specification of the present application.

[0173] Specifically, the oxime compound is preferably a compound represented by the following formula (OX-1). The NO bond of the oxime may be an oxime compound in the (E) form, an oxime compound in the (Z) form, or a mixture of the (E) form and the (Z) form.

[0174] [Chemical formula 8]

[0175]

[0176] In the general formula (OX-1), R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.

[0177] In the general formula (OX-1), the monovalent substituent represented by R is preferably a monovalent non-metal atomic group.

[0178] Examples of the monovalent non-metallic atomic group include alkyl, aryl, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocyclic, alkylthiocarbonyl, arylthiocarbonyl, etc. Furthermore, these groups may have one or more substituents. Furthermore, the substituents may be further substituted by other substituents.

[0179] Examples of the substituent include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.

[0180] In the general formula (OX-1), the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group or a heterocyclic carbonyl group. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.

[0181] In the general formula (OX-1), the divalent organic group represented by A is preferably an alkylene group, a cycloalkylene group, or an alkynylene group having 1 to 12 carbon atoms. These groups may have one or more substituents. As the substituent, the above-mentioned substituents can be exemplified.

[0182] As other photopolymerization initiators, compounds represented by the following general formula (1) or (2) can also be used.

[0183] [Chemical formula 9]

[0184]

[0185] In formula (1), R 1 and R 2R 1 and R 2 When the phenyl group is a phenyl group, the phenyl groups may also be bonded to each other to form a fluorenyl group. 3 and R 4 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, and X represents a direct bond or a carbonyl group.

[0186] In formula (2), R 1 , R 2 , R 3 and R 4 With R in formula (1) 1 , R 2 , R 3 and R 4 Same meaning, R 5 Indicates -R 6 、-OR 6 、-SR 6 、-COR 6 、-CONR 6 R 6 、-NR 6 COR 6 、-OCOR 6 、-COOR 6 ,-SCOR 6 、-OCSR 6 ,-COSR 6 ,-CSOR 6 , -CN, halogen atom or hydroxyl group, R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 4 to 20 carbon atoms, X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.

[0187] In the above formula (1) and formula (2), R 1 and R 2 Preferably, each R is independently methyl, ethyl, n-propyl, isopropyl, cyclohexyl or phenyl. 3 Preferably, it is methyl, ethyl, phenyl, tolyl or xylyl. 4 It is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group. 5 It is preferably methyl, ethyl, phenyl, tolyl or naphthyl. X is preferably directly bonded.

[0188] Specific examples of the compounds represented by formula (1) and formula (2) include compounds described in paragraphs 0076 to 0079 of JP-A-2014-137466, which are incorporated herein by reference.

[0189] The content of other photopolymerization initiators can be set to 10 to 90% by mass, 10 to 80% by mass, or 10 to 70% by mass relative to the mass of all photopolymerization initiators contained in the coloring composition. In addition, it can be set to less than 50% by mass, less than 25% by mass, or less than 10% by mass relative to the mass of all photopolymerization initiators contained in the coloring composition. In addition, it can also be set to a composition that substantially does not contain other photopolymerization initiators. Substantially containing no other photopolymerization initiators means that the content of other photopolymerization initiators is preferably less than 1% by mass, more preferably less than 0.1% by mass, and further preferably does not contain other photopolymerization initiators relative to the mass of all photopolymerization initiators.

[0190] Furthermore, the coloring composition of the present invention may also be configured to be substantially free of oxime-based photopolymerization initiators other than fluorine-containing oxime ester-based photopolymerization initiators (hereinafter, also referred to as other oxime-based photopolymerization initiators). Substantially free of other oxime-based photopolymerization initiators means, for example, that the content of other oxime-based photopolymerization initiators is preferably 1% by mass or less, more preferably 0.1% by mass or less, and further preferably free of other oxime-based photopolymerization initiators relative to the mass of all photopolymerization initiators. In addition, other oxime-based photopolymerization initiators refer to oxime compounds that do not contain fluorine atoms, and the oxime compounds described in the above-mentioned other photopolymerization initiators can be cited.

[0191] Furthermore, the coloring composition of the present invention may also be configured to use a fluorine-containing oxime ester photopolymerization initiator in combination with other oxime photopolymerization initiators. According to this mode, it is easy to manufacture a cured film with suppressed fading. When a fluorine-containing oxime ester photopolymerization initiator and other oxime photopolymerization initiators are used in combination, the other oxime photopolymerization initiator is preferably 30 to 300 parts by mass, more preferably 50 to 250 parts by mass, and further preferably 70 to 200 parts by mass relative to a total of 100 parts by mass of the fluorine-containing oxime ester photopolymerization initiator and other oxime photopolymerization initiators. According to this range, sensitivity and adhesion are good, and it is easy to manufacture a cured film with suppressed fading.

[0192] Colorants

[0193] The coloring composition of the present invention contains a colorant. The colorant may be a pigment or a dye.

[0194] The content of the colorant is preferably 1 to 80% by mass relative to the total solid content of the coloring composition. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more. The upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less.

[0195] 《<Pigment>》

[0196] Examples of the pigment include various conventionally known inorganic pigments and organic pigments.

[0197] Examples of the inorganic pigment include metal oxides such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

[0198] Examples of organic pigments include the following, but the present invention is not limited thereto.

[0199] 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.,

[0200] CI 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.

[0201] CI 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, 1 44, 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, 270, 272, 279,

[0202] CI Pigment Green 7, 10, 36, 37, 58, 59,

[0203] CI Pigment Violet 1, 19, 23, 27, 32, 37, 42,

[0204] CI Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66, 79, 80.

[0205] Among organic pigments, the zinc phthalocyanine halogenide pigment (also referred to as zinc phthalocyanine halogenide pigment A) has an average number of 14 to 16 halogen atoms in one phthalocyanine molecule and preferably an average number of 12 or less bromine atoms. The zinc phthalocyanine halogenide pigment A is preferably a compound represented by the following general formula (A1).

[0206] [Chemical formula 10]

[0207]

[0208] In the general formula (A1), X 1 ~X 16 Each independently represents a halogen atom, a hydrogen atom, or a substituent.

[0209] Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

[0210] As substituents, the descriptions in paragraphs 0025 to 0027 of JP-A-2013-209623 can be referred to, and the contents are incorporated into the present specification.

[0211] The average number of halogen atoms in one phthalocyanine molecule of the zinc phthalocyanine halide pigment A is 14 to 16, preferably 15 to 16.

[0212] The average number of bromine atoms in one phthalocyanine molecule of the zinc phthalocyanine halide pigment A is 0 to 12, preferably 1 to 8, more preferably 1 to 7, and even more preferably 2 to 7.

[0213] When the average number of halogen atoms and the average number of bromine atoms are within the above ranges, the generation of needle-shaped crystals can be suppressed. In addition, a cured film of a color filter or the like having less uneven brightness and excellent spectral characteristics can be produced.

[0214] In the halogenated zinc phthalocyanine pigment A, the halogen atom other than the bromine atom includes a chlorine atom, a fluorine atom and an iodine atom. From the viewpoint of suppressing needle-like foreign matter and uneven brightness, a chlorine atom and a fluorine atom are preferred, and a chlorine atom is more preferred.

[0215] The average number of halogen atoms and the average number of bromine atoms in one phthalocyanine molecule in the zinc phthalocyanine halide pigment A can be calculated from mass analysis and halogen content analysis by bottle combustion ion chromatography.

[0216] These organic pigments may be used alone or in combination in order to improve color purity.

[0217] 《《Black Pigment》》

[0218] In the present invention, a black pigment may also be used as the pigment. The black pigment will be described in further detail below.

[0219] Various known black pigments can be used for the black pigment. In particular, carbon black, titanium black, titanium oxide, iron oxide, manganese oxide, graphite, etc. are preferably used from the viewpoint of achieving high optical density with a small amount, wherein at least one of carbon black and titanium black is preferably included, and titanium black is particularly preferably included.

[0220] More specifically, commercially available organic pigments such as CI Pigment Black 1 and inorganic pigments such as CI Pigment Black 7 may be used.

[0221] The black pigment preferably contains titanium black.

[0222] Titanium black refers to black particles containing titanium atoms. Preferably, they are low-valent titanium oxide or titanium oxynitride. The titanium black particles can be surface-modified as needed for the purpose of improving dispersibility, inhibiting cohesion, etc. They can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide, and can also be treated with a water-repellent substance as shown in Japanese Patent Publication No. 2007-302836.

[0223] Titanium black is typically titanium black particles, and it is preferred that both the primary particle size and the average primary particle size of each particle are small.

[0224] Specifically, it is preferably in the range of 10nm to 45nm in the average primary particle diameter. In addition, the particle size in the present invention, i.e., the particle diameter, is the diameter of a circle having an area equal to the projected area of ​​the outer surface of the particle. The projected area of ​​the particle is obtained by measuring the area obtained by photography in an electron microscope photograph and correcting the shooting magnification.

[0225] The specific surface area of ​​titanium black is not particularly limited. In order to make the water repellency of titanium black surface treated with a water repellent to reach a predetermined performance, the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5 m 2 / g and above and 150m 2 / g or less, more preferably 20m 2 / g and above 120m 2 / g or less.

[0226] Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, and 13M-T (trade names: manufactured by Mitsubishi Materials Corporation) and Tilack D (trade name: manufactured by AkoKasei Co., Ltd.).

[0227] Furthermore, titanium black may be preferably contained as a dispersed body containing titanium black and Si atoms.

[0228] In this embodiment, titanium black is contained as a dispersed body in the composition, and the content ratio of Si atoms to Ti atoms in the dispersed body (Si / Ti) is preferably 0.05 or more, more preferably 0.05 to 0.5, and further preferably 0.07 to 0.4 in terms of mass.

[0229] The dispersed body includes two types: titanium black in the form of primary particles and titanium black in the form of aggregates (secondary particles).

[0230] In order to change the Si / Ti ratio of the dispersed body (to 0.05 or more, for example), the following method can be used.

[0231] First, titanium oxide and silicon oxide particles are dispersed using a disperser to obtain a dispersion, and the dispersion is subjected to a reduction treatment at a high temperature (e.g., 850 to 1000° C.) to obtain a dispersion having titanium black particles as a main component and containing Si and Ti. The reduction treatment can also be performed in an environment of a reducing gas such as ammonium.

[0232] Examples of titanium oxide include TTO-51N (trade name: manufactured by ISHIHARA SANGYO KAISHA, LTD.).

[0233] Commercially available products of silicon oxide particles include AFROSIL (registered trademark) 90, 130, 150, 200, 255, 300, and 380 (trade name: manufactured by EVONIK).

[0234] The titanium oxide and silicon oxide particles may be dispersed using a dispersant. Examples of the dispersant include those described in the section of the dispersant described later.

[0235] The above dispersion may be carried out in a solvent. Examples of the solvent include water and an organic solvent. Examples of the solvent include the solvents described in the section of the organic solvent described later.

[0236] Si / Ti can be produced by adjusting titanium black to 0.05 or more, for example, by the method described in paragraphs

[0005] and

[0016] to

[0021] of JP-A-2008-266045.

[0237] By adjusting the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed body containing titanium black and Si atoms to a suitable range (e.g., 0.05 or more), when a light-shielding film is formed using the composition containing the dispersed body, the residue derived from the composition outside the formation area of ​​the light-shielding film is reduced. In addition, the residue is a substance containing components of the composition such as titanium black particles and resin components.

[0238] The reason for the reduction in residues is not yet clear, but the dispersed body tends to have a small particle size (for example, a particle size of less than 30 nm) as described above, and as the Si atom content of the dispersed body increases, the adsorption to the base of the entire film decreases, which is speculated to help improve the development and removal of the uncured composition (especially titanium black) when forming a light-shielding film.

[0239] Furthermore, titanium black has excellent light-shielding properties for light in a wide range of wavelengths from ultraviolet light to infrared light, and thus a light-shielding film formed using the above-mentioned dispersed body containing titanium black and Si atoms (preferably Si / Ti is greater than 0.05 in terms of mass) exhibits excellent light-shielding properties.

[0240] The content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed body can be measured using, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP-A-2013-249417.

[0241] Furthermore, to determine whether the content ratio of Si atoms to Ti atoms (Si / Ti) in the dispersed body contained in the light-shielding film obtained by curing the composition is greater than or equal to 0.05, the method (2) described in paragraph 0035 of JP-A-2013-249417 is used.

[0242] In the dispersed body containing titanium black and Si atoms, the titanium black may be the one described above.

[0243] Furthermore, in the dispersed body, for the purpose of adjusting dispersibility, coloring, etc., one or more black pigments including composite oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline black, etc. can be combined with titanium black to be used as dispersed bodies. At this time, the dispersed body including titanium black in all dispersed bodies preferably accounts for more than 50% by mass. Furthermore, in the dispersed body, for the purpose of adjusting light-shielding properties, etc., other colorants (organic pigments or dyes, etc.) can also be used in combination with titanium black as needed as long as the effect of the present invention is not impaired.

[0244] The following describes the materials used when introducing Si atoms into the dispersed body. When introducing Si atoms into the dispersed body, a Si-containing substance such as silicon oxide may be used.

[0245] As silicon oxide that can be used, there can be mentioned precipitated silicon oxide, fumed silicon oxide, colloidal silicon oxide, synthetic silicon oxide and the like, and these silicon oxides may be appropriately selected.

[0246] Furthermore, if the particle size of the silicon oxide particles is smaller than the film thickness when forming the light-shielding film, the light-shielding property is more excellent, and thus, as the silicon oxide particles, microparticle-type silicon oxide is preferably used. In addition, as a specific example of microparticle-type silicon oxide, for example, the silicon oxide described in paragraph 0039 of Japanese Patent Publication No. 2013-249417 can be cited, and these contents are introduced into this specification.

[0247] 《<Dye>》

[0248] As dyes, for example, those disclosed in Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, Japanese Patent Application No. 2592207, U.S. Patent No. 4808501, U.S. Patent No. 5667920, U.S. Patent No. 505950, Japanese Patent Application Laid-Open No. 5-333207, Japanese Patent Application Laid-Open No. 6-35183, Japanese Patent Application Laid-Open No. 6-51115, Japanese Patent Application Laid-Open No. 6-194828, etc. can be used. If distinguished as chemical structure, pyrazole azo compounds, pyrrole methylene compounds, anilino azo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolo pyrazole azomethine compounds etc. can be used. And, as dye, pigment polymers can also be used. As pigment polymers, compounds described in Japanese Patent Publication No. 2011-213925 and Japanese Patent Publication No. 2013-041097 can be cited.

[0249] Furthermore, in the present invention, as the colorant, a colorant having a maximum absorption in the wavelength range of 800 to 900 nm can be used.

[0250] Examples of colorants having such spectral characteristics include pyrrolopyrrole compounds, copper compounds, cyanine compounds, phthalocyanine compounds, imine compounds, thiol complex compounds, transition metal oxide compounds, squarylium cyanine, naphthalocyanine compounds, quaterylene compounds, dithiol metal complex compounds, and croconium compounds.

[0251] Phthalocyanine compounds, naphthalocyanine compounds, imine compounds, cyanine compounds, squarylium compounds and keto acid compounds, compounds disclosed in paragraphs 0010 to 0081 of Japanese Patent Publication No. 2010-111750, and the contents are incorporated into this specification. For example, cyanine compounds can refer to "Functional pigments, Okawara Nobuyuki / Matsuoka Ken / Kitao Teijiro / Hirajima Tsuneaki, Kodansha Scientific", and the contents are incorporated into this application specification.

[0252] As a colorant having the above-mentioned spectral characteristics, compounds disclosed in paragraphs 0004 to 0016 of Japanese Patent Application Laid-Open No. 07-164729, compounds disclosed in paragraphs 0027 to 0062 of Japanese Patent Application Laid-Open No. 2002-146254, and near-infrared absorbing particles comprising microcrystals of oxides of Cu and / or P and having a number average agglomerated particle size of 5 to 200 nm disclosed in paragraphs 0034 to 0067 of Japanese Patent Application Laid-Open No. 2011-164583 can also be used.

[0253] In the present invention, the colorant having maximum absorption in the wavelength range of 800 to 900 nm is preferably a pyrrolopyrrole compound. The pyrrolopyrrole compound may be a pigment or a dye, but a pigment is preferred because a coloring composition capable of forming a film having excellent heat resistance can be easily obtained.

[0254] The pyrrolopyrrole compound is preferably a compound represented by the following general formula (1).

[0255] [Chemical formula 11]

[0256]

[0257] In the general formula (1), R 1a and R 1b Each independently represents an alkyl group, an aryl group or a heteroaryl group, and R 2 and R 3 Each independently represents a hydrogen atom or a substituent, R 2 and R 3 At least one of them is an electron-withdrawing group, R 2 and R 3 They can also be bonded to form a ring, R 4 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a substituted boron group, or a metal atom, and R 4 Can also be selected from R 1a , R 1b and R 3 One or more of them are covalently bonded or coordinately bonded.

[0258] In the general formula (1), R 1a or R 1b The alkyl group represented is an alkyl group having preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, examples of which include methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, and cyclohexyl.

[0259] As R 1a or R 1bThe aryl group represented is an aryl group having preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, o-tolyl, p-tolyl, biphenylyl, naphthyl, anthracenyl, and phenanthryl.

[0260] As R 1a or R 1b The heteroaryl group represented by is a heteroaryl group having preferably 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the heteroatom include a nitrogen atom, an oxygen atom, and a sulfur atom. Specific examples of the heteroaryl group include imidazolyl, pyridyl, quinolyl, furyl, thienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, naphthylthiazolyl, m-carbazolyl, and azepinyl.

[0261] R in the general formula (1) 1a and R 1b They may be the same as or different from each other.

[0262] R 2 and R 3 R each independently represents a hydrogen atom or a substituent, and at least one of them is an electron withdrawing group. 2 and R 3 They may be bonded to form a ring. Examples of the substituent include the substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. The above contents are incorporated into the present specification.

[0263] As R 2 or R 3 The electron-withdrawing group represented by means of a Hammett's σp value (Sigma Para Value) preferably being 0.2 or more, for example, includes a cyano group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a sulfamoyl group, a sulfinyl group, a heterocyclic group, etc. These electron-withdrawing groups may be further substituted.

[0264] The following is an explanation of the Hammett's substituent constant σ value. The Hammett equation is an empirical rule advocated by LP Hammett in 1935 in order to quantitatively discuss the effects of substituents on the reaction or equilibrium of benzene derivatives. Today, its effectiveness is widely recognized. The substituent constants obtained by Hammett include σp values ​​and σm values, most of which can be found in general books. For example, J.A. Dean, ed., "Lange's Handbook of Chemistry", 12th edition, 1979 (Mc Graw-Hill) or "Field of Chemistry", Supplement No. 122, pp. 96-103, 1979 (Nankodo), Chem. Rev., 1991, Vol. 91, pp. 165-195, etc., which are more detailed.

[0265] In the present invention, a substituent having a Hammett σp value of 0.2 or more can be exemplified as an electron-withdrawing group. The σp value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more. The upper limit is not particularly limited, but is preferably 0.80 or less.

[0266] Specific examples include cyano (0.66), carboxyl (-COOH: 0.45), alkoxycarbonyl (-COOMe: 0.45), aryloxycarbonyl (-COOPh: 0.44), carbamoyl (-CONH 2 :0.36)、alkylcarbonyl(-COMe:0.50)、arylcarbonyl(-COPh:0.43)、alkylsulfonyl(-SO 2 Me: 0.72) or arylsulfonyl (-SO 2 Ph: 0.68) etc. In this specification, Me represents a methyl group and Ph represents a phenyl group. The values ​​in parentheses are σp values ​​of representative substituents extracted from Chem. Rev., 1991, Vol. 91, pp. 165-195.

[0267] R 2 and R 3 When bonding forms a ring, preferably a 5 to 7-membered ring (preferably a 5 to 6-membered ring) is formed. As the formed ring, it is usually preferred that the merocyanine dye is used as the ring of the acidic core, as its specific example, can refer to paragraph number 0026 of Japanese Patent Publication No. 2009-263614, this content is introduced into the present application specification.

[0268] In addition, although it is impossible to define the R 2 and R 3 σp value, but in the present invention, it is regarded as R 2 and R 3 The partial structure of each ring is replaced and defined as the σp value when the ring is formed. For example, when forming a 1,3-indandione ring, it is considered that R 2 and R 3 are substituted by benzoyl groups.

[0269] As R 2 and R 3The ring formed by bonding is preferably a 1,3-dicarbonyl core, a pyrazolone core, a 2,4,6-triketohexahydropyrimidine core (including thione forms), a 2-thio-2,4-thiazolidinedione core, a 2-thio-2,4-oxazolidinedione core, a 2-thio-2,5-thiazolidinedione core, a 2,4-thiazolidinedione core, a 2,4-imidazolidinedione core, a 2-thio-2,4-imidazolidinedione core, a 2-imidazolin-5-one core, a 3,5-pyrazolidinedione core, a benzothiophene-3-one core, or an indenone core, and more preferably a 1,3-dicarbonyl core, a 2,4,6-triketohexahydropyrimidine core (including thione forms), a 3,5-pyrazolidinedione core, a benzothiophene-3-one core, or an indenone core.

[0270] R 3 A heterocyclic ring is particularly preferred.

[0271] The two R in the general formula (1) 2 can be the same or different from each other, and the two R 3 They may be the same as or different from each other.

[0272] R 4 The alkyl, aryl, heteroaryl and R 1a and R 1b The substituents described in have the same meanings and the same preferred ranges. 4 The substituents of the substituted boron are the same as those mentioned above. 2 and R 3 The substituents of have the same meanings, and are preferably alkyl, aryl, or heteroaryl. 4 The metal atom represented is preferably a transition metal, magnesium, aluminum, calcium, barium, zinc, or tin, more preferably aluminum, zinc, tin, vanadium, iron, cobalt, nickel, copper, palladium, iridium, or platinum, and particularly preferably aluminum, zinc, vanadium, iron, copper, palladium, iridium, or platinum.

[0273] R 4 Can also be selected from R 1a , R 1b and R 3 One or more covalent bonds or coordinate bonds are present.

[0274] In the general formula (1), the two R 4 They may be the same as or different from each other.

[0275] For details of the compound represented by the general formula (1), reference may be made to paragraphs 0017 to 0047 of Japanese Patent Application Publication No. 2009-263614, which are incorporated herein by reference. Specific examples of the compound represented by the general formula (1) include compounds described in paragraphs 0049 to 0058 of Japanese Patent Application Publication No. 2009-263614, which are incorporated herein by reference.

[0276] 《Polymeric Compounds》

[0277] The coloring composition of the present invention contains a polymerizable compound having an ethylenically unsaturated bond. The polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups, and further preferably having three or more groups. The upper limit is, for example, preferably 15 or less, more preferably 6 or less. As the group having an ethylenically unsaturated bond, vinyl, (meth)allyl, (meth)acryloyl, etc. can be cited.

[0278] The polymerizable compound may be, for example, a monomer, a prepolymer (ie, a dimer, a trimer), an oligomer, or a mixture thereof, or any chemical form of such polymers. The polymerizable compound is preferably a monomer.

[0279] The molecular weight of the polymerizable compound is preferably 100 to 3,000, more preferably 250 to 1,500.

[0280] The polymerizable compound is preferably a tri- to penta-functional (meth)acrylate compound, and more preferably a tri- to hexa-functional (meth)acrylate compound.

[0281] As examples of monomers and prepolymers, unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or their esters, amides, and such polymers can be cited, preferably esters of unsaturated carboxylic acids and aliphatic polyol compounds, and amides of unsaturated carboxylic acids and aliphatic polyamine compounds, and such polymers. In addition, addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl, amine, sulfhydryl groups and monofunctional or polyfunctional isocyanates or epoxies, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids, etc. can also be appropriately used. In addition, the reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as an isocyanate group or an epoxy group and monofunctional or polyfunctional alcohols, amines, and thiols, and the reaction products of unsaturated carboxylic acid esters or amides having a dissociative substituent such as a halogen group or a tosyloxy group and monofunctional or polyfunctional alcohols, amines, and thiols can also be used appropriately. In addition, the above-mentioned unsaturated carboxylic acids can be replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, and the like.

[0282] As these specific compounds, compounds described in paragraphs

[0095] to

[0108] of JP-A-2009-288705 can also be appropriately used in the present invention.

[0283] In the present invention, the polymerizable compound is a compound having one or more groups having an ethylenically unsaturated bond and preferably having a boiling point of 100° C. or higher at normal pressure. Examples thereof include compounds described in paragraph 0227 of Japanese Unexamined Patent Application Publication No. 2013-29760 and paragraphs 0254 to 0257 of Japanese Unexamined Patent Application Publication No. 2008-292970, and the contents are incorporated herein by reference.

[0284] The polymerizable compound is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310; manufactured by NIPPON KAYAKU CO., LTD.), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA; manufactured by NIPPON KAYAKU CO., LTD., A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), and a structure in which the (meth)acryloyl group thereof is connected through an ethylene glycol or propylene glycol residue (for example, SR454 and SR499 commercially available from SARTOMER Company, Inc.). Such oligomer types may also be used. In addition, NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), KAYARAD RP-1040 (manufactured by NIPPON KAYAKU CO., LTD.), and the like may also be used.

[0285] Preferred embodiments of the polymerizable compound are shown below.

[0286] The polymerizable compound may also have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. As the polymerizable compound having an acid group, an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferred, and a polymerizable compound having an acid group by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound is more preferred, and it is particularly preferred that the aliphatic polyhydroxy compound in the ester is pentaerythritol and / or dipentaerythritol. As commercially available products, for example, ARONIX TO-2349, M-305, M-510, and M-520 manufactured by TOAGOSEICO., LTD. can be cited.

[0287] The acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mgKOH / g, and particularly preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the developing dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curing property is excellent.

[0288] As the polymerizable compound, a compound having a structure derived from a cyclic ester is also a preferred embodiment. Examples of the cyclic ester include caprolactone and valerolactone, and caprolactone is preferred.

[0289] The compound having a caprolactone-derived structure is not particularly limited as long as it has a caprolactone-derived structure in the molecule, and examples thereof include ε-caprolactone-modified multifunctional (meth)acrylates obtained by esterifying a polyol such as trimethylolethane, di-trimethylolethane, trimethylolpropane, di-trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerol, diglycerol, trimethylolmelamine with (meth)acrylic acid and ε-caprolactone. Among them, a compound having a caprolactone-derived structure represented by the following general formula (Z-1) is preferred.

[0290] [Chemical formula 12]

[0291]

[0292] In the general formula (Z-1), all six Rs are groups represented by the following general formula (Z-2), or one to five of the six Rs are groups represented by the following general formula (Z-2), and the rest are groups represented by the following general formula (Z-3).

[0293] [Chemical formula 13]

[0294]

[0295] In the general formula (Z-2), R 1 represents a hydrogen atom or a methyl group, m represents a number of 1 or 2, and "*" represents a bonding bond.

[0296] [Chemical formula 14]

[0297]

[0298] In the general formula (Z-3), R 1 represents a hydrogen atom or a methyl group, and "*" represents a bonding bond.

[0299] The polymerizable compound having a caprolactone-derived structure is commercially available, for example, from NIPPON KAYAKU CO., LTD. as the KAYARAD DPCA series, and DPCA-20 (in the above formulas (Z-1) to (Z-3), m = 1, the number of groups represented by the formula (Z-2) = 2, R 1 All of the compounds are hydrogen atoms), DPCA-30 (in the above formulas (Z-1) to (Z-3), m = 1, the number of groups represented by formula (Z-2) = 3, R 1 All of the compounds are hydrogen atoms), DPCA-60 (in the above formulas (Z-1) to (Z-3), m = 1, the number of groups represented by formula (Z-2) = 6, R 1 All of the compounds are hydrogen atoms), DPCA-120 (in the above formulas (Z-1) to (Z-3), m = 2, the number of groups represented by formula (Z-2) = 6, R 1 All hydrogen atoms) etc.

[0300] As the polymerizable compound, a compound represented by the following general formula (Z-4) or (Z-5) may be used.

[0301] [Chemical formula 15]

[0302]

[0303] In the general formulae (Z-4) and (Z-5), E each independently represents -((CH 2 ) y CH 2 O)-, or -((CH 2 ) y CH(CH 3 )O)-, y each independently represents an integer of 0 to 10, and X each independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxyl group.

[0304] In the general formula (Z-4), the total number of the (meth)acryloyl groups is 3 or 4, m each independently represents an integer of 0 to 10, and the total number of m is an integer of 0 to 40.

[0305] In the general formula (Z-5), the total number of the (meth)acryloyl groups is 5 or 6, n each independently represents an integer of 0 to 10, and the total number of n is an integer of 0 to 60.

[0306] In the general formula (Z-4), m is preferably an integer of 0-6, and more preferably an integer of 0-4.

[0307] Furthermore, the total of each m is preferably an integer of 2-40, more preferably an integer of 2-16, and particularly preferably an integer of 4-8.

[0308] In the general formula (Z-5), n is preferably an integer of 0-6, and more preferably an integer of 0-4.

[0309] Furthermore, the total of each n is preferably an integer of 3-60, more preferably an integer of 3-24, and particularly preferably an integer of 6-12.

[0310] Furthermore, in the general formula (Z-4) or the general formula (Z-5), -((CH 2 ) y CH 2 O)-or-((CH 2 ) y CH(CH 3 )O)- is preferably a form in which the terminal on the oxygen atom side is bonded to X.

[0311] The compound represented by the general formula (Z-4) or the general formula (Z-5) may be used alone or in combination of two or more. In particular, in the general formula (Z-5), all six Xs are acryloyl groups, and in the general formula (Z-5), all six Xs are acryloyl groups, and in the general formula (Z-5), the compound is a mixture of a compound in which at least one of the six Xs is preferably a hydrogen atom. By setting such a structure, the developability can be further improved.

[0312] Furthermore, the total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.

[0313] The compound represented by the general formula (Z-4) or the general formula (Z-5) can be synthesized by a conventionally known process: a process of bonding the ring-opening skeleton of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol by a ring-opening addition reaction; and a process of introducing a (meth)acryloyl group by reacting, for example, (meth)acryloyl chloride with the terminal hydroxyl group of the ring-opening skeleton. Each process is a conventionally known process. ， A person skilled in the art can easily synthesize the compound represented by the general formula (Z-4) or (Z-5).

[0314] Among the compounds represented by the general formula (Z-4) or (Z-5), a pentaerythritol derivative and / or a dipentaerythritol derivative is more preferred.

[0315] Specifically, compounds represented by the following formulae (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”) are mentioned, among which exemplified compounds (a), (b), (e) and (f) are preferred.

[0316] [Chemical formula 16]

[0317]

[0318] [Chemical formula 17]

[0319]

[0320] Commercially available products of the polymerizable compound represented by the general formula (Z-4) or (Z-5) include, for example, SR-494, a tetrafunctional acrylate having four vinyloxy chains manufactured by SARTOMER Company, Inc., DPCA-60, a hexafunctional acrylate having six pentyloxy chains manufactured by NIPPONKAYAKU CO., LTD., and TPA-330, a trifunctional acrylate having three isobutyleneoxy chains.

[0321] As the polymerizable compound, urethane acrylates described in Japanese Patent Publication No. 48-41708, Japanese Patent Publication No. 51-37193, Japanese Patent Publication No. 2-32293, and Japanese Patent Publication No. 2-16765, and urethane compounds having an ethylene oxide 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. In addition, by using addition polymerizable compounds having an amino structure and a sulfide structure in the molecule described in Japanese Patent Publication No. 63-277653, Japanese Patent Publication No. 63-260909, and Japanese Patent Publication No. 1-105238, a coloring composition having a very excellent photosensitivity can be obtained.

[0322] Commercially available products include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo-Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nipponkayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Co., Ltd.), and the like.

[0323] In the coloring composition of the present invention, the content of the polymerizable compound relative to the total solid content of the coloring composition is preferably 0.1 to 40% by mass. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and more preferably 20% by mass or less. The polymerizable compound can be used alone or in combination of two or more. When two or more are used in combination, the total amount is preferably set to the above range.

[0324] 《Multifunctional thiol compounds》

[0325] The colored curable composition of the present invention may contain a polyfunctional thiol compound having two or more mercapto groups in the molecule for the purpose of promoting the reaction of the polymerizable compound, etc. The polyfunctional thiol compound is preferably a secondary alkane thiol, and particularly preferably a compound having a structure represented by the following general formula (T1).

[0326] General formula (T1)

[0327] [Chemical formula 18]

[0328]

[0329] (In formula (T1), n ​​represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.)

[0330] In the above general formula (T1), the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, n is 2, and L is particularly preferably an alkylene group having 2 to 12 carbon atoms. Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and compounds represented by formula (T2) are particularly preferred. These polyfunctional thiols may be used alone or in combination of multiple types.

[0331] [Chemical formula 19]

[0332]

[0333] When the coloring composition of the present invention contains a polyfunctional thiol compound, the content of the polyfunctional thiol compound relative to the total solid content of the coloring composition is preferably 0.3 to 8.9 mass %, more preferably 0.8 to 6.4 mass %. In addition, the polyfunctional thiol may be added for the purpose of improving stability, odor, resolution, developability, adhesion, etc.

[0334] 《<Compounds having epoxy groups>》

[0335] The colored composition of the present invention also preferably contains a compound having an epoxy group.

[0336] As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferred. The compound having 2 to 10 epoxy groups in one molecule is preferred, 2 to 5 epoxy groups are more preferred, and 3 epoxy groups are particularly preferred.

[0337] The compound having an epoxy group may also be a compound having a structure in which two benzene rings are linked by a hydrocarbon group. The hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms.

[0338] The epoxy group is preferably connected via a linking group. Examples of the linking group include a group selected from an alkylene group, an arylene group, -O-, a structure represented by -NR'- (R' represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, preferably a hydrogen atom), -SO 2 -, -CO-, -O- and -S-.

[0339] The epoxy equivalent (=molecular weight of the compound having an epoxy group / number of epoxy groups) of the compound having an epoxy group is preferably 500 g / eq or less, more preferably 100 to 400 g / eq, and even more preferably 100 to 300 g / eq.

[0340] The compound having an epoxy group may be a low molecular weight compound (e.g., a molecular weight of less than 2000, or even a molecular weight of less than 1000), or a high molecular weight compound (e.g., a molecular weight of 1000 or more, or a weight average molecular weight of 1000 or more in the case of a polymer). The weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000.

[0341] As the compound having an epoxy group, compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, paragraphs 0147 to 0156 of JP-A-2014-043556, and paragraphs 0085 to 0092 of JP-A-2014-089408 can be used. These contents are incorporated into the present specification.

[0342] Examples of commercially available products include "EHPE3150 (manufactured by DAICEL CHEMICAL INDUSTRIES, CO., LTD.)" and "EPICLON N660 (manufactured by DIC Corporation)".

[0343] When the 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 relative to the total solid content of the coloring composition. The lower limit is, for example, more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is, for example, more preferably 30% by mass or less, and more preferably 20% by mass or less. The compound having an epoxy group can be used alone or in combination of two or more. When two or more are used in combination, the total amount is preferably set to the above range.

[0344] 《Curing compound having specific groups》

[0345] The coloring composition of the present invention contains one or more selected from the group consisting of fluorine atoms, silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms, and a curable compound (hereinafter also referred to as curable compound A) which preferably also has a curable functional group.

[0346] The curable compound A is preferably a curable compound containing a fluorine atom and a curable functional group. According to this embodiment, a cured film having a low reflectivity can be easily formed.

[0347] In addition, in the present invention, curable compound A is a compound having the above-mentioned polymerizable compound, an epoxy group, and a compound different from the resin described later. In the present invention, a compound containing a fluorine atom and an ethylenically unsaturated bond is considered to be included in curable compound A. In addition, a compound containing a fluorine atom and an epoxy group is considered to be included in curable compound A.

[0348] The curable compound A may be a monomer or a polymer. When the curable compound A is a polymer, it is preferably a (meth)acrylate polymer, and more preferably a fluorine-containing (meth)acrylate polymer.

[0349] As one preferred embodiment of the curable compound A, a compound having no benzene ring structure is mentioned, and a compound having a fluorine atom and having no benzene ring structure is preferred.

[0350] In addition, the curable compound A does not contain a silane coupling agent described below.

[0351] When the curable compound A contains a fluorine atom, the curable compound preferably has at least one selected from the group consisting of an alkylene group substituted with a fluorine atom, an alkyl group substituted with a fluorine atom, and an aryl group substituted with a fluorine atom.

[0352] The alkylene group substituted with a fluorine atom is preferably a linear, branched or cyclic alkylene group in which at least one hydrogen atom is substituted with a fluorine atom.

[0353] The alkyl group substituted with a fluorine atom is preferably a linear, branched or cyclic alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

[0354] The number of carbon atoms in the alkylene group substituted with a fluorine atom and the alkyl group substituted with a fluorine atom is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.

[0355] The aryl group substituted with a fluorine atom is preferably an aryl group directly substituted with a fluorine atom, or substituted with a trifluoromethyl group.

[0356] The alkylene group substituted with a fluorine atom, the alkyl group substituted with a fluorine atom, and the aryl group substituted with a fluorine atom may further contain a substituent other than a fluorine atom.

[0357] As specific examples of the alkyl group substituted with a fluorine atom and the aryl group substituted with a fluorine atom, for example, reference can be made to paragraphs 0266 to 0272 of JP-A-2011-100089, the contents of which are incorporated herein.

[0358] In the curable compound A, it is preferred that an "alkylene group substituted with a fluorine atom" and an "oxygen atom" are connected to the group X (the group (repeating unit) represented by the formula (X)), and it is more preferred that a perfluoroalkylene ether group be contained.

[0359] Formula (X)-(L A -O)-

[0360] The above L A represents an alkylene group substituted with a fluorine atom. The number of carbon atoms in the alkylene group is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 5. The alkylene group substituted with a fluorine atom may contain an oxygen atom.

[0361] Furthermore, the alkylene group substituted with a fluorine atom may be linear or branched.

[0362] The perfluoroalkylene ether group means that the above L A The perfluoroalkylene group is a group in which all hydrogen atoms in the alkylene group are substituted with fluorine atoms.

[0363] The groups (repeating units) represented by formula (X) may be repeatedly linked. The number of the repeating units is not particularly limited, but is preferably 1 to 50, more preferably 1 to 20, from the viewpoint of achieving more excellent effects of the present invention.

[0364] That is, a group represented by formula (X-1) is preferred.

[0365] Formula (X-1)-(L A -O) r -

[0366] In formula (X-1), L A As described above, r represents the number of repeating units, and its preferred range is as described above.

[0367] In addition, multiple-(L A -O)-L A Can be the same or different.

[0368] When the curable compound A contains a silicon atom, the curable compound preferably has an alkylsilyl group, an arylsilyl group, or the following partial structure (S) (* represents a bonding site to other atoms). Partial structure (S)

[0369] [Chemical formula 20]

[0370]

[0371] The total number of carbon atoms in the alkyl chain of the alkylsilyl group is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6. An alkylsilyl group and a trialkylsilyl group are preferred.

[0372] Examples of the aryl group in the arylsilyl group include a phenyl group.

[0373] When the above-mentioned partial structure (S) is included, the partial structure (s) may also be included to form a ring structure. The partial structure (S) preferably used in the present invention is preferably -Si(R) 2 -O-Si(R) 2 -(R is an alkyl group having 1 to 3 carbon atoms), alkoxysilyl group. Examples of the structure including the partial structure (S) include paragraphs 0277 to 0279 of JP-A-2011-100089, the contents of which are incorporated herein.

[0374] When the curable compound A contains a linear alkyl group having 8 or more carbon atoms, the linear alkyl group preferably has 8 to 30 carbon atoms, and more preferably has 12 to 20 carbon atoms.

[0375] When the curable compound A contains a branched alkyl group having 3 or more carbon atoms, the branched alkyl group preferably has 3 to 20 carbon atoms, and more preferably has 5 to 15 carbon atoms. The branched alkyl group having 3 or more carbon atoms preferably has -CH(CH 3 ) 2 、-C(CH 3 ) 3 .

[0376] The curable compound A may have at least one selected from the group consisting of a fluorine atom, a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a branched alkyl group having 3 or more carbon atoms, or may have at least two selected from the group consisting of a fluorine atom, a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a branched alkyl group having 3 or more carbon atoms. Furthermore, the curable compound A may contain a combination of at least one selected from the group consisting of a fluorine atom, a silicon atom, a linear alkyl group having 8 or more carbon atoms, and a branched alkyl group having 3 or more carbon atoms.

[0377] The curable compound A has one or more curable functional groups, or two or more curable functional groups. The curable functional groups may be one or more. The curable functional groups may be thermosetting functional groups or photocurable functional groups.

[0378] The curable functional group is preferably one or more selected from the group consisting of a (meth)acryloyloxy group, an epoxy group, an oxetane group, an isocyanate group, a hydroxyl group, an amine group, a carboxyl group, a thiol group, an alkoxysilyl group, a hydroxymethyl group, a vinyl group, a (meth)acrylamide group, a vinyl group, and a maleimide group, and more preferably one or more selected from the group consisting of a (meth)acryloyloxy group, an epoxy group, and an oxetane group.

[0379] When an ethylenically unsaturated group is contained as a curable functional group, the amount of the ethylenically unsaturated group in the curable compound A is preferably 0.1 to 10.0 mol / g, and more preferably 1.0 to 5.0 mol / g.

[0380] When the curable compound A is a monomer, the number of one or more groups selected from the group consisting of fluorine atoms, silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms in one molecule is preferably 1 to 20, more preferably 3 to 15.

[0381] The number of curable functional groups in one molecule is not particularly limited, but is preferably 2 or more, and more preferably 4 or more, from the viewpoint of more excellent effects of the present invention. The upper limit is not particularly limited, but is often 10 or less, and more often 6 or less.

[0382] When the curable compound A is a polymer, the polymer preferably has at least one of a repeating unit represented by the following formula (B1), a repeating unit represented by the following formula (B2), and a repeating unit represented by the following formula (B3).

[0383] [Chemical formula 21]

[0384]

[0385] In formulas (B1) to (B3), R 1 ~R 11 L each independently represents a hydrogen atom, an alkyl group, or a halogen atom. 1 ~L 4 Each independently represents a single bond or a divalent linking group. 1 represents a (meth)acryloyloxy group, an epoxy group, or an oxetane group, X 2 represents an alkyl group substituted with a fluorine atom, an aryl group substituted with a fluorine atom, an alkylsilyl group, an arylsilyl group, a group of the above partial structure (S), a linear alkyl group having 8 or more carbon atoms, or a branched alkyl group having 3 or more carbon atoms, and X 3 It represents the repeating unit represented by formula (X-1).

[0386] In formulas (B1) to (B3), R is preferably 1 ~R 11Each independently represents a hydrogen atom or an alkyl group. 1 ~R 11 When it represents an alkyl group, it is preferably an alkyl group having 1 to 3 carbon atoms. 1 ~R 11 When it represents a halogen atom, it is preferably a fluorine atom.

[0387] In formulas (B1) to (B3), when L 1 ~L 4 When a divalent linking group is represented, examples of the divalent linking group include an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, -NR 12 -、-CONR 12 -、-CO-、-CO 2 -、SO 2 NR 12 -、-O-、-S-、-SO 2 Among them, preferably at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms which may be substituted by a halogen atom and an arylene group having 6 to 12 carbon atoms which may be substituted by a halogen atom, or a group selected from these groups and -NR 12 -、-CONR 12 -、-CO-、-CO 2 -、SO 2 NR 12 -, -O-, -S-, and SO 2 -, more preferably an alkylene group having 2 to 10 carbon atoms which may be substituted with a halogen atom, -CO 2 -、-O-、-CO-、-CONR 12 -, or a group composed of a combination of these groups. 12 represents a hydrogen atom or a methyl group.

[0388] Specific examples of the repeating unit represented by formula (B1) include the following, but the present invention is not limited thereto.

[0389] [Chemical formula 22]

[0390]

[0391] Furthermore, as specific examples of the repeating unit represented by the above formula (B2), the following examples can be cited, but the present invention is not limited thereto. 1 Represents a hydrogen atom, -CH 3 , -F, or -CF 3 , more preferably a hydrogen atom or a methyl group. Me represents a methyl group.

[0392] In addition, the repeating unit described in paragraph 0073 of JP-A-2015-017244 can also be mentioned. This content is incorporated into the present specification.

[0393] [Chemical formula 23]

[0394]

[0395] Furthermore, specific examples of the repeating unit represented by the above formula (B3) include the following, but the present invention is not limited thereto.

[0396] [Chemical formula 24]

[0397]

[0398] The content of the repeating unit represented by the formula (B1) is preferably 30 to 95 mol%, more preferably 45 to 90 mol%, relative to the total repeating units in the curable compound A. The content of the repeating unit represented by the formula (B1) is preferably 30 mol% or more, more preferably 45 mol% or more, relative to the total repeating units in the curable compound A.

[0399] The total content of the repeating unit represented by the above formula (B2) and the repeating unit represented by the formula (B3) is preferably 5 to 70 mol%, more preferably 10 to 60 mol%, relative to the total repeating units in the curable compound A. The total content of the repeating unit represented by the above formula (B2) and the repeating unit represented by the formula (B3) is preferably 5 mol% or more, more preferably 10 mol% or more, relative to the total repeating units in the curable compound A.

[0400] In addition, when the repeating unit represented by formula (B2) is not included but the repeating unit represented by formula (B3) is included, it is preferred that the content of the repeating unit represented by formula (B2) is set to 0 mol% and the content of the repeating unit represented by formula (B3) is within the above range.

[0401] Furthermore, curable compound A may have other repeating units other than the repeating units represented by the above formulae (B1) to (B3). The content of other repeating units relative to the total repeating units in curable compound A is preferably 10 mol % or less, more preferably 1 mol % or less.

[0402] When curable compound A is a polymer, the weight average molecular weight (Mw: polystyrene conversion) is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. When curable compound A is a polymer, the weight average molecular weight is preferably 5,000 or more, more preferably 7,000 or more.

[0403] Furthermore, when the curable compound A is a polymer, the dispersion degree (weight average molecular weight / number average molecular weight) is preferably 1.80 to 3.00, and more preferably 2.00 to 2.90.

[0404] As commercially available products of the curable compound A, for example, as a curable compound containing fluorine atoms, MEGAFAC RS-72-K, MEGAFAC RS-75, MEGAFAC RS-76-E, MEGAFAC RS-76-NS, and MEGAFAC RS-77 manufactured by DICCORPORATION can be used; as a curable compound having a silicon atom, BYK-UV 3500, BYK-UV 3530, and BYK-UV3570 manufactured by BYK-Chemie GmbH; and TEGO Rad 2010, TEGO Rad 2011, TEGO Rad 2100, TEGO Rad 2200N, TEGO Rad 2250, TEGO Rad 2300, TEGO Rad 2500, TEGORad 2600, TEGO Rad 2650, and TEGO Rad 2700 manufactured by EVONIK can be used.

[0405] The curable compound A is preferably capable of forming a film having a refractive index of 1.1 to 1.5 at a wavelength of 550 nm by itself. That is, the refractive index of a film formed only from the curable compound A is preferably 1.1 to 1.5 at a wavelength of 550 nm.

[0406] The preferred range of the refractive index is preferably 1.2 to 1.5, more preferably 1.3 to 1.5, from the viewpoint of low reflectivity of the light-shielding film.

[0407] The content of the curable compound A is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass, and further preferably 1.0 to 10% by mass, based on the total solid content in the colored composition.

[0408] The coloring composition may contain one type of curable compound A alone, or may contain two or more types. When the coloring composition contains two or more types of curable compounds A, the total amount thereof is preferably within the above range.

[0409] Resin

[0410] The coloring composition of the present invention preferably contains a resin. The resin is formulated for purposes such as dispersing or bonding a colorant in the composition. In addition, a resin used mainly for dispersing a colorant is also referred to as a dispersant. However, this use of the resin is only an example, and the resin may also be used for purposes other than this use.

[0411] The weight average molecular weight (Mw) of the resin is preferably 2,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 3,000 or more, more preferably 5,000 or more.

[0412] In the coloring composition of the present invention, the content of the resin is preferably 10 to 80% by mass of the total solid content of the coloring composition, and more preferably 20 to 60% by mass. The composition of the present invention may contain only one resin or two or more. When containing two or more, the total amount is preferably within the above range.

[0413] 《<Alkali-soluble resin>》

[0414] The coloring composition of the present invention contains an alkali-soluble resin as a resin. By containing the alkali-soluble resin, the developability and pattern forming properties are improved. In addition, the alkali-soluble resin can also be used as a dispersant and a binder.

[0415] The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5000 to 100,000, and the number average molecular weight (Mn) is preferably 1000 to 20,000.

[0416] The alkali-soluble resin may be a linear organic high molecular weight polymer, and may be appropriately selected from alkali-soluble resins having at least one group promoting alkali solubility in the molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain).

[0417] As the alkali-soluble resin, from the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred, and from the viewpoint of controlling developability, acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred.

[0418] As the group promoting alkali solubility (hereinafter also referred to as acid group), for example, carboxyl group, phosphoric acid group, sulfonic acid group, phenolic hydroxyl group, etc. can be mentioned, preferably a group soluble in an organic solvent and can be developed using a weak alkaline aqueous solution, and as a particularly preferred group, (meth) acrylic acid can be mentioned. These acid groups can be only one kind or two or more kinds.

[0419] When producing the alkali-soluble resin, for example, a known method using a free radical polymerization method can be applied. When producing the alkali-soluble resin using the free radical polymerization method, polymerization conditions such as temperature, pressure, type and amount of free radical initiator, type of solvent, etc. can be easily set by a person skilled in the art, or the conditions can be set experimentally.

[0420] As the alkali-soluble resin, a polymer having a carboxylic acid in the side chain is preferred, and examples thereof include alkali-soluble phenolic resins such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, and novolac resins; as well as acidic cellulose derivatives having carboxyl groups in the side chains, and polymers obtained by adding anhydrides to polymers having hydroxyl groups. In particular, copolymers of (meth)acrylic acid and other monomers copolymerizable therewith are suitable as alkali-soluble resins. As other monomers copolymerizable with (meth)acrylic acid, examples thereof include alkyl (meth)acrylates, aryl (meth)acrylates, vinyl compounds, and the like. Examples of the alkyl (meth)acrylate and aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, toluene (meth)acrylate, naphthyl (meth)acrylate, and cyclohexyl (meth)acrylate. Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomers, and polymethyl methacrylate macromonomers. Examples of the N-substituted maleimide monomer described in Japanese Patent Application Laid-Open No. 10-300922 include N-phenylmaleimide and N-cyclohexylmaleimide. Moreover, the other monomer copolymerizable with these (meth)acrylic acids may be only one kind or two or more kinds.

[0421] In addition, in order to improve the crosslinking efficiency of the coloring composition in the present invention, an alkali-soluble resin having a polymerizable group can be used. Examples of the polymerizable group include (meth)allyl and (meth)acryloyl groups. Alkali-soluble resins having polymerizable groups, alkali-soluble resins containing polymerizable groups in side chains, and the like are useful.

[0422] Examples of the alkali-soluble resin containing a polymerizable group include DIANAL NR series (manufactured by MITSUBISHIRAYON SHARES CO., LTD.), Photomer 6173 (polyurethane acrylic oligomer containing COOH, manufactured by Diamond Shamrock Co., LTD.), VISCOAT R-264, KS RESIST 106 (both manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (both manufactured by DAICEL CHEMICAL INDUSTRIES CO., LTD.), Ebecryl 3800 (manufactured by DAICEL UC B CO., LTD.), and Akurikiua-RD-F8 (manufactured by NIPPON SHOKUBAI CO., LTD.).

[0423] As the alkali-soluble resin, benzyl (meth)acrylate / (meth)acrylic acid copolymer, benzyl (meth)acrylate / (meth)acrylic acid / (meth)acrylic acid-2-hydroxyethyl copolymer, and a multi-component copolymer comprising benzyl (meth)acrylate / (meth)acrylic acid / other monomers can be preferably used. In addition, copolymers obtained by copolymerizing 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymers described in Japanese Patent Application Laid-Open No. 7-140654, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymers, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymers, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymers, and the like can also be preferably used.

[0424] Furthermore, as a commercially available product, for example, FF-426 (manufactured by FUJIKURA KASEI CO., LTD.) etc. can also be used.

[0425] The alkali-soluble resin also preferably includes a polymer (a) obtained by polymerizing monomer components including a compound represented by the following general formula (ED1) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers").

[0426] [Chemical formula 25]

[0427]

[0428] In the general formula (ED1), R 1 and R 2 Each independently represents a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

[0429] [Chemical formula 26]

[0430]

[0431] In the general formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. Specific examples of the general formula (ED2) can be found in Japanese Unexamined Patent Application Publication No. 2010-168539.

[0432] In the general formula (ED1), as R 1 and R 2 The hydrocarbon group having 1 to 25 carbon atoms which may have a substituent is not particularly limited, and examples thereof include straight-chain or branched alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, and 2-ethylhexyl; aryl groups such as phenyl; alicyclic groups such as cyclohexyl, tert-butylcyclohexyl, dicyclopentadienyl, tricyclodecyl, isobornyl, adamantyl, and 2-methyl-2-adamantyl; alkyl groups substituted with alkoxy groups such as 1-methoxyethyl and 1-ethoxyethyl; alkyl groups substituted with aryl groups such as benzyl, etc. Among them, in particular, from the viewpoint of heat resistance, substituents of primary or secondary carbons which are not easily removed by acid or heat such as methyl, ethyl, cyclohexyl, and benzyl are preferred.

[0433] As a specific example of the ether dimer, for example, reference can be made to paragraph 0317 of Japanese Patent Publication No. 2013-29760, which is incorporated herein by reference. The ether dimer may be only one kind or two or more kinds. The structure derived from the compound represented by the general formula (ED) may also be copolymerized with other monomers.

[0434] The alkali-soluble resin may contain a structural unit derived from a compound represented by the following formula (X).

[0435] [Chemical formula 27]

[0436]

[0437] 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, R 3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may contain a benzene ring. n represents an integer of 1 to 15.

[0438] In the above formula (X), R 2 The number of carbon atoms of the alkylene group is preferably 2 to 3. 3 The number of carbon atoms of the alkyl group is 1 to 20, more preferably 1 to 10, and R 3 The alkyl group may also contain a benzene ring. 3 Examples of the benzene ring-containing alkyl group represented by include benzyl and 2-phenyl(iso)propyl.

[0439] Specific examples of the alkali-soluble resin include the following.

[0440] [Chemical formula 28]

[0441]

[0442] For the alkali-soluble resin, reference may be made to the description in paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of the specification of US Patent Application Publication No. 2012 / 0235099), and the contents are incorporated into the specification of the present application.

[0443] In addition, the copolymer (B) described in paragraphs 0029 to 0063 of JP-A-2012-32767 and the alkali-soluble resin used in the examples, the binder resin described in paragraphs 0088 to 0098 of JP-A-2012-208474 and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP-A-2012-137531 and the binder resin used in the examples, the binder resin described in paragraphs 0132 to 0143 of JP-A-2013-024934 and the binder resin used in the examples, the binder resin described in paragraphs 0092 to 0098 of JP-A-2011-242752 and the binder resin used in the examples, and the binder resin described in paragraphs 0030 to 0072 of JP-A-2012-032770 can also be used. These contents are incorporated into the description of this application.

[0444] The acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g. The lower limit is more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more. The upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, particularly preferably 150 mgKOH / g or less, and further preferably 120 mgKOH / g or less.

[0445] The content of the alkali-soluble resin is preferably 0.1 to 20% by mass relative to the total solid content of the coloring composition. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, and particularly preferably 3% by mass or more. The upper limit is more preferably 12% by mass or less, and further preferably 10% by mass or less. The coloring composition of the present invention may contain only one alkali-soluble resin or two or more. When containing two or more, the total amount is preferably within the above range.

[0446] 《<Dispersant>》

[0447] The coloring composition of the present invention may contain a dispersant as a resin.

[0448] The dispersant preferably contains one or more selected from the group consisting of acidic resins, basic resins, and bivalent resins.

[0449] In the present invention, the acidic resin refers to a resin having an acid group, wherein the acid value of the resin is 5 mgKOH / g or more and the amine value is less than 5 mgKOH / g. The acidic resin preferably does not have a basic group.

[0450] Preferred examples of the acid group of the acidic resin include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. The carboxyl group is used.

[0451] The acidic resin may be used in the form of a block copolymer, a random copolymer or a graft copolymer.

[0452] The acid value of the acidic resin is preferably 5 to 200 mgKOH / g, more preferably 10 to 150 mgKOH / g, and even more preferably 50 to 150 mgKOH / g.

[0453] In the present invention, the basic resin refers to a resin having a basic group, wherein the resin refers to a resin having an amine value of 5 mgKOH / g or more and an acid value of less than 5 mgKOH / g. The basic resin preferably does not have an acid group.

[0454] As the basic group of the basic resin, an amine group is preferred. The basic resin may be any of a block copolymer, a random copolymer, and a graft copolymer.

[0455] The amine value of the basic resin is preferably 5 to 200 mgKOH / g, more preferably 5 to 150 mgKOH / g, and even more preferably 5 to 100 mgKOH / g.

[0456] In the present invention, the bifunctional resin refers to a resin having an acid group and a basic group, wherein the acid value of the resin is 5 mgKOH / g or more, and the amine value is 5 mgKOH / g or more. The acid group may be the acid group as described above, preferably a carboxyl group. The basic group is preferably an amine group. The bifunctional resin may also be a block copolymer, a random copolymer, or a graft copolymer.

[0457] The acid value of the bifunctional resin is preferably 5 mgKOH / g or more and the amine value is preferably 5 mgKOH / g or more. The acid value is preferably 5 to 200 mgKOH / g, more preferably 10 to 200 mgKOH / g, further preferably 30 to 200 mgKOH / g, and particularly preferably 30 to 180 mgKOH / g. The amine value is preferably 5 to 200 mgKOH / g, more preferably 10 to 150 mgKOH / g, and particularly preferably 10 to 130 mgKOH / g.

[0458] The ratio of the acid value to the amine value of the bivalent resin is preferably 1:3 to 3:1, more preferably 1:2 to 2:1. When the ratio of the acid value to the amine value is within the above range, both the dispersibility and the developability of the colorant can be more effectively achieved.

[0459] When an acidic resin, a basic resin and an amphoteric resin are used in combination, the basic resin is preferably 10 to 150 parts by mass, and the amphoteric resin is preferably 30 to 170 parts by mass relative to 100 parts by mass of the acidic resin. The basic resin is more preferably 30 to 130 parts by mass, and further preferably 50 to 110 parts by mass. The amphoteric resin is more preferably 50 to 150 parts by mass, and further preferably 90 to 150 parts by mass. According to this embodiment, the above-mentioned effect can be obtained more effectively. Furthermore, the acidic resin preferably contains 1 to 30% by mass, and more preferably 1 to 20% by mass, relative to the total solid content of the coloring composition. Furthermore, the basic resin preferably contains 1 to 30% by mass, and more preferably 1 to 20% by mass, relative to the total solid content of the coloring composition. Furthermore, the amphoteric resin preferably contains 1 to 30% by mass, and more preferably 1 to 20% by mass, relative to the total solid content of the coloring composition.

[0460] The resin can also be obtained as a commercial product. Specific examples thereof include "DA-7301" manufactured by KUSUMOTO Chemicals, LTD.; BYK-Chemie "Disperbyk-101 (polyamide-amine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing acid group), 111 (phosphoric acid dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170, 190 (polymer copolymer)", "BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)" manufactured by GmbH, "EFKA4047, 4050-4010-4165 (polyurethane series), EFKA4330-4340 (block copolymer), 4400-4402 (modified polyacrylate), 5010 (polyester amide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative)" manufactured by EFKA, Co., Inc., "AJISPER PB821, PB822, PB880, PB881", "FLOWLENT G-710 (urethane oligomer)", "POLYFLOW No.50E, No.300 (acrylic copolymer)" manufactured by KYOEISHA Chemical Co., LTD., "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic polycarboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725" manufactured by KUSUMOTOChemicals, LTD., "DEMOL RN, N (naphthalenesulfonic acid formalin condensation product), MS, C, SN-B (aromatic sulfonic acid formalin condensation product)", "HOMOGENOL L-18 (polymer polycarboxylic acid)", "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether)", "ACETAMIN 86 (stearylamine acetate)", "SOLSPERSE 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 12000, 17000, 20000, 27000 (polymer with functional part at the terminal), 24000, 28000, 32000, 38500 (graft copolymer)" manufactured by Nikko Chemicals Co., Ltd."NIKKORT106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate)" manufactured by KAWAKEN FINECHEMICALS CO., LTD. "HINOACT T-8000E" etc.; "Organosiloxane polymer KP-341" manufactured by SHIN-ETSU CHEMICAL CO., LTD.; CO., LTD., nonionic surfactants such as "W001: cationic surfactant", polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, anionic surfactants such as "W004, W005, W017", "EFKA-46, EFKA-47, EFKA-47EA, EFKA polymer 100, EFKA polymer 400, EFKA polymer 401, EFKA polymer 450" manufactured by MORISHITA & CO., LTD., polymer dispersants such as "DISPERSE AID 6, DISPERSE AID 8, DISPERSE AID 15, DISPERSEAID 9100" manufactured by SUN NOPCO LIMITED, "ADEKA PLURONIC L31, F38, L42, L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123", and "IONET (trade name) S-20" manufactured by SANYOCHEMICAL INDUSTRIES, LTD. In addition, ACRYBASE FFS-6752, ACRYBASE FFS-187, ACRYCURE-RD-F8, and CYCLOMER P can also be used.

[0461] In addition, as commercially available products of the bifunctional resin, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2010, DISPERBYK-2012, DISPERBYK-2025, BYK-9076 manufactured by BYK-Chemie GmbH, AJISPER PB821, AJISPER PB822, AJISPER PB881 manufactured by AJINOMOTO FINE-TECHNO Co., Inc., etc. can be mentioned.

[0462] The resin used as the dispersant preferably contains a repeating unit having an acid group. When the resin contains a repeating unit having an acid group, the residue generated on the base of the color pixel can be further reduced when the color pattern is formed by photolithography.

[0463] The repeating unit having an acid group can be constituted using a monomer having an acid group. Examples of the monomer derived from an acid group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having a phosphoric acid group.

[0464] As the vinyl monomer having a carboxyl group, (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, acrylic acid dimer, etc. can be cited. In addition, the addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride, succinic anhydride, and cyclohexane dicarboxylic anhydride, ω-carboxyl-polycaprolactone mono (meth) acrylate, etc. can also be used. In addition, as a precursor of the carboxyl group, anhydride-containing monomers such as maleic anhydride, itaconic anhydride, and citraconic anhydride can be used. Among them, from the perspective of the development removability of the unexposed part, the addition reaction products of monomers having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and cyclic anhydrides such as maleic anhydride, phthalic anhydride, succinic anhydride, and cyclohexane dicarboxylic anhydride are preferred.

[0465] Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamide-2-methylpropanesulfonic acid and the like.

[0466] Examples of the vinyl monomer having a phosphoric acid group include mono(2-acryloyloxyethyl) phosphate and mono(1-methyl-2-acryloyloxyethyl) phosphate.

[0467] In addition, as the repeating unit having an acid group, the description in paragraphs 0067 to 0069 of JP-A-2008-165059 can be referred to, and the contents are included in the present specification.

[0468] Furthermore, the resin used as a dispersant may also be a graft copolymer. The graft copolymer has affinity with the solvent through the graft chain, thereby the dispersibility of the colorant and the dispersion stability after the passage of time are excellent. In addition, the composition has affinity with polymerizable compounds and alkali-soluble resins due to the presence of the graft chain, thereby making it difficult to generate residues during alkaline development.

[0469] In the present invention, the graft copolymer refers to a resin having a graft chain, and the graft chain refers to the portion from the root of the main chain of the polymer to the terminal of the group branching from the main chain.

[0470] In the present invention, as the graft copolymer, a resin having a graft chain having an atomic number of 40 to 10,000 excluding hydrogen atoms is preferred.

[0471] Furthermore, the number of atoms excluding hydrogen atoms per graft chain is preferably 40 to 10,000, more preferably 50 to 2,000, and even more preferably 60 to 500.

[0472] Examples of the main chain structure of the graft copolymer include (meth)acrylic resins, polyester resins, polyurethane resins, polyurea resins, polyamide resins, polyether resins, etc. Among them, (meth)acrylic resins are preferred.

[0473] In order to enhance the interaction between the grafted part and the solvent and thus enhance the dispersibility, the graft chain of the graft copolymer is preferably a graft chain having poly(meth)acrylic acid, polyester, or polyether, and more preferably a graft chain having polyester or polyether.

[0474] The graft copolymer preferably contains 2 to 90% by mass, more preferably 5 to 30% by mass of the repeating unit having a graft chain relative to the total mass of the graft copolymer. If the content of the repeating unit having a graft chain is within this range, the dispersibility of the colorant is good.

[0475] As the macromonomer used when producing the graft copolymer by free radical polymerization, a known macromonomer can be used, and examples thereof include AA-6 (polymethyl methacrylate having a methacryloyl terminal group), AS-6 (polystyrene having a methacryloyl terminal group), AN-6S (copolymer of styrene and acrylonitrile having a methacryloyl terminal group), AB-6 (polybutyl acrylate having a methacryloyl terminal group), PLACCEL FM5 (5 molar equivalent of ε-caprolactone added product of 2-hydroxyethyl methacrylate) and FA10L (10 molar equivalent of ε-caprolactone added product of 2-hydroxyethyl acrylate) manufactured by TOAGOSEI CO., LTD., and polyester-based macromonomers described in Japanese Patent Application Publication No. 2-272009.

[0476] In the present invention, an oligoimine-based graft copolymer containing a nitrogen atom in at least one of the main chain and the side chain can also be preferably used as the graft copolymer.

[0477] As the oligoimine-based graft copolymer, a resin having a repeating unit and a side chain and having a basic nitrogen atom in at least one of the main chain and the side chain is preferred, wherein the repeating unit contains a basic nitrogen atom having a pK a The partial structure X having 14 or less functional groups, wherein the side chain contains an oligomer chain or polymer chain Y having 40 to 10,000 atoms.

[0478] Here, the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom. The oligoimine-based graft copolymer preferably contains a basicity pK b 14 or less nitrogen atoms, preferably containing b The structure of nitrogen atoms with less than 10 atoms.

[0479] In the present invention, the basicity pK b Refers to the pK at water temperature of 25°C b , is one of the indicators used to quantitatively express the alkalinity value, and has the same meaning as the alkalinity constant. Alkalinity pK b and the acid strength pK described below a With pK b =14-pK a relationship.

[0480] The oligoimine graft copolymer preferably has a repeating unit (i) and a side chain (ii), wherein the repeating unit (i) is at least one repeating unit having a basic nitrogen atom selected from the group consisting of a poly(lower alkylene imine) repeating unit, a polyallylamine repeating unit, a polydiallylamine repeating unit, a meta-xylene diamine-epichlorohydrin condensate repeating unit, and a polyvinylamine repeating unit, and has a side chain (ii) bonded to the basic nitrogen atom and having a pK a The partial structure X has 14 or less functional groups, and the side chain (ii) contains an oligomer chain or polymer chain Y having 40 to 10,000 atoms.

[0481] Examples of the oligoimine-based graft copolymer include resins containing a repeating unit represented by the following general formula (I-1) and a repeating unit represented by the following general formula (I-2).

[0482] [Chemical formula 29]

[0483]

[0484] In the general formulas (I-1) and (I-2), R 1 and R 2 Each independently represents a hydrogen atom, a halogen atom or an alkyl group, a each independently represents an integer of 1 to 5, * represents a linker between repeating units, and X represents a group having a pK a A group having 14 or less functional groups, wherein Y represents an oligomer chain or polymer chain having 40 to 10,000 atoms.

[0485] The oligoimine-based graft copolymer preferably further contains a repeating unit represented by the general formula (I-3). According to this embodiment, the dispersibility stability of the pigment body is further improved.

[0486] [Chemical formula 30]

[0487]

[0488] In the general formula (I-3), R 1 , R 2 and a and R in the general formula (I-1) 1 , R 2 and a have the same meaning. Y' represents an oligomer chain or polymer chain having an anionic group with an atomic number of 40 to 10,000. The repeating unit represented by the general formula (I-3) can be formed by adding an oligomer or polymer having a group that reacts with an amine to form a salt to a resin having a primary or secondary amine group in the main chain and reacting them.

[0489] In the general formula (I-1), the general formula (I-2) and the general formula (I-3), R 1 and R 2A hydrogen atom is preferred. From the viewpoint of raw material availability, a is preferably 2.

[0490] In addition to the repeating units represented by the general formula (I-1), the general formula (I-2) and the general formula (I-3), the oligoimine-based graft copolymer may also contain a lower alkylene imine containing a primary or tertiary amine group as a repeating unit. In addition, the nitrogen atom in the lower alkylene imine repeating unit may be further bonded to a group represented by X, Y or Y'.

[0491] The repeating unit represented by the general formula (I-1) is preferably contained in an amount of 1 to 80 mol %, particularly preferably 3 to 50 mol %, based on the total repeating units contained in the oligoimine-based graft copolymer.

[0492] The repeating unit represented by the general formula (I-2) is preferably contained in an amount of 10 to 90 mol %, particularly preferably 30 to 70 mol %, of the total repeating units contained in the oligoimine-based graft copolymer.

[0493] From the viewpoint of dispersion stability and hydrophilic-hydrophobic balance, the content ratio of the repeating unit (I-1) to the repeating unit (I-2) [(I-1):(I-2)] is preferably in the range of 10:1 to 1:100, more preferably 1:1 to 1:10, in terms of molar ratio.

[0494] In addition, the repeating unit represented by the general formula (I-3) used in combination as needed contains a partial structure of an oligomer chain or polymer chain Y' having an atomic number of 40 to 10,000 and ionically bonded to the nitrogen atom of the main chain, and preferably contains 0.5 to 20 mol%, and most preferably 1 to 10 mol%, of the total repeating units contained in the oligoimine-based graft copolymer from the viewpoint of effect. In addition, the ionically bonded polymer chain Y' can be confirmed by infrared spectroscopy or alkali titration.

[0495] (with pK a Partial structure of functional groups below 14 (X)

[0496] Part of the structure X has a pK at 25°C water a The functional group is 14 or less. a ” refers to the content defined in Chemical Handbook (II) (revised 4th edition, 1993, edited by the Chemical Society of Japan, MARUZEN Co., LTD.).

[0497] “pK a The structure of the functional group having a pK of less than 14 is not particularly limited as long as the physical properties satisfy the condition. Examples of the functional group include known functional groups that satisfy pK a For functional groups within the above range, in particular, pK aPreferably the functional group has a pK of 12 or less. a Particularly preferred are functional groups with 11 or less functional groups. Specific examples of the partial structure X include carboxylic acid groups (pK a :3~5 degrees), sulfonic acid group (pK a :-3~-2 degrees), -COCH 2 CO-(pK a :8~10 degrees), -COCH 2 CN(pK a :8~11 degrees), -CONHCO-, phenolic hydroxyl group, -R F CH 2 OH or -(R F ) 2 CHOH(R F represents a perfluoroalkyl group. a :9~11 degrees), sulfonamide group (pK a : 9 to 11), etc., and particularly preferably a carboxylic acid group (pK a :3~5 degrees), sulfonic acid group (pK a :-3~-2 degrees), -COCH 2 CO-(pK a : 8 to 10 degrees).

[0498] The partial structure X is preferably directly bonded to the basic nitrogen atom. The basic nitrogen atom and the partial structure X may be linked not only by covalent bonding but also by ionic bonding to form a salt.

[0499] As the partial structure X, a structure represented by the following general formula (V-1), general formula (V-2) or general formula (V-3) is particularly preferred.

[0500] [Chemical formula 31]

[0501]

[0502] In the general formula (V-1) and the general formula (V-2), U represents a single bond or a divalent linking group. d and e each independently represent 0 or 1. In the general formula (V-3), Q represents an acyl group or an alkoxycarbonyl group.

[0503] Examples of the divalent linking group represented by U include an alkylene group, an arylene group, an alkyleneoxy group, etc. which may have an oxygen atom, and an alkylene group having 1 to 30 carbon atoms or an arylene group having 6 to 20 carbon atoms is particularly preferred, and an alkylene group having 1 to 20 carbon atoms or an arylene group having 6 to 15 carbon atoms is particularly preferred. In addition, from the viewpoint of productivity, d is preferably 1, and e is preferably 0.

[0504] Q represents an acyl group or an alkoxycarbonyl group. As the acyl group in Q, an acyl group having 1 to 30 carbon atoms is preferred, and an acetyl group is particularly preferred. As the alkoxycarbonyl group in Q, from the viewpoint of ease of production and availability of raw materials (X', a precursor of X), Q is preferably an acetyl group.

[0505] (oligomer or polymer chain Y with 40 to 10,000 atoms)

[0506] Examples of the oligomer or polymer chain Y having 40 to 10,000 atoms include known polymer chains such as polyester, polyamide, polyimide, and poly(meth)acrylate that can be linked to the main chain of the oligoimide graft copolymer. The bond site of Y to the oligoimide graft copolymer is preferably the terminal of Y.

[0507] Y is preferably bonded to a basic nitrogen atom. The bonding form between the basic nitrogen atom and Y is a covalent bond, an ionic bond, or a mixed covalent bond and an ionic bond. The ratio of the bonding form between the basic nitrogen atom and Y is covalent bond: preferably ionic bond = 100:0 to 0:100, more preferably 95:5 to 5:95, and particularly preferably 90:10 to 10:90. Y is preferably amide-bonded to the basic nitrogen atom, or ionically bonded as a carboxylate.

[0508] The number of atoms in the oligomer chain or polymer chain Y is preferably 50 to 5,000, more preferably 60 to 3,000, from the viewpoint of dispersibility, dispersion stability, and developability.

[0509] The number average molecular weight of Y can be measured as a polystyrene conversion value by the GPC method. The number average molecular weight of Y is particularly preferably 1,000 to 50,000, and most preferably 1,000 to 30,000 from the viewpoint of dispersibility, dispersion stability, and developability.

[0510] The side chain structure represented by Y is preferably connected to the main chain in two or more, and particularly preferably connected in five or more, numbers in one molecule of the resin.

[0511] For details of Y, reference can be made to paragraphs 0086 to 0098 of Japanese Patent Application Laid-Open No. 2013-064979, the contents of which are incorporated herein by reference.

[0512] The oligoimine-based graft copolymer can be synthesized by the method described in paragraphs 0110 to 0117 of JP-A-2013-064979.

[0513] Specific examples of the oligoimine-based graft copolymer include the following: In addition, the resins described in paragraphs 0099 to 0109 and 0119 to 0124 of JP-A-2013-064979 are also included, and the contents are incorporated herein.

[0514] [Chemical formula 32]

[0515]

[0516] In the present invention, a copolymer containing a repeating unit represented by any one of the following formulae (1) to (4) may be used as a graft copolymer. The graft copolymer is particularly preferably used as a dispersant for a black pigment.

[0517] [Chemical formula 33]

[0518]

[0519] In formula (1) to formula (4), W 1 , W 2 , W 3 , and W 4 W each independently represents an oxygen atom or NH. 1 , W 2 , W 3 , and W 4 Preferred is an oxygen atom.

[0520] In formula (1) to formula (4), X 1 , X 2 , X 3 , X 4 , and X 5 Each independently represents a hydrogen atom or a monovalent organic group. 1 , X 2 , X 3 , X 4 , and X 5 , from the viewpoint of synthetic constraints, preferably each independently represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, more preferably each independently represents a hydrogen atom or a methyl group, and particularly preferably a methyl group.

[0521] In formula (1) to formula (4), Y 1 , Y 2 , Y 3 , and Y 4 Each independently represents a divalent linking group, and the linking group is not particularly restricted in structure. 1 , Y 2 , Y 3 , and Y 4Specifically, the divalent linking group represented by is exemplified by the following linking groups (Y-1) to (Y-21). In the structures shown below, A and B represent the bonding sites to the left and right terminal groups in formulae (1) to (4), respectively.

[0522] [Chemical formula 34]

[0523]

[0524] In formula (1) to formula (4), Z 1 , Z 2 , Z 3 , and Z 4 Each independently represents a monovalent organic group. The structure of the organic group is not particularly limited, and specific examples thereof include alkyl, hydroxyl, alkoxy, aryloxy, heteroaryloxy, alkyl thioether, aryl thioether, heteroaryl thioether, and amine groups. 1 , Z 2 , Z 3 , and Z 4 The organic group represented by is preferably a group having a steric repulsion effect from the viewpoint of improving dispersibility, and is preferably independently an alkyl group or an alkoxy group having 5 to 24 carbon atoms, and particularly preferably independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms. In addition, the alkyl group contained in the alkoxy group may be any of a linear, branched, or cyclic type.

[0525] In formula (1) to formula (4), n, m, p, and q are each independently an integer of 1 to 500.

[0526] In formula (1) and formula (2), j and k each independently represent an integer of 2 to 8. From the viewpoint of dispersion stability and developability, j and k in formula (1) and formula (2) are preferably integers of 4 to 6, and particularly preferably 5.

[0527] In formula (3), R 3 represents a branched or linear alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When p is 2 to 500, there are a plurality of R 3 They may be the same as or different from each other.

[0528] In formula (4), R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not particularly limited in structure. 4 Preferred are hydrogen atom, alkyl group, aryl group, and heteroaryl group, and more preferred is hydrogen atom or alkyl group. 4When X is an alkyl group, the alkyl group is preferably a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms, more preferably a linear alkyl group having 1 to 20 carbon atoms, and particularly preferably a linear alkyl group having 1 to 6 carbon atoms. In formula (4), when q is 2 to 500, a plurality of Xs are present in the graft copolymer. 5 and R 4 They may be the same as or different from each other.

[0529] As the repeating unit represented by the formula (1), a repeating unit represented by the following formula (1A) is more preferable from the viewpoint of dispersion stability and developability.

[0530] Furthermore, as the repeating unit represented by the formula (2), from the viewpoint of dispersion stability and developability, a repeating unit represented by the following formula (2A) is more preferable.

[0531] Furthermore, as the repeating unit represented by the formula (3), from the viewpoint of dispersion stability and developability, a repeating unit represented by the following formula (3A) or formula (3B) is more preferable.

[0532] [Chemical formula 35]

[0533]

[0534] In formula (1A), X 1 , Y 1 , Z 1 and n and X in formula (1) 1 , Y 1 , Z 1 and n have the same meanings and the preferred ranges are also the same.

[0535] In formula (2A), X 2 , Y 2 , Z 2 and m and X in formula (2) 2 , Y 2 , Z 2 and m have the same meanings and the preferred ranges are also the same.

[0536] In formula (3A) or (3B), X 3 , Y 3 , Z 3 and p and X in formula (3) 3 , Y 3 , Z 3 and p have the same meanings and the preferred ranges are also the same.

[0537] Furthermore, the graft copolymer may have a hydrophobic repeating unit in addition to the repeating units represented by the above formulae (1) to (4). However, in the present invention, the hydrophobic repeating unit is a repeating unit having no acid group (e.g., carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).

[0538] The hydrophobic repeating unit is preferably a repeating unit derived from a compound (monomer) having a ClogP value of 1.2 or more (correspondingly), and more preferably a repeating unit derived from a compound having a ClogP value of 1.2 to 8.

[0539] The ClogP value can be a value calculated by the program "CLOGP" obtained from Daylight Chemical Information System, INC. The program provides a "calculated logP" value calculated according to the fragmentation method of Hansch and Leo (refer to the following document). The fragmentation method is based on the chemical structure of the compound, and the chemical structure is divided into partial structures (fragments), and the allocated parts that contribute to its fragment logP are totaled to estimate the logP value of the compound. The details are described in the following document. The present invention uses the ClogP value calculated by the program CLOGP v4.82.

[0540] AJLeo, Comprehensive Medicinal Chemistry, Vol.4, C.Hansch, PGSammnens, JBTaylor and CARamsden, Eds., p.295, Pergamon Press, 1990 C.Hansch&A.J.Leo.SUbstituent Constants For Correlation Analysis in Chemistry and Biology.John Wiley&Sons.AJLeo.Calculating logPoct fromstructure.Chem.Rev., 93, 1281-1306, 1993.

[0541] logP represents the common logarithm of the partition coefficient P (Partition Coefficient), and is a physical property value that quantitatively expresses how a certain organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water, and is represented by the following formula.

[0542] logP=log(Coil / Cwater)

[0543] Wherein, Coil represents the molar concentration of the compound in the oil phase, and Cwater represents the molar concentration of the compound in the water phase.

[0544] If the logP value increases with a positive number around 0, it means that the oil solubility increases, and if it increases with a negative absolute value, it means that the water solubility increases. The water solubility of organic compounds is related to negative numbers, and it is widely used as a parameter for estimating the hydrophilicity of organic compounds.

[0545] The graft copolymer preferably has, as the hydrophobic repeating unit, one or more repeating units selected from repeating units derived from monomers represented by the following general formulae (i) to (iii).

[0546] [Chemical formula 36]

[0547]

[0548] In the above formulas (i) to (iii), R 1 , R 2 , and R 3 Each independently represents a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, methyl, ethyl, propyl, etc.).

[0549] R 1 , R 2 , and R 3 More preferably, it is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably, it is a hydrogen atom or a methyl group. 2 and R 3 A hydrogen atom is particularly preferred.

[0550] X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

[0551] L is a single bond or a divalent linking group. Examples of the divalent linking group include a divalent aliphatic group (e.g., an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, a substituted alkynylene group), a divalent aromatic group (e.g., an arylene group, a substituted arylene group), a divalent heterocyclic group, an oxygen atom (-O-), a sulfur atom (-S-), an imino group (-NH-), a substituted imino group (-NR-), and a divalent aromatic group (e.g., an arylene group, a substituted arylene group). 31 -, where R 31 is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), or a combination thereof.

[0552] L is preferably a divalent linking group containing a single bond, an alkylene group or an oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may also contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is -(OCH2 CH 2 ) n - represents that n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

[0553] Examples of Z include an aliphatic group (e.g., an alkyl group, a substituted alkyl group, an unsaturated alkyl group, a substituted unsaturated alkyl group), an aromatic group (e.g., an arylene group, a substituted arylene group), a heterocyclic group, an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 -, where R 31 is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (-CO-), or a combination thereof.

[0554] The aliphatic group may also have a cyclic structure or a branched structure. The number of carbon atoms in the aliphatic group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The aliphatic group further includes a ring-assembled hydrocarbon group and a cross-linked cyclic hydrocarbon group. Examples of the ring-assembled hydrocarbon group include bicyclohexyl, perhydronaphthyl, biphenyl, 4-cyclohexylphenyl, and the like. Examples of the cross-linked cyclic hydrocarbon ring include pinane, camphane, norpinane, norbornane, bicyclooctane ring (bicyclo[2.2.2]octane ring, bicyclo[3.2.1]octane ring, etc.), homobledanes, adamantane, tricyclo[5.2.1.0 2，6 ]Decane ring, tricyclic [4.3.1.1 2，5 ] undecane ring and other tricyclic hydrocarbon rings, tetracyclic [4.4.0.1 2，5 .1 7，10 ] dodecane, perhydro-1,4-methylene-5,8-methylenenaphthalene ring and other four-ring hydrocarbon rings. In addition, the cross-linked cyclic hydrocarbon ring also includes a condensed hydrocarbon ring, for example, a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as perhydronaphthalene (decahydronaphthalene), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenalene rings are condensed. For an aliphatic group, a saturated aliphatic group is preferred over an unsaturated aliphatic group. In addition, an aliphatic group may also have a substituent. Examples of substituents include halogen atoms, aromatic groups and heterocyclic groups. However, an aliphatic group does not have an acid group as a substituent.

[0555] The number of carbon atoms in the aromatic group is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. In addition, the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group. However, the aromatic group does not have an acid group as a substituent.

[0556] The heterocyclic group preferably has a 5-membered ring or a 6-membered ring as the heterocyclic ring. Other heterocyclic rings, aliphatic rings or aromatic rings may also be present in a condensed state on the heterocyclic ring. In addition, the heterocyclic group may also have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an oxy group (=O), a thiol group (=S), an imino group (=NH), a substituted imino group (=NR 32 , where R 32 is an aliphatic group, an aromatic group or a heterocyclic group). However, the heterocyclic group does not have an acid group as a substituent.

[0557] In the above formula (iii), R 4 , R 5 , and R 6 Each independently represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, etc.), Z, or -LZ. L and Z have the same meanings as above. 4 , R 5 , and R 6 It is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.

[0558] In the monomer represented by the above general formula (i), R 1 , R 2 , and R 3 is a hydrogen atom or a methyl group, L is a divalent linking group containing a single bond or an alkylene or oxyalkylene structure, X is an oxygen atom or an imino group, and Z is preferably a compound of an aliphatic group, a heterocyclic group or an aromatic group. 1 is a hydrogen atom or a methyl group, L is an alkylene group, and Z is preferably an aliphatic group, a heterocyclic group or an aromatic group. 4 , R 5 , and R 6 A compound in which Z is preferably a hydrogen atom or a methyl group and Z is preferably an aliphatic group, a heterocyclic group or an aromatic group.

[0559] Representative examples of compounds represented by formula (i) to (iii) include free radical polymerizable compounds selected from acrylates, methacrylates, styrenes, etc. In addition, examples of compounds represented by formula (i) to (iii) can refer to the compounds described in paragraphs 0089 to 0093 of Japanese Patent Application Publication No. 2013-249417, and such contents are incorporated into this specification.

[0560] In the graft copolymer, the hydrophobic repeating unit is preferably contained in an amount of 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the graft copolymer. A sufficient pattern can be formed when the content is within the above range.

[0561] The graft copolymer preferably includes a repeating unit having a functional group capable of interacting with a colorant or the like, in addition to the repeating unit represented by the formulae (1) to (4).

[0562] The acid group includes, for example, a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and is preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. In particular, a carboxylic acid group having good adsorption capacity for colorants such as black pigments and high dispersibility is preferred.

[0563] The graft copolymer may contain one or two or more repeating units having an acid group.

[0564] The graft copolymer may or may not contain repeating units having an acid group. When containing repeating units having an acid group, the content of the repeating units having an acid group is preferably 5 to 80% by mass, more preferably 10 to 60% by mass, based on the total mass of the graft copolymer.

[0565] Examples of the basic group include primary amine groups, secondary amine groups, tertiary amine groups, heterocyclic rings containing N atoms, and amide groups, and tertiary amine groups are particularly preferred because they have good adsorption to the colorant and high dispersibility. The graft copolymer may also have one or more of these basic groups.

[0566] The graft copolymer may or may not contain a repeating unit having a basic group. When contained, the content of the repeating unit having a basic group is preferably 0.01 to 50% by mass based on the total mass of the graft copolymer, and more preferably 0.01 to 30% by mass from the viewpoint of suppressing the development property.

[0567] As the above-mentioned coordination group and reactive functional group, for example, acetyl acetoxy, trialkoxy silyl, isocyanate, acid anhydride, acid chloride, etc. are mentioned. Preferably, acetyl acetoxy has good adsorption to the colorant and high dispersibility. The graft copolymer may also have one or more of these groups.

[0568] The graft copolymer may or may not contain repeating units having a coordinating group or repeating units having a reactive functional group. When contained, the content of such repeating units is preferably 10 to 80% by mass relative to the total mass of the graft copolymer in terms of mass conversion, and more preferably 20 to 60% by mass from the viewpoint of suppressing the obstruction of developability.

[0569] When the graft copolymer has functional groups capable of interacting with the colorant in addition to the graft chain, there is no particular limitation on how such functional groups are introduced. Preferably, the graft copolymer has one or more repeating units selected from repeating units derived from monomers represented by the following general formulae (iv) to (vi).

[0570] [Chemical formula 37]

[0571]

[0572] In the general formulae (iv) to (vi), R 11 , R 12 , and R 13 Each independently represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.).

[0573] In the general formulae (iv) to (vi), R 11 , R 12 , and R 13 Preferably, they are each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and most preferably, they are each independently a hydrogen atom or a methyl group. 12 and R 13 are hydrogen atoms respectively.

[0574] X in the general formula (iv) 1 It represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.

[0575] Y in the general formula (v) represents a methine group or a nitrogen atom.

[0576] L in the general formula (iv) to (v) 1 represents a single bond or a divalent linking group. Examples of divalent linking groups include divalent aliphatic groups (e.g., alkylene, substituted alkylene, alkenylene, substituted alkenylene, alkynylene, and substituted alkynylene), divalent aromatic groups (e.g., arylene, and substituted arylene), divalent heterocyclic groups, oxygen atoms (-O-), sulfur atoms (-S-), imino groups (-NH-), substituted imino bonds (-NR-), and the like. 31’ -, where R 31’ is an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (-CO-), or a combination thereof.

[0577] L 1Preferably, it is a single bond, a divalent linking group containing an alkylene or oxyalkylene structure. The oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure. In addition, L may also contain a polyoxyalkylene structure containing two or more oxyalkylene structures repeatedly. The polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure. The polyoxyethylene structure is -(OCH 2 CH 2 ) n - represents that n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.

[0578] In the general formulae (iv) to (vi), Z 1 It refers to a functional group other than the graft chain that can interact with the colorant, and is preferably a carboxylic acid group or a tertiary amine group, and more preferably a carboxylic acid group.

[0579] In the general formula (vi), R 14 , R 15 , and R 16 each independently represents a hydrogen atom, a halogen atom (e.g., fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (e.g., methyl, ethyl, propyl, etc.), -Z 1 , or -L 1 -Z 1 Among them, L 1 and Z 1 With the above L 1 and Z 1 The meanings are the same, and preferred examples are also the same. 14 , R 15 , and R 16 , are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.

[0580] Among the monomers represented by the general formula (iv), R 11 , R 12 , and R 13 are independently a hydrogen atom or a methyl group, L 1 is a compound containing a divalent linking group having an alkylene or oxyalkylene structure, X is an oxygen atom or an imino group, and Z is a carboxylic acid group. 11 is a hydrogen atom or a methyl group, L 1 is an alkylene group, Z 1 is a carboxylic acid group, and Y is preferably a methine group. 14 , R 15 , and R 16 A compound in which each is independently a hydrogen atom or a methyl group, L is a single bond or an alkylene group, and Z is a carboxylic acid group.

[0581] Specific examples of the graft copolymer include the following: In addition, reference may be made to the polymer compounds described in paragraphs 0127 to 0129 of JP-A-2013-249417, the contents of which are incorporated herein.

[0582] [Chemical formula 38]

[0583]

[0584] Pigment derivatives

[0585] The coloring composition of the present invention may also contain a pigment derivative. The pigment derivative is preferably a compound having a part of the structure of the organic pigment substituted with an acidic group, a basic group or a phthalic group. As the pigment derivative, from the viewpoint of the dispersibility and dispersion stability of the colorant A, a pigment derivative having an acidic group or a basic group is preferred. A pigment derivative having a basic group is particularly preferred. In addition, with respect to the combination of the above-mentioned resin (dispersant) and the pigment derivative, a combination in which the dispersant is an acidic dispersant and the pigment derivative has a basic group is preferred.

[0586] Examples of organic pigments used to constitute the pigment derivatives include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, threonine pigments, and metal complex pigments.

[0587] The acidic group possessed by the pigment derivative is preferably a sulfonic acid group, a carboxylic acid group and salts thereof, more preferably a carboxylic acid group and a sulfonic acid group, and particularly preferably a sulfonic acid group. The basic group possessed by the pigment derivative is preferably an amine group, and particularly preferably a tertiary amine group.

[0588] When the coloring composition of the present invention contains a pigment derivative, the content of the pigment derivative is preferably 1 to 30% by mass, more preferably 3 to 20% by mass, based on the mass of the pigment. The pigment derivative may be used alone or in combination of two or more.

[0589] Organic Solvents

[0590] The coloring composition of the present invention may contain an organic solvent.

[0591] The organic solvent is not particularly limited as long as it satisfies the solubility of each component and the coating property of the coloring composition, but is preferably selected from the viewpoints of the solubility, coating property, and safety of the polymerizable compound, alkali-soluble resin, etc.

[0592] Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetates (e.g., methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate), etc.)), 3-oxopropionic acid alkyl esters (e.g., 3-oxopropionic acid methyl ester, 3-oxopropionic acid ethyl ester, etc. (e.g., 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-ethoxypropionic acid methyl ester, 3-ethoxypropionic acid ethyl ester, etc.)), 2-oxopropionic acid alkyl esters (e.g., 2-oxopropionic acid methyl ester, 2-oxopropionic acid ethyl ester, 2-oxopropionic acid propyl ester, etc. (e.g., 2-methoxypropionic acid methyl ester, 2-methoxypropionic acid ethyl ester, 2-methoxypropionic acid propyl ester, 2 Esters such as methyl 2-methoxypropionate, ethyl 2-ethoxypropionate), methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, and esters such as 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, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and aromatic hydrocarbons such as toluene and xylene.

[0593] It is also preferred to mix two or more of these organic solvents from the viewpoints of solubility of polymerizable compounds, alkali-soluble resins, etc., improvement of the coating surface, etc. In this case, a mixed solution consisting of two or more selected from the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate is particularly preferred.

[0594] 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.

[0595] The content of the organic solvent in the coloring composition is preferably an amount such that the total solid content of the coloring composition is 5% to 80% by mass, more preferably 5 to 60% by mass, and particularly preferably 10 to 50% by mass, from the viewpoint of coating properties.

[0596] The coloring composition of the present invention may contain only one organic solvent or two or more organic solvents. When containing two or more organic solvents, the total amount thereof is preferably within the above range.

[0597] 《Polymerization Inhibitors》

[0598] In the colored composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during production or storage of the colored composition.

[0599] Examples of the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxylamine first cerium salt.

[0600] When the colored 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 mass of the colored composition.

[0601] The colored composition of the present invention may contain only one type or two or more types of polymerization inhibitors. When containing two or more types, the total amount thereof is preferably within the above range.

[0602] Surfactants

[0603] From the viewpoint of further improving coating properties, various surfactants may be added to the coloring composition of the present invention. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants may be used.

[0604] For example, by containing a fluorine-based surfactant, the liquid properties (especially fluidity) when prepared as a coating liquid are further improved. That is, when a film is formed using a coloring composition containing a fluorine-based surfactant, the wettability of the coated surface is improved by reducing the interfacial tension between the coated surface and the coating liquid, and the coating property of the coated surface is improved. Thus, even when a thin film of several μm is formed with a small amount of liquid, a film with less uneven thickness and uniform thickness can be formed more appropriately, which is effective in this regard.

[0605] 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. Fluorine-based surfactants having a fluorine content within this range are effective in terms of uniformity of thickness of the coating film and liquid saving, and also have good solubility in the coloring composition.

[0606] Examples of the fluorine-based surfactant include MEGAFAC F171, MEGAFAC F172, MEGAFAC F173, MEGAFAC F176, MEGAFAC F177, MEGAFAC F141, MEGAFAC F142, MEGAFAC F143, MEGAFAC F144, MEGAFAC R30, MEGAFAC F437, MEGAFAC F475, MEGAFAC F479, MEGAFAC F482, MEGAFAC F554, MEGAFAC F780, MEGAFAC F781 (all manufactured by DIC CORPORATION), FLUORAD FC430, FLUORAD FC431, FLUORAD FC171 (all manufactured by SUMITOMO 3M Limited), SURFLON S-382, SURFLON SC-101, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON SC-1068, SURFLON SC-381, SURFLON SC-383, SURFLON S-393, SURFLON KH-40 (all manufactured by ASAHI GLASS CO., LTD.), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA SOLUTIONS INC.), etc. In addition, block polymers can also be used as fluorine-based surfactants, and specific examples thereof include compounds described in Japanese Patent Application Publication No. 2011-89090.

[0607] The fluorine-containing surfactant may also preferably be a fluorine-containing polymer compound containing repeating units derived from a (meth)acrylate compound containing a fluorine atom, and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy groups). The following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.

[0608] [Chemical formula 39]

[0609]

[0610] The weight average molecular weight of the compound is preferably 3,000 to 50,000, for example, 14,000.

[0611] Specific examples of the nonionic surfactant include glycerin, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (e.g., propoxylated glycerin, ethoxylated glycerin, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2, TETRONIC 304, 701, 704, 901, 904, 150R1 manufactured by BASF), SOLSPERSE 20000 (LUBRIZOL JAPAN, LTD.), and the like. Furthermore, PIONIN D-6112-W manufactured by TAKEMOTO OIL & FAT CO., LTD., NCW-101, NCW-1001, NCW-1002 manufactured by Wako Pure Chemical Industries, LTD., PIONIN D-6315 manufactured by TAKEMOTO OIL & FAT CO., LTD., and the like can also be used.

[0612] Specific examples of cationic surfactants include phthalocyanine derivatives (trade name: EFKA-745, manufactured by MORISHITA & CO., LTD.), organosilicone polymer KP-341 (manufactured by Shin-Etsu Chemical Co., LTD.), (meth)acrylic (co)polymers POLYFLOW No. 75, No. 90, No. 95 (manufactured by KYOEISHA CHEMICAL CO., LTD.), and W001 (manufactured by YUSHO CO., LTD.).

[0613] Specific examples of the anionic surfactant include W004, W005, and W017 (manufactured by YUSHO CO., LTD.).

[0614] Examples of the silicone surfactant include "TORAY SILICONE DC3PA", "TORAY SILICONE SH7PA", "TORAY SILICONE DC11PA", "TORAY SILICONE SH21PA", "TORAY SILICONE SH28PA", "TORAY SILICONE SH29PA", "TORAY SILICONE SH30PA", and "TORAY SILICO NE SH8400" manufactured by DOW CORNING TORAY CO., LTD., "TSF-4440", "TSF-4300", "TSF-4445", "TSF-4460", and "TSF-4452" manufactured by MOMENTIVE PERFORMANCE MATERIALS Inc., "KP-341", "KF6001", and "KF6002" manufactured by Shin-Etsu Chemical Co., Ltd., BYK Chemie "BYK307", "BYK323", "BYK330" and so on manufactured by the company.

[0615] When the colored composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, relative to the total mass of the colored composition.

[0616] The coloring composition of the present invention may contain only one surfactant or two or more surfactants. When containing two or more surfactants, the total amount thereof is preferably within the above range.

[0617] 《Silane coupling agent》

[0618] The coloring composition of the present invention may contain a silane coupling agent for the purpose of improving adhesion to a substrate.

[0619] The silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule. In addition, a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.

[0620] The so-called hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond through a hydrolysis reaction and / or a condensation reaction. Examples of the hydrolyzable group include halogen atoms, alkoxy groups, acyloxy groups, and alkenyloxy groups. When the hydrolyzable group has carbon atoms, it is preferably 6 or less carbon atoms, more preferably 4 or less. An alkoxy group having 4 or less carbon atoms or an alkenyloxy group having 4 or less carbon atoms is particularly preferred.

[0621] Furthermore, since the silane coupling agent improves the adhesion of the cured film, it preferably does not contain fluorine atoms and silicon atoms (but excluding silicon atoms bonded to hydrolyzable groups), and ideally does not contain fluorine atoms, silicon atoms (but excluding silicon atoms bonded to hydrolyzable groups), alkylene groups substituted with silicon atoms, linear alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms.

[0622] In the present invention, the silane coupling agent is a compound different from the above-mentioned polymerizable compound and curable compound. That is, the silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule.

[0623] The silane coupling agent preferably has a group represented by the following formula (Z): * represents a bonding position.

[0624] Formula (Z)*-Si(R z1 ) 3-m (R z2 ) m

[0625] R z1 represents an alkyl group, R z2 represents a hydrolyzable group, and m represents an integer of 1 to 3. z1 The number of carbon atoms in the alkyl group represented by is preferably 1 to 5, more preferably 1 to 3. z2 The hydrolyzable groups represented are as defined above.

[0626] The silane coupling agent preferably has a curable functional group. As the curable functional group, it is preferably selected from the group consisting of (meth) acryloyloxy, epoxy, oxetane, isocyanate, hydroxyl, amine, carboxyl, thiol, alkoxysilyl, methylol, vinyl, (meth) acrylamide, vinyl, and maleimide, more preferably selected from the group consisting of (meth) acryloyloxy, epoxy, and oxetane. The curable functional group can be directly bonded to the silicon atom or bonded to the silicon atom through a linking group.

[0627] The molecular weight of the alkyl coupling agent is not particularly limited, but is preferably 100 to 1000 from the viewpoint of operability, and is preferably 270 or more, and more preferably 270 to 1000 from the viewpoint of achieving a more excellent effect of the present invention.

[0628] As a preferred embodiment of the silane coupling agent, a silane coupling agent X represented by formula (W) can be mentioned.

[0629] Formula (W)R z3 -Lz-Si(R z1 ) 3-m (R z2 ) m

[0630] R z1 represents an alkyl group, R z2 Represents a hydrolyzable group, R z3 represents a curable functional group, Lz represents a single bond or a divalent linking group, and m represents an integer of 1 to 3.

[0631] R z1 The alkyl group represented by is as defined above. z2 The hydrolyzable groups represented by are defined as above. z3 The definition of the curable functional group represented is as described above, and the preferred range is also as described above.

[0632] Lz represents a single bond or a divalent linking group. Examples of the divalent linking group include an alkylene group, an arylene group, and -NR 12 -、-CONR 12 -、-CO-、-CO 2 -、-SO 2 NR 12 -、-O-、-S-、-SO 2 -, or a combination thereof.

[0633] The number of carbon atoms in the alkylene group is preferably 1 to 20. The alkylene group is either a straight chain or a branched chain. The alkylene group and the arylene group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group.

[0634] Lz is at least one selected from the group consisting of an alkylene group having 2 to 10 carbon atoms and an arylene group having 6 to 12 carbon atoms, or preferably these groups and -NR 12 -、-CONR 12 -、-CO-、-CO 2 -、SO 2 NR 12 -, -O-, -S-, and -SO 2 -, more preferably an alkylene group having 2 to 10 carbon atoms, -CO 2 -、-O-、-CO-、-CONR 12 -, or a combination of these groups. 12 represents a hydrogen atom or a methyl group.

[0635] m represents 1 to 3, preferably 2 to 3, and more preferably 3.

[0636] Examples of the silane coupling agent X include N-β-aminoethyl-γ-aminopropyl-methyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., trade name KBM-602), N-β-aminoethyl-γ-aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., trade name KBM-603), N-β-aminoethyl-γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., trade name KBE-602), γ-aminopropyl-trimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., trade name KBM-903), γ-aminopropyl-triethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., trade name KBE-903), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., trade name KBE-903), and 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., LTD., trade name KBE-903). Co., LTD., trade name KBM-503), glycidyl ether octyl trimethoxysilane (Shin-Etsu Chemical Co., LTD., trade name KBM-4803), etc.

[0637] A preferred embodiment of the silane coupling agent is a silane coupling agent Y having at least a silicon atom, a nitrogen atom, and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom.

[0638] As long as the silane coupling agent Y has at least one silicon atom in the molecule, the silicon atom can be bonded to the following atoms and substituents. Such atoms and substituents can be the same or different. Atoms and substituents that can be bonded include hydrogen atoms, halogen atoms, hydroxyl groups, alkyl groups with 1 to 20 carbon atoms, alkenyl groups, alkynyl groups, aryl groups, amine groups that can be substituted by alkyl and / or aryl groups, silanyl groups, alkoxy groups with 1 to 20 carbon atoms, aryloxy groups, etc. These substituents can also be further substituted by silanyl groups, alkenyl groups, alkynyl groups, aryl groups, alkoxy groups, aryloxy groups, thioalkoxy groups, amine groups that can be substituted by alkyl and / or aryl groups, halogen atoms, sulfonamide groups, alkoxycarbonyl groups, amide groups, urea groups, ammonium groups, alkylammonium groups, carboxyl groups, or salts thereof, sulfonic groups, or salts thereof.

[0639] In addition, at least one hydrolyzable group is bonded to the silicon atom. The definition of the hydrolyzable group is as described above.

[0640] The silane coupling agent Y may contain a group represented by formula (Z).

[0641] Silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amine group or a tertiary amine group, that is, the nitrogen atom is preferably present as a substituent, and preferably has at least one organic group. In addition, the structure as an amine group can also be present in the molecule in the form of a partial structure of a nitrogen-containing heterocyclic ring, or can be present as a substituted amine group such as aniline. Among them, as an organic group, alkyl, alkenyl, alkynyl, aryl, or such combinations can be cited. These can also have a substituent further, and as a substituent that can be introduced, silanyl, alkenyl, alkynyl, aryl, alkoxy, aryloxy, thioalkoxy, amine, halogen atom, sulfonamide, alkoxycarbonyl, carbonyloxy, amide, urea, alkyleneoxy, ammonium, alkylammonium, carboxyl, or its salt, sulfonic group, etc. can be cited.

[0642] Furthermore, the nitrogen atom is preferably bonded to the curable functional group via an arbitrary organic linking group. Preferred organic linking groups include substituents that can be introduced into the above-mentioned nitrogen atom and the organic group bonded thereto.

[0643] The definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.

[0644] The silane coupling agent Y may have at least one curable functional group in one molecule, and may have two or more curable functional groups. From the viewpoint of sensitivity and stability, it is preferred to have 2 to 20 curable functional groups, more preferably 4 to 15, and particularly preferably 6 to 10 curable functional groups in one molecule.

[0645] Examples of the silane coupling agent Y include compounds represented by the following formula (Y).

[0646] Formula(Y)(R y3 ) n -LN-Si(R y1 ) 3-m (R y2 ) m

[0647] R y1 represents an alkyl group, R y2 Represents a hydrolyzable group, R y3 represents a curable functional group,

[0648] LN represents an (n+1)-valent linking group having a nitrogen atom,

[0649] m represents an integer of 1 to 3, and n represents an integer of 1 or greater.

[0650] In formula (Y), R y1 , R y2 , R y3 and m and R of formula (W)z1 , R z2 , R z3 and m have the same meanings and the preferred ranges are also the same.

[0651] n in formula (Y) represents an integer greater than or equal to 1. The upper limit is, for example, preferably less than or equal to 20, more preferably less than or equal to 15, and further preferably less than or equal to 10. The lower limit is, for example, preferably greater than or equal to 2, more preferably greater than or equal to 4, and further preferably greater than or equal to 6. Furthermore, n may also be set to 1.

[0652] LN in the formula (Y) represents a group having a nitrogen atom.

[0653] Examples of the group having a nitrogen atom include at least one selected from the following formulae (LN-1) to (LN-4), or a group selected from the following formulae (LN-1) to (LN-4) and -CO-, -CO 2 -, -O-, -S- and -SO 2 - is a group composed of at least one combination of the following. The alkylene group is any one of a straight chain and a branched chain. The alkylene group and the arylene group may be unsubstituted or may have a substituent. As the substituent, a halogen atom or a hydroxyl group may be mentioned.

[0654] [Chemical formula 40]

[0655]

[0656] In the formula, * represents a connecting bond.

[0657] Specific examples of the silane coupling agent Y include the following compounds: wherein Et represents an ethyl group. In addition, compounds described in paragraphs 0018 to 0036 of JP-A-2009-288703 are also included, and the contents are incorporated herein by reference.

[0658] [Chemical formula 41]

[0659]

[0660] The molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, and may be within the above range (preferably 270 or more).

[0661] The content of the silane coupling agent is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, and further preferably 1.0 to 6% by mass relative to the total solid content in the coloring composition of the present invention. The silane coupling agent can be used alone or in combination of two or more. When two or more are used in combination, the total amount is preferably within the above range.

[0662] 《Other additives》

[0663] The coloring composition of the present invention may contain various additives as needed, such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, aggregation inhibitors, etc. Examples of such additives include those described in paragraphs 0155 to 0156 of Japanese Unexamined Patent Application Publication No. 2004-295116, and such contents are incorporated into the present specification.

[0664] The colored composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph 0078 of JP-A-2004-295116, and a thermal polymerization inhibitor described in paragraph 0081 of the same publication.

[0665] Depending on the raw materials used, the coloring composition may contain metal elements. From the perspective of suppressing the generation of defects, the content of Group 2 elements (calcium, magnesium, etc.) in the coloring composition is preferably 50 ppm or less, more preferably 0.01 to 10 ppm. In addition, the total amount of inorganic metal salts in the coloring composition is preferably 100 ppm or less, more preferably 0.5 to 50 ppm.

[0666] In the coloring composition of the present invention, the total amount of monochlorobenzene and methyl tert-butyl ether is preferably 2 ppm or less, more preferably 1 ppm or less relative to the total mass of the coloring composition. It is further preferred that monochlorobenzene and methyl tert-butyl ether are substantially not contained. By setting such a structure, the safety of the coloring composition can be made excellent.

[0667] Furthermore, “substantially containing neither monochlorobenzene nor methyl tert-butyl ether” means that the total amount of monochlorobenzene and methyl tert-butyl ether is preferably, for example, 0.5 ppm or less, more preferably 0.1 ppm or less, and even more preferably, no monochlorobenzene and tert-butyl ether are contained relative to the total mass of the coloring composition.

[0668] <Preferred Embodiment of Coloring Composition>

[0669] 《Method 1》

[0670] A preferred embodiment (first embodiment) of the coloring composition of the present invention is a composition comprising a fluorine-containing oxime ester photopolymerization initiator, a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a coloring agent, wherein:

[0671] A coloring composition containing an organic pigment, wherein the ratio A / B of the minimum absorbance A in the range of a wavelength of 400 nm to less than 580 nm and the minimum absorbance B in the range of a wavelength of 580 nm to 750 nm is 0.3 to 3, and the ratio C / D of the minimum absorbance C in the range of a wavelength of 400 nm to 750 nm to the maximum absorbance D in the range of a wavelength of 1000 nm to 1300 nm is 5 or more.

[0672] By using the colored composition, a film having spectral characteristics in which the maximum transmittance in the wavelength range of 400 to 700 nm is 20% or less and the minimum transmittance in a specific wavelength range of 850 to 1300 nm is 80% or more can be suitably formed.

[0673] The absorbance Aλ at a certain wavelength λ is defined by the following formula (1).

[0674] Aλ=-log(Tλ)……(1)

[0675] Aλ is the absorbance at wavelength λ, and Tλ is the transmittance at wavelength λ.

[0676] In the present invention, the absorbance value may be a value measured in a solution state or a value measured in a film state made using the coloring composition. When measuring the absorbance in a film state, it is preferred to use a film prepared as described below, apply the coloring composition on a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined film thickness, and dry it at 100°C for 120 seconds using a hot plate. The film thickness of the film can be measured using a stylus-type surface shape measuring instrument (DEKTAK150 manufactured by ULVAC, INC.) on a substrate having a film.

[0677] Furthermore, the absorbance can be measured using a spectrophotometer known in the past. The conditions for measuring the absorbance are not particularly limited. It is preferred that the minimum value A of the absorbance in the range of wavelengths of 400 nm or more and less than 580 nm is adjusted to 0.1 to 3.0, and the minimum value B of the absorbance in the range of wavelengths of 580 nm or more and 750 nm or less, the minimum value C of the absorbance in the range of wavelengths of 400 nm or more and 750 nm or less, and the maximum value D of the absorbance in the range of wavelengths of 1000 nm or more and 1300 nm or less are measured. By measuring the absorbance under such conditions, the measurement error can be made smaller. There is no particular limitation on the method for adjusting the minimum value A of the absorbance in the range of wavelengths of 400 nm or more and less than 580 nm to 0.1 to 3.0. For example, a method for adjusting the optical path length of the sample unit when measuring the absorbance in the state of a colored composition can be cited. Furthermore, when measuring the absorbance in the state of a film, a method for adjusting the film thickness can be cited.

[0678] The following describes methods for measuring the spectral characteristics, film thickness, and the like of a film formed from the colored composition of the present invention.

[0679] The colored composition of the present invention is applied on a glass substrate by a method such as spin coating so that the film thickness after drying becomes the above-specified film thickness, and dried at 100° C. for 120 seconds using a hot plate.

[0680] The film thickness of the film was measured using a stylus-type surface profile measuring instrument (DEKTAK150 manufactured by ULVAC, INC.) on a substrate having the film after drying.

[0681] The transmittance of the dried substrate having the film was measured in the wavelength range of 300 to 1300 nm using a spectrophotometer of an ultraviolet-visible-near-infrared spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation).

[0682] In the coloring composition of the first embodiment, when a red pigment, a yellow pigment, a blue pigment, and a violet pigment are combined, the mass ratio of the red pigment to the total pigment is preferably 0.2 or more and 0.5 or less, the mass ratio of the yellow pigment to the total pigment is 0.1 or more and 0.2 or less, the mass ratio of the blue pigment to the total pigment is 0.25 or more and 0.55 or less, and the mass ratio of the violet pigment to the total pigment is 0.05 or more and 0.15 or less, and the mass ratio of the red pigment to the total pigment is more preferably 0.3 or more and 0.4 or less, the mass ratio of the yellow pigment to the total pigment is 0.1 or more and 0.2 or less, the mass ratio of the blue pigment to the total pigment is 0.3 or more and 0.4 or less, and the mass ratio of the violet pigment to the total pigment is more preferably 0.05 or more and 0.15 or less.

[0683] By combining red pigment, yellow pigment, blue pigment and violet pigment as described above, a film having the following spectral characteristics is appropriately formed, wherein the maximum transmittance in the wavelength range of 400 to 700 nm is less than 20% and the minimum transmittance in the wavelength range of 900 to 1300 nm is more than 80%.

[0684] Furthermore, in the coloring composition of the first embodiment, by containing one or more first coloring agents having maximum absorption in the wavelength range of 800 to 900 nm and two or more second coloring agents having maximum absorption in the wavelength range of 400 to 700 nm, a film having spectral characteristics in which the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less and the minimum value of the transmittance in the wavelength range of 1000 to 1300 nm is 80% or more can be appropriately formed.

[0685] The first colorant is preferably the above-mentioned pyrrolopyrrole compound.

[0686] As the second colorant, it is preferred to contain two or more pigments selected from red pigment, yellow pigment, blue pigment, and violet pigment, and it is more preferred to contain red pigment, yellow pigment, blue pigment, and violet pigment. As a preferred specific example, it is preferred to contain CT Pigment Red 254 as a red pigment, CI Pigment Yellow 139 as a yellow pigment, CI Pigment Blue 15:6 as a blue pigment, and CI Pigment Violet 23 as a violet pigment.

[0687] When the second colorant is a combination of a red pigment, a yellow pigment, a blue pigment, and a violet pigment, preferably, the mass ratio of the red pigment to the total amount of the second colorant is 0.1 to 0.4, the mass ratio of the yellow pigment to the total amount of the second colorant is 0.1 to 0.4, the mass ratio of the blue pigment to the total amount of the second colorant is 0.20 to 0.60, and the mass ratio of the violet pigment to the total amount of the second colorant is 0.01 to 0.30. More preferably, the mass ratio of the red pigment to the total amount of the second colorant is 0.1 to 0.3, the mass ratio of the yellow pigment to the total amount of the second colorant is 0.1 to 0.3, the mass ratio of the blue pigment to the total amount of the second colorant is 0.3 to 0.5, and the mass ratio of the violet pigment to the total amount of the second colorant is 0.05 to 0.25.

[0688] The first colorant is preferably contained in an amount of 10 to 200 parts by mass based on 100 parts by mass of the second colorant. This allows the above-mentioned absorbance conditions of the colored composition to be appropriately achieved.

[0689] In the coloring composition of the present invention, the content of the first coloring agent is preferably 0 to 60% by mass of the total solid content of the coloring composition, and more preferably 10 to 40% by mass. The content of the second coloring agent is preferably 10 to 60% by mass of the total solid content of the coloring composition, and more preferably 30 to 50% by mass. The total amount of the first coloring agent and the second coloring agent is preferably 1 to 80% by mass, more preferably 20 to 70% by mass, and further preferably 30 to 70% by mass relative to the total solid content of the coloring composition.

[0690] 《Method 2》

[0691] A preferred embodiment (second embodiment) of the coloring composition of the present invention is a composition comprising a fluorine-containing oxime ester photopolymerization initiator, a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a colorant, and further comprising a curable compound having a fluorine atom and a curable functional group.

[0692] By using such a colored composition, a cured film having excellent adhesion to a support and low reflectivity can be formed.

[0693] In this embodiment, it is preferable to use a black pigment as a colorant. When the coloring composition of the second embodiment contains a black pigment, a cured film having excellent performance as a light-shielding film can be easily formed.

[0694] In the second embodiment, the content of the black pigment is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, and even more preferably 35 to 60% by mass based on the total solid content in the coloring composition.

[0695] 《Method 3》

[0696] A preferred embodiment (third embodiment) of the coloring composition of the present invention is a composition comprising a fluorine-containing oxime ester photopolymerization initiator, a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a colorant, and further comprising an α-aminoketone photopolymerization initiator, wherein the mass ratio of the fluorine-containing oxime ester photopolymerization initiator to the α-aminoketone photopolymerization initiator is 1:1.5 to 1:10.

[0697] By using such a colored composition, a cured film having excellent adhesion to a support and excellent rectangularity can be formed.

[0698] 《Method 4》

[0699] A preferred embodiment (fourth embodiment) of the coloring composition of the present invention is a composition comprising a fluorine-containing oxime ester photopolymerization initiator, a polymerizable compound having an ethylenically unsaturated double bond, an alkali-soluble resin, and a coloring agent, and further comprising an oxime photopolymerization initiator other than the fluorine-containing oxime ester photopolymerization initiator (other oxime photopolymerization initiator). By using such a coloring composition, it is easy to produce a cured film having good sensitivity and adhesion and suppressed fading.

[0700] <Method for preparing coloring composition>

[0701] The coloring composition of the present invention can be prepared by mixing the above components.

[0702] When preparing a coloring composition, the components constituting the coloring composition may be mixed together, or the components may be mixed sequentially after being dissolved and dispersed in a solvent. In addition, the order of addition and the operating conditions during mixing are not particularly restricted. For example, all components may be dissolved and dispersed in a solvent at the same time to prepare a composition. As required, each component may be appropriately prepared into two or more solutions or dispersions, and these may be mixed to prepare a composition when used (when applied).

[0703] The coloring composition of the present invention is preferably filtered with a filter for the purpose of removing foreign matter and reducing defects. As a filter, as long as it is used for filtering purposes in the past, it can be used without particular limitation. For example, a filter composed of fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon-6, nylon-6,6, polyethylene, polyolefin resins such as polypropylene (PP) (including high density, ultra-high molecular weight) and the like can be cited. Polypropylene (including high-density polypropylene) is preferred among these raw materials.

[0704] 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. By setting the pore size within this range, fine foreign matter that prevents uniform and smooth preparation of the colored curable composition can be reliably removed in the subsequent steps.

[0705] When using the filter, different filters may be used in combination. In this case, filtering by the first filter may be performed only once or twice or more.

[0706] Furthermore, the first filter having different pore diameters may be combined within the above range. The pore diameter here may refer to the nominal value of the filter manufacturer. As commercially available filters, for example, various filters provided by NIHON PALL LTD. (DFA4201NXEY, etc.), ADVANTECH TOYO KAISHA, LTD., NIHON ENTEGRIS KK (Mykrolis Corporation), or KITZMICROFILTER CORPORATION can be selected.

[0707] As the second filter, a filter made of the same material as the first filter can be used.

[0708] For example, filtration with the first filter may be performed only on the dispersion, or filtration with the second filter may be performed after mixing other components.

[0709] <Cured film, pattern forming method>

[0710] Next, the cured film and pattern forming method of the present invention will be described.

[0711] The cured film of the present invention is formed using the colored composition of the present invention. The cured film of the present invention can be preferably used as a color filter and a light-shielding film.

[0712] Color filters can be used in solid imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), and are particularly suitable for CCD and CMOS with a high resolution of more than 1 million pixels. Color filters can be used by being arranged between the light receiving portion of each pixel constituting the CCD or CMOS and the microlens for focusing light.

[0713] Furthermore, the color filter can be preferably used as an organic electroluminescent (organic EL) element. As the organic EL element, a white organic EL element is preferably used. The organic EL element is preferably a tandem structure. The tandem structure of the organic EL element is described in Japanese Patent Gazette No. 2003-45676, supervised by Akiyoshi Mikami, "The Forefront of Organic EL Technology Development - High Brightness, High Precision, Long Life, Technology Collection", Technical Information Association, pages 326-328, 2008, etc. As the tandem structure of the organic EL element, for example, a structure in which an organic EL layer is provided between a lower electrode having light reflectivity and an upper electrode having light transmittance on one side of a substrate can be cited. The lower electrode is preferably made of a material having sufficient reflectivity in the wavelength domain of visible light. The organic EL layer includes a plurality of light-emitting layers, and these plurality of light-emitting layers preferably have a stacked stacked structure (tandem structure). The organic EL layer, for example, a plurality of light-emitting layers can include a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer. Furthermore, it is preferred that a plurality of light-emitting layers are provided together with a plurality of light-emitting auxiliary layers for making these light-emitting layers emit light. The organic EL layer can be set to, for example, a stacked structure in which light-emitting layers and light-emitting auxiliary layers are alternately stacked. An organic EL element having an organic EL layer of such a structure can emit white light. In this case, it is preferred that the spectrum of white light emitted by the organic EL element has strong maximum emission peaks in the blue region (430nm-485nm), the green region (530nm-580nm) and the yellow region (580nm-620nm). It is more preferred that on the basis of these emission peaks, a maximum emission peak is further provided in the red region (650nm-700nm). By combining an organic EL element emitting white light (white organic EL element) with the color filter of the present invention, a spectral distribution with excellent color reproducibility is obtained, and clearer videos and images can be displayed.

[0714] The film thickness of the colored pattern (colored pixel) in the color filter is preferably 2.0 μm or less, more preferably 1.0 μm or less, and further preferably 0.7 μm or less. The lower limit may be, for example, 0.1 μm or more, or 0.2 μm or more.

[0715] The size (pattern width) of the colored pattern (colored pixel) is preferably 2.5 μm or less, more preferably 2.0 μm or less, and particularly preferably 1.7 μm or less. The lower limit may be, for example, 0.1 μm or more, or 0.2 μm or more.

[0716] The light-shielding film can be formed and used in various components in image display devices and sensor elements (for example, infrared light cutoff filters, the periphery of solid-state imaging elements, the periphery of wafer-level lenses, the inside of solid-state imaging elements, etc.).

[0717] Furthermore, a light-shielding film may be formed on at least a portion of the surface of the infrared cut filter to provide an infrared cut filter with a light-shielding film.

[0718] The thickness of the light-shielding film is not particularly limited, but is preferably 0.2 to 25 μm, more preferably 1.0 to 10 μm. The thickness is an average thickness, which is a value obtained by measuring the thickness at any five or more points of the light-shielding film and averaging the thickness.

[0719] The reflectivity of the light-shielding film is preferably 10% or less, more preferably 8% or less, further preferably 6% or less, and particularly preferably 4% or less. In addition, the reflectivity of the light-shielding film is measured by the following method: light of 400 to 700 nm is incident on the light-shielding film at an incident angle of 5°, and its reflectivity is measured by a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.

[0720] <Pattern Formation Method>

[0721] Next, the pattern forming method of the present invention will be described.

[0722] The pattern forming method of the present invention can be manufactured through the following steps: a step of forming a colored composition layer on a support using the colored composition of the present invention, a step of exposing the colored composition layer to a pattern, and a step of developing and removing the unexposed portion of the colored composition layer to form a colored pattern. And as needed, the following steps may be further provided, a step of drying the colored composition layer (pre-drying step), and a step of drying the formed colored pattern (post-drying step). Below, each step is described in detail.

[0723] <<Step of forming a colored composition layer>>

[0724] The step of forming a colored composition layer is to form a colored composition layer on a support using the colored composition of the present invention.

[0725] Examples of the support include transparent substrates of glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. A thin film transistor for driving an organic EL element may be formed on the transparent substrate.

[0726] Furthermore, a solid-state imaging element substrate in which a solid-state imaging element (light-receiving element) such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) is provided on a substrate may be used.

[0727] As a method for applying the colored composition of the present invention to a support, various methods such as slit coating, slit inkjet method, spin coating, cast coating, roll coating, screen printing method, etc. can be used.

[0728] The colored composition layer formed on the support is preferably heated (pre-baked). It is preferably heated at 120°C or less, more preferably 50 to 120°C, further preferably 80 to 110°C, and particularly preferably 90 to 105°C. By heating at 120°C or less, when an organic EL element is used as a light source for an image display device, and when a photoelectric conversion film of an image sensor is formed using an organic raw material, these characteristics can be more effectively maintained.

[0729] The heating time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Heating can be performed on a hot plate, an oven, or the like.

[0730] 《<Exposure process>》

[0731] Next, the colored composition layer formed on the support is exposed in a pattern (exposure step). For example, the colored composition layer formed on the support is exposed through a mask having a predetermined mask pattern using an exposure device such as a stepper, thereby performing pattern exposure. This allows the exposed portion to be cured.

[0732] As radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays are preferably used (i-rays are particularly preferred). The irradiation amount (exposure amount) is preferably 30 to 1500 mJ / cm 2 , more preferably 50 to 1000 mJ / cm 2 , most preferably 50 to 500 mJ / cm 2 The above range is preferred from the perspectives of low-energy production and stable production.

[0733] The oxygen concentration during exposure can be appropriately selected. For example, exposure can be performed in a low oxygen environment with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high oxygen environment with an oxygen concentration greater than 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). In addition, the illumination of the exposure energy can be appropriately set, usually from 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m2 , 15000W / m 2 、35000W / m 2 The oxygen concentration and exposure illuminance conditions can be appropriately combined, for example, the oxygen concentration can be set to 10 volume % and the illuminance can be set to 10000 W / m 2 , oxygen concentration 25 volume % and illumination 25000W / m 2 wait.

[0734] The thickness of the cured film is preferably 1.0 μm or less, more preferably 0.1 to 0.9 μm, and still more preferably 0.2 to 0.8 μm. When the thickness is 1.0 μm or less, high resolution and high adhesion are easily obtained.

[0735] 《<Development process>》

[0736] Next, the unexposed portion is removed by development to form a colored pattern. The unexposed portion can be removed by development using a developer. Thus, the unexposed portion of the colored composition layer in the exposure step is dissolved in the developer, and only the photocured portion remains.

[0737] As the developer, an organic alkaline developer which does not damage the solid imaging element and circuit on the substrate is preferable.

[0738] The temperature of the developer is preferably, for example, 20 to 30° C. The development time is preferably 20 to 180 seconds.

[0739] Examples of the alkaline agent used in the developer include organic alkaline compounds such as ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene. An alkaline aqueous solution obtained by diluting these alkaline agents with pure water to a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass, is preferably used as the developer.

[0740] In addition, an inorganic base may be used in the developer. As the inorganic base, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, sodium metasilicate, etc. are preferred. In addition, a surfactant may be used in the developer. As examples of surfactants, the surfactants described in the above-mentioned coloring composition can be cited, preferably a nonionic surfactant.

[0741] When a developer containing such an alkaline aqueous solution is used, it is usually preferred to perform cleaning (rinsing) with pure water after development.

[0742] After development, drying is preferably performed and then heat treatment (post-baking) is performed. If a multi-color coloring pattern is formed, the steps can be repeated sequentially for each color to produce a cured film. In this way, a color filter can be obtained.

[0743] Post-baking is a heat treatment after development for promoting curing, and the heating temperature is preferably, for example, 100 to 240° C. Furthermore, when an organic electroluminescent (organic EL) element is used as a light source of an image display device, and when a photoelectric conversion film of an image sensor is composed of an organic raw material, it is preferably heated (post-baking) at 50 to 120° C. (more preferably 80 to 100° C., and even more preferably 80 to 90° C.).

[0744] The developed film can be post-dried in a continuous or batch manner using a heating mechanism such as a hot plate, a convection oven (hot air circulation dryer), or a high-frequency heater so as to achieve the above conditions.

[0745] Furthermore, when a coloring composition containing the above-mentioned fluorine-containing oxime ester-based photopolymerization initiator and α-aminoketone-based photopolymerization initiator is used, in the above-mentioned exposure step, exposure is performed using light with a wavelength greater than 350 nm and less than 380 nm (preferably light with a wavelength of 355 to 370 nm, particularly preferably i-rays), and the coloring composition layer after the development step is further preferably exposed to light with a wavelength of 254 to 350 nm (preferably light with a wavelength of 254 nm).

[0746] Furthermore, the difference between the wavelength of light used in the exposure before the development step and the wavelength of light used in the exposure after the development step is preferably 200 nm or less, and more preferably 100 to 150 nm or less.

[0747] By exposing the colored composition layer in two stages, before and after the development process, the colored composition can be appropriately cured in the initial exposure, and the entire colored composition can be substantially cured in the subsequent exposure. As a result, the curability of the colored composition can be improved even under low temperature conditions of about 210°C without post-baking, and the solvent resistance of the color filter can be improved. In addition, color mixing with other colors can be suppressed.

[0748] The exposure before the development step may be performed under the conditions described in the above exposure step with respect to the irradiation amount (exposure amount) of light having a wavelength of more than 350 nm and less than or equal to 380 nm and the oxygen concentration during the exposure.

[0749] Furthermore, the reaction rate of the polymerizable compound in the exposure before the development step is preferably 30 to 60%. By setting such a reaction rate, the polymerizable compound can be made into a moderately cured state. Among them, the reaction rate of the compound having the polymerizable compound refers to the ratio of the unsaturated double bonds that have reacted among all the unsaturated double bonds possessed by the polymerizable compound.

[0750] In the exposure after the development step, the irradiation amount (exposure amount) of light with a wavelength of 254 to 300 nm is preferably 30 mJ / cm 2 ~4000mJ / cm 2 , more preferably 50 mJ / cm 2 ~3500mJ / cm 2 .

[0751] Furthermore, the reaction rate of the polymerizable compound in the exposure after the development step is preferably 60 to 90%. By setting such a reaction rate, the cured state of the colored composition layer after the exposure can be made better.

[0752] In this method, after the exposure after the development process, post-baking can be further performed. When an organic EL element is used as the light source of the image display device, and when the photoelectric conversion film of the image sensor is composed of organic raw materials, it is preferably heated (post-baking) at 50 to 120°C (more preferably 80 to 100°C, and even more preferably 80 to 90°C).

[0753] <Solid State Imaging Device>

[0754] The solid imaging device of the present invention has the above-mentioned cured film of the present invention (color filter, light shielding film, etc.). The structure of the solid imaging device of the present invention is not particularly limited as long as it has the cured film of the present invention and functions as a solid imaging device, and for example, the following structures can be cited.

[0755] On a support body, there are "multiple photodiodes" and "transfer electrodes containing polysilicon and the like" that constitute the light-receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.). On these photodiodes and transfer electrodes, there is a light-shielding film in which only the light-receiving portion of the photodiode is opened. On the light-shielding film, there is a device protection film containing silicon nitride and the like that is formed in a manner covering the entire surface of the light-shielding film and the light-receiving portion of the photodiode. On the device protection film, there is a color filter. In addition, a focusing mechanism (such as a microlens, etc., the same below) may be provided on the device protection film and on the lower side of the color filter (the side close to the support body), or a focusing mechanism may be provided on the color filter.

[0756] <Image Display Device>

[0757] The cured film (color filter, light-shielding film, etc.) of the present invention can be used in image display devices such as liquid crystal display devices and organic electroluminescent display devices.

[0758] The definition of display devices and the details of each display device are described in, for example, "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosakai Publishing Co., LTD. in 1990)" and "Display Devices (written by Junsho Ibuki, published by Sangyo Tosho Co., LTD. in 1991)". In addition, regarding liquid crystal display devices, it is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., LTD. in 1994)".

[0759] The liquid crystal display device to which the present invention can be applied is not particularly limited, and for example, the present invention can be applied to liquid crystal display devices of various types described in the above-mentioned "Next-generation liquid crystal display technology".

[0760] The color filter of the present invention can also be used in a color TFT (Thin Film Transistor) liquid crystal display device. Regarding the color TFT liquid crystal display device, for example, it is recorded in "Color TFT Liquid Crystal Display (KYORITSUSHUPPAN CO., LTD., published in 1996)". In addition, the present invention can also be applied to a liquid crystal display device with a widened viewing angle such as a lateral electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), or STN (Super-Twist Nematic), TN (Twisted Nematic), VA (Vertical Alignment), OCS (on-chip spacer), FFS (fringe field switching), and R-OCB (Reflective Optically Compensated Bend).

[0761] Furthermore, the color filter of the present invention can also be provided in a bright and high-definition COA (Color-filter On Array) mode. In a liquid crystal display device of the COA mode, in addition to the usual required characteristics as described above, the required characteristics of the color filter sometimes also require the required characteristics of the interlayer insulating film, i.e., low dielectric constant and resistance to stripping liquid. The color filter of the present invention is excellent in light resistance, etc., and thus can provide a liquid crystal display device of the COA mode with high resolution and excellent long-term durability. In addition, in order to meet the required characteristics of low dielectric constant, a resin film can also be provided on the color filter layer.

[0762] These image display methods are described, for example, in "EL, PDP, LCD Displays - Latest Trends in Technology and Market - (Toray Research Center, Inc. Research Department, published in 2001)", page 43, etc.

[0763] The image display device of the present invention is composed of various components such as an electrode substrate, a polarizing film, a phase difference film, a backlight device, a spacer, and a viewing angle compensation film in addition to the color filter of the present invention. The color filter of the present invention can be applied to a liquid crystal display device composed of these well-known components. These components are described in, for example, "'94 Market of Liquid Crystal Display Peripheral Materials and Chemical Products (published by Kentaro Shima CMC CO., LTD. in 1994)" and "2003 Current Situation and Future Prospects of Liquid Crystal Related Market (Volume 2) (published by FUJI CHIMERA RESEARCH INSTITUTE, INC. in 2003)".

[0764] The backlight is described in SID meeting Digest 1380 (2005) (A. Konno et al.), Monthly Display, December 2005, pages 18 to 24 (Yasuhiro Shima), Monthly Display, pages 25 to 30 (Takaaki Yagi), and the like.

[0765] <Infrared sensor>

[0766] The infrared sensor of the present invention comprises the cured film of the present invention. The structure of the infrared sensor of the present invention is a structure comprising the cured film of the present invention, and is not particularly limited as long as it functions as a solid imaging element, and examples thereof include the following structures.

[0767] On the substrate, there are "multiple photodiodes" and "transfer electrodes made of polysilicon or the like" constituting the light receiving area of ​​the solid imaging element (CCD sensor, CMOS sensor, organic CMOS sensor, etc.). On these photodiodes and transfer electrodes, there is a light shielding film made of tungsten or the like with only the light receiving part of the photodiode open. On the light shielding film, there is a device protection film made of silicon nitride or the like formed in a manner covering the entire surface of the light shielding film and the light receiving part of the photodiode. On the device protection film, there is a cured film of the present invention.

[0768] Furthermore, a light focusing mechanism (such as a microlens, etc., the same applies hereinafter) may be provided on the device protection film and on the lower side (the side close to the substrate) of the cured film of the present invention, or a light focusing mechanism may be provided on the cured film of the present invention.

[0769] Hereinafter, one embodiment of the infrared sensor of the present invention will be described with reference to FIG. 2 .

[0770] The infrared sensor 100 includes a solid-state imaging element 110 .

[0771] The imaging region provided on the solid-state imaging element 110 includes a near infrared absorption filter 111 and a color filter 112 .

[0772] The near infrared absorption filter 111 is constructed so as to transmit light in the visible light region (e.g., light with a wavelength of 400 to 700 nm) and shield light in the infrared region (e.g., light with a wavelength of 800 to 1300 nm, preferably light with a wavelength of 900 to 1200 nm, and more preferably light with a wavelength of 900 to 1000 nm).

[0773] The color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible light region, and for example, color filters forming red, green, and blue pixels can be used. The color filter can be formed using the cured film of the present invention.

[0774] A region 114 without the near infrared absorption filter 111 is provided between the near infrared transmission filter 113 and the solid imaging element 110. The region 114 is provided with a resin layer (eg, a transparent resin layer) that transmits light having a wavelength of the near infrared transmission filter 113.

[0775] The near infrared transmission filter 113 has visible light shielding properties and is a filter that transmits infrared light of a specific wavelength. The near infrared transmission filter 113 is composed of the cured film of the present invention having the above-mentioned spectrum.

[0776] A microlens 115 is disposed on the incident light hv side of the color filter 112 and the near infrared transmission filter 113. A planarization layer 116 is formed so as to cover the microlens 115.

[0777] In the embodiment shown in FIG. 2 , the resin layer is disposed in the region 114 , but the near infrared transmission filter 113 may be formed in the region 114 . That is, the near infrared transmission filter 113 may be formed on the solid state imaging element 110 .

[0778] And, in Figure 2 In the illustrated embodiment, the film thickness of the color filter 112 is the same as the film thickness of the near-infrared transmission filter 113 , but the film thicknesses of the two may be different.

[0779] and, Figure 2 In the illustrated embodiment, the color filter 112 is disposed on a side closer to the incident light hν than the near-infrared absorption filter 111, but the order of the near-infrared absorption filter 111 and the color filter 112 may be replaced by disposing the near-infrared absorption filter 111 on a side closer to the incident light hν than the color filter 112.

[0780] and, Figure 2 In the illustrated embodiment, the near infrared absorption filter 111 and the color filter 112 are stacked adjacent to each other, but the two color filters do not necessarily need to be adjacent to each other, and another layer may be provided therebetween.

[0781] The infrared sensor can simultaneously acquire image information, thereby enabling sensing of moving objects, etc. Furthermore, since distance information can be acquired, it is also possible to capture images containing three-dimensional information, etc.

[0782] Example

[0783] The present invention will be described in further detail below by way of examples, but the present invention is not limited to the following examples unless it departs from the spirit of the present invention. In addition, "%" and "part" are based on mass unless otherwise specified.

[0784] (Measurement of optical density (OD value))

[0785] The optical density of the film was measured by measuring the transmittance of light incident at a wavelength of 365 nm using a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.

[0786] (Determination of weight average molecular weight)

[0787] The weight average molecular weight (Mw) was measured under the following conditions.

[0788] Column type: TSKgel Super AWM-H (manufactured by TOSOH CORPORATION, 6.0 mm ID (inner diameter) × 15.0 cm)

[0789] Developing solvent: 10 mmol / L lithium bromide NMP (N-methylpyrrolidone) solution Column temperature: 25°C Flow rate (sample injection amount): 0.6 mL / min Apparatus name: HLC-8220 (manufactured by TOSOH CORPORATION)

[0790] Calibration curve base resin: polystyrene resin

[0791] <Test Example 1>

[0792] Pigment dispersions 1 to 4 were prepared by mixing the mixed liquids of the following compositions for 2 hours using zirconium beads having a diameter of 0.3 mm with a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by NIHONB.EECO., LTD.)).

[0793] [Composition of pigment dispersion 1]

[0794] ·CI Pigment Green 58……3.5 parts

[0795] ·Basic resin 1...2.1 parts

[0796] ·Organic solvent 1……22.75 parts

[0797] [Composition of Pigment Dispersion Liquid 2]

[0798] ·CI Pigment Green 36……3.9 parts

[0799] ·CI Pigment Yellow 150……0.6 parts

[0800] CT Pigment Yellow 185……0.2 parts

[0801] ·CI Pigment Yellow 138 Sulfonate……0.5 parts

[0802] ·Bipolar resin 1...1.6 parts

[0803] Resin A1...1.6 parts

[0804] ·Organic solvent 1...25.0 parts

[0805] [Composition of pigment dispersion 3]

[0806] CT Pigment Yellow 150……1.6 parts

[0807] · Acidic resin 1...1.2 parts

[0808] ·Organic solvent 1……9.2 parts

[0809] ·Organic solvent 2...1.6 parts

[0810] [Composition of Pigment Dispersion Liquid 4]

[0811] ·CI Pigment Yellow 139……2.1 parts

[0812] Resin A1……0.4 parts

[0813] ·Bipolar resin 2……0.4 parts

[0814] ·Organic solvent 1...13.5 parts

[0815] Resin A1: The following structure (the numerical values ​​recorded together in each repeating unit represent the content (mass ratio) of each repeating unit. Mw = 11,000)

[0816] The synthesis was carried out by the method described in paragraphs 0304 to 0307 of JP-A-2012-173356. Resin A1 is also an alkali-soluble resin.

[0817] [Chemical formula 42]

[0818]

[0819] Basic resin 1: (product name: Diperbyk162, manufactured by BYK Chemie company, amine value: 13 mgKOH / g)

[0820] Acidic resin 1: (product name: Diperbyk111, manufactured by BYK Chemie company, acid value: 129 mgKOH / g)

[0821] · Bifunctional resin 1: the following structure (the numerical value recorded together in each repeating unit represents the content (mass ratio) of each repeating unit. The numerical value recorded together in the repeating part of the side chain represents the number of repeating parts of the repeating part. Acid value 32.3 mgKOH / g, amine value 45.0 mgKOH / g, Mw=9000)

[0822] [Chemical formula 43]

[0823]

[0824] · Bifunctional resin 2: the following structure (the numerical value recorded together in each repeating unit represents the content of each repeating unit (mass ratio). The numerical value recorded together in the repeating part of the side chain represents the number of repeats of the repeating part. Acid value 44.3 mgKOH / g, amine value 40.0 mgKOH / g, Mw = 10400)

[0825] [Chemical formula 44]

[0826]

[0827] Organic solvent 1: Propylene glycol methyl ether acetate

[0828] Organic solvent 2: Cyclohexanone

[0829] [Preparation of coloring composition]

[0830] The raw materials shown in Table 1 below were mixed and stirred at the ratios (parts by mass) shown in Table 1, and then filtered using a nylon color filter having a pore size of 0.45 μm (manufactured by NIHON PALL LTD., DFA4201NXEY) to prepare a coloring composition.

[0831] (Production of Color Filters)

[0832] The obtained coloring composition was applied to a 200 mm (8 inch) silicon wafer (substrate) pre-sprayed with hexamethyldisilazane to form a coating film, which was then heated for 150 seconds using a 90° C. hot plate (pre-baking) to a dry film thickness of 2.0 μm.

[0833] Next, the film was exposed using an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.) at a wavelength of 365 nm and an island pattern mask with a transmission pattern of 3.0 μm square. The exposure conditions were 50 to 1200 mJ / cm 2 Various exposure amounts, illumination 10000W, atmospheric conditions (oxygen concentration 21 volume %).

[0834] Then, the silicon wafer with the exposed coating film formed thereon was placed on a horizontal rotating table of a rotary shower developer (DW-30 model, manufactured by CHEMITRONICS CO., LTD.), and paddle developed at 23° C. for 60 seconds using CD-2000 (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.). Thus, a colored pattern (square pixel pattern with a square of 3.0 μm) was formed on the silicon wafer with the undercoat layer.

[0835] The silicon wafer with the colored pattern was fixed on a horizontal rotating table by vacuum chuck, and the silicon wafer was rotated at 50 rpm by a rotating device, and pure water was supplied from a spray nozzle from above the rotation center to rinse. Then, the silicon wafer was spin-dried.

[0836] The obtained silicon wafer was irradiated with ultraviolet light at an exposure amount of 10 J using a UV curing device UMA-802-HC552FFAL (manufactured by USHIO INC.).

[0837] As described above, a color filter (silicon wafer with a color pattern) was obtained.

[0838] (Sensitivity evaluation)

[0839] The optimum exposure amount (mJ) for analyzing the above-mentioned colored pattern (square pixel pattern with a corner of 3.0 μm) was determined and used as the sensitivity.

[0840] (Evaluation of close fit sensitivity)

[0841] The silicon wafer evaluated for sensitivity was observed using an optical microscope, and the minimum exposure dose (mJ) at which a square pixel pattern with a square angle of 3.0 μm was not completely peeled off was determined and taken as the adhesion sensitivity.

[0842] (Rectangularity evaluation)

[0843] The cross section of the silicon wafer evaluated for sensitivity was observed using a scanning electron microscope, and the angle between the side wall of the 3.0 μm square pixel pattern formed at the optimal exposure amount and the silicon wafer surface was measured and evaluated according to the following evaluation criteria.

[0844] "3": The angle of the side wall is greater than 80° and less than 100°,

[0845] "2": The angle of the side wall is greater than 70° and less than 80° or greater than 100° and less than 110°,

[0846] "1": The angle of the side wall is less than 70° or greater than 110°.

[0847] (Evaluation of stability over time)

[0848] The obtained coloring composition was stored at room temperature (25°C) for 1 month. The color filter was prepared using the coloring composition stored at room temperature for 1 month. The exposure was set to the optimal exposure before storage at room temperature for 1 month. The difference in pixel line width of the prepared color filter was measured, and the stability over time was evaluated according to the following evaluation criteria.

[0849] "3": The change in line width difference between pixels before and after storage at room temperature for one month is less than 0.10 μm,

[0850] “2”: The variation in line width difference between pixels before and after storage at room temperature for one month is 0.10 μm or more and less than 0.15 μm,

[0851] “1”: The variation in line width difference between pixels before and after storage at room temperature for one month is 0.15 μm or more.

[0852]

[0853] According to the above results, in Examples, a cured film having low adhesion sensitivity and excellent adhesion can be formed at a relatively low sensitivity. Furthermore, in Examples, the sensitivity, rectangularity, and stability over time are excellent.

[0854] On the other hand, in the comparative examples, the adhesion sensitivity was larger than that in the examples, and it was difficult to form a cured film having good adhesion.

[0855] The raw materials shown in the above Table 1 are as follows.

[0856] Alkali-soluble resin 1: the following structure (the numerical values ​​recorded together in each repeating unit represent the content (mass ratio) of each repeating unit. Mw=11,000)

[0857] [Chemical formula 45]

[0858]

[0859] Alkali-soluble resin 2: the following structure (the numerical values ​​recorded together in each repeating unit represent the content (mass ratio) of each repeating unit. Mw = 14,000)

[0860] [Chemical formula 46]

[0861]

[0862] · Polymerizable compound 1: the following structure (a mixture of the left-hand compound and the right-hand compound in a molar ratio of 7:3)

[0863] [Chemical formula 47]

[0864]

[0865] ·Polymerizable compound 3: The following structure

[0866] [Chemical formula 48]

[0867]

[0868] Polymerizable compound 4: Carboxylic acid-containing multifunctional acrylate (ARONIX M-520) manufactured by TOAGOSEI CO., LTD.

[0869] ·Polymerizable compound 5: The following structure

[0870] [Chemical formula 49]

[0871]

[0872] Compounds having epoxy groups (epoxy compounds): EHPE3150, manufactured by DAICEL CHEMICAL INDUSTRIES, CO., LTD.

[0873] Photopolymerization initiators A1 to A3, 2, 2B, 3, 3B, 4: the following structures

[0874] [Chemical formula 50]

[0875]

[0876] ·Inhibitor: p-Methoxyphenol

[0877] Silane coupling agent: the following structure

[0878] [Chemical formula 51]

[0879]

[0880] Surfactant: The following mixture (Mw = 14000)

[0881] [Chemical formula 52]

[0882]

[0883] Organic solvent 2: Cyclohexanone

[0884] Good results were also obtained by using the pigment dispersion B-1 or B-2 of the following Test Example 3 instead of the pigment dispersions 1, 2, 3, and 4 of Example 1-1.

[0885] <Test Example 2>

[0886] [Production of Titanium Black A-1]

[0887] The BET specific surface area is 110 m 2 / g titanium oxide ("TTO-51N" trade name: manufactured by ISHIHARA SANGYOKAISHA, LTD.) 120g, BET specific surface area 300m 2 / g of silicon oxide particles ("AEROSIL (registered trademark) 300", manufactured by EVONIK) 25g, and dispersant "Disperbyk190" (trade name: manufactured by BYK Chemie company) 100g, ion-exchanged water 71g, using MAZERSTAR KK-400W manufactured by KURABO INDUSTRIES LTD., by treating at a revolution speed of 1360rpm and a rotation speed of 1047rpm for 30 minutes to obtain a uniform mixture aqueous solution. The mixture aqueous solution is filled into a quartz container, and heated to 920°C in an oxygen atmosphere using a small rotary furnace (manufactured by Motoyama co., LTD.), and then replaced with nitrogen. Nitriding reduction treatment is performed by flowing ammonia gas at 100mL / min for 5 hours at the same temperature. After completion, the recovered powder is crushed in a mortar. A powdery Si-atom-containing BET specific surface area of ​​85m 2 / g of titanium black (A-1) [a dispersed body comprising titanium black particles and Si atoms].

[0888] [Preparation of titanium black dispersion (TB dispersion 1)]

[0889] The components shown in the following composition 1 were mixed for 15 minutes using a stirrer (EUROSTAR manufactured by IKA company) to obtain a dispersion a.

[0890] The obtained dispersion a was dispersed under the following dispersion conditions using Ultra Apex Mill UAM015 manufactured by KOTOBUKI KOGYOU CO., LTD. Then, it was filtered using a nylon color filter with a pore size of 0.45 μm (DFA4201NXEY manufactured by NIHONPALL LTD.), thereby obtaining a titanium black dispersion (hereinafter referred to as TB dispersion 1).

[0891] (Composition 1)

[0892] Titanium black (A-1) obtained as described above: 25 parts by mass

[0893] · Propylene glycol monomethyl ether acetate (PGMEA) 30 mass % solution of resin 1 ... 25 mass parts

[0894] ·PGMEA……50 parts by mass

[0895] Resin 1: The following structure. Synthesis was performed with reference to the description of Japanese Patent Application Publication No. 2013-249417. In the formula of Resin 1, x is 43% by mass, y is 49% by mass, and z is 8% by mass. In addition, Resin 1 has a weight average molecular weight of 30,000, an acid value of 60 mgKOH / g, and the number of atoms in the graft chain (excluding hydrogen atoms) is 117.

[0896] [Chemical formula 53]

[0897]

[0898] (Dispersion conditions)

[0899] Bead diameter: 0.05mm

[0900] Bead filling rate: 75 volume %

[0901] ·Pearl circumferential speed: 8m / sec

[0902] ·Amount of mixed liquid for dispersion treatment: 500g

[0903] ·Circulation flow rate (pump supply): 13kg / hour

[0904] ·Processing liquid temperature: 25~30℃

[0905] Cooling water: tap water

[0906] · Volume of bead mill annular passage: 0.15L

[0907] Number of passes: 90

[0908] [Preparation of coloring composition]

[0909] The raw materials shown in the following Table 2 were mixed at a ratio shown in the following composition, and then filtered using a nylon color filter having a pore size of 0.45 μm (manufactured by NIHON PALL LTD., DFA4201NXEY) to prepare a coloring composition.

[0910] The following MEGAFAC RS-72-K contains an alkylene group containing a fluorine atom and an acryloyloxy group. More specifically, MEGAFAC RS-72-K contains a repeating unit represented by the formula (B1-1) and a repeating unit represented by the formula (B3-1) as described below, and the weight average molecular weight is 7400. In addition, in the formula (B3-1), X represents a perfluoromethylene group or a perfluoroethylene group, and r represents the number of repeating units.

[0911] [Chemical formula 54]

[0912]

[0913] (composition)

[0914] TB dispersion 1 ... 63.9 parts by mass

[0915] Alkali-soluble resin (specific resin 2 or 3 described below) ... 10.24 parts by mass

[0916] Photopolymerization initiator: 1.81 parts by mass

[0917] ·Polymerizable compound……6.29 parts by mass

[0918] Surfactant……0.02 parts by mass

[0919] Solvent (cyclohexanone) ...... 4.66 parts by mass

[0920] Curable compound (MEGAFAC RS-72-K (manufactured by DIC CORPORATION, solid content 30%, solvent: PGMEA)): 10.65 parts by mass

[0921] Silane coupling agent (KBM-4803 (manufactured by Shin-Etsu Chemical Co., LTD.)): 0.36 parts by mass

[0922] The raw materials shown in Table 2 below are as follows.

[0923] As polymerizable compounds 1 and 4, a photopolymerization initiator, and a surfactant, the same materials as those of the colored composition of Test Example 1 were used.

[0924] ·Polymerizable compound 6: The following structure

[0925] [Chemical formula 55]

[0926]

[0927] Specific resin 2: The following structure. It was synthesized according to the manufacturing method of paragraphs 0338 to 0340 of Japanese Patent Publication No. 2010-106268. In the following formula, x is 90% by mass and z is 10% by mass. In addition, the weight average molecular weight of specific resin 2 is 40,000, the acid value is 100 mgKOH / g, and the number of atoms in the graft chain (excluding hydrogen atoms) is 117.

[0928] [Chemical formula 56]

[0929]

[0930] · Specific resin 3: the following structure (Mw = 24000)

[0931] [Chemical formula 57]

[0932]

[0933] (Production of Cured Film (Light-Shielding Film))

[0934] The coloring composition prepared above was applied to a 200 mm (8 inch) glass substrate EagleXG (manufactured by Corning Incorporated) by spin coating, and then heated for 120 seconds using a hot plate at 80°C (pre-baking). Next, an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.) was used to expose the film at 200 mJ / cm through a shield having a line type of 300 μm (width 300 μm, length 4 mm). 2 The film was exposed to an exposure amount of 1000 μm. Then, AD-1200 (manufactured by MIKASA CO., LTD.) was used to develop the film under rotary immersion for 40 seconds using a surfactant NCW-101 (nonionic surfactant) manufactured by Wako Pure Chemical Industries, LTD. containing 0.3% by mass and an aqueous solution of tetramethylammonium hydroxide (TMAH) containing 0.01% by mass. Then, a heat treatment (post-baking) was performed at 150° C. for 1 hour using a clean oven CLH-21CDH (manufactured by KOYOTHERMO SYSTEMS CO., LTD.). Thus, a light-shielding film (width 300 μm, length 4 mm) with a film thickness of 2 μm was formed.

[0935] (Reflectivity evaluation)

[0936] The formed light-shielding film was incident with light of 400 to 700 nm at an incident angle of 5°, and the reflectance thereof was measured using a spectrometer UV4100 (trade name) manufactured by Hitachi High-Technologies Corporation.

[0937] (Defect Evaluation)

[0938] CT-18 (manufactured by Nichiban Co., LTD.) was pressed firmly on the formed linear 300μm (width 300μm, length 4mm) shading film, and the tape was peeled off at an angle of 45 degrees from the end of the tape at one time. The state of the shading film after the tape was peeled off (pulling the tape) was compared with the state of the shading film before pulling the tape using an optical microscope MT-3600LW (manufactured by FLOVEL CO., LTD.), and the evaluation was performed according to the following evaluation criteria. "2" or more is the allowable range.

[0939] "3": No damage was observed on the pattern edge of the 300μm linear light-shielding film on the glass substrate.

[0940] "2": There are less than 5 damages on the pattern edge of the 300μm linear light-shielding film on the glass substrate.

[0941] "1": Six or more damages were found on the edge of the pattern of the 300 μm linear light-shielding film on the glass substrate.

[0942] (Linearity evaluation)

[0943] The line width of the formed light shielding film with a line shape of 300 μm was measured at 255 points using an optical microscope MT-3600LW (manufactured by FLOVEL CO., LTD.) 3σ of the measured line width was calculated and evaluated according to the following evaluation criteria: "2" or more is the allowable range.

[0944] “3”: 3σ of line width of 300μm is less than 1μm

[0945] "2": 3σ of the line width of a line type of 300 μm is 1 μm or more and less than 5 μm

[0946] "1": 3σ of line width of 300μm is 5μm or more

[0947] (Adhesion Evaluation)

[0948] The obtained colored composition was applied on a glass wafer using a spin coater so that the film thickness after drying became 2.0 μm, and a heat treatment (pre-baking) was performed using a 100° C. hot plate for 120 seconds.

[0949] Next, using a photomask having a square pixel pattern of 100 μm in angle, an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.) was used to increase the exposure dose by 50 mJ / cm 2 The method increases to 50~750mJ / cm 2 The glass wafer having the square pixel pattern was observed and analyzed using an optical microscope and evaluated based on the following evaluation criteria.

[0950] “3”: Exposure is 50mJ / cm 2 No pattern peeling

[0951] “2”: Exposure is 50 mJ / cm 2 And there is pattern peeling, the exposure is 100mJ / cm 2 And no patterned glass

[0952] “1”: Exposure is 100mJ / cm 2 And there is pattern peeling

[0953] (Rectangularity evaluation)

[0954] The cross section of the glass wafer for which the adhesion value was evaluated was observed using a scanning electron microscope. The exposure dose was measured at 200 mJ / cm 2 The angle of the glass wafer surface relative to the side wall of the square pixel pattern in the case of was evaluated according to the following evaluation criteria.

[0955] "3": The angle of the side wall is greater than 80° and less than 100°

[0956] "2": The angle of the side wall is 70° or more and less than 80° or 100° or more and less than 110°

[0957] "1": The angle of the side wall is less than 70° or more than 110°

[0958]

[0959] As shown in the above table, the adhesion in the examples was excellent. Furthermore, the reflectivity of the cured film was low. Furthermore, the linearity and defect evaluations were also good.

[0960] On the other hand, the adhesion in the comparative example was poor.

[0961] <Test Example 3>

[0962] [Preparation of pigment dispersion B-1]

[0963] The mixed solution of the following composition was mixed and dispersed for 3 hours using zirconium beads with a diameter of 0.3 mm using a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by NIHONB.EECO., LTD.)) to prepare a pigment dispersion B-1.

[0964] (composition)

[0965] · Mixed pigment containing red pigment (CI Pigment Red 254) and yellow pigment (CI Pigment Yellow 139) (CI Pigment Red 254:CI Pigment Yellow 139=4:1 (mass ratio)) ... 11.8 parts by mass

[0966] Resin 1 (dispersant) (BYK-111 manufactured by BYK-Chemie GmbH) ... 9.1 parts by mass

[0967] Propylene glycol methyl ether acetate...79.1 parts by mass

[0968] [Preparation of Pigment Dispersion Liquid B-2]

[0969] The mixed solution of the following composition was mixed and dispersed for 3 hours using zirconium beads with a diameter of 0.3 mm using a bead mill (high-pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by NIHONB.EECO., LTD.)) to prepare a pigment dispersion B-2.

[0970] (composition)

[0971] Mixed pigment containing a blue pigment (CI Pigment Blue 15:6) and a violet pigment (CI Pigment Violet 23) (CI Pigment Blue 15:6:CI Pigment Violet 23=9:4 (mass ratio)) ... 12.6 parts by mass

[0972] Resin 1 (dispersant) (BYK-111 manufactured by BYK-Chemie GmbH) ... 2.0 parts by mass

[0973] Resin 2 (dispersant) ... 3.3 parts by mass

[0974] Cyclohexanone: 31.2 parts by mass

[0975] Propylene glycol methyl ether acetate...50 parts by mass

[0976] Resin 2: The following structure (the numerical values ​​described together in each repeating unit represent the content (mass ratio) of each repeating unit. Mw=14,000) Resin 2 is also an alkali-soluble resin.

[0977] [Chemical formula 58]

[0978]

[0979] [Preparation of coloring composition]

[0980] The raw materials shown in Table 3 below were mixed and stirred at the ratios (parts by mass) shown in Table 3, and then filtered through a nylon color filter having a pore size of 0.45 μm (DFA4201NXEY manufactured by NIHON PALL LTD.) to prepare a coloring composition.

[0981] [Absorbance]

[0982] The obtained colored composition was applied to a glass substrate using a spin coater to a film thickness of 1.0 μm after post-baking. Next, it was dried for 120 seconds using a 100° C. hot plate, and then heated for 300 seconds using a 200° C. hot plate (post-baking). Thus, a colored layer was formed on the glass substrate.

[0983] The glass substrate having the colored layer formed thereon was subjected to absorbance measurement using an ultraviolet-visible-near-infrared spectrophotometer U-4100 (manufactured by Hitachi High-Technologies Corporation). Specifically, the minimum absorbance value A in the range of wavelengths from 400 nm to less than 580 nm, the minimum absorbance value B in the range of wavelengths from 580 nm to 750 nm, the minimum absorbance value C in the range of wavelengths from 400 nm to 750 nm, and the maximum absorbance value D in the range of wavelengths from 1000 nm to 1300 nm were measured.

[0984] [Production of color filters]

[0985] The obtained coloring composition was applied on a silicon wafer using a spin coater to a film thickness of 2.0 μm after drying, and then heated for 120 seconds using a 100° C. hot plate (pre-baking). Thus, a coating film was formed on the silicon wafer.

[0986] Next, using a photomask formed with a square pixel pattern of 3.0 μm corners, exposure was performed at an optimal exposure dose using an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.). The optimal exposure dose was obtained by increasing the exposure dose by 50 mJ / cm 2 The method increases to 50~750mJ / cm 2 The coating film was exposed, and the exposure amount was determined based on the analysis of the above-mentioned square pixel pattern.

[0987] Then, the silicon wafer with the exposed coating film formed thereon was placed on a horizontal rotating table of a rotary shower developer (DW-30 model, manufactured by CHEMITRONICS CO., LTD.), and subjected to stirring development at 23° C. for 60 seconds using CD-2060 (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.). Thus, a colored pattern was formed on the silicon wafer.

[0988] The silicon wafer on which the colored pattern was formed was rinsed with pure water and then spin-dried.

[0989] Furthermore, a heat treatment (post-baking) was performed using a 200° C. hot plate for 300 seconds to obtain a color filter (silicon wafer with a color pattern).

[0990] (Sensitivity evaluation)

[0991] The obtained coloring composition was applied onto a silicon wafer using a spin coater so that the film thickness after drying became 2.0 μm, and a heat treatment (pre-baking) was performed using a 100° C. hot plate for 120 seconds.

[0992] Next, using a photomask having a square pixel pattern of 3.0 μm in angle, and using an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.), the exposure dose was increased by 50 mJ / cm 2 The method increases to 50~750mJ / cm 2 The optimum exposure (mJ) for analyzing the above square pixel pattern was determined and used as the sensitivity.

[0993] (Evaluation of close fit sensitivity)

[0994] The silicon wafer evaluated for sensitivity was observed using an optical microscope, and the lowest exposure dose (mJ) at which a square pixel pattern with a corner of 3.0 μm formed at the optimum exposure dose was not completely peeled off was determined and taken as the adhesion sensitivity.

[0995] (Rectangularity evaluation)

[0996] The cross section of the silicon wafer evaluated for sensitivity was observed using a scanning electron microscope, and the angle of the side wall of the 3.0 μm square pixel pattern formed at the optimal exposure amount relative to the silicon wafer surface was measured and evaluated according to the following evaluation criteria.

[0997] "3": The angle of the side wall is greater than 80° and less than 100°,

[0998] "2": The angle of the side wall is 70° or more and less than 80° or 100° or more and less than 110°,

[0999] "1": The angle of the side wall is less than 70° or greater than 110°.

[1000] [Table 3]

[1001]

[1002] As shown in Table 3 above, in the embodiment, the close sensitivity is small, and a cured film with excellent close adhesion can be formed with less exposure. In the embodiment, the evaluation of sensitivity and rectangularity is also good. In addition, the color filter of the embodiment can transmit infrared (especially near infrared) in a state with less noise from visible light components. On the other hand, compared with the embodiment, the close sensitivity of the comparative example is high, and it is difficult to form a cured film with excellent close adhesion.

[1003] In Table 3, alkali-soluble resin 1, alkali-soluble resin 2, polymerizable compound 1, polymerizable compounds 3 to 5, photopolymerization initiators A1 to A3, photopolymerization initiator 2, photopolymerization initiator 3, photopolymerization initiator 4, silane coupling agent, and surfactant are the same as those of the coloring composition of Test Example 1. In addition, propylene glycol methyl ether acetate (PGMEA) is used as organic solvent 1. In addition, the values ​​of the blending amount of the surfactant in the table are values ​​of a 1 mass % PGMEA solution.

[1004] <Test Example 4>

[1005] (Preparation of Green Pigment Dispersion)

[1006] A mixed solution containing 587.55 parts by mass of CI Pigment Green, 1851.89 parts by mass of CI Pigment Yellow, 0.94 parts by mass of Pigment Derivative A, 3.7 parts by mass of resin (dispersant A), and 65.7 parts by mass of PGMEA was mixed and dispersed for 15 hours using a bead mill to prepare a Green pigment dispersion.

[1007] Pigment derivative A: Structure shown below

[1008] [Chemical formula 59]

[1009]

[1010] Dispersant A: Structure shown below (the numerical value recorded together in each repeating unit represents the content (mass ratio) of each repeating unit. The numerical value recorded together in the repeating part of the side chain represents the number of repeating parts of the repeating part. Acid value = 50 mgKOH / g, Mw = 24000)

[1011] [Chemical formula 60]

[1012]

[1013] (Preparation of Green Pigment-Containing Coloring Composition (Coating Liquid))

[1014] The Green pigment dispersion was used to achieve the composition ratio (parts by mass) described in Table 4 below, and the respective raw materials were mixed and stirred to prepare a Green pigment-containing coloring composition.

[1015] (Pattern Formation 1)

[1016] A 200 mm (8 inch) silicon wafer was heat treated at 200° C. for 30 minutes in an oven. Then, CT-4000L (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.) was coated on the silicon wafer to a film thickness of 0.1 μm after post-baking, and further heated and dried for 5 minutes using a 220° C. hot plate to form an undercoat layer. Thus, a silicon wafer with an undercoat layer was obtained.

[1017] Each coloring composition was applied onto the undercoat layer of the silicon wafer with an undercoat layer to form a coloring composition layer (coating film), and then the coating film was heated for 120 seconds using a hot plate at 100° C. (pre-baking) to a dry film thickness of 0.5 μm.

[1018] Next, exposure was performed at a wavelength of 365 nm using an i-ray stepper exposure apparatus FPA-3000i5+ (manufactured by CANON Inc.) through a Bayer pattern mask having a 1.1 μm square pattern.

[1019] Then, the silicon wafer with the exposed coating film formed thereon was placed on a horizontal rotating table of a rotary shower developer (DW-30 model, manufactured by CHEMITRONICS CO., LTD.), and subjected to stirring development at 23° C. for 60 seconds using CD-2060 (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.). Thus, a 1.1 μm×1.1 μm green colored pattern (1.1 μm pattern) was formed on the silicon wafer.

[1020] The silicon wafer with the colored pattern was fixed on a horizontal rotating table by vacuum chuck, and the silicon wafer was rotated at a speed of 50 rpm by a rotating device, and pure water was supplied from the nozzle in a spraying manner from above the center of rotation for rinsing. Then, spin drying was performed. Then, a heating treatment (post-drying) was performed for 300 seconds using a heating plate at 230°C. Thus, a silicon wafer with colored pixels was obtained.

[1021] <Sensitivity Evaluation>

[1022] The silicon wafer having colored pixels was observed after being magnified 20,000 times using an electron microscope S9260A (manufactured by Hitachi High-Technologies Corporation) for line width measurement, and the pattern size was measured. The sensitivity evaluation was performed according to the following evaluation criteria.

[1023] A: Exposure is 100mJ / cm 2The difference between the pattern size and the shield size is greater than -0.020 μm and less than 0.020 μm.

[1024] B: Exposure is 100mJ / cm 2 The difference between the pattern size and the shield size is greater than -0.040 μm and less than -0.020 μm, or greater than 0.020 μm and less than 0.040 μm.

[1025] C: Exposure is 100mJ / cm 2 The difference between the pattern size and the shield size is greater than -0.060 μm and less than -0.040 μm, or greater than 0.040 μm and less than 0.060 μm.

[1026] D: Exposure is 100mJ / cm 2 The difference between the pattern size and the shield size is greater than -0.100 μm and less than -0.060 μm, or greater than 0.060 μm and less than 0.100 μm.

[1027] E: Exposure is 100mJ / cm 2 The difference between the pattern size and the shield size is less than -0.100 μm, or greater than 0.100 μm.

[1028] <Adhesion Evaluation>

[1029] The silicon wafer having colored pixels was observed using an optical microscope at a bright field magnification of 50. The number of peeled pieces of the 1.1 μm square pattern was measured and judged based on the following criteria.

[1030] A: The number of peeled pieces of 1.1 μm □ pattern is 0

[1031] B: The number of peeled 1.1 μm □ patterns is 1 to 5

[1032] C: The number of peeled 1.1 μm □ patterns is 6 to 10

[1033] D: The number of peeled 1.1 μm □ patterns is 10 or more

[1034] E: The 1.1 μm□ pattern was completely peeled off.

[1035] (Pattern formation 2)

[1036] A 200 mm (8 inch) glass wafer was heat treated at 200° C. for 30 minutes in an oven. Then, CT-4000L (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.) was coated on the glass wafer to a film thickness of 0.1 μm after post-baking, and further heated and dried on a hot plate at 220° C. for 5 minutes to form an undercoat layer. Thus, a glass wafer with an undercoat layer was obtained.

[1037] Each coloring composition was applied to the undercoat layer of the glass wafer with an undercoat layer to form a coloring composition layer (coating film). Then, a heating treatment (pre-baking) was performed for 120 seconds using a hot plate at 100° C. so that the dry film thickness of the coating film was 0.5 μm. Next, the spectral transmittance (spectral 1) of the glass wafer was measured using MCPD-3000 (manufactured by OTSUKA ELECTRONICS CO., LTD.).

[1038] Next, an i-ray stepper exposure device FPA-3000i5+ (manufactured by CANON Inc.) was used at a wavelength of 365 nm and 500 mJ / cm2 without shielding (open frame). 2 The exposure was performed with the exposure amount.

[1039] Then, the glass wafer with the exposed coating film formed thereon was placed on a horizontal rotating table of a rotary shower developer (DW-30 model, manufactured by CHEMITRONICS CO., LTD.), and subjected to stirring development at 23° C. for 60 seconds using CD-2060 (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.). Thus, a green colored pattern of approximately 2.0 cm×2.0 cm was formed on the glass wafer.

[1040] The glass wafer with the colored pattern was fixed on a horizontal rotating table by vacuum chuck, and the glass wafer was rotated at a speed of 50 rpm by a rotating device, and pure water was supplied from the spray nozzle in a spraying manner from above the rotation center for rinsing. Then, spin drying was performed. Next, the transmittance of the pattern after development was measured using MCPD-3000 in the same manner as Spectrum 1 (Spectrum 2).

[1041] <Development and fading evaluation>

[1042] The discoloration was evaluated according to the following evaluation criteria.

[1043] A: The difference in transmittance (ΔT%) between the light spectrum 1 and the light spectrum 2 at a wavelength of 450 nm is less than 1.0%.

[1044] B: The difference in transmittance (ΔT%) between the light spectrum 1 and the light spectrum 2 at a wavelength of 450 nm is 1.0% or more and less than 2.5%.

[1045] C: The difference in transmittance (ΔT%) between the light spectrum 1 and the light spectrum 2 at a wavelength of 450 nm is 2.5% or more and less than 4.0%.

[1046] D: The difference in transmittance (ΔT%) between the light spectrum 1 and the light spectrum 2 at a wavelength of 450 nm is 4.0% or more and less than 5.5%.

[1047] E: The difference in transmittance (ΔT%) between the light spectrum 1 and the light spectrum 2 at a wavelength of 450 nm is 5.5% or more.

[1048] [Table 4]

[1049]

[1050] The above results show that the examples have good adhesion. In addition, Examples 4-1 and 4-2 containing a fluorine-based oxime ester photopolymerization initiator and an oxime-based photopolymerization initiator other than the fluorine-based oxime ester photopolymerization initiator have excellent sensitivity. Furthermore, the fading during development is suppressed.

[1051] On the other hand, the adhesion of the comparative examples was inferior to that of the examples.

[1052] The raw materials shown in the above Table 4 are as follows.

[1053] Green pigment dispersion: Green pigment dispersion prepared by the above method.

[1054] Photopolymerization initiator A1, 2, 2B: a compound having the following structure

[1055] [Chemical formula 61]

[1056]

[1057] · Polymerizable compound: NK ester A-TMMT (pentaerythritol tetraacrylate, manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.)

[1058] Alkali-soluble binder: ACA230AA (manufactured by DAICEL CHEMICAL INDUSTRIES, CO., LTD.), Mw = 14000, acid value = 37 mgKOH / g)

[1059] ·Inhibitor: p-Methoxyphenol

[1060] Epoxy compound: EHPE3150, manufactured by DAICEL CHEMICAL INDUSTRIES, CO., LTD.

[1061] Surfactant 1: PIONIN D-6315 (manufactured by TAKEMOTO OIL & FAT CO., LTD., nonionic surfactant)

[1062] Surfactant 2: 0.2 mass PGMEA solution of the following mixture (Mw = 14000)

[1063] [Chemical formula 62]

[1064]

[1065] Solvent: PGMEA

[1066] <Test Example 5>

[1067] 〔Production of color filters〕

[1068] On an 8-inch (200 mm) silicon wafer (substrate), a transparent organic film layer (CT-4000L: manufactured by FUJIFILM Electronic Materials Co., LTD.) was formed so that the film thickness after post-baking would be 0.1 μm.

[1069] [CT-4000L formation conditions]

[1070] Spin coating

[1071] No pre-drying

[1072] Post-drying (heating plate) 220℃×300 seconds

[1073] The coloring composition prepared in Examples 1-4 was applied onto the transparent organic film layer of the silicon wafer having the transparent organic film layer formed thereon using a spin coater so that the film thickness after post-baking became 0.5 μm, and then heated for 120 seconds using a 100° C. hot plate (pre-baking). Thus, a coloring layer was formed.

[1074] Next, exposure was performed using an i-ray (wavelength 365 nm) stepper exposure apparatus FPA-5510iZ (manufactured by CANON Inc.) and an Island pattern mask having a transmission pattern of 3.0 μm square under the following pattern exposure conditions.

[1075] Then, the silicon wafer with the exposed colored layer formed thereon was placed on a horizontal rotating table of a rotary shower developer (DW-30 model, manufactured by CHEMITRONICS CO., LTD.), and subjected to stirring development at 23° C. for 60 seconds using CD-2060 (manufactured by FUJIFILM ELECTRONIC MATERIALS CO., LTD.). Thus, a colored pattern was formed on the silicon wafer.

[1076] The silicon wafer with the colored pattern was fixed on a horizontal rotating table by vacuum chuck, and the glass wafer was rotated at a speed of 200 rpm by a rotating device, and pure water was supplied from the nozzle in a spraying state from above the center of rotation for 30 seconds of rinsing. Then, spin drying was performed. Next, a 220°C hot plate was used for 300 seconds of heating treatment (post-drying). Thus, a bayer pattern with a width of 1.0 μm in the color filter pixel portion was formed, and a color filter was obtained.

[1077] (Pattern exposure conditions)

[1078] The pattern exposure conditions are as follows.

[1079] ·Lighting conditions: NA 3 / σ=0.57 / 0.40

[1080] Exposure illuminance (W / m 2 ): Refer to Table 5 below

[1081] Exposure energy: Swing exposure was performed from 30 mJ to 10 mJ in each process, and the optimal exposure energy (Eopt) was examined. The optimal exposure energy refers to the exposure energy condition that can reproduce the shielding design value on the substrate.

[1082] Oxygen concentration (volume %): Refer to Table 5 below (21 volume % is atmospheric conditions)

[1083] The color filter manufacturing was performed using Clean track ACT8 manufactured by Tokyo Electron Limited. In addition, the device was set to control the oxygen concentration in the device chamber. Specifically, there were pipes for injecting oxygen and dilution gas, and a measuring instrument capable of monitoring the oxygen concentration was provided in the chamber. The measuring instrument was used to check the oxygen concentration in the chamber during exposure.

[1084] The thickness of the colored layer (cured product of the colored composition) was measured using an optical film thickness meter (Filmetrics F50 (manufactured by Filmetrics, INC.)) and the average value of five points within a plane of 8 inches (200 mm) was set as the film thickness setting value.

[1085] The line width after patterning was measured by observation using an electron microscope S9260A (manufactured by Hitachi High-Technologies Corporation) for line width measurement, and the average value of the pixel measurement dimensions at 5 points was set as the set value of the line width.

[1086] <Sensitivity Evaluation>

[1087] The silicon wafer on which the bayer pattern was formed was observed after being magnified 20,000 times using an electron microscope S9260A (manufactured by Hitachi High-Technologies Corporation) for line width measurement, and the pattern size was measured. The sensitivity evaluation was performed according to the following evaluation criteria.

[1088] A: Eopt is 50mJ / cm 2 Above and less than 500mJ / cm 2 . It is the best from the perspective of energy and manufacturing stability.

[1089] B: Eopt is 500mJ / cm 2 Above and less than 1000mJ / cm 2 . Although more energy is required than the evaluation "A", there is no problem in practical use.

[1090] C: Eopt is 1000mJ / cm 2 Above. Eopt is larger and less practical.

[1091] L: Eopt is less than 50mJ / cm 2 . The likelihood is smaller and the manufacturing stability is slightly worse.

[1092] [Table 5]

[1093]

[1094] According to the above results, by adjusting the oxygen concentration during exposure, both low-energy manufacturing and stable manufacturing can be achieved. Specifically, as the illuminance during exposure is increased, the oxygen concentration is increased, so that both low-energy manufacturing and stable manufacturing can be achieved.

[1095] Explanation of symbols

[1096] 100 - infrared sensor, 110 - solid imaging element, 111 - near infrared absorption filter, 112 - filter, 113 - near infrared transmission filter, 114 - region, 115 - microlens, 116 - planarization layer, 200 - cured film, 201 - substrate, 202 - coloring layer, 203 - coating layer.

Claims

1. A colored photosensitive composition comprising: Fluorine-containing oxime ester photopolymerization initiators; Polymerizable compounds having ethylenically unsaturated double bonds; Alkali soluble resin; and Colorants, among which The fluorine-containing oxime ester photopolymerization initiator comprises a compound represented by the following formula (1): In formula (1), Ar 1 represents a benzene ring which may have a substituent, Ar 2 represents a naphthalene ring which may have a substituent, R 1 represents an aryl group having a fluorine atom-containing group, R 2 and R 3 each independently represents an alkyl group or an aryl group, The colorant comprises an organic pigment, The coloring photosensitive composition has a ratio A / B of 0.3 to 3 of a minimum value A of absorbance in a wavelength range of 400 nm to less than 580 nm to a minimum value B of absorbance in a wavelength range of 580 nm to 750 nm. The ratio C / D of the minimum absorbance value C in the wavelength range of 400 nm to 750 nm to the maximum absorbance value D in the wavelength range of 1000 nm to 1300 nm is 5 or more, When a film having a thickness of 2.0 μm after drying is prepared using the colored photosensitive composition, the optical density of the film at a wavelength of 365 nm is 1.5 or more.

2. The colored photosensitive composition according to claim 1, wherein The fluorine-containing oxime ester-based photopolymerization initiator contains at least one selected from an alkyl group having a fluorine atom and a group containing an alkyl group having a fluorine atom.

3. The colored photosensitive composition according to claim 1 or 2, wherein In the formula (1), R 1 Indicates that there is a -OR X11 represents an aryl group, the R X11 It represents an alkyl group containing a fluorine atom.

4. The colored photosensitive composition according to claim 3, wherein The R X11 It represents an alkyl group having 1 to 4 carbon atoms and containing a fluorine atom.

5. The colored photosensitive composition according to claim 1 or 2, wherein It further contains a curable compound having a fluorine atom and a curable functional group. The colored photosensitive composition according to claim 5 , further comprising a black pigment.

7. The colored photosensitive composition according to claim 1 or 2, further comprising an α-aminoketone-based photopolymerization initiator, The mass ratio of the fluorine-containing oxime ester photopolymerization initiator to the α-amino ketone photopolymerization initiator is 1:1.5 to 1:

10.

8. The colored photosensitive composition according to claim 1 or 2, wherein The sum of the masses of monochlorobenzene and methyl tert-butyl ether is 2 ppm or less based on the total mass of the colored photosensitive composition. 9 . The colored photosensitive composition according to claim 1 , which is used for i-ray exposure.

10. The colored photosensitive composition according to claim 1 or 2, wherein The number of fluorine atoms in the compound represented by the formula (1) is 3 or more. 11 . A cured film using the colored photosensitive composition according to claim 1 . 12 . The cured film according to claim 11 , which is a color filter or a light-shielding film.

13. A pattern forming method, comprising: A step of forming a colored composition layer on a support using the colored photosensitive composition according to any one of claims 1 to 10; A step of exposing the colored composition layer to light in a pattern; and A step of developing and removing the unexposed portion of the colored composition layer to form a colored pattern.

14. The pattern forming method according to claim 13, wherein the exposure is performed using i-rays.

15. An infrared light cutoff filter with a light-shielding film, comprising: an infrared cutoff filter; and A light-shielding film disposed on at least a portion of the surface of the infrared cut filter, the light-shielding film being formed by curing the colored photosensitive composition according to claim 6. 16 . A solid imaging device comprising the cured film according to claim 11 . 17 . An image display device comprising the cured film according to claim 11 .

18. An infrared sensor comprising the cured film according to claim 11.

Images