TW202024139A - Colored composition, method for forming cured film, method for manufacturing color filter, and method for manufacturing display device - Google Patents

Abstract

The present invention pertains to a colored composition containing a colorant, a radical-polymerizable monomer, and a radical photopolymerization initiator, wherein the radical photopolymerization initiator content of the total solid content of the colored composition is 3 mass% or more, and the colored composition is exposed using light having a wavelength of greater than 350 nm and no more than 380 nm at an exposure dose of 200 mJ/cm2 or more to form a cured film, the temperature being 150 DEG C or less throughout the entire process. The present invention also pertains to a method for manufacturing a cured film, a method for manufacturing a color filter, and a method for manufacturing a display device that use this colored composition.

Description

Coloring composition, curing film forming method, color filter manufacturing method, and display device manufacturing method

The present invention relates to a coloring composition, a method for forming a cured film, a method for manufacturing a color filter, and a method for manufacturing a display device.

Conventionally, in various display devices and solid-state imaging elements, color filters have been used to color display images. This kind of color filter is usually manufactured by forming a coating film of a curable coloring composition containing a resin and a coloring agent and curing the coating film into a pattern.

In recent years, it has been studied to use organic semiconductor materials and plastic members as part of the raw materials of the above-mentioned display devices and the like, and it is expected that color filters can also be manufactured at temperatures below 150°C. For example, Patent Document 1 describes the following: A color filter imparted with chemical resistance is manufactured by using a composition at a low curing temperature of 150°C or less, and the composition contains 45% by weight in all constituent units. The alkali-soluble resin (A) of the above specific structural unit, the photopolymerizable monomer (B) containing the specific compound, the photopolymerization initiator (C), and the coloring agent (D). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2018-091940

However, it is known that the cured film (color filter) of Patent Document 1 easily fluctuates in the spectroscopic characteristics in the high temperature and high humidity test. The present invention was completed in view of the above-mentioned problems, and its object is to provide a coloring composition capable of forming a cured film with excellent stability of spectral characteristics at low temperatures.

Furthermore, an object of the present invention is to provide a method for forming a cured film using the colored composition, a method for manufacturing a color filter, and a method for manufacturing a display device.

The above-mentioned problem can be solved by increasing the content of the photo-radical polymerization initiator in the coloring composition compared to the past, and generating more photo-radicals in the composition during exposure than before. Specifically, the above-mentioned problems are solved by the following methods <1>, preferably <2> to <21>.

式中，Rv¹ 表示取代基，Rv² 及Rv³ 分別獨立地表示氫原子或取代基，Rv² 與Rv³ 亦可以彼此鍵結而形成環，m表示0～5的整數。 ＜12＞ 如＜6＞至＜11＞中任一項所述之感光性著色組成物，其中 著色組成物的總固體成分中的光聚合起始劑A1與光聚合起始劑A2的合計含量為5～15質量%。 ＜13＞ 如＜1＞至＜12＞中任一項所述之著色組成物，其中 該著色組成物還含有樹脂，該樹脂包含來自於由下述式（I）表示之化合物的重複單元， [化學式2]

式中，X¹ 表示O或NH， R¹ 表示氫原子或甲基， L¹ 表示2價的連接基， R¹⁰ 表示取代基， m表示0～2的整數， p表示0以上的整數。 ＜14＞ 如＜1＞至＜13＞中任一項所述之著色組成物，其還含有包含呋喃基之化合物。 ＜15＞ 如＜14＞所述之著色組成物，其中 包含呋喃基之化合物為選自樹脂中之至少1種，該樹脂包含來自於由下述式（fur-1）表示之化合物及由下述式（fur-1）表示之化合物的重複單元， 式（fur-1）： [化學式3]

式中，Rf¹ 表示氫原子或甲基，Rf² 表示2價的連接基。 ＜16＞ 一種硬化膜的形成方法，其具有： 將＜1＞至＜15＞中任一項所述之著色組成物塗佈於支撐體上而形成著色組成物層之製程；及 以200mJ/cm² 以上的曝光量對著色組成物層照射具有大於350nm且380nm以下的波長之光，從而對著色組成物層進行曝光之曝光製程， 在整個製程中在150℃以下的溫度下獲得著色組成物層硬化而成之膜亦即硬化膜。 ＜17＞ 如＜16＞所述之硬化膜的形成方法，其中 曝光製程中的曝光量為1J/cm² 以上。 ＜18＞ 如＜16＞或＜17＞所述之硬化膜的形成方法，其中 曝光製程中的曝光照度為1000mW/cm² 以上。 ＜19＞ 如＜16＞至＜18＞中任一項所述之硬化膜的形成方法，其中 在整個製程中，在100℃以下的溫度下獲得硬化膜。 ＜20＞ 一種濾色器的製造方法，其包括＜16＞至＜19＞中任一項所述之硬化膜的形成方法。 ＜21＞ 一種顯示裝置的製造方法，其包括＜16＞至＜19＞中任一項所述之硬化膜的形成方法。 [發明效果]<1> A coloring composition containing a coloring agent, a radical polymerizable monomer and a photoradical polymerization initiator, wherein the content of the photoradical polymerization initiator in the total solid content of the coloring composition is 3 mass % Or more, the coloring composition uses light having a wavelength greater than 350 nm and less than 380 nm, exposed at an exposure amount of 200 mJ/cm ² or more, and used to form a cured film at a temperature of 150° C. or less throughout the process. <2> The colored composition as described in <1>, wherein the content of the radical photopolymerization initiator is 9% by mass or more. <3> The coloring composition as described in <1> or <2>, wherein the content M of the radical polymerizable monomer in the total solid content of the color composition and the above-mentioned content I of the photo radical polymerization initiator are The ratio M/I is 20 or less in terms of mass ratio. <4> The colored composition according to any one of <1> to <3>, wherein the photoradical polymerization initiator contains an oxime compound. <5> The colored composition as described in <4>, wherein the content of the oxime compound is 10% by mass or more. <6> The coloring composition according to any one of <1> to <5>, wherein the photoradical polymerization initiator contains light with an absorption coefficient of 1.0×10 ³ mL/gcm or more in methanol at a wavelength of 365 nm The polymerization initiator A1 and the photopolymerization initiator A2 in which the absorption coefficient at a wavelength of 365 nm in methanol is 1.0×10 ² mL/gcm or less and the absorption coefficient at a wavelength of 254 nm is 1.0×10 ³ mL/gcm or more. <7> The colored composition according to <6>, wherein the content of the photopolymerization initiator A1 is 10% by mass or more. <8> The coloring composition as described in <6> or <7>, wherein the content M of the radical polymerizable monomer in the total solid content of the coloring composition and the above-mentioned content I _A1 of the photopolymerization initiator _A1 The ratio M/I _A1 is 20 or less in mass ratio. <9> The colored composition according to any one of <6> to <8>, wherein the photopolymerization initiator A1 contains an oxime compound containing a fluorine atom. <10> The colored composition according to any one of <6> to <9>, wherein the photopolymerization initiator A2 contains a hydroxyalkylphenone compound. <11> The colored composition as described in <10>, wherein the hydroxyalkyl phenone compound is a compound represented by the following formula (V), formula (V): [Chemical formula 1]

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent, Rv ² and Rv ³ may be bonded to each other to form a ring, and m represents an integer of 0-5. <12> The photosensitive coloring composition according to any one of <6> to <11>, wherein the total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the coloring composition It is 5-15 mass%. <13> The colored composition according to any one of <1> to <12>, wherein the colored composition further contains a resin containing a repeating unit derived from a compound represented by the following formula (I), [Chemical formula 2]

In the formula, X ¹ represents O or NH, R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a divalent linking group, R ¹⁰ represents a substituent, m represents an integer of 0 to 2, and p represents an integer of 0 or more. <14> The colored composition as described in any one of <1> to <13>, which further contains a furan group-containing compound. <15> The coloring composition as described in <14>, wherein the furan group-containing compound is at least one resin selected from the group consisting of a compound derived from the following formula (fur-1) and The repeating unit of the compound represented by the formula (fur-1), the formula (fur-1): [Chemical formula 3]

In the formula, Rf ¹ represents a hydrogen atom or a methyl group, and Rf ² represents a divalent linking group. <16> A method for forming a cured film, comprising: a process of coating the colored composition described in any one of <1> to <15> on a support to form a colored composition layer; and 200 mJ/ The exposure amount above cm ² irradiates the colored composition layer with light having a wavelength greater than 350nm and less than 380nm, thereby exposing the colored composition layer to an exposure process, and the colored composition is obtained at a temperature below 150°C in the entire process The cured film is the cured film. <17> The method for forming a cured film as described in <16>, wherein the exposure amount in the exposure process is 1 J/cm ² or more. <18> The method for forming a cured film as described in <16> or <17>, wherein the exposure illuminance in the exposure process is 1000 mW/cm ² or more. <19> The method for forming a cured film as described in any one of <16> to <18>, wherein the cured film is obtained at a temperature of 100°C or less throughout the process. <20> A method of manufacturing a color filter, including the method for forming a cured film according to any one of <16> to <19>. <21> A method of manufacturing a display device, including the method for forming a cured film according to any one of <16> to <19>. [Invention Effect]

With the coloring composition of the present invention, a cured film with excellent stability of spectral characteristics can be formed at low temperatures. Furthermore, with the colored composition of the present invention, it is possible to provide a method for forming a cured film, a method for manufacturing a color filter, and a method for manufacturing a display device of the present invention.

Hereinafter, the main embodiment of the present invention will be described. However, the present invention is not limited to the illustrated embodiment.

In this specification, the numerical range indicated by the symbol "～" refers to a range that includes the numerical values described before and after "～" as the lower limit and the upper limit, respectively.

In this specification, the term "process" not only includes independent processes, but also includes processes that cannot be clearly distinguished from other processes as long as the process can achieve the expected effect of the process.

Regarding the label of the group (atomic group) in this specification, the label not marked with substituted and unsubstituted means that it includes a group without a substituent, and also includes a group with a substituent. For example, when only described as "alkyl", this means that both an unsubstituted alkyl group (unsubstituted alkyl group) and a substituted alkyl group (substituted alkyl group) are included.

In this specification, “(meth)acrylate” refers to both or either of “acrylate” and “methacrylate”, and “(meth)acrylic acid” refers to “acrylic acid” and “methacrylate”. Both "acrylic acid" and "(meth)acryloyl" mean both or either of "acryloyl" and "methacryloyl".

In this specification, the concentration of the total solid content in the composition is represented by the mass percentage of the components other than the solvent with respect to the total mass of the composition.

In this specification, unless otherwise specified, the temperature is set to 23°C.

In this specification, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed as polystyrene conversion values based on gel permeation chromatography (GPC measurement). The weight average molecular weight (Mw) and number average molecular weight (Mn) can be used, for example, by using HLC-8220 (manufactured by TOSOH CORPORATION), and protecting columns HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000 and TSKgel Super HZ2000 (manufactured by TOSOH CORPORATION) are calculated. In addition, unless otherwise specified, measurement was performed using THF (tetrahydrofuran) as an eluent. In addition, unless otherwise specified, a UV ray (ultraviolet) wavelength 254 nm detector is used for detection in GPC measurement.

In this specification, when describing the positional relationship of the layers constituting the layered body as "upper" or "lower", it is only necessary to have another layer on the upper or lower side of the layer to be the reference among the plurality of layers of interest . In other words, a third layer or element may be further interposed between the layer serving as the reference and the other layer described above, and the layer serving as the reference need not be in contact with the other layer described above. Also, unless otherwise specified, the direction in which the layers are stacked on the substrate is called "up", or when a photosensitive layer is present, the direction from the substrate to the photosensitive layer is called "up", and the opposite direction is called As "under". In addition, the setting of this vertical direction is for convenience in this specification, and in an actual aspect, the "up" direction in this specification can also be different from the vertical upward direction.

In this specification, regarding electromagnetic waves other than the visible region, the term "light" is also used for convenience. For electromagnetic waves other than the visible region, "light" has the same meaning as "electromagnetic waves".

<Coloring composition> The coloring composition of the present invention contains a coloring agent, a radical polymerizable monomer (hereinafter also referred to as a single "polymerizable monomer"), and a photoradical polymerization initiator (hereinafter also referred to as "Photopolymerization initiator".). Furthermore, in the coloring composition of the present invention, the content of the photopolymerization initiator in the total solid content of the coloring composition is 3% by mass or more. Furthermore, the coloring composition with light having a wavelength of 350nm is greater than and 380nm or less, the exposure amount of ² or more 200mJ / cm exposure, and for forming a cured film at a temperature of 150 deg.] C throughout the manufacturing process, the hardening The film can be used as a color filter used in a display device or the like.

The coloring composition of the present invention is used to form a cured film at a temperature below 150°C in the entire process, and preferably used to form a cured film at a temperature below 120°C in the entire process. In this specification, the formation of a cured film at a temperature below 150°C throughout the process refers to the use of a colored composition and a support to form a cured film on the support at a temperature of the support below 150°C and the ambient temperature. A series of the entire process. For example, the process of forming a cured film and a patterned cured film using a colored composition and a support includes a process of coating the colored composition on the support, a process of drying the coating film containing the composition, and The process of exposing the dried film, the process of developing the exposed film, the process of heating the support after exposure or development (so-called post-baking), etc. Post-baking is implemented according to needs, or not.

The solid content concentration of the colored composition of the present invention is preferably 5 to 25% by mass. The upper limit is preferably 22.5% by mass or less, more preferably 20% by mass or less, and even more preferably 18% by mass or less. If the solid content concentration is in the above range, even when a cured film is formed at a temperature of 150°C or less (preferably a temperature of 120°C or less) throughout the process, a film with excellent flatness can be formed.

In the coloring composition of the present invention, the content of the photopolymerization initiator in the coloring composition is set to be 3% by mass or more than before, and the coloring composition is 200mJ/cm ² or more than before. The amount of exposure is exposed. Thereby, even if the heat curing treatment of more than 150°C is not performed, a cured film with excellent stability of the spectral characteristics can be formed at a low temperature. It is considered that this is because, with more photopolymerization initiators and more exposure than before, the same amount of photo radicals as in the conventional heat hardening treatment at high temperature (for example, greater than 150°C) after development is generated. That is, in the present invention, it is considered that the same dense cross-linked state as the cross-linked state produced by the heat hardening treatment at high temperature can be achieved by exposure that generates a large amount of light radicals.

Furthermore, in the present invention, in particular, the photopolymerization initiator includes a compound having an aromatic ring described later. In addition, when the resin contains resin b1 described later, or the coloring composition contains a furan group-containing compound described later, it is considered that radical light is generated. The decomposition product of the radical polymerization initiator gathers around the aromatic ring of the resin and fills the gaps of the resin. As a result, the film quality of the cured film becomes a denser state, the moisture resistance, etc. are improved, and it contributes to the stability of the spectral characteristics.

The coloring composition of the present invention is, for example, a coloring composition for forming pixels (pattern-shaped cured film) constituting a color filter for a display device. Color filters usually have pixels corresponding to three colors of red (R), green (G), and blue (B), and these pixels are patterned by coloring a cured film formed of colored compositions corresponding to each color. manufacture. The type of display device is not particularly limited, but the coloring composition of the present invention is particularly effective in the case of a display device in which a color filter is formed on a support having low heat resistance, such as a support including an organic semiconductor layer. Examples of such display devices include display devices having organic semiconductor elements as light sources, such as organic electroluminescence display devices.

The thickness of the cured film and pixels formed from the coloring composition of the present invention is preferably 0.5 to 3.0 μm. The lower limit is preferably 0.8 μm or more, more preferably 1.0 μm or more, and even more preferably 1.1 μm or more. The upper limit is preferably 2.5 μm or less, more preferably 2.0 μm or less, and even more preferably 1.8 μm or less.

Moreover, it is preferable that the line width (pattern size) of the pixel formed by the coloring composition of the present invention is 2.0 to 10.0 μm. The upper limit is preferably 7.5 μm or less, more preferably 5.0 μm or less, and even more preferably 4.0 μm or less. The lower limit is preferably 2.25 μm or more, more preferably 2.5 μm or more, and even more preferably 2.75 μm or more. When the line width (pattern size) of the pixel is within the above range, the usefulness of the present invention is great.

Hereinafter, each component that can constitute the colored composition will be described.

＜＜Colorant＞＞ The coloring composition of the present invention contains a coloring agent. Examples of the coloring agent include coloring agents such as red coloring agents, green coloring agents, blue coloring agents, yellow coloring agents, purple coloring agents, and orange coloring agents. In the present invention, the colorant may be a pigment or a dye. Pigments and dyes can also be used together. In addition, the pigment may be any of an inorganic pigment and an organic pigment. In addition, it is also possible to use materials obtained by replacing part of inorganic pigments or organic-inorganic pigments with organic chromophores. By replacing part of inorganic pigments or organic-inorganic pigments with organic chromophores, the hue can be easily designed.

The coloring agent used in the present invention preferably contains a pigment. In addition, the content of the pigment in the colorant is preferably 50% by mass or more, more preferably 70% by mass or more, more preferably 80% by mass or more, and particularly preferably 90% by mass or more. In addition, the colorant may only be a pigment. Examples of the pigment include those shown below.

Color Index (CI) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175, 176,177,179,180,181,182,185,187,188,193,194,199,213,214,215,228,231,232 (methine series), 233 (quinoline series), 234 (Amino ketone series), 235 (amino ketone series), 236 (amino ketone series), etc. (The above are yellow pigments. Hereinafter, also referred to as "PY1" etc.). 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. (the above are orange pigments). Hereinafter, it is also simply referred to as "PO2" and the like. ). 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, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184 , 185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291 , 294 (Kou Yamaguchi Galaxy, Organo Ultramarine, Bluish Red), 295 (monoazo series), 296 (diazo series), 297 (amino ketone series), etc. (the above are red pigments. Hereinafter, also referred to as "PR1" "Wait.). CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64 (phthalocyanine series), 65 (phthalocyanine series), 66 (phthalocyanine series), etc. (The above are green pigments. Hereinafter, also referred to as As "PG7" etc.). C.I. Pigment Violet 1,19,23,27,32,37,42,60 (triarylmethane series), 61 (koushankou galaxy), etc. (The above are purple pigments. Hereinafter, also referred to as "PV1" etc.). CI Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 29, 60, 64, 66, 79, 80, 87 (monoazo Series), 88 (methine series), etc. (The above are blue pigments. Hereinafter, also referred to as "PB1" etc.).

In addition, as the green pigment, a zinc halide pigment having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can be used. Specific examples include the compounds described in International Publication No. 2015/118720. In addition, as the green pigment, the compound described in the specification of Chinese Patent Application Publication No. 106909027, the phthalocyanine compound having the phosphate ester described in International Publication No. 2012/102395 as a ligand, and JP 2019 The phthalocyanine compound described in -008014, the phthalocyanine compound described in JP 2018-180023, the compound described in JP 2019-038958, etc.

In addition, as the blue pigment, an aluminum phthalocyanine compound having a phosphorus atom can also be used. As specific examples, the compounds described in paragraphs 0022 to 0030 of JP 2012-247591 and paragraph 0047 of JP 2011-157478 can be cited.

In addition, as the yellow pigment, the compounds described in JP 2017-201003 A, the compounds described in JP 2017-197719, and paragraphs 0011 to 0062 of JP 2017-171912 can also be used. , Compounds described in 0137 to 0276, JP 2017-171913 Paragraphs 0010 to 0062, Compounds 0138 to 0295, JP 2017-171914 Paragraphs 0011 to 0062, 0139 to 0190 The compound described in paragraphs, the compounds described in paragraphs 0010 to 0065, 0142 to 0222 of Japanese Patent Application Publication No. 2017-171915, the quinolines described in paragraphs 0011 to 0034 of Japanese Patent Application Publication No. 2013-054339 Yellow compounds, quinoline yellow compounds described in paragraphs 0013 to 0058 of JP 2014-026228, isoindoline compounds described in JP 2018-062644, and JP 2018-203798 The quinoline yellow compound described in the publication, the quinoline yellow compound described in Japanese Patent Application Publication No. 2018-062578, the quinoline yellow compound described in Japanese Patent Publication No. 6432076, and Japanese Patent Application Publication No. 2018-155881 The quinoline yellow compound described in JP 2018-111757 A, the quinoline yellow compound described in JP 2018-040835 A, JP 2017-197640 The quinoline yellow compound described in the publication, the quinoline yellow compound described in JP 2016-145282 A, the quinoline yellow compound described in JP 2014-085565 A, and the JP 2014-021139 The quinoline yellow compound described in Japanese Patent Application Publication No. 2013-209614, the quinoline yellow compound described in Japanese Patent Application Publication No. 2013-209435, and the quinoline yellow compound described in Japanese Patent Application Publication No. 2013-209435. The quinoline yellow compound described in No. 181015, the quinoline yellow compound described in JP 2013-061622 A, the quinoline yellow compound described in JP 2013-032486 A, JP 2012 The quinoline yellow compound described in 226110, the quinoline yellow compound described in JP 2008-074987, the quinoline yellow compound described in JP 2008-081565, and the JP The quinoline yellow compound described in 2008-074986, the quinoline yellow compound described in JP 2008-074985, and the quinoline yellow compound described in JP 2008-050420 The quinoline yellow compound described in Japanese Patent Application Publication No. 2008-031281, the quinoline yellow compound described in Japanese Patent Publication No. 48-032765, and the quinoline described in Japanese Patent Application Publication No. 2019-008014 Yellow compound, a compound represented by the following formula (QP1), and a compound represented by the following formula (QP2).

[Chemical formula 4]

In the formula (QP1), X ¹ to X ¹⁶ each independently represent a hydrogen atom or a halogen atom, and Z ¹ represents an alkylene group having 1 to 3 carbon atoms. As specific examples of the compound represented by the formula (QP1), the compound described in paragraph 0016 of Japanese Patent No. 6443711 can be cited.

[Chemical formula 5]

In formula (QP2), Y ¹ to Y ³ each independently represent a halogen atom. n and m represent an integer of 0-6, and p represents an integer of 0-5. (N+m) is 1 or more. As specific examples of the compound represented by the formula (QP2), the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077 can be cited.

As the red pigment, it is also possible to use the diketopyrrolopyrrole compound having at least one skatole atom substituted in the structure described in JP 2017-201384 A, and the two described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838 Ketopyrrolopyrrole compounds, diketopyrrolopyrrole compounds described in International Publication No. 2012/102399, diketopyrrolopyrrole compounds described in International Publication No. 2012/117965, JP 2012-229344 A The naphthol azo compound described in, the red color material described in Japanese Patent No. 6516119, the red color material described in Japanese Patent No. 6525101, and the like. In addition, as the red pigment, a compound having a structure in which an aromatic ring group formed by introducing a group bonding an oxygen atom, a sulfur atom, or a nitrogen atom to the aromatic ring is bonded to the diketopyrrolopyrrole skeleton can also be used.

The dye is not particularly limited, and known dyes can be used. For example, pyrazole azo series, anilino azo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonine series, pyrazolo triazole series Nitrogen series, pyridone azo series, cyanine series, phenanthrene series, pyrrolopyrazole imide series, Kouyamaguchi system, phthalocyanine series, benzopyran series, indigo series, pyrromethene series, etc. dye. In addition, the thiazole compound described in JP 2012-158649 A, the azo compound described in JP 2011-184493 A, and the azo compound described in JP 2011-145540 A can also be preferably used. The azo compound, the intramolecular imine type Kouyamaguchi star dye described in JP 2018-012863 A. In addition, as the yellow dye, the quinophthalone compound described in paragraphs 0011 to 0034 of JP 2013-054339 A, and the quinophthalone compound described in paragraphs 0013 to 0058 of JP 2014-026228 A can also be used. The quinoline yellow compounds and so on.

As the yellow coloring agent, the dyes described in International Publication No. 2012/128233 and JP 2017-201003 A can be used. In addition, as the red colorant, the dyes described in International Publication No. 2012/102399, International Publication No. 2012/117965, and JP 2012-229344 A can be used. In addition, as a green coloring agent, the pigment described in International Publication No. 2012/102395 can be used. In addition, the salt-forming dyes described in International Publication No. 2011/037195 can also be used.

In the present invention, a dye multimer can also be used as a coloring agent. The pigment polymer system is dissolved in a solvent and the dye used is preferably, but the pigment polymer can form particles. When the pigment polymer is a particle, it is usually used in a state dispersed in the solvent. The pigment multimer in the particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and the production method described in JP 2015-214682 A. The pigment polymer system has two or more pigment structures in one molecule, and it is preferable to have three or more pigment structures. The upper limit is not particularly limited, and can be 100 or less. The plural pigment structures in a molecule can be the same pigment structure or different pigment structures. The weight average molecular weight (Mw) of the pigment multimer is preferably 2,000 to 50,000. The lower limit is more preferably 3000 or more, and more preferably 6000 or more. The upper limit is more preferably 30,000 or less, and more preferably 20,000 or less.

The pigment structure possessed by the pigment multimer can be exemplified by a structure derived from a pigment compound that has absorption in the visible region (preferably in the range of 400 to 700 nm, more preferably in the range of 400 to 650 nm). For example, triarylmethane pigment structure, Kouyamaguchi pigment structure, anthraquinone pigment structure, cyanine pigment structure, squaraine pigment structure, quinoline yellow pigment structure, phthalocyanine pigment structure, subphthalocyanine Pigment structure, azo pigment structure, pyrazolotriazole pigment structure, dipyrromethorphan pigment structure, isoindoline pigment structure, thiazole pigment structure, benzimidazole pigment structure, purple ring copper pigment structure, diketopyrrolopyrrole Pigment structure, diiminium pigment structure, naphthalocyanine pigment structure, rui pigment structure, dibenzofuranone pigment structure, merocyanine pigment structure, crotonium pigment structure, oxacyanine pigment structure, etc.

Pigment multimeric system: Pigment multimers with repeating units represented by formula (A), pigment multimers with repeating units represented by formula (B), pigment multimers with repeating units represented by formula (C) The dye multimer represented by the formula (D) is preferable, and the dye multimer having the repeating unit represented by the formula (A) and the dye multimer represented by the formula (D) are more preferable.

[Chemical formula 6]

In the formula (A), X ¹ represents the main chain of the repeating unit, L ¹ represents a single bond or a divalent linking group, and D ¹ represents a dye structure. For details of the formula (A), refer to paragraphs 0138 to 0152 of JP 2013-029760 A, and this content is incorporated in this specification.

In formula (B), X ² represents the main chain of the repeating unit, L ² represents a single bond or a divalent linking group, and D ² represents a dye structure having a group capable of ionic bonding or coordinate bonding with Y ² , Y ² represents a group capable of ionic bonding or coordinate bonding with D ² . For details of the formula (B), refer to paragraphs 0156 to 0161 of JP 2013-029760 A, and this content is incorporated into this specification.

In the formula (C), L ³ represents a single bond or a divalent linking group, D ³ represents a dye structure, and m represents 0 or 1. For details of the formula (C), refer to paragraphs 0165 to 0167 of JP 2013-029760 A, and this content is incorporated in this specification.

In formula (D), L ⁴ represents a (n+k) valent linking group, L ⁴¹ and L ⁴² each independently represent a single bond or a divalent linking group, D ⁴ represents a dye structure, and P ⁴ represents a substituent; n Represents 2-15, k represents 0-13, and n+k represents 2-15. When n is 2 or more, a plurality of D ⁴ may be different from each other or may be the same. When k is 2 or more, a plurality of P ⁴ may be different from each other or may be the same. As the linking group of the (n+k) valence represented by L ⁴ , the linking group described in paragraphs 0071 to 0072 of Japanese Patent Application Publication No. 2008-222950 and paragraph 0176 of Japanese Patent Application Publication No. 2013-029760 can be cited. The described linker, etc. Examples of the substituent represented by P ⁴ include an acid group and a polymerizable group. As the polymerizable group, an ethylenically unsaturated group (a group having an ethylenically unsaturated bond), an epoxy group, an oxazoline, a methylol group, and the like can be mentioned. As an ethylenically unsaturated group, a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned. As an acid group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned. The substituent represented by P ⁴ may be a monovalent polymer chain having a repeating unit. The monovalent polymer chain having repeating units is preferably a polymer chain having monovalent repeating units derived from a vinyl compound.

The pigment polymer can also use Japanese Patent Application Publication No. 2011-213925, Japanese Patent Application Publication No. 2013-041097, Japanese Patent Application Publication No. 2015-028144, Japanese Patent Application Publication No. 2015-030742, and International Publication No. 2016/031442. The compound described in etc.

The content of the coloring agent is preferably 5 to 70% by mass in the total solid content of the coloring composition. The lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. The upper limit is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less.

In addition, in the coloring composition of the present invention, the content of the red colorant and the green colorant can be set to 10% by mass or more, and more preferably 20% by mass or more in the total solid content of the coloring composition. More preferably, it can also be 30 mass% or more. In particular, the content of the blue colorant that easily absorbs light in the ultraviolet region can also be 3% by mass or more in the total solid content of the coloring composition, more preferably 5% by mass or more, and still more preferably also It can be 10% by mass or more. If the content of the coloring agent is set to a high concentration, the thickness of the color filter can be reduced. On the other hand, as described above, when the content of the coloring agent becomes a high concentration, the light during exposure hardly reaches the deep layer part of the film, and hardening of the deep layer part of the film may become insufficient. However, in the present invention, since a sufficient amount of exposure is ensured so that sufficient light reaches the deep layer of the film, even when the content of the colorant becomes a high concentration, it is possible to perform more sufficient curing than before. In particular, when the content of the blue colorant that easily absorbs light in the ultraviolet region and does not easily reach the deep layer of the film is set to a high concentration, the present invention has great utility.

As the coloring agent, the coloring composition of the present invention preferably includes at least one of PR177, PG7, PG36, PY139, PY150, and PY185, and more preferably includes at least one of PR177, PG7, and PY150. In particular, in the coloring composition for red, it is preferable to contain at least PR177 and PY139 as a colorant. Moreover, in the coloring composition for green, it is preferable to contain at least the combination of PG7, PG36, and PY139, the combination of PG7, PG36, and PY150, or the combination of PG36, PY150, and PY185 as a coloring agent.

In the red color composition, the content of PR177 is preferably 0 to 60% by mass in the total solid content of the color composition. The upper limit of this numerical range is more preferably 55% by mass or less, and more preferably 50% by mass or less. The lower limit of the numerical range is more preferably 10% by mass or more, and more preferably 20% by mass or more. In the green coloring composition, the content of PG7 in the total solid content of the coloring composition is preferably 0-50% by mass. The upper limit of the numerical range is more preferably 40% by mass or less, and more preferably 30% by mass or less. The lower limit of the numerical range is more preferably 5% by mass or more, and more preferably 10% by mass or more. In the green coloring composition, the content of PY150 is preferably 0 to 30% by mass in the total solid content of the coloring composition. The upper limit of the numerical range is more preferably 25% by mass or less, and more preferably 20% by mass or less. The lower limit of the numerical range is more preferably 5% by mass or more, and more preferably 10% by mass or more.

＜＜Free radical polymerizable monomer＞＞ The coloring composition of the present invention contains a radical polymerizable monomer as a compound capable of radical polymerization. As the polymerizable monomer, a compound having an ethylenically unsaturated group and the like can be mentioned. As an ethylenically unsaturated group, a vinyl group, a (meth)allyl group, a (meth)acryloyl group, etc. are mentioned.

The molecular weight of the polymerizable monomer is preferably 100 to 2,000. The upper limit is less than 2000, more preferably 1500 or less, more preferably 1000 or less, especially less than 1000. The lower limit is more preferably 150 or more, and more preferably 250 or more.

From the viewpoint of the stability of the composition over time, the ethylenically unsaturated group value (hereinafter referred to as C=C value) of the polymerizable monomer is preferably 2 to 14 mmol/g. The lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and more preferably 5 mmol/g or more. The upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less. The C=C value of the polymerizable monomer is calculated by dividing the number of ethylenically unsaturated groups contained in one molecule of the polymerizable monomer by the molecular weight of the polymerizable monomer.

It is preferable that the polymerizable monomer contains 3 or more ethylenically unsaturated groups, and it is more preferable to contain 4 or more ethylenically unsaturated groups. With this aspect, the curing property of the colored composition based on exposure is good. From the viewpoint of the stability of the composition over time, the upper limit of the number of ethylenically unsaturated groups is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less. In addition, the polymerizable monomer is preferably a (meth)acrylate compound with three or more functions, more preferably a (meth)acrylate compound with 3 to 15 functions, and a (meth)acrylate compound with 3 to 10 functions. To be more preferred, 3 to 6 functional (meth)acrylate compounds are particularly preferred.

A compound containing an ethylenically unsaturated group and an alkoxyl group in a polymerizable single system is also preferable. Such polymerizable monomers have high flexibility and easily move ethylenically unsaturated groups. Therefore, the polymerizable monomers easily react with each other during exposure and can form a cured film with excellent adhesion to a support or the like. In addition, when a hydroxyalkylphenone compound is used as a photopolymerization initiator, it can be presumed that the polymerizable monomer is close to the photopolymerization initiator and the initiator generates radicals near the polymerizable monomer to allow polymerization The reactive monomer reacts more efficiently, and it is easy to form a cured film with better adhesion and solvent resistance.

The number of alkoxyl groups contained in one molecule of the polymerizable monomer is preferably 3 or more, and more preferably 4 or more. From the viewpoint of the stability of the composition over time, the upper limit is preferably 20 or less.

In addition, from the viewpoint of compatibility with other components in the composition, the SP value (Solubility Parameter) of the compound containing an ethylenically unsaturated group and an alkoxyl group is preferably 9.0 to 11.0. The upper limit is preferably 10.75 or less, and more preferably 10.5 or less. The lower limit is preferably 9.25 or more, and more preferably 9.5 or more. In addition, in this specification, the SP value uses the calculated value based on the Fedors method.

Examples of the compound having an ethylenically unsaturated group and an alkoxy group include a compound represented by the following formula (M-1).

Formula (M-1) [Chemical Formula 7]

In the formula, A ¹ represents an ethylenically unsaturated group, L ¹ represents a single bond or a divalent linking group, R ¹ represents an alkylene group, m represents an integer of 1-30, n represents an integer of 3 or more, and L ² represents an n-valent的linker.

Examples of the ethylenically unsaturated group represented by A ¹ include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. Among them, a (meth)acryloyl group is preferred.

The divalent linking group represented by L ¹ includes alkylene, arylene, -O-, -CO-, -COO-, -OCO-, -NH- and combinations of two or more The group. The carbon number of the alkylene group is preferably 1-30, more preferably 1-20, and still more preferably 1-15. The alkylene group may be any of linear, branched, and cyclic. The carbon number of the arylene group is preferably 6-30, more preferably 6-20, and still more preferably 6-10.

The carbon number of the alkylene group represented by R ¹ is preferably from 1 to 10, more preferably from 1 to 5, more preferably from 1 to 3, particularly preferably 2 or 3, and 2 is the most preferred. The alkylene represented by R ¹ is preferably a straight chain or a branched chain, and more preferably a straight chain. Specific examples of the alkylene represented by R ¹ include ethylene, linear or branched propylene, and the like, among which ethylene is preferred.

m represents an integer of 1 to 30, and an integer of 1 to 20 is preferred, an integer of 1 to 10 is more preferred, and an integer of 1 to 5 is even more preferred. n represents an integer of 3 or more, and an integer of 4 or more is preferable. The upper limit of n is preferably an integer of 15 or less, more preferably an integer of 10 or less, and more preferably an integer of 6 or less.

Examples of the n-valent linking group represented by L ² include aliphatic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, and groups including combinations thereof, and groups selected from aliphatic hydrocarbon groups, aromatic hydrocarbon groups, and heterocyclic groups A group consisting of a combination of at least one of and at least one selected from -O-, -CO-, -COO-, -OCO- and -NH-. The carbon number of the aliphatic hydrocarbon group is preferably 1-30, more preferably 1-20, and even more preferably 1-15. The aliphatic hydrocarbon group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the aromatic hydrocarbon group is preferably 6-30, more preferably 6-20, and still more preferably 6-10. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the types of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number system of the heteroatom constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring. It is also preferable that the n-valent linking group represented by L ² is a group derived from a polyfunctional alcohol.

As the compound having an ethylenically unsaturated group and an alkoxy group, a compound represented by the following formula (M-2) is more preferable.

Formula (M-2) [Chemical Formula 8]

In the formula, R ² represents a hydrogen atom or a methyl group, R ¹ represents an alkylene group, m represents an integer of 1 to 30, n represents an integer of 3 or more, and L ² represents an n-valent linking group. R of formula (M-2) is ^{1, L 2, m, R} n in the formula (M-1) is ^1, L ^2, m, n are the same, the preferred range is also the same.

As a commercially available product of a polymerizable monomer having an ethylenically unsaturated group and an alkoxy group, KAYARAD T-1420 (T), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and the like can be mentioned.

As polymerizable monomers, dineopentylene erythritol triacrylate (as a commercially available product is KAYARAD D-330; manufactured by NIPPON KAYAKU CO., Ltd.), dineopentylene erythritol tetraacrylate (as a commercially available product) can also be used The product is KAYARAD D-320; manufactured by NIPPON KAYAKU CO., Ltd.), dineopentaerythritol penta(meth)acrylate (as a commercially available product is KAYARAD D-310; manufactured by NIPPON KAYAKU CO., Ltd.), Dineopentaerythritol hexa(meth)acrylate (as a commercially available product is KAYARAD DPHA; manufactured by NIPPON KAYAKU CO., Ltd., NK ester A-DPH-12E; manufactured by SHIN-NAKAMURA CHEMICAL CO., Ltd.), Compounds with a structure in which the (meth)acrylic groups are bonded via ethylene glycol and/or propylene glycol residues (for example, SR454 and SR499 commercially available from Sartomer Company, Inc.) are preferred.

In addition, as the polymerizable monomer, it is also preferable to use ARONIX M-402 (manufactured by TOAGOSEI CO., LTD., a mixture of dineopentaerythritol hexaacrylate and dineopentaerythritol pentaacrylate).

In addition, as polymerizable monomers, trimethylolpropane tri(meth)acrylate, trimethylolpropane propyleneoxy can be used to modify tri(meth)acrylate, trimethylolpropane ethyleneoxy Trifunctional (meth)acrylate compounds such as modified tri(meth)acrylate, vinyl isocyanurate modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate are also preferred . Examples of commercially available products of trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, and M-306 , M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A- TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (Nippon Kayaku Co., Ltd.) etc.

As the polymerizable monomer, it is also preferable to use a polymerizable monomer having an acid group. By using a polymerizable monomer having an acid group, the coloring composition layer in the unexposed part can be easily removed during development, and the generation of development residue can be suppressed. As an acid group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. are mentioned, and a carboxyl group is preferable. As a polymerizable monomer having an acid group, succinic acid modified dineopentaerythritol penta(meth)acrylate and the like can be mentioned. Examples of commercially available products of polymerizable monomers having acid groups include ARONIX M-510, M-520, ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), and the like. The preferable acid value of the polymerizable monomer having an acid group is 0.1 to 40 mgKOH/g, and more preferably 5 to 30 mgKOH/g. If the acid value of the polymerizable monomer is 0.1 mgKOH/g or more, the solubility to the developer is good, and if it is 40 mgKOH/g or less, it is advantageous in terms of production or handling.

A compound having a caprolactone structure in a polymerizable single system is also preferable. Polymerizable monomers having a caprolactone structure are marketed, for example, as KAYARAD DPCA series by NIPPON KAYAKU CO., Ltd., and examples thereof include DPCA-20, DPCA-30, DPCA-60, DPCA-120, and the like.

As the polymerizable monomer, the compound described in Japanese Patent Application Publication No. 2017-048367, Japanese Patent No. 6057891, Japanese Patent No. 6031807, and the compound described in Japanese Patent Application Publication No. 2017-194662, 8UH-1006 , 8UH-1012 (above, manufactured by Taisei Fine Chemical Co., Ltd.), Light-Acrylate POB-A0 (manufactured by KYOEISHA CHEMICAL Co., LTD.), etc. are also preferred.

The content of the polymerizable monomer is preferably 5.0 to 35% by mass in the total solid content of the coloring composition. The upper limit is more preferably 30% by mass or less, and more preferably 25% by mass or less. The lower limit is more preferably 7.5% by mass or more, and more preferably 10% by mass or more. A polymerizable monomer may be used individually by 1 type, and may use 2 or more types together. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

＜＜Light radical polymerization initiator＞＞ The coloring composition of the present invention contains a photoradical polymerization initiator. Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), phosphine compounds such as phosphine oxides, and hexaarylbisimidazole compounds , Oxime derivatives and other oxime compounds, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, amino alkyl phenone compounds, hydroxy alkyl phenone compounds, benzoic acid esters Compound etc. As specific examples of the photopolymerization initiator, for example, paragraphs 0265 to 0268 of JP 2013-029760 A, and the descriptions of Japanese Patent No. 6301489 can be referred to, and these contents are incorporated in this specification.

As the benzoate compound, methyl benzoate and the like can be mentioned. As a commercial item, DAROCUR-MBF (made by BASF Corporation) etc. are mentioned.

As an amino alkyl phenone compound, the amino alkyl phenone compound described in Unexamined-Japanese-Patent No. 10-291969 can be mentioned, for example. In addition, as the amino alkyl phenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (all manufactured by BASF) can also be used.

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

Examples of the hydroxyalkylphenone compound include compounds represented by the following formula (V).

Formula (V) [Chemical formula 9]

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent, Rv ² and Rv ³ may be bonded to each other to form a ring, and m represents an integer of 0-5.

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

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

As specific examples of the compound represented by formula (V), the following compounds can be cited. [Chemical formula 10]

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

Examples of the oxime compound include the compounds described in JP 2001-233842, the compounds described in JP 2000-080068, the compounds described in JP 2006-342166, and JCS Perkin The compound described in II (1979, pp.1653-1660), the compound described in JCS Perkin II (1979, pp.156-162), Journal of Photopolymer Science and Technology (1995, pp.202- 232) The compound described in Japanese Patent Application Publication No. 2000-066385, the compound described in Japanese Patent Application Publication No. 2000-080068, the compound described in Japanese Patent Application Publication No. 2004-534797, The compound described in Japanese Patent Application Publication No. 2006-342166, the compound described in Japanese Patent Application Publication No. 2017-019766, the compound described in Japanese Patent Publication No. 6065596, and the compound described in International Publication No. 2015/152153 The compound described in International Publication No. 2017/051680, the compound described in JP 2017-198865 A, the compound described in Paragraphs 0025 to 0038 of International Publication No. 2017/164127, etc. Specific examples of the oxime compound include 3-benzyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, and 3-propionyloxyimine. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzyloxy Imino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1 -Phenylpropan-1-one, etc. Commercially available products include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF Corporation), TR-PBG-304 (manufactured by Changzhou Tronly New Electronic Materials CO., LTD.), Adeka Optomer N-1919 (manufactured by ADEKA CORPORATION, photopolymerization initiator 2 described in JP 2012-014052 A).

In addition, as the oxime compound, the compound described in Japanese Patent Application Publication No. 2009-519904 in which the oxime is attached to the N position of the carbazole ring, and US Patent No. 7626957 in which heterosubstituents are introduced into the diphenyl ketone site can also be used The compound described in the specification, the nitro group is introduced into the pigment site, and the compound described in the specification of Japanese Patent Application Laid-Open No. 2010-015025 and U.S. Patent Application Publication No. 2009/0292039, and the compound described in International Publication No. 2009/131189 The ketoxime compound, the compound described in the specification of U.S. Patent No. 7556910, which contains a triazine skeleton and an oxime skeleton in the same molecule, has a maximum absorption at 405 nm and has good sensitivity to g-ray light sources. Japanese Patent Publication 2009 -The compounds described in Bulletin No. 221114, etc. Preferably, for example, paragraphs 0274 to 0306 of JP 2013-029760 A can be referred to, and these contents are incorporated into this specification.

From the viewpoint of efficiently generating free radical active species, the oxime compound is preferably an oxime compound containing a fluorine atom. The oxime compound containing a fluorine atom preferably has a group containing a fluorine atom. The group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing alkyl group) and a group containing an alkyl group having a fluorine atom (hereinafter, also referred to as a fluorine-containing group). As the fluorine-containing group, selected from -OR ^F1 , -SR ^F1 , -COR ^F1 , -COOR ^F1 , -OCOR ^F1 , -NR ^F1 R ^F2 , -NHCOR ^F1 , -CONR ^F1 R ^F2 , -NHCONR ^F1 R ^F2 , At least one of -NHCOOR ^F1 , -SO ₂ R ^F1 , -SO ₂ OR ^F1 and -NHSO ₂ R ^F1 is preferred. R ^F1 represents a fluorine-containing alkyl group, and R ^F2 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group, or a heterocyclic group. The fluorine-containing group is preferably -OR ^F1 .

The carbon number of the alkyl group and the fluoroalkyl group is preferably from 1 to 20, more preferably from 1 to 15, more preferably from 1 to 10, and particularly preferably from 1 to 4. The alkyl group and the fluorine-containing alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. In the fluorine-containing alkyl group, the substitution rate of fluorine atoms is preferably from 40 to 100%, more preferably from 50 to 100%, and even more preferably from 60 to 100%. In addition, the substitution rate of fluorine atoms means the ratio (%) of the number of substitutions by fluorine atoms to the number of all hydrogen atoms possessed by the alkyl group.

The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.

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 condensation number is preferably 2-8, more preferably 2-6, more preferably 3-5, and particularly preferably 3-4. The number system of carbon atoms constituting the heterocyclic group is preferably 3-40, more preferably 3-30, and more preferably 3-20. The number system of the heteroatom 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 a nitrogen atom is more preferred.

The group containing a fluorine atom preferably has a terminal structure represented by formula (1) or (2). The * in the formula represents the connection key. *-CHF ₂ (1) *-CF ₃ (2) The number of all fluorine atoms in the oxime compound containing fluorine atoms is preferably 3 or more, more preferably 4-10.

The oxime compound containing a fluorine atom is preferably a compound represented by formula (OX-1). (OX-1) [Chemical formula 11]

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

Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon ring which may have a substituent. The aromatic hydrocarbon ring may be a single ring or a condensed ring. The number of carbon atoms of the ring constituting the aromatic hydrocarbon ring is preferably 6-20, more preferably 6-15, and particularly preferably 6-10. The aromatic hydrocarbon ring system is preferably a benzene ring and a naphthalene ring. Among them, at least one of Ar ¹ and Ar ² is preferably a benzene ring, and Ar ¹ is a benzene ring. Ar ² is preferably a benzene ring or a naphthalene ring, and more preferably a naphthalene ring.

Examples of substituents that Ar ¹ and Ar ² may have include alkyl groups, aryl groups, heterocyclic groups, nitro groups, cyano groups, halogen atoms, -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 and so on. R ^X1 and R ^X2 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. The alkyl group as a substituent and the alkyl group represented by R ^X1 and R ^X2 preferably have 1 to 30 carbon atoms. The alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. In the alkyl group, part or all of the hydrogen atoms may be substituted by halogen atoms (preferably fluorine atoms). In addition, in the alkyl group, part or all of the hydrogen atoms may be substituted with the above-mentioned substituents. The aryl group as the substituent and the aryl group represented by R ^X1 and R ^X2 preferably have a carbon number of 6-20, more preferably 6-15, and still more preferably 6-10. The aryl group may be a single ring or a condensed ring. In addition, in the aryl group, part or all of the hydrogen atoms may be substituted with the above-mentioned substituents. The heterocyclic group as a substituent and the heterocyclic group represented by R ^X1 and R ^X2 are preferably a 5-membered ring or a 6-membered ring. The heterocyclic group may be a monocyclic ring or a condensed ring. The number system of carbon atoms constituting the heterocyclic group is preferably 3-30, more preferably 3-18, and more preferably 3-12. The number system of the heteroatom constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In addition, in the heterocyclic group, part or all of the hydrogen atoms may be substituted with the above-mentioned substituents.

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

R ¹ represents an aryl group having a group containing a fluorine atom. The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and still more preferably 6-10. The group containing a fluorine atom is preferably a group containing an alkyl group having a fluorine atom (fluorine-containing alkyl group) and a group having an alkyl group having a fluorine atom (fluorine-containing group). Regarding the group containing a fluorine atom, it has the same meaning as the above range, and the preferred range is also the same.

R ² represents an alkyl group or an aryl group, and an alkyl group is preferred. The alkyl group and the aryl group may be unsubstituted or may have a substituent. As a substituent, the substituent demonstrated by the above-mentioned Ar ¹ and Ar ² may have a substituent. The carbon number of the alkyl group is preferably from 1 to 20, more preferably from 1 to 15, more preferably from 1 to 10, and particularly preferably from 1 to 4. The alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the aryl group is preferably 6-20, more preferably 6-15, and still more preferably 6-10.

R ³ represents an alkyl group or an aryl group, and an alkyl group is preferred. The alkyl group and the aryl group may be unsubstituted or may have a substituent. As a substituent, the substituent demonstrated by the above-mentioned Ar ¹ and Ar ² may have a substituent. The number of carbon atoms in the alkyl group represented by R ³ is preferably 1-20, more preferably 1-15, and still more preferably 1-10. The alkyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the aryl group represented by R ³ is preferably 6-20, more preferably 6-15, and still more preferably 6-10.

Specific examples of the oxime compound having a fluorine atom include the compounds described in JP 2010-262028 A, the compounds 24, 36 to 40 described in JP 2014-500852 A, and JP 2013 The compound (C-3) described in 164471 bulletin, etc.

In addition, as the oxime compound, an oxime compound having a stilbene ring can also be used. As specific examples of the oxime compound having a sulphur ring, the compounds described in JP 2014-137466 A can be cited. This content is incorporated into this manual.

In addition, as the oxime compound, an oxime compound having a benzofuran skeleton can also be used. As a specific example, the compounds OE-01 to OE-75 described in International Publication No. 2015/036910 can be cited.

In addition, as the oxime compound, at least one benzene ring having a carbazole ring can also be used as a naphthalene ring skeleton. As a specific example of such an oxime compound, the compound of International Publication No. 2013/083505 can be cited.

Furthermore, as the photopolymerization initiator, an oxime compound obtained by bonding a substituent having a hydroxyl group to a carbazole skeleton can also be used. As such a photopolymerization initiator, the compounds described in International Publication No. 2019/088055 and the like can be cited.

In addition, as the oxime compound, an oxime compound having a nitro group can be used. It is also preferable that the oxime compound having a nitro group is a dimer. Specific examples of oxime compounds having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and paragraphs 0070 to 0079 of JP 2014-137466. , Japanese Patent No. 4223071, the compound described in paragraphs 0007 to 0025, etc.

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

[Chemical formula 12]

[Chemical formula 13]

In the present invention, as the photopolymerization initiator, the photopolymerization initiator A1 having an absorption coefficient of 1.0×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol and an absorption coefficient of 1.0×10 The photopolymerization initiator A2 having a wavelength of 10 ² mL/gcm or less and an absorption coefficient of 1.0×10 ³ mL/gcm or more at a wavelength of 254 nm is preferable. According to this aspect, it is easy to fully harden the composition by exposure, and in a low-temperature process (for example, at a temperature of 150°C or less, preferably 120°C or less in the entire process), excellent adhesion and solvent resistance can be formed A cured film with excellent properties, flatness, and pattern rectangularity. As the photopolymerization initiator A1 and the photopolymerization initiator A2, a compound having the above-mentioned light absorption coefficient is preferably selected from the above-mentioned compounds.

In addition, in the present invention, the absorbance coefficient at the aforementioned wavelength of the photopolymerization initiator is a value measured as follows. That is, it is calculated by dissolving the photopolymerization initiator in methanol to prepare a measuring solution, and measuring the absorbance of the aforementioned measuring solution. Specifically, the aforementioned measurement solution was added to a glass dish with a width of 1 cm, and the absorbance was measured using a UV-Vis-NIR spectrometer (Cary5000) manufactured by Agilent Technologies, and substituted into the following formula to calculate the absorbance coefficient at a wavelength of 365 nm and a wavelength of 254 nm (ML/gcm).

[Numerical formula 1]

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

The absorbance coefficient of the photopolymerization initiator A1 at a wavelength of 365 nm in methanol is 1.0×10 ³ mL/gcm or more, preferably 1.0×10 ⁴ mL/gcm or more, and more preferably 1.1×10 ⁴ mL/gcm or more, 1.2×10 ⁴ ～1.0×10 ⁵ mL/gcm is more preferable, 1.3×10 ⁴ ～5.0×10 ⁴ mL/gcm is still more preferable, 1.5×10 ⁴ ～3.0×10 ⁴ mL/gcm is particularly preferable .

In addition, the absorbance coefficient of light at a wavelength of 254 nm in methanol of the photopolymerization initiator A1 is preferably 1.0×10 ⁴ to 1.0×10 ⁵ mL/gcm, and more preferably 1.5×10 ⁴ to 9.5×10 ⁴ mL/gcm Preferably, 3.0×10 ⁴ to 8.0×10 ⁴ mL/gcm is more preferable.

As the photopolymerization initiator A1, oxime compounds, amino alkyl phenone compounds, and acyl phosphine compounds are preferred, oxime compounds and acyl phosphine compounds are more preferred, and oxime compounds are further preferred. From the viewpoint of compatibility of other components contained, an oxime compound containing a fluorine atom is particularly preferred. As the oxime compound containing a fluorine atom, the compound represented by the above formula (OX-1) is preferred. Specific examples of the photopolymerization initiator A1 include 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzyl oxime)] (as a commercial product , For example, IRGACURE-OXE01, manufactured by BASF Corporation), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O -Acetoxime) (as a commercial product, for example, IRGACURE-OXE02, manufactured by BASF Corporation), bis(2,4,6-trimethylbenzyl)-phenylphosphine oxide (as a commercial product, for example, IRGACURE -819, manufactured by BASF Corporation), (C-13), (C-14), etc. shown in the specific examples of the above-mentioned oxime compound.

The absorbance coefficient of light with a wavelength of 365 nm in methanol of the photopolymerization initiator A2 is 1.0×10 ² mL/gcm or less, preferably 10 to 1.0×10 ² mL/gcm, and 20 to 1.0×10 ² mL/gcm is Better. In addition, the difference between the absorbance coefficient of the photopolymerization initiator A1 in methanol at a wavelength of 365 nm and the absorbance coefficient of the photopolymerization initiator A2 in methanol at a wavelength of 365 nm is 9.0×10 ² mL/gcm or more, 1.0 ×10 ³ mL/gcm or more is preferable, 5.0×10 ³ to 3.0×10 ⁴ mL/gcm is more preferable, and 1.0×10 ⁴ to 2.0×10 ⁴ mL/gcm is still more preferable. In addition, the light absorption coefficient of light at a wavelength of 254 nm in methanol of the photopolymerization initiator A2 is 1.0×10 ³ mL/gcm or more, preferably 1.0×10 ³ to 1.0×10 ⁶ mL/gcm, and 5.0×10 ³ to 1.0×10 ⁵ mL/gcm is more preferable.

As the photopolymerization initiator A2, hydroxyalkylphenone compounds, benzoic acid ester compounds, aminoalkylphenone compounds, and phosphine compounds are preferred, and hydroxyalkylphenone compounds and benzophenone compounds are preferred. The acid ester compound is more preferable, and the hydroxyalkylphenone compound is still more preferable. Furthermore, as the hydroxyalkylphenone compound, a compound represented by the above formula (V) is preferred. Specific examples of the photopolymerization initiator A2 include 1-hydroxy-cyclohexyl-phenyl-ketone (as a commercially available product, for example, IRGACURE-184, manufactured by BASF Corporation), 1-[4-(2-hydroxyethyl) (Oxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one (as a commercially available product, for example, IRGACURE-2959, manufactured by BASF Corporation) and the like.

As the combination of the photopolymerization initiator A1 and the photopolymerization initiator A2, the photopolymerization initiator A1 is preferably an oxime compound and the photopolymerization initiator A2 is a hydroxyalkylphenone compound. It is more preferable that the agent A1 is an oxime compound and the photopolymerization initiator A2 is a combination of compounds represented by the above formula (V), the photopolymerization initiator A1 is an oxime compound containing a fluorine atom, and the photopolymerization initiator A2 is The combination of the compounds represented by the above formula (V) is particularly preferred.

The content of the photopolymerization initiator is preferably 3 to 25% by mass in the total solid content of the coloring composition. In addition, the lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, more preferably 8% by mass or more, more preferably 9% by mass or more, and particularly preferably 10% by mass or more. In addition, the upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and more preferably 15% by mass or less. The photopolymerization initiator may be used alone or in combination of two or more kinds. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

In addition, in the coloring composition of the present invention, expressed in mass %, the ratio M/I of the content M of the polymerizable monomer in the total solid content to the content I of the photopolymerization initiator in the total solid content is 20 or less For better. In addition, the upper limit is preferably 10 or less, more preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. In addition, the lower limit is preferably 0.1 or more, and more preferably 0.5 or more. With this aspect, the stability of the spectral characteristics is improved. When two or more types of polymerizable monomers and photopolymerization initiators are used in combination, it is preferable that the total amount of each satisfies the above requirements.

In the coloring composition of the present invention, when the above-mentioned oxime compound is used as the photopolymerization initiator, the content of the oxime compound is preferably 3 to 25% by mass in the total solid content of the coloring composition. In addition, the lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, more preferably 8% by mass or more, more preferably 9% by mass or more, and particularly preferably 10% by mass or more. In addition, the upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and more preferably 15% by mass or less. Since the content of the oxime compound is within the above range, the adhesion between the cured film after development and the support is improved, and the pattern can be made finer. The oxime compound may be used individually by 1 type, and may use 2 or more types together. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

In addition, in the coloring composition of the present invention, expressed in mass %, the ratio M/I _O of the content M of the polymerizable monomer in the total solid content to the content I _O of the oxime compound in the total solid content is 20 or less. Better. In addition, the upper limit is preferably 10 or less, more preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. In addition, the lower limit is preferably 0.1 or more, and more preferably 0.5 or more. With this aspect, the stability of the spectral characteristics is further improved. When two or more polymerizable monomers and oxime compounds are used in combination, it is preferable that the total amount of each satisfies the above requirements.

In the coloring composition of the present invention, when the above-mentioned photopolymerization initiator A1 is used as the photopolymerization initiator, the content of the photopolymerization initiator A1 in the total solid content of the coloring composition is 3-25% by mass. Better. In addition, the lower limit is preferably 5% by mass or more, more preferably 7.5% by mass or more, more preferably 8% by mass or more, more preferably 9% by mass or more, and particularly preferably 10% by mass or more. In addition, the upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and more preferably 15% by mass or less. Since the content of the photopolymerization initiator A1 is within the above range, the adhesion between the cured film after development and the support is improved, and the pattern can be made finer. The photopolymerization initiator A1 may be used alone or in combination of two or more kinds. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

In addition, in the coloring composition of the present invention, the ratio of the content M of the polymerizable monomer in the total solid content to the content I _A1 of the photopolymerization initiator A1 in the total solid content M/I _{A1 is} shown in mass% It is preferably 20 or less. In addition, the upper limit is preferably 10 or less, more preferably 5 or less, more preferably 3 or less, and particularly preferably 2 or less. In addition, the lower limit is preferably 0.1 or more, and more preferably 0.5 or more. With this aspect, the stability of the spectral characteristics is further improved. When two or more types of polymerizable monomers and photopolymerization initiator A1 are used in combination, it is preferable that the total amount of each satisfies the above requirements.

In the coloring composition of the present invention, when the photopolymerization initiator A2 is used as the photopolymerization initiator, the content of the photopolymerization initiator A2 is 0.1 to 10.0% by mass in the total solid content of the coloring composition. Better. In addition, the lower limit is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, and more preferably 1.5% by mass or more. In addition, the upper limit is preferably 9.0% by mass or less, more preferably 8.0% by mass or less, and even more preferably 7.0% by mass or less. Since the content of the photopolymerization initiator A2 is within the above-mentioned range, the solvent resistance type of the cured film after development is improved, and the pattern refinement becomes easy. The photopolymerization initiator A2 may be used alone or in combination of two or more. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

In the coloring composition of the present invention, when the above-mentioned photopolymerization initiator A1 and the photopolymerization initiator A2 are used as the photopolymerization initiator, the coloring composition of the present invention is relative to 100 parts by mass of the photopolymerization initiator A1 It is preferable to contain 50 to 200 parts by mass of the photopolymerization initiator A2. In addition, the upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less. In addition, the lower limit is preferably 60 parts by mass or more, and more preferably 70 parts by mass or more. With this aspect, a cured film having excellent solvent resistance and other characteristics can be formed in a low-temperature process (for example, a process at a temperature of 150° C. or lower, preferably 120° C. or lower in the entire process). When two or more kinds of photopolymerization initiator A1 and photopolymerization initiator A2 are used in combination, it is preferable that the total amount of each satisfies the above requirements.

In the coloring composition of the present invention, when the photopolymerization initiator A1 and the photopolymerization initiator A2 are used as the photopolymerization initiator, the photopolymerization initiator A1 and the photopolymerization initiator in the total solid content of the coloring composition The total content of the initiator A2 is preferably 3.1 to 25% by mass. In addition, the lower limit is preferably 3.1 mass% or more, preferably 5 mass% or more, more preferably 7.5% by mass or more, more preferably 8 mass% or more, more preferably 9 mass% or more, and 10 mass% The above is particularly good. In addition, the upper limit is preferably 20% by mass or less, more preferably 17.5% by mass or less, and more preferably 15% by mass or less. When two or more types of photopolymerization initiators and photopolymerization initiator A2 are used in combination, it is preferable that the total amount of each meets the above requirements.

The coloring composition of the present invention can also contain photopolymerization initiators (hereinafter, also referred to as other photopolymerization initiators) other than the photopolymerization initiator A1 and the photopolymerization initiator A2 as the photopolymerization initiator, However, it is preferable not to contain other photopolymerization initiators in practice. The fact that other photopolymerization initiators are not substantially contained means that the content of other photopolymerization initiators is 1 part by mass or less, 0.5 parts by mass relative to the total of 100 parts by mass of photopolymerization initiator A1 and photopolymerization initiator A2. Part by mass or less is more preferable, 0.1 parts by mass or less is more preferable, and it is still more preferable not to contain other photopolymerization initiators.

＜＜Resin＞＞ The coloring composition of the present invention preferably contains a resin. The resin is blended for, for example, the use of dispersing particles such as pigments in the composition and the use of a binder. In addition, the resin mainly used to disperse particles and the like in the composition is also called a dispersant. However, these uses of resin are an example, and resin can also be used for purposes other than these uses.

The weight average molecular weight (Mw) of the resin is preferably 2,000-2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 3000 or more, more preferably 4000 or more, and more preferably 5000 or more.

Examples of resins include (meth)acrylic resins, (meth)acrylamide resins, epoxy resins, ene mercaptan resins, polycarbonate resins, polyether resins, polyarylate resins, polycarbonate resins, and polyether resins. Ether resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, silicon Oxyane resin etc.

The resin used in the present invention may have an acid group. As an acid group, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group, etc. are mentioned, for example. These acid groups may be only one type, or two or more types may be used in combination. Resins with acid groups can also be used as alkali-soluble resins or dispersants.

The acid value of the resin having an acid group is preferably 30 to 500 mgKOH/g. The lower limit is more preferably 50 mgKOH/g or more, and more preferably 70 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, particularly preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.

As the resin having an acid group, a polymer having a carboxyl group in the side chain is preferred. For example, methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth)acrylic acid, vinyl benzoic acid, partially esterified maleic acid, etc. Copolymers of repeating monomers, alkali-soluble phenolic resins such as novolac resins, acidic cellulose derivatives with carboxyl groups in the side chains, polymers with hydroxyl groups and acid anhydride addition polymers. In particular, copolymers of (meth)acrylic acid and other monomers that can be copolymerized therewith are preferred. Examples of other monomers that can be copolymerized with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, and vinyl compounds. Examples of alkyl (meth)acrylates and aryl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, and (meth)acrylic acid. Butyl ester, isobutyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate Ester, toluene (meth)acrylate, naphthyl (meth)acrylate, cyclohexyl (meth)acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc. Examples of vinyl compounds include styrene, α-methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, polystyrene macromonomers, and polymethylmethacrylate macromonomers. Molecular monomers, etc. The other monomers that can be copolymerized with these (meth)acrylic acids may be only one type or two or more types.

The resin having an acid group may have a repeating unit derived from a maleimide compound. Examples of the maleimide compound include N-alkyl maleimide, N-aryl maleimide, and the like. As the repeating unit derived from the maleimide compound, the repeating unit represented by the formula (C-mi) can be cited.

[Chemical formula 14]

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

The resin system having an acid group includes a compound derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may also be referred to as "ether dimers" .) The resin of the repeating unit is also preferred.

[Chemical formula 15]

In formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

[Chemical formula 16]

As a specific example of the formula (ED2), refer to the description in JP 2010-168539 A.

For specific examples of ether dimers, for example, paragraph 0317 of JP 2013-029760 A can be referred to, and this content is incorporated in this specification.

Examples of resins containing repeating units derived from ether dimers include polymers having the following structures. In the following structural formula, Me represents a methyl group.

[Chemical formula 17]

The resin used in the present invention may have a polymerizable group. As a polymerizable group, ethylenic unsaturated groups, such as a vinyl group, a (meth)allyl group, and a (meth)acryloyl group, are mentioned. Commercial products of resins having polymerizable groups include DIANAL NR series (manufactured by MITSUBISHI RAYON CO., LTD.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co. ., Ltd.), VISCOAT R-264, KS RESIST 106 (all made by OSAKA ORGANIC CHEMICAL INDUSTRY LTD.), CYCLOMER P series (for example, ACA230AA), PLACCEL CF200 series (all made by Daicel Corporation), Ebecry l3800 ( DAICEL UCB CO., LTD.), ACRYCURE RD-F8 (NIPPON SHOKUBAI CO., LTD.), DP-1305 (FUJIFILM Finechemicals Co., Ltd.), etc.

The resin used in the present invention preferably contains a resin b1 containing a repeating unit (hereinafter, also referred to as repeating unit b1-1) derived from a compound represented by formula (I). By using the resin having the repeating unit b1-1, the low-temperature curability and transparency are excellent. In addition, when the resin contains resin b1 and the photopolymerization initiator contains at least one of the above-mentioned hydroxyalkylphenone compound and the oxime compound represented by formula (OX-1), the photopolymerization initiator that generates radicals The decomposed product easily aggregates around the aromatic ring of the resin b1 due to the π-π interaction between the aromatic rings. As a result, the gaps between the resins are filled with their decomposition products, the film quality of the cured film becomes more dense, and the stability of the spectral characteristics is further improved.

[Chemical formula 18]

X ¹ represents O or NH, O is preferred. R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a divalent linking group. Examples of the bivalent linking group include hydrocarbon groups, heterocyclic groups, -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, -OCO-, -S- and combinations thereof A group composed of two or more kinds. As a hydrocarbon group, an alkyl group, an aryl group, etc. are mentioned. The heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the types of heteroatoms constituting the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number system of the heteroatom constituting the heterocyclic group is preferably 1 to 3. The heterocyclic group may be a monocyclic ring or a condensed ring. The hydrocarbon group and heterocyclic group may have a substituent. As a substituent, an alkyl group, an aryl group, a hydroxyl group, a halogen atom, etc. are mentioned. R ¹⁰ represents a substituent. Examples of the substituent represented by R ¹⁰ include the substituent T shown below. A hydrocarbon group is preferred, and an alkyl group that may have an aryl group as a substituent is more preferred. m represents an integer of 0-2, 0 or 1 is preferable, and 0 is more preferable. p represents an integer greater than or equal to 0, 0-4 is preferable, 0-3 is more preferable, 0-2 is more preferable, 0 or 1 is still more preferable, and 1 is particularly preferable.

(Substituent T) Examples of the substituent T include halogen atom, cyano group, nitro group, hydrocarbon group, heterocyclic group, -ORt ¹ , -CORt ¹ , -COORt ¹ , -OCORt ¹ , -NRt ¹ Rt ² ,- NHCORt ¹ , -CONRt ¹ Rt ² , -NHCONRt ¹ Rt ² , -NHCOORt ¹ , -SRt ¹ , -SO ₂ Rt ¹ , -SO ₂ ORt ¹ , -NHSO ₂ Rt ¹ or -SO ₂ NRt ¹ Rt ² . Rt ¹ and Rt ² each independently represent a hydrogen atom, a hydrocarbon group, or a heterocyclic group. Rt ¹ and Rt ² may be bonded to form a ring.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, and an aryl group. The carbon number of the alkyl group is preferably 1-30, more preferably 1-15, and still more preferably 1-8. The alkyl group may be any of straight chain, branched chain, and cyclic, and straight chain or branched chain is preferred, and branched chain is more preferred. The carbon number of the alkenyl group is preferably 2-30, more preferably 2-12, particularly preferably 2-8. The alkenyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number system of the alkynyl group is preferably 2-30, more preferably 2-25. The alkynyl group may be any of linear, branched, and cyclic, and linear or branched is preferred. The carbon number of the aryl group is preferably 6-30, more preferably 6-20, and still more preferably 6-12. The heterocyclic group may be a monocyclic ring or a condensed ring. The heterocyclic group is preferably a monocyclic ring or a condensed ring having a condensation number of 2 to 4. The number system of the heteroatoms constituting the heterocyclic group is preferably 1 to 3. The hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. The number of carbon atoms constituting the heterocyclic group is preferably 3-30, more preferably 3-18, and more preferably 3-12. The hydrocarbon group and heterocyclic group may have a substituent or may be unsubstituted. As a substituent, the substituent demonstrated in the above-mentioned substituent T is mentioned.

The compound represented by the formula (I) is preferably a compound represented by the following formula (I-1). [Chemical formula 19]

X ¹ represents O or NH, O is preferred. R ¹ represents a hydrogen atom or a methyl group. R ² , R ³ and R ¹¹ each independently represent a hydrocarbon group. The hydrocarbon group represented by R ² and R ³ is preferably an alkylene group or an arylene group, and more preferably an alkylene group. The carbon number of the alkylene group is preferably 1-10, more preferably 1-5, more preferably 1-3, and particularly preferably 2 or 3. The hydrocarbon group represented by R ³ is preferably an alkyl group which may have an aryl group as a substituent, and an alkyl group which has an aryl group as a substituent is more preferable. The carbon number of the alkyl group is preferably 1-20, more preferably 1-10, and still more preferably 1-5. In addition, when the alkyl group has an aryl group as a substituent, the carbon number of the alkyl group refers to the carbon number of the alkyl group. R ¹² represents a substituent. Examples of the substituent represented by R ¹² include the aforementioned substituent T. n represents an integer of 0-15, preferably an integer of 0-5, more preferably an integer of 0-4, and even more preferably an integer of 0-3. m represents an integer of 0-2, 0 or 1 is preferable, and 0 is more preferable. p1 represents an integer of 0 or more, 0-4 is preferable, 0-3 is more preferable, 0-2 is more preferable, 0-1 is still more preferable, and 0 is particularly preferable. q1 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 3, more preferably 1 to 2, and particularly preferably 1.

The compound represented by the formula (I) is preferably a compound represented by the following formula (III). [Chemical formula 20]

In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0-15. The number of carbon atoms of the alkylene represented by R ²¹ and R ²² is preferably 1-10, more preferably 1-5, more preferably 1-3, and particularly preferably 2 or 3. n represents an integer of 0-15, preferably an integer of 0-5, more preferably an integer of 0-4, and even more preferably an integer of 0-3.

As the compound represented by formula (I), ethylene oxide or propylene oxide modified (meth)acrylate of p-cumylphenol can be cited. As a commercially available product, ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.) and the like can be cited.

In the resin b1, among all the repeating units, the ratio of the repeating units derived from the compound represented by formula (I) (preferably formula (III)) is preferably 1 to 99 mol%. The lower limit is more preferably 3 mol% or more, and more preferably 5 mol% or more. The upper limit is more preferably 95 mol% or less, and more preferably 90 mol% or less.

The resin b1 may further include repeating units other than repeating units derived from the compound represented by formula (I). For example, the resin b1 can contain a repeating unit derived from (meth)acrylate, and it is preferable to include a repeating unit derived from alkyl (meth)acrylate. The carbon number of the alkyl part of the alkyl (meth)acrylate is preferably 3-10, more preferably 3-8, and still more preferably 3-6. As a preferable specific example of alkyl (meth)acrylate, n-butyl (meth)acrylate etc. are mentioned. Also, for example, it is also preferable that the resin b1 includes a repeating unit having an acid group. In addition, for example, it is also preferable that the resin b1 contains a repeating unit derived from a (meth)acrylate having an acid group.

The coloring composition of the present invention can contain a resin as a dispersant. As the dispersant, an acidic dispersant (acidic resin) and a basic dispersant (alkaline resin) can be mentioned. Here, the acidic dispersant (acidic resin) means a resin in which the amount of acid groups is greater than the amount of basic groups. As an acidic dispersant (acidic resin), when the total amount of the amount of acid groups and the amount of basic groups is set to 100 mol%, a resin with the amount of acid groups accounting for 70 mol% or more is preferable. A resin containing an acid group is more preferable. The acid group of the acidic dispersant (acid resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. In addition, the basic dispersant (basic resin) means a resin in which the amount of basic groups is greater than the amount of acid groups. As a basic dispersant (alkaline resin), when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, a resin having an amount of basic groups greater than 50 mol% is preferred. The basic group of the basic dispersant is preferably an amino group.

As a dispersant, for example, a polymer dispersant [eg, polyamide and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly(methyl) ) Acrylic acid ester, (meth)acrylic acid copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate, polyoxyethylene alkyl amine, alkanolamine, etc. Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers from their structure. The polymer dispersant adsorbs on the surface of particles such as pigments to prevent re-aggregation. Therefore, terminally modified polymers, graft-type polymers, and block-type polymers having fixed sites on the surface of particles such as pigments can be cited as preferable structures. In addition, the dispersant described in paragraphs 0028 to 0124 of JP 2011-070156 A and the dispersant described in JP 2007-277514 A are also preferably used. These contents are incorporated into this manual.

In the present invention, a graft copolymer can also be used in the dispersant. For the details of the graft copolymer, reference can be made to the description in paragraphs 0131 to 0160 of JP 2012-137564 A, and this content is incorporated into this specification. Furthermore, in the present invention, an oligoimine-based copolymer containing a nitrogen atom in at least one of the main chain and the side chain can also be used in the dispersant. Regarding the oligoimine-based copolymer, the description in paragraphs 0102 to 0174 of JP 2012-255128 A can be referred to, and the content is incorporated in this specification.

The dispersant can also be obtained as a commercially available product. Specific examples of this include the Disperbyk series manufactured by BYK Chemie (for example, Disperbyk-111, 2001, etc.), and the SOLSPERSE series manufactured by Lubrizol Japan Ltd. (for example, SOLSPERSE20000, 76500). Etc.), AJISPER series manufactured by Ajinomoto Fine-Techno Co., Inc., etc. In addition, the product described in paragraph 0129 of JP 2012-137564 A and the product described in paragraph 0235 of JP 2017-194662 A can also be used as a dispersant.

In addition, the resins described in paragraphs 0041 to 0060 of JP 2017-206689 A can also be used appropriately.

The content of the resin is preferably 5 to 50% by mass in the total solid content of the coloring composition. In addition, the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. In addition, the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. In addition, the content of the resin is preferably 25 to 500 parts by mass relative to 100 parts by mass of the polymerizable monomer. In addition, the upper limit is preferably 250 parts by mass or less, and more preferably 150 parts by mass or less. In addition, the lower limit is preferably 50 parts by mass or more, and more preferably 75 parts by mass or more. The resin may be one type alone or two or more types may be used in combination. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

The content of the resin b1 (including the repeating unit derived from the compound represented by the formula (III)) in the total amount of the resin contained in the coloring composition of the present invention is preferably 0.1-100% by mass, 5- 100% by mass is better. The upper limit can also be 90% by mass or less, 80% by mass or less, or 70% by mass or less. In addition, the content of the resin b1 is preferably 5 to 50% by mass in the total solid content of the coloring composition. In addition, the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less. In addition, the lower limit is preferably 10% by mass or more, and more preferably 12.5% by mass or more. The resin b1 may be one type alone, or two or more types may be used in combination. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

＜＜Furyl-containing compounds＞＞ The colored composition of the present invention preferably contains a furan group-containing compound (hereinafter, also referred to as a furan group-containing compound). With this aspect, the furan group and the ethylenically unsaturated group possessed by the polymerizable monomer can form a bond even at a low temperature of 150° C. or lower due to the Diels-Alder reaction, so that the low-temperature curing is excellent. In addition, when the coloring composition contains a furan group-containing compound, and the photopolymerization initiator contains at least one of the above-mentioned hydroxyalkylphenone compound and the oxime compound represented by formula (OX-1), free radical light is generated The decomposed product of the polymerization initiator easily aggregates around the aromatic ring of the furan group-containing compound by the π-π interaction between the aromatic rings. As a result, the gaps between the resins are filled with their decomposition products, the film quality of the cured film becomes more dense, and the stability of the spectral characteristics is further improved.

As long as the furyl group-containing compound contains a furyl group (a group obtained by removing one hydrogen atom from furan), the structure is not particularly limited. For the furyl-containing compound, the compound described in paragraphs 0049 to 0089 of JP 2017-194662 A can be used. In addition, Japanese Patent Application Publication No. 2000-233581, Japanese Patent Application Publication No. 1994-271558, Japanese Patent Application Publication No. 1994-293830, Japanese Patent Application Publication No. 1996-239421, Japanese Patent Application Publication No. 1998-508655, Japanese Patent Application Publication No. 2000-001529, Japanese Patent Application Publication No. 2003-183348, Japanese Patent Application Publication No. 2006-193628, Japanese Patent Application Publication No. 2007-186684, Japanese Patent Application Publication No. 2010-265377, Japanese Patent Application Publication 2011- Compounds described in 170069 gazette and others.

The furan group-containing compound may be a monomer, an oligomer, or a polymer. In view of the ease of improving the durability of the obtained film, a polymer is preferred. In the case of a polymer, the weight average molecular weight is preferably 2,000 to 70,000. In addition, the upper limit is preferably 60,000 or less, and more preferably 50,000 or less. In addition, the lower limit is preferably 3000 or more, more preferably 4000 or more, and more preferably 5000 or more. When it is a monomer, the weight average molecular weight is preferably less than 2,000. In addition, the upper limit is preferably 1800 or less, and more preferably 1500 or less. In addition, the lower limit is preferably 100 or more, more preferably 150 or more, and more preferably 175 or more. In addition, the furan group-containing compound of the polymer type is also a component corresponding to the resin in the coloring composition of the present invention, and the furan group-containing compound of the radical polymerizable monomer type is also the same as the coloring composition of the present invention. The corresponding component of the polymerizable monomer in.

As the furan group-containing compound of the monomer type (hereinafter, also referred to as a furan group-containing monomer), a compound represented by the following formula (fur-1) can be cited. This compound is a compound which has a radical polymerizable group in addition to a furyl group.

Formula (fur-1) [Chemical formula 21]

In the formula, Rf ¹ represents a hydrogen atom or a methyl group, and Rf ² represents a divalent linking group.

Examples of the divalent linking group represented by Rf ² include alkylene, aryl, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations thereof. A group made of more than species. The carbon number of the alkylene group is preferably 1-30, more preferably 1-20, and still more preferably 1-15. The alkylene group may be any of linear, branched, and cyclic. The carbon number of the arylene group is preferably 6-30, more preferably 6-20, and still more preferably 6-10. The alkylene group and the arylene group may have a substituent. As a substituent, a hydroxyl group etc. are mentioned.

The furan group-containing single system is preferably a compound represented by the following formula (fur-2).

Formula (fur-2) [Chemical formula 22]

In the formula, Rf ¹ represents a hydrogen atom or a methyl group, Rf ¹¹ represents -O- or -NH-, and Rf ¹² represents a single bond or a divalent linking group. Examples of the divalent linking group represented by Rf ¹² include alkylene, aryl, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations thereof. A group made of more than species. The carbon number of the alkylene group is preferably 1-30, more preferably 1-20, and still more preferably 1-15. The alkylene group may be any of linear, branched, and cyclic. The carbon number of the arylene group is preferably 6-30, more preferably 6-20, and still more preferably 6-10. The alkylene group and the arylene group may have a substituent. As a substituent, a hydroxyl group etc. are mentioned.

As a specific example of the monomer containing a furan group, the compound of the following structure can be mentioned. In the following structural formulae, Rf ¹ represents a hydrogen atom or a methyl group.

[Chemical formula 23]

As a polymer type of a furan group-containing compound (hereinafter, also referred to as a furan group-containing polymer), a resin containing a furan group-containing repeating unit is preferable, and the resin is derived from the formula (fur-1) The resin of the repeating unit of the compound is more preferable. In the furan group-containing polymer, the ratio of the furan group-containing repeating unit among all the repeating units is preferably 30 to 70% by mass. The lower limit is more preferably 35% by mass or more, and more preferably 40% by mass or more. The upper limit is more preferably 65% by mass or less, and more preferably 60% by mass or less. Regarding the furan group concentration in the furan group-containing polymer, 0.5 to 6.0 mmol per 1 g of the furan group-containing polymer is preferable, and 1.0 to 4.0 mmol is more preferable. If the furan group concentration is 0.5 mmol or more, preferably 1.0 mmol or more, it is easy to form a more excellent pixel due to solvent resistance and the like. When the furan group concentration is 6.0 mmol or less, preferably 4.0 mmol or less, the stability of the coloring composition over time is more favorable.

The furan group-containing polymer may include a repeating unit having an acid group and/or a repeating unit having a polymerizable group in addition to a repeating unit having a furan group. As an acid group, a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxyl group, etc. are mentioned. As a polymerizable group, ethylenic unsaturated groups, such as a vinyl group, a (meth)allyl group, and a (meth)acryloyl group, are mentioned. When the furan group-containing polymer contains repeating units with acid groups, the acid value is preferably 10 to 200 mgKOH/g, and more preferably 40 to 130 mgKOH/g. In the furan group-containing polymer, the ratio of the acid group-containing repeating unit among all repeating units is preferably 2-25% by mass. The lower limit is more preferably 4 mass mol% or more, and more preferably 5 mass% or more. The upper limit is more preferably 20% by mass or less, and more preferably 15% by mass or less. On the other hand, in the furan group-containing polymer, the ratio of the repeating unit having a polymerizable group in all repeating units is preferably 20-60% by mass. The lower limit is more preferably 25% by mass or more, and more preferably 30% by mass or more. The upper limit is more preferably 55% by mass or less, and more preferably 50% by mass or less. When the furan group-containing polymer contains a repeating unit having a polymerizable group, it is easy to form a cured film with more excellent solvent resistance and the like.

The furan group-containing polymer can be produced by the method described in paragraphs 0052 to 0101 of JP 2017-194662 A.

The content of the furan group-containing compound is preferably 0.1 to 70% by mass in the total solid content of the coloring composition. In addition, the lower limit is preferably 2.5% by mass or more, more preferably 5.0% by mass or more, and even more preferably 7.5% by mass or more. In addition, the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less, and more preferably 50% by mass or less. Furthermore, when a furan group-containing polymer is used as the furan group-containing compound, the content of the furan group-containing polymer in the resin contained in the coloring composition is preferably 0.1-100% by mass. In addition, the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. In addition, the upper limit is preferably 90% by mass or less, and more preferably 80% by mass or less.

In addition, when the resin used in the coloring composition of the present invention contains the above-mentioned resin b1, and a furan group-containing polymer is used as the furan group-containing compound, the content of the furan group-containing polymer is relative to 100 parts by mass of the resin b1 It is preferably 10 to 200 parts by mass. In addition, the upper limit is preferably 175 parts by mass or less, and more preferably 150 parts by mass or less. In addition, the lower limit is preferably 25 parts by mass or more, and more preferably 150 parts by mass or more. By using the resin b1 and the furan group-containing polymer together, the effect of excellent low-temperature curability and transparency can be expected. In addition, when the ratio of the two is in the above range, the effect of further improving the durability of the obtained film can be expected.

The furan group-containing compound may be used alone or in combination of two or more kinds. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

＜＜Compounds with cyclic ether groups＞＞ The coloring composition of the present invention can contain a compound having a cyclic ether group. As a cyclic ether group, an epoxy group, an oxetanyl group, etc. are mentioned. The compound having a cyclic ether group is preferably a compound having an epoxy group.

As the compound having an epoxy group, a compound having two or more epoxy groups in one molecule is preferred. It is preferable to have 2-100 epoxy groups in one molecule. The upper limit can also be 10 or less, for example, and can also be 5 or less. The epoxy equivalent of the compound having an epoxy group (= the molecular weight of the compound having an epoxy group/the number of epoxy groups) is preferably 500 g/eq or less, more preferably 100 to 400 g/eq, and 100 to 300 g/ eq is further preferred. The compound having an epoxy group may be a low molecular compound (for example, a molecular weight of less than 1000) or a macromolecule compound (for example, in the case of a polymer with a molecular weight of 1000 or more, the weight average molecular weight is 1000 or more). The molecular weight (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. The upper limit of the molecular weight (in the case of a polymer, the weight average molecular weight) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1500 or less.

As a compound having an epoxy group, for example, paragraphs 0034 to 0036 of JP 2013-011869, paragraphs 0147 to 0156 of JP 2014-043556, and 0085 of JP 2014-089408 can also be used. The compound described in paragraph -0092, and the compound described in JP 2017-179172 A. In addition, as the compound having oxetanyl group, for example, the compound described in JP 2019-133052 A can be used. These contents are incorporated into this manual.

When the coloring composition of the present invention contains a compound having a cyclic ether group, the content of the compound having a cyclic ether group is preferably 0.1 to 40% by mass in the total solid content of the coloring composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, and more preferably 20% by mass or less. The compound having a cyclic ether group may be one type alone or two or more types may be used in combination. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

Especially 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 in the total solid content of the coloring composition. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is more preferably 30% by mass or less, more preferably 20% by mass or less, and particularly preferably 10% by mass or less. The compound having an epoxy group may be used alone or in combination of two or more kinds. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

＜＜Solvent＞＞ The colored composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the coloring composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For the details, please refer to paragraph 0223 of International Publication No. 2015/166779, which is incorporated into this specification. In addition, ester solvents substituted with cyclic alkyl groups and ketone solvents substituted with cyclic alkyl groups can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethyl cellosolve acetate. , Ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Ester, butyl carbitol acetate, propylene glycol monomethyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), 3-methoxy-N,N-dimethylpropanamide, 3- Butoxy-N,N-dimethylpropanamide etc. However, aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as solvents may be reduced due to environmental reasons (for example, relative to the total amount of organic solvents, it can be set to 50 mass ppm ( Parts per million (parts per million) or less, can also be set to 10 mass ppm or less, or can be set to 1 mass ppm or less).

In the present invention, from the viewpoint of effective use of the solvent, the solvent is preferably an organic solvent having a boiling point of 160°C or less. The boiling point of the organic solvent is more preferably 140°C or less, and more preferably 130°C or less. The lower limit of the boiling point is not particularly limited, and for example, it is actually 100°C or higher. As such an organic solvent, for example, butyl acetate, PGME, PGMEA, cyclohexanone, ethyl lactate, etc. can be cited, and in particular, butyl acetate, PGME, and PGMEA are preferred.

In the present invention, it is better to use a solvent with less metal content. For example, the metal content of the solvent is preferably 10 mass ppb (parts per billion) or less. If necessary, you can also use quality ppt (parts per trillion) solvents, such high purity solvents are provided by TOYO Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015 ).

As a method for removing impurities such as metals from the solvent, for example, filtration using distillation (molecular distillation, thin film distillation, etc.) or filter can be cited. As the filter pore size of the filter used for filtration, 10 μm or less is preferable, 5 μm or less is more preferable, and 3 μm or less is more preferable. The filter material is preferably PTFE, polyethylene or nylon.

The solvent may contain isomers (compounds with the same number of atoms but different structures). In addition, the isomer may include only one type or a plurality of types.

In the present invention, the peroxide content in the organic solvent is preferably 0.8 mmol/L or less, and it is more preferred that the peroxide content is not substantially contained.

The content of the solvent in the coloring composition is preferably 60 to 95% by mass. In addition, the upper limit is preferably 90% by mass or less, more preferably 87.5% by mass or less, and more preferably 85% by mass or less. In addition, the lower limit is preferably 65% by mass or more, more preferably 70% by mass or more, and more preferably 75% by mass or more. A solvent may be used individually by 1 type, and may use 2 or more types together. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

In addition, from the viewpoint of environmental regulations, it is preferable that the colored composition of the present invention does not substantially contain environmental regulations. In addition, in the present invention, the fact that the content of environmental regulatory substances is not substantially contained means that the content of environmental regulatory substances in the coloring composition is 50 mass ppm or less, preferably 30 mass ppm or less, and 10 mass ppm or less is more preferably, 1 mass ppm Below ppm is particularly good. Examples of environmental regulatory substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene. These are registered as environmental regulatory substances under REACH (Registration Evaluation Authorization and Restriction of CHemicals) regulations, PRTR (Pollutant Release and Transfer Register) laws, VOC (Volatile Organic Compounds) regulations, etc., and their usage and disposal methods are strictly controlled. These compounds are sometimes used as solvents in the production of the respective components of the coloring composition used in the present invention, and are mixed into the coloring composition as a residual solvent. From the viewpoint of human safety and environmental considerations, it is better to reduce these substances as much as possible. As a method of reducing environmental regulations, heating and depressurizing the inside of the system to make it above the boiling point of the environmental regulations, and distilling and reducing the environmental regulations from the system can be cited. In addition, when a small amount of environmentally regulated substances is removed by distillation, it is also useful to azeotrope a solvent having the same boiling point as the solvent in order to improve efficiency. In addition, when a compound having radical polymerizability is contained, it can be removed by distillation under reduced pressure after adding a polymerization inhibitor, so as to suppress the progress of the radical polymerization reaction during the removal under reduced pressure to cause crosslinking between molecules. These distillation removal methods can be used in any of the stages of raw materials, the stages of reacting raw materials (such as polymerized resin solutions and polyfunctional monomer solutions), or the stage of coloring compositions produced by mixing these compounds In the phase.

＜＜Pigment derivatives＞＞ The coloring composition of the present invention can contain a pigment derivative. As the pigment derivative, a compound having a structure in which a part of the chromophore is substituted with an acid group, a basic group, or a phthaliminomethyl group is mentioned. Examples of chromophores constituting pigment derivatives include quinoline-based skeletons, benzimidazolone-based skeletons, diketopyrrolopyrrole-based skeletons, azo-based skeletons, phthalocyanine-based skeletons, anthraquinone-based skeletons, and quinacridones System skeleton, two-hole well system skeleton, perylene skeleton, perylene skeleton, thioindigo blue skeleton, isoindoline skeleton, isoindolinone skeleton, quinoline yellow skeleton, styrene series Framework, metal complex system framework, etc., quinoline framework, benzimidazolone framework, diketopyrrolopyrrole framework, azo framework, quinoline yellow framework, isoindoline framework and phthalocyanine The skeleton is preferable, and the azo skeleton and the benzimidazolone skeleton are more preferable. As the acid group possessed by the pigment derivative, a sulfo group and a carboxyl group are preferred, and a sulfo group is more preferred. As the basic group possessed by the pigment derivative, an amino group is preferred, and a tertiary amino group is more preferred. As a specific example of a pigment derivative, for example, the description in paragraphs 0162 to 0183 of JP 2011-252065 A can be referred to, and this content is incorporated in this specification.

In addition, specific examples of pigment derivatives include Japanese Patent Application Publication No. 56-118462, Japanese Patent Application Publication No. 63-264674, Japanese Patent Application Publication No. 01-217077, Japanese Patent Application Publication No. 03-009961, Japanese Patent Application Publication No. 03-026767, Japanese Patent Application Publication No. 03-153780, Japanese Patent Application Publication No. 03-045662, Japanese Patent Application Publication No. 04-285669, Japanese Patent Application Publication No. 06-145546, Japanese Patent Application Publication No. 06- 212088, Japanese Patent Application Publication No. 06-240158, Japanese Patent Application Publication No. 10-030063, Japanese Patent Application Publication No. 10-195326, International Publication No. 2011/024896, paragraphs 0086 to 0098, International Publication No. 2012/102399 No. 0063 to 0094, International Publication No. 2017/038252, paragraph 0082, Japanese Patent Application Publication No. 2015-151530, paragraph 0171, Japanese Patent Application Publication No. 2011-252065, paragraphs 0162 to 0183, Japanese Patent Application Publication No. 2003-081972 No. 5299151, Japanese Patent Application No. 2015-172732, Japanese Patent Application Publication No. 2014-199308, Japanese Patent Application Publication No. 2014-085562, Japanese Patent Application Publication No. 2014-035351, Japanese Patent Application Publication No. 2008 -081565, Japanese Patent Application Publication No. 2019-109512, and Japanese Patent Application Publication No. 2019-133154.

The content of the pigment derivative is preferably 0.1-30 parts by mass relative to 100 parts by mass of the pigment. The lower limit of the range is more preferably 0.25 parts by mass or more, more preferably 0.5 parts by mass or more, particularly preferably 0.75 parts by mass or more, and more preferably 1 part by mass or more. In addition, the upper limit of the range is more preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and particularly preferably 15 parts by mass or less. Since the content of the pigment derivative is within the above range, there is an effect of further improving stability over time. Only one type of pigment derivative may be used, or two or more types may be used. When two or more types are used in combination, the total amount of these is preferably in the above-mentioned range.

＜＜Curing accelerator＞＞ The coloring composition of the present invention may add a hardening accelerator for the purpose of promoting the reaction of polymerizable monomers or lowering the hardening temperature. Examples of the curing accelerator include polyfunctional thiol compounds having two or more mercapto groups in the molecule. The multifunctional thiol compound can also be added for the purpose of improving stability, odor, resolution, developability, adhesion, and the like. The polyfunctional thiol compound is preferably a secondary alkyl thiol, and the compound represented by formula (T1) is more preferred.

Formula (T1) [Chemical Formula 24]

In formula (T1), n represents an integer of 2 to 4, and L represents a linking group of 2 to 4 valence. In the formula (T1), the linking group L is preferably an aliphatic group having 2-12 carbons, n is 2, and L is an alkylene group having 2-12 carbons.

In addition, the hardening accelerator can also use methylol-based compounds (for example, compounds exemplified as cross-linking agents in paragraph 0246 of JP 2015-034963 A), amines, phosphonium salts, amidine salts, and amides. Compound (above, for example, the hardener described in paragraph 0186 of JP 2013-041165 A), an alkali generator (for example, an ionic compound described in JP 2014-055114 A), cyanic acid Ester compound (for example, the compound described in paragraph 0071 of JP 2012-150180 A), alkoxysilane compound (for example, the alkoxy having an epoxy group described in JP 2011-253054 A Silane compound), onium salt compound (for example, the compound exemplified as an acid generator in paragraph 0216 of JP 2015-034963 A, the compound described in JP 2009-180949 A), and the like.

When the colored composition of the present invention contains a hardening accelerator, the content of the hardening accelerator is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass in the total solid content of the colored composition.

＜＜Silane coupling agent＞＞ The coloring composition of the present invention can contain a silane coupling agent. As the silane coupling agent, a silane compound having at least two functional groups with different reactivity in one molecule is preferred. The silane coupling agent has at least one selected from vinyl group, epoxy group, styryl group, methacryl group, amine group, isocyanurate group, urea group, mercapto group, thioether group and isocyanate group Groups and silane compounds having alkoxy groups and the like are preferred. As a specific example of the silane coupling agent, N-2-(aminoethyl)-3-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM- 602), N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-603), 3-aminopropyltrimethoxy Silane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-903), 3-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methyl Propyloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., KBM-503), 3-glycidoxypropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd. System, KBM-403) etc. For the details of the silane coupling agent, refer to the description in paragraphs 0155 to 0158 of JP 2013-254047 A, and this content is incorporated in this specification. When the coloring composition of the present invention contains a silane coupling agent, the content of the silane coupling agent in the total solid content of the coloring composition is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, and 0.1 to 10% by mass. 5 mass% is particularly preferred. The coloring composition of the present invention may contain only one type or two or more types of silane coupling agents. When two or more types are contained, the total amount is preferably in the above-mentioned range.

＜＜Polymerization inhibitor＞＞ The coloring composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, pyrogallol, tertiary butyl catechol, benzoquinone, 4,4'-sulfur Substituted bis (3-methyl-6-tertiary butyl phenol), 2,2'-methylene bis (4-methyl-6-tertiary butyl phenol), N-nitroso bishydroxy amine salt (Ammonium salt, first cerium salt, etc.) etc. When the colored composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass in the total solid content of the colored composition. The coloring composition of the present invention may contain only one type or two or more types of polymerization inhibitors. When two or more types are contained, the total amount is preferably in the above-mentioned range.

＜＜Ultraviolet absorber＞＞ The colored composition of the present invention can contain an ultraviolet absorber. UV absorbers can use conjugated diene compounds, amino diene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazole compounds, indole compounds, Three 𠯤 compounds and so on. For details of these, please refer to paragraphs 0052 to 0072 of JP 2012-208374, paragraphs 0317 to 0334 of JP 2013-068814, and paragraphs 0061 to 0080 of JP 2016-162946. The contents are incorporated into this manual. As a commercially available product of an ultraviolet absorber, UV-503 (made by DAITO CHEMICAL CO., LTD.) etc. are mentioned, for example. Also, as the benzotriazole compound, the MYUA series manufactured by MIYOSHI OIL & FAT CO., LTD. (Chemical Industry Daily, February 1, 2016) can be cited. In addition, as the ultraviolet absorber, the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 can also be used. When the coloring composition of the present invention contains an ultraviolet absorber, the content of the ultraviolet absorber in the total solid content of the coloring composition is preferably 0.1-10% by mass, more preferably 0.1-5% by mass, and 0.1-3% by mass % Is particularly good. In addition, only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, the total amount of these is preferably in the above-mentioned range.

＜＜Surface active agent＞＞ The coloring composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used. Regarding the surfactant, refer to paragraphs 0238 to 0245 of International Publication No. 2015/166779, and the content is incorporated into this specification.

In the present invention, the surfactant-based fluorine-based surfactant is preferred. By containing a fluorine-based surfactant in the coloring composition, liquid properties (especially fluidity) can be further improved, and liquid-saving properties can be further improved. In addition, a film with less uneven thickness can be formed.

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

Examples of fluorine-based surfactants include those described in paragraphs 0060 to 0064 of Japanese Unexamined Patent Publication No. 2014-041318 (corresponding to paragraphs 0060 to 0064 of International Publication No. 2014/017669). The surfactants described in paragraphs 0117 to 0132 of the Open Publication No. 2011-132503 are incorporated into this specification. Commercial products of fluorine-based surfactants include, for example, Magaface F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F-781F , EXP, MFS-330 (above, manufactured by DIC CORPORATION), Fluorad FC430, FC431, FC171 (above, manufactured by Sumitomo 3M Limited), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, KH-40 (above, manufactured by ASAHI GLASS CO., LTD.), PolyFox PF636, PF656, PF6320, PF6520, PF7002 (above, manufactured by OMNOVA SOLUTIONS INC.) )Wait.

In addition, as the fluorine-based surfactant, it is also possible to preferably use an acrylic compound containing a molecular structure having a functional group containing a fluorine atom, and a part of the functional group containing a fluorine atom is cleaved and the fluorine atom is volatilized when heated. Examples of such fluorine-based surfactants include Magaface DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016), for example, Magaface DS-21.

Furthermore, it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorine-based surfactant. For this type of fluorine-based surfactant, refer to the description of JP 2016-216602 A, and the content is incorporated in this specification.

Block polymers can also be used as the fluorine-based surfactant. For example, the compounds described in JP 2011-089090 A can be cited. Fluorine-based surfactants can also preferably use fluorine-containing polymer compounds containing: repeating units derived from (meth)acrylate compounds having fluorine atoms; and derived from having two or more ( Preferably 5 or more) repeating units of (meth)acrylate compounds of alkoxyl groups (preferably ethoxyl groups and propoxyl groups). As the fluorine-based surfactant used in the present invention, the following compounds are also exemplified.

[Chemical formula 25]

The weight average molecular weight of the above-mentioned compound is preferably 3,000 to 50,000, for example, 14,000. In the above compound, the% representing the proportion of the repeating unit is mole %.

In addition, as the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group on the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and paragraphs 0289 to 0295 of JP 2010-164965 A, such as MEGAFACE RS-101, RS-102, RS-718K, RS- by DIC CORPORATION. 72-K etc. The fluorine-based surfactant can also use the compounds described in paragraphs 0015 to 0158 of JP 2015-117327 A.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate). Etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilauric acid Ester, polyethylene glycol distearate, sorbitan fatty acid ester, PLURONIC L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF), TETRONIC 304, 701, 704, 901, 904 , 150R1 (manufactured by BASF Corporation), SOLSPERSE 20000 (manufactured by Lubrizol Japan Ltd.), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D -6315 (manufactured by Takemoto Oil & Fat Co., Ltd.), OLFIN E1010, Surfynol 104, 400, 440 (manufactured by Nissin Chemical Co., Ltd.), etc.

Examples of silicone-based surfactants include Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (above, Dow Corning Toray Co. , Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials Inc.), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Chemical Co., Ltd.), BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie GmbH), etc.

The content of the surfactant in the total solid content of the coloring composition is preferably 0.001 to 5.0% by mass, and more preferably 0.005 to 3.0% by mass. The surfactant may be only one type or two or more types. When it is 2 or more types, it is preferable that these total amounts are the said range.

＜＜Other additives＞＞ Various additives, such as fillers, adhesion promoters, antioxidants, anti-cohesion agents, etc., can be blended into the coloring composition of the present invention as needed. As these additives, the additives described in paragraphs 0155 to 0156 of JP 2004-295116 A can be cited, and this content is incorporated in this specification. In addition, as the antioxidant, for example, a phenolic compound, a phosphorus compound (for example, the compound described in paragraph 0042 of JP 2011-090147 A), a thioether compound, and the like can be used. As a commercially available product, for example, Adekastab series manufactured by ADEKA CORPORATION (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO-330 Wait). In addition, as the antioxidant, the multifunctional hindered amine antioxidant described in International Publication No. 2017/006600, the antioxidant described in International Publication No. 2017/164024, and 0023 to Japanese Patent No. 6268967 can also be used. Antioxidant described in paragraph 0048. Only 1 type of antioxidant may be used, and 2 or more types may be used. In addition, the colored composition of the present invention may further contain a latent antioxidant as necessary. As the latent antioxidant, a compound in which the part that functions as an antioxidant is protected by a protective group can be cited, and the protective group is heated at 100 to 250°C or in the presence of an acid/base catalyst at 80 to 200°C A compound that is released by heating and functions as an antioxidant. Specific examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and Japanese Patent Application Laid-Open No. 2017-008219. As a commercially available product, ADEKAARKLS GPA-5001 (manufactured by ADEKA CORPORATION) and the like can be cited. In addition, the colored composition of the present invention can contain the sensitizer and the light stabilizer described in paragraph 0078 of JP 2004-295116 A, and the thermal polymerization described in paragraph 0081 of JP 2004-295116 Inhibitor, storage stabilizer described in paragraph 0242 of JP 2018-091940 A.

In addition, the colored composition of the present invention may contain a metal oxide in order to adjust the refractive index of the obtained film. Examples of metal oxides include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , and SiO ₂ . The primary particle size of the metal oxide is preferably from 1 to 100 nm, more preferably from 3 to 70 nm, and most preferably from 5 to 50 nm. The metal oxide may have a core-shell structure, and in this case, the core may be hollow.

In addition, the colored composition of the present invention may include a light resistance improver. Examples of the light resistance improver include the compounds described in paragraphs 0036 to 0037 of JP 2017-198787, the compounds described in paragraphs 0029 to 0034 of JP 2017-146350, and JP 2017 -129774, the compound described in paragraphs 0036 to 0037, 0049 to 0052, the compound described in paragraphs 0031 to 0034, and 0058 to 0059 of JP 2017-129674, JP 2017-122803 The compounds described in paragraphs 0036 to 0037, 0051 to 0054, the compounds described in paragraphs 0025 to 0039 of International Publication No. 2017/164127, and paragraphs 0034 to 0047 of JP 2017-186546 The compound described in Japanese Patent Application Publication No. 2015-025116, the compound described in paragraphs 0019 to 0041, the compound described in Japanese Patent Application Publication No. 2012-145604, the compound described in paragraphs 0101 to 0125, and Japanese Patent Application Publication No. 2012-103475 The compound described in paragraphs 0018 to 0021 of the publication, the compound described in paragraphs 0015 to 0018 of JP 2011-257591 A, the compound described in paragraphs 0017 to 0021 of JP 2011-191483, The compound described in paragraphs 0108 to 0116 of JP 2011-145668 A, the compound described in paragraphs 0103 to 0153 of JP 2011-253174, and the like.

In the coloring composition of the present invention, the content of free metals that are not bonded or coordinated with pigments or the like is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, and more preferably 10 mass ppm or less. It is especially good to not contain it. With this aspect, stabilization of pigment dispersibility (inhibition of aggregation), improvement of spectroscopic properties due to improvement of dispersibility, stabilization of curable components, and changes in conductivity due to elution of metal atoms and metal ions can be expected. Suppression and improvement of display characteristics. In addition, Japanese Patent Application Publication No. 2012-153796, Japanese Patent Application Publication No. 2000-345085, Japanese Patent Application Publication No. 2005-200560, Japanese Patent Application Publication No. 08-043620, Japanese Patent Application Publication No. 2004-145078, Japanese Patent Application Publication No. 2014-119487, Japanese Patent Application Publication No. 2010-083997, Japanese Patent Application Publication No. 2017-090930, Japanese Patent Application Publication No. 2018-025612, Japanese Patent Application Publication No. 2018-025797, Japanese Patent Application Publication No. 2017- The effects described in Bulletin No. 155228, Japanese Patent Application Publication No. 2018-036521, etc. Examples of the types of the above-mentioned free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Fe, Co, Mg, Al, Ti, Sn, Zn, Zr, Ga, Ge, Ag, Au, Pt, Cs, Bi, etc. In addition, in the coloring composition of the present invention, the content of free halogen that is not bonded or coordinated with a pigment or the like is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, and more preferably 10 mass ppm or less , It is especially good if it does not contain substantially. As a method for reducing free metals or halogens in the coloring composition, methods such as washing by ion exchange water, filtration, ultrafiltration, and purification by ion exchange resins can be cited.

It is also preferable that the coloring composition of the present invention does not substantially contain terephthalate. Here, "substantially not included" means that the content of terephthalate is 1000 mass ppb or less in the total solid content of the composition, 100 mass ppb or less is more preferable, and 0 is particularly preferable.

＜Container Container＞ The storage container of the colored composition of the present invention is not particularly limited, and a known storage container can be used. In addition, for the purpose of suppressing the mixing of impurities into the raw material or the coloring composition as the container, it is also preferable to use a multi-layer bottle in which the inner wall of the container is composed of 6 kinds of 6-layer resins or a bottle with 6 kinds of resins in a 7-layer structure. As such a container, for example, the container described in JP 2015-123351 A can be cited. In addition, from the viewpoint of preventing the elution of metal from the inner wall of the container, improving the storage stability of the composition, and suppressing the deterioration of the components, the inner wall of the storage container is preferably made of glass or stainless steel.

＜Method of manufacturing colored composition＞ The colored composition of the present invention can be produced by mixing the aforementioned components. When manufacturing a coloring composition, all the components can be dissolved and/or dispersed in a solvent at the same time to manufacture a coloring composition, or each component can be appropriately prepared as two or more solutions or dispersions as needed, and used (At the time of coating) These are mixed to produce a composition.

In addition, when manufacturing the coloring composition, a process of dispersing particles such as pigments may be included. In the step of dispersing the pigment, as the mechanical force used in the dispersion of the pigment, compression, pressing, impact, shearing, cavitation, etc. can be cited. Specific examples of these steps include bead mills, sand mills, roller mills, ball mills, pain shakers, microfluidizers, high-speed impellers, sand mills, Flowjet mixer, high pressure wet micronization, ultrasonic dispersion, etc. In addition, in the pulverization of the pigment in the sand mixer (bead mill), it is better to perform the treatment under the condition that the pulverization efficiency is improved by using beads with a small diameter and increasing the filling rate of the beads. Furthermore, after the pulverization treatment, it is preferable to remove coarse particles by filtration, centrifugal separation, or the like. In addition, the steps to disperse the pigment and the dispersing machine can preferably use "Dispersion Technology Encyclopedia, issued by JOHOKIKO CO., LTD., July 15, 2005" or "Suspension (solid/liquid dispersion system) as the center The actual comprehensive data collection of dispersion technology and industrial applications, issued by the Publishing Department of the Management Development Center, October 10, 1978", the steps and dispersion machines described in paragraph 0022 of Japanese Patent Application Publication No. 2015-157893. In addition, in the step of dispersing the pigment, a salt milling step can be used to refine the particles. The materials, equipment, processing conditions, etc. used in the salt milling step can be referred to, for example, the descriptions in Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629.

When manufacturing the colored composition, it is preferable to filter the colored composition with a filter for the purpose of removing foreign matter and reducing defects. As the filter, as long as it is a filter that has been used for filtration purposes, etc., it can be used without particular limitation. For example, fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (such as nylon-6, nylon-6, 6), and polyolefin resins such as polyethylene and polypropylene (PP) are used. (Including high-density, ultra-high molecular weight polyolefin resin) and other raw materials filter. Among these raw materials, polypropylene (including high-density polypropylene) and nylon are preferred.

The pore size of the filter is preferably 0.01 to 7.0 μm, more preferably 0.01 to 3.0 μm, and even more preferably 0.05 to 0.5 μm. As long as the pore size of the filter is within the above range, fine foreign matter can be reliably removed. For the pore size value of the filter, you can refer to the nominal value of the filter manufacturer. The filter can use various filters provided by NIHON PALL LTD. (DFA4201NIEY, etc.), Advantec Toyo Kaisha, Ltd., Nihon Entegris K.K. (formerly Nippon Mykrolis Corporation) and KITZ MICROFILTER CORPORATION.

Furthermore, it is also preferable to use a fibrous filter material as a filter. As a fibrous filter material, polypropylene fiber, nylon fiber, glass fiber, etc. are mentioned, for example. As commercially available products, SBP type series (SBP008, etc.) manufactured by ROKI GROUP CO., Ltd., TPR type series (TPR002, TPR005, etc.), and SHPX type series (SHPX003, etc.) can be cited.

When using filters, you can also combine different filters (for example, the first filter and the second filter, etc.). At this time, the filtration in each filter may be performed only once, or it may be performed more than twice. In addition, filters with different pore diameters can be combined within the above range. In addition, the filtration in the first filter is performed only on the dispersion liquid, and it may be filtered by the second filter after mixing other components.

＜Formation method of cured film and pixels＞ The method for forming a cured film of the present invention includes a process of coating the colored composition of the present invention on a support to form a colored composition layer and a process of exposing the colored composition layer. In particular, the method for forming a pixel (patterned cured film) also includes a process of exposing in a pattern in the above-mentioned exposure process, and then developing the exposed coloring composition layer. Furthermore, in the present invention, it is characterized in that it is carried out at a temperature of 150°C or less throughout the process. In addition, in the present invention, "the entire process is performed at a temperature below 150°C" means that the entire process of forming pixels using the coloring composition is performed at a temperature below 150°C. After the exposed coloring composition layer is developed, when a further heating process is provided, it means that the heating process is also performed at a temperature below 150°C. Hereinafter, each manufacturing process will be described in detail.

In the process of forming the coloring composition layer, the coloring composition of the present invention is coated on the support to form the coloring composition layer. As the support, for example, a glass substrate or a resin substrate. Examples of the resin substrate include polycarbonate substrates, polyester substrates, aromatic polyimide substrates, polyimide substrates, polyimide substrates, and the like. Organic light-emitting layers may be formed on these substrates. In addition, a primer layer is provided on the substrate in order to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the surface.

As the coating method of the coloring composition, a known method can be used. For example, dropping method (drop casting); slit coating method; spray method; roll coating method; spin coating method (spin coating); cast coating method; slit and spin coating method; pre-wet method (such as , The method described in Japanese Patent Laid-Open No. 2009-145395); inkjet method (for example, on-demand spraying method, piezoelectric method, thermal method), nozzle spraying and other discharge system printing, flexographic printing, screen printing, gravure Printing, reverse offset printing, metal mask printing and other printing methods; transfer methods using molds, etc.; nanoimprinting methods, etc. The inkjet-based application method is not particularly limited. For example, "Diffusion, usable inkjet-the infinite possibilities seen in the patent-issued in February 2005, SB Techno-Research Co., Ltd. The method shown in "(especially, pages 115 to 133) or Japanese Patent Application Publication No. 2003-262716, Japanese Patent Application Publication No. 2003-185831, Japanese Patent Application Publication No. 2003-261827, Japanese Patent Application Publication No. 2012-126830 The method described in Bulletin No. 2006-169325, etc. In addition, regarding the coating method of the coloring composition, reference can be made to the description of International Publication No. 2017/030174 and International Publication No. 2017/018419, and these contents are incorporated in this specification.

The colored composition layer formed on the support can be dried (pre-baked). In the case of pre-baking, the pre-baking temperature is preferably 80°C or lower, more preferably 70°C or lower, more preferably 60°C or lower, and particularly preferably 50°C or lower. The lower limit can be set to 40°C or higher, for example. The pre-baking time is preferably 10 to 3600 seconds. Pre-baking can be performed by a hot plate, an oven, or the like.

Next, the colored composition layer is exposed (exposure process). For example, by using a stepper exposure machine, a scanner exposure machine, etc., to expose the colored composition layer through a mask having a predetermined mask pattern as required, the exposure can be performed in a pattern. Thereby, the exposed part can be hardened.

As the light that can be used for exposure, ultraviolet rays such as g-ray (wavelength: 436nm) and i-ray (wavelength: 365nm) can be cited. As described in Korean Patent Publication No. 1020170122130, it is possible to perform exposure using i-rays while cutting light of a wavelength shorter than i-rays. In addition, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and the like. KrF rays (wavelength 248 nm) are preferred. In addition, a long-wave light source of 300 nm or more can also be used.

In addition, at the time of exposure, light may be continuously irradiated for exposure, or pulsed irradiation may be used for exposure (pulse exposure). In addition, pulse exposure refers to an exposure method in which light is irradiated and paused repeatedly in a short-time (for example, millisecond or less) cycle. In pulse exposure, the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and more preferably 30 nanoseconds or less. The lower limit of the pulse width is not particularly limited, and it can be 1 femtosecond (fs) or more, or 10 femtosecond or more. The frequency is preferably above 1 kHz, more preferably above 2 kHz, and even more preferably above 4 kHz. The upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less. Maximum instantaneous illuminance 5000W / cm ² or more is preferred, 10000W / cm ² or more is more preferred, 20000W / cm ² or more is further preferred. Further, the upper limit of the maximum instantaneous illuminance 100000W / cm ² or less is preferred, 80000W / cm ² or less is more preferred, 50000W / cm ² or less is further preferred. In addition, the pulse width refers to the time of irradiating light in the pulse period. In addition, frequency refers to the number of pulse cycles per second. In addition, the maximum instantaneous illuminance refers to the average illuminance during the pulse period during which light is irradiated. In addition, the pulse period refers to a period in which the irradiation and pause of light in pulse exposure are regarded as one cycle.

In the method for forming a cured film of the present invention, the exposure dose (irradiation dose) is 200 mJ/cm ² or more. In this way, by exposing with a larger amount of exposure than before, a large amount of light radicals are generated, and the hardening of the composition is promoted in the same way as the heat hardening treatment at a high temperature of more than 150°C. The lower limit of the exposure amount is preferably 800 mJ/cm ² or more, and more preferably 1 J/cm ² or more. The upper limit of the exposure amount of 2.5J / cm ² or less is preferred, 2.0J / cm ² or less is more preferred, 1.5J / cm ² or less is further preferred. In addition, the exposure illuminance can be appropriately set, and for example, it is preferably 50 mW/cm ² to 10 W/cm ² . Further, exposure illuminance lower limit of 500mW / cm ² or more is preferred, 800mW / cm ² or more is more preferred, 1000mW / cm ² or more is further preferred. In addition, the upper limit of the exposure illuminance is preferably 10 W/cm ² or less, more preferably 7 W/cm ² or less, and even more preferably 5 W/cm ² or less.

Regarding the oxygen concentration during exposure, it can be appropriately selected. In addition to carrying out in the atmosphere, it can also be performed in a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially oxygen-free ) Exposure can also be carried out in a high oxygen environment with an oxygen concentration greater than 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). The oxygen concentration and the exposure illuminance can be combined with appropriate conditions. For example, the illuminance can be set to 1 W/cm ² when the oxygen concentration is 10% by volume, and the illuminance 2W/cm ² when the oxygen concentration is 35% by volume.

Next, the exposed coloring composition layer is developed. That is, development removes the unexposed portion of the colored composition layer and forms the cured film into a pattern to form pixels. The development and removal of the unexposed part of the colored composition layer can be performed using a developer. Thereby, the coloring composition layer of the unexposed part in the exposure step dissolves in the developing solution, leaving only the light-hardened part. As the developer, an organic solvent, an alkali developer, etc. can be cited, and an alkali developer is preferred. The temperature of the developer is preferably 20 to 30°C, for example. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal performance, the following steps may be repeated several times: the developer is shaken off every 60 seconds, and the developer is further supplied again.

The alkaline developer is preferably an alkaline aqueous solution obtained by diluting an alkaline agent with pure water. Examples of alkali agents include amine, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, Tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, Organic alkaline compounds such as pyrrole, piperidine, 1,8-diazabicyclo[5.4.0]-7-undecene or sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, Inorganic alkaline compounds such as sodium metasilicate. Regarding the alkali agent, a compound with a large molecular weight is preferable in terms of environment and safety. The concentration of the alkali agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. In addition, the developer may further contain a surfactant. As the surfactant, the above-mentioned surfactants can be cited, and nonionic surfactants are preferred. From the viewpoint of convenient transportation and storage, the developer is temporarily made into a concentrated solution, or it can be diluted to the concentration required for use. The dilution ratio is not particularly limited, but it can be set in the range of 1.5 to 100 times, for example. Furthermore, it is also preferable to wash (rinse) with pure water after development. In addition, rinsing is preferably performed by supplying rinsing liquid to the developed coloring composition layer while rotating the support on which the developed coloring composition layer is formed. Moreover, it is also preferable to perform it by moving the nozzle which discharges a rinse liquid from the center part of a support body to the peripheral part of a support body. At this time, when moving from the center portion of the support body of the nozzle to the peripheral edge portion, the nozzle can be moved while gradually reducing the movement speed of the nozzle. By performing rinsing in this way, the in-plane deviation of rinsing can be suppressed. In addition, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the center of the support to the peripheral edge.

After development, it is also preferable to perform additional exposure treatment and heat treatment (post-baking) after drying. Additional exposure treatment and post-baking are curing treatments after development to complete curing.

When performing post-baking, the heating temperature is preferably 150°C or lower. The upper limit of the heating temperature is more preferably 120°C or less, and more preferably 100°C or less. As long as the hardening of the composition can be promoted, the lower limit of the heating temperature is not particularly limited. It is more preferably 50°C or higher, and more preferably 75°C or higher. The heating time is preferably 1 minute or more, more preferably 5 minutes or more, and more preferably 10 minutes or more. The upper limit is not particularly limited, but from the viewpoint of productivity, 20 minutes or less is preferable. It is also better to perform post-baking in an inert gas environment. With this aspect, it is possible to perform thermal polymerization with very high efficiency without being hindered by oxygen. Even when pixels are manufactured at a temperature below 120°C in the entire process, it is possible to manufacture good flatness and durability. Pixels with excellent solvent properties. As the inert gas, nitrogen, argon, helium, etc. can be cited, and nitrogen is preferred. The oxygen concentration during post-baking is preferably 100 ppm or less.

When performing additional exposure processing, it is preferable to perform exposure by irradiating light with a wavelength of 254 to 350 nm. As a more preferable aspect, the process of exposing the colored composition layer in a pattern (exposure before development) irradiates the colored composition layer with light having a wavelength greater than 350nm and less than 380nm (preferably light with a wavelength of 355-370nm, It is more preferably i-ray) to perform additional exposure treatment (exposure after development) to expose the developed coloring composition layer by irradiating light with a wavelength of 254 to 350 nm (preferably light with a wavelength of 254 nm). With this aspect, the coloring composition layer can be properly cured by the first exposure (exposure before development), and the entire coloring composition layer can be almost completely cured for the next exposure (exposure after development). Therefore, even in The colored composition layer can be sufficiently hardened even under low temperature conditions, thereby forming pixels with excellent characteristics such as solvent resistance, adhesion, and pattern rectangularity. When the exposure is carried out in two stages, the coloring composition contains a photopolymerization initiator A1 with an absorption coefficient of 1.0×10 ³ mL/gcm or more at a wavelength of 365 nm in methanol and an absorption coefficient of 1.0 at a wavelength of 365 nm in methanol. × 10 ² mL / gcm absorption coefficient and the wavelength of 254nm was 1.0 × 10 ³ mL / gcm or more persons A2 photopolymerization initiator as the photopolymerization initiator is preferred.

Exposure after development can be performed using, for example, an ultraviolet photoresist curing device. It is also possible to irradiate other light (for example, i-ray) with light having a wavelength of 254 to 350 nm from an ultraviolet photoresist curing device.

The exposure amount (exposure amount) under the exposure after development is preferably 30 to 4000 mJ/cm ² and more preferably 50 to 3500 mJ/cm ² . The difference between the wavelength of the light used in the exposure before development and the wavelength of the light used in the exposure after development is preferably 200 nm or less, and more preferably 100 to 150 nm.

<Method of manufacturing color filter> The manufacturing method of the color filter of the present invention includes the above-mentioned method of forming the cured film of the present invention, and particularly includes the method of forming a pixel. When the color filter has pixels of a plurality of colors, the pixel forming method described above is performed on the pixels of each color, so that a color filter having pixels of a plurality of colors can be formed. Examples of the color filter include a filter having one or more colors of colored pixels such as red pixels, blue pixels, green pixels, cyan pixels, magenta pixels, and yellow pixels. Specific examples of the color filter include filters having at least red pixels, blue pixels, and green pixels, filters having at least cyan pixels, magenta pixels, and yellow pixels, and the like. The color filter may have a structure in which each colored pixel is embedded in a space separated by a partition wall, for example, in a grid shape. In this case, the partition system preferably has a low refractive index with respect to each colored pixel. In addition, the partition wall may be formed with the structure described in the specification of U.S. Patent Application Publication No. 2018/0040656.

＜Manufacturing method of display device＞ The manufacturing method of the display device of the present invention includes the above-mentioned method of forming the pixel of the present invention. As the display device, a liquid crystal display device, an organic electroluminescence display device, and the like can be cited. The definition of the display device and the details of each image display device are described in, for example, "Electronic Display Equipment (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd. in 1990)", "Display Equipment (by Ibuki Jun, Sangyo-Tosho Publishing Co. Ltd., issued in 1989)” etc. In addition, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (Edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited, and it can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology".

The organic electroluminescence display device may be one having a light source including a white organic electroluminescence element. As a white organic electroluminescence element, a series structure is preferable. Regarding the tandem structure of organic electroluminescent elements, it is described in Japanese Patent Application Publication No. 2003-045676, supervised by Akira Mikami, "The front line of organic EL technology development-high brightness, high precision, long life, and skill collection -", Technical Information Institute Co., Ltd., page 326-page 328, 2008, etc. It is preferable that the spectrum of white light emitted by the organic EL element has a strong maximum emission peak in the blue region (430nm-485nm), green region (530nm-580nm) and yellow region (580nm-620nm). In addition to these luminescence peaks, it is better to have a very large luminescence peak in the red region (650nm-700nm).

In addition, the organic electroluminescence display device may have a lens on the color filter. As the shape of the lens, various shapes derived by the design of the optical system can be adopted, and examples thereof include a convex shape and a concave shape. For example, by adopting a concave shape (concave lens), it is easy to improve the condensability of light. This kind of lens is used by being arranged on the optical path of light passing through the color filter of the display device with the color filter. The lens of the present invention may be provided on the side where light enters the color filter, or may be provided on the side where light is emitted from the color filter. When it is installed on the side where light enters the color filter, the amount of light condensed on the color filter can be increased. In addition, when it is installed on the side where light is emitted from the color filter, the amount of light condensed on the display can be increased. In addition, the lens may be in direct contact with the color filter, or other layers such as an adhesion layer and a planarization layer may be provided between the lens and the color filter. In addition, the lens can also be used in the configuration described in International Publication No. 2018/135189. [Example]

Examples are listed below to illustrate the present invention in more detail. The materials, usage amount, ratio, processing content, processing order, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are quality standards.

<Preparation of pigment dispersion> (Pigment dispersion liquid P-R) After uniformly stirring and mixing the mixture of the following composition, using zirconia beads with a diameter of 1 mm, Eiger Motor Mill ("Mini Model M-250MKII" manufactured by EIGER CO., Ltd.) was dispersed for 5 hours. Then, filtration was performed using a filter having a pore diameter of 5 μm to prepare a pigment dispersion liquid P-R. •C.I. Pigment Red 254 8.96 parts by mass •C.I. Pigment Red 177 1.42 parts by mass •C.I. Pigment Yellow 150 1.16 parts by mass • Dispersant (manufactured by The Lubrizol Corporation, SOLSPERSE20000) 2.29 parts by mass •Pigment derivatives (pigment derivatives 1 with the following structure) 2.69 parts by mass •Alkali-soluble resin solution D2 7.66 parts by mass • Cyclohexanone 75.82 parts by mass

Pigment derivative 1: [Chemical formula 26]

The alkali-soluble resin solution D2 is produced by the following method. Put 90.0 parts by mass of cyclohexanone in a reaction vessel equipped with a stirrer, a thermometer, a dropping device, a reflux cooler, and a gas introduction tube, and heat to 60°C while injecting nitrogen into the vessel, and heat it at the same temperature. 20.0 parts by mass of methacrylic acid, 10.0 parts by mass of methyl methacrylate, 55.0 parts by mass of n-butyl methacrylate, 15 parts by mass of benzyl methacrylate, and 2,2'-azobisisobutyronitrile were added dropwise for 2 hours 2.5 parts by mass of the mixture was subjected to polymerization reaction. After the dropping was completed, the reaction was further carried out at 60°C for 1 hour, and 0.5 parts by mass of 2,2'-azobisisobutyronitrile was dissolved in 10.0 parts by mass of propylene glycol monomethyl ether acetate (PGMEA). The winner was then stirred at the same temperature for 3 hours to obtain a copolymer. After cooling to room temperature, it was diluted with cyclohexanone to obtain an alkali-soluble resin solution D2 having a solid content concentration of 20%. The weight average molecular weight is 30,000.

(Pigment dispersion liquid P-G) After uniformly stirring and mixing the mixture of the following composition, using zirconia beads with a diameter of 1 mm, Eiger Motor Mill ("Mini Model M-250MKII" manufactured by EIGER CO., Ltd.) was dispersed for 5 hours. Then, filtration was performed using a filter having a pore diameter of 5 μm to prepare a pigment dispersion liquid P-G. •C.I. Pigment Green 58 7.53 parts by mass •C.I. Pigment Yellow 150 4.14 parts by mass • Dispersant (manufactured by BYK Chemie, Disperbyk-2001, solid content 46% by mass) 6.09 parts by mass •Alkali-soluble resin solution D2 5.53 parts by mass •PGMEA 76.71 parts by mass

(Pigment dispersion P-B) After uniformly stirring and mixing the mixture of the following composition, using zirconia beads with a diameter of 1 mm, Eiger Motor Mill ("Mini Model M-250MKII" manufactured by EIGER CO., Ltd.) was dispersed for 5 hours. Then, filtration was performed using a filter having a pore diameter of 5 μm to prepare a pigment dispersion liquid P-B. •C.I. Pigment Blue 15: 6 12.88 parts by mass • Dispersant (manufactured by The Lubrizol Corporation, SOLSPERSE20000) 5.62 parts by mass •Alkali-soluble resin solution D2 1.50 parts by mass • Cyclohexanone 80.00 parts by mass

(Pigment dispersion P-X) After uniformly stirring and mixing the mixture of the following composition, using zirconia beads with a diameter of 1 mm, Eiger Motor Mill ("Mini Model M-250MKII" manufactured by EIGER CO., Ltd.) was dispersed for 5 hours. Then, filtration was performed using a filter with a pore diameter of 5 μm to prepare a pigment dispersion liquid P-X. •C.I. Pigment Red 254 13.33 parts by mass •Pigment derivative (Pigment derivative 2A with the following structure) 1.67 parts by mass • The first dispersant (resin K with the following structure) 2.50 parts by mass • The second dispersant (resin PA-1 synthesized by the following method) 2.50 parts by mass •PGMEA 80.00 parts by mass

Pigment derivative 2A: [Chemical formula 27]

Resin K: A compound having the following structure. The numerical value in the bracket attached to the main chain indicates the molar ratio of each repeating unit, and the numerical value in the bracket attached to the side chain indicates the repeating number of each repeating unit. The weight average molecular weight is 20,000. [Chemical formula 28]

Resin PA-1: -Synthesis method of resin PA-1- The following raw materials were introduced into a three-necked flask to obtain a mixture. Next, while blowing in nitrogen gas, the above mixture was stirred, and then, while nitrogen gas was introduced into the flask, the temperature of the mixture was raised to 75°C. Next, dodecyl mercaptan (0.82 g), 0.43 g of 2,2'-azobis(methyl 2-methylpropionate), (hereinafter, also referred to as "V-601") were added to the mixture. , Start the polymerization reaction. After the mixture was heated at 75°C for 2 hours, V-601 (0.43 g) was further added to the mixture. After 2 hours, V-601 (0.43 g) was further added to the mixture. After further reacting for 2 hours, the mixture was heated to 90°C and stirred for 3 hours. The polymerization reaction was ended by the above operation. After the reaction, add dimethyldodecylamine (9.6g) as an amine compound and 2,2,6,6,-tetramethylpiperidine 1-oxy as a polymerization inhibitor in the air (0.3g), then, 4-hydroxybutyl acrylate glycidyl ether (9.01g) was added dropwise as a reactive compound. After the dropping, the reaction was continued for 24 hours at 90°C in air. The end of the reaction was confirmed by acid value measurement. PGMEA was added to the obtained mixture so that it became a 30 mass% solution, and resin PA-1 was obtained. The weight average molecular weight of the obtained resin PA-1 was 17,200, and the acid value was 70 mgKOH/mg. -Raw material of resin PA-1- • Monomer B-1 solution prepared by the following method (50% by mass solid content) 60.78g •Polymerizable monomer (ω-carboxy-polycaprolactone monoacrylate, ARONIX M-5300, manufactured by TOAGOSEI CO., LTD.) 50.99g •PGMEA 159.5g

The acid value of the resin was obtained by neutralization titration using an aqueous sodium hydroxide solution. Specifically, it is determined by the following method: in a solution obtained by dissolving the obtained resin in a solvent, titrating with a sodium hydroxide aqueous solution using a potential difference measurement method, and calculating the resin content in 1 g of solid content The number of millimoles of acid, and then multiply this value by the molecular weight of potassium hydroxide (KOH), 56.1.

-Preparation method of monomer B-1 solution- Into a three-necked flask was introduced ε-caprolactone (1256.62 parts, corresponding to the cyclic compound.) and 2-ethyl-1-hexanol (143.38 parts, corresponding to the ring opening Polymerization initiator.), a mixture was obtained. Next, the above mixture was stirred while blowing in nitrogen. Next, monobutyltin oxide (0.63 parts) was added to the mixture, and the obtained mixture was heated to 90°C. After 6 hours while maintaining 90°C, ¹ H-NMR (nuclear magnetic resonance) was used to confirm that the signal from 2-ethyl-1-hexanol in the mixture disappeared. Then, the mixture was heated to 110°C, and the polymerization reaction was continued for 2 hours at 110°C under nitrogen. The disappearance of the signal derived from ε-caprolactone was confirmed by ¹ H-NMR, and the temperature of the above mixture was lowered to 80°C. Then, 2,6-di-tert-butyl-4-methylphenol (0.78 parts) was added to the above mixture, and then 2-methacryloxy group was added dropwise to the obtained mixture over 30 minutes Ethyl isocyanate (MOI, 174.15 parts). One hour after the completion of the dropping, it was confirmed by ¹ H-NMR that the signal from the MOI disappeared. Then, PGMEA (1575.57 parts) was added to the mixture, and a monomer B-1 solution with a solid content of 50% by mass was obtained. The structure of monomer B-1 can be confirmed by ¹ H-NMR, as shown by the following formula (B-1). The weight average molecular weight of the obtained monomer B-1 was 3,000.

[Chemical formula 29]

(Pigment dispersion liquid P-Y) After uniformly stirring and mixing the mixture of the following composition, using zirconia beads with a diameter of 1 mm, Eiger Motor Mill ("Mini Model M-250MKII" manufactured by EIGER CO., Ltd.) was dispersed for 5 hours. Then, filtration was performed using a filter having a pore diameter of 5 μm to prepare a pigment dispersion liquid P-Y. •C.I. Pigment Red 254 13.33 parts by mass •Pigment derivative (Pigment derivative 2A of the above structure) 1.67 parts by mass • The first dispersant (resin K of the above structure) 2.50 parts by mass • The second dispersant (resin L with the following structure) 2.50 parts by mass •PGMEA 80.00 parts by mass

Resin L: A compound having the following structure. The numerical value in the parentheses attached to the main chain indicates the molar ratio of each repeating unit, and the numerical value in the parentheses attached to the side chain indicates the repeating number of the repeating unit. The weight average molecular weight is 20,000. [Chemical formula 30]

(Pigment dispersion P-Z) After uniformly stirring and mixing the mixture of the following composition, using zirconia beads with a diameter of 1 mm, Eiger Motor Mill ("Mini Model M-250MKII" manufactured by EIGER CO., Ltd.) was dispersed for 5 hours. Then, filtration was performed using a filter having a pore diameter of 5 μm to prepare a pigment dispersion liquid P-Z. •C.I. Pigment Yellow 139 13.33 parts by mass •Pigment derivative (Pigment derivative 2A of the above structure) 1.67 parts by mass • The first dispersant (resin K of the above structure) 2.50 parts by mass • The second dispersant (resin L of the above structure) 2.50 parts by mass •PGMEA 80.00 parts by mass

<Preparation of coloring composition> (The coloring composition of Example 1) After mixing and stirring the raw materials shown below, filtration was performed using a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm to prepare a colored composition with a solid content concentration of 19.05% by mass. In addition, the solid content concentration of the coloring composition was adjusted by the blending amount of PGMEA. •Pigment dispersion liquid P-R 65 parts by mass • Initiator for light radical polymerization (initiator 1) 2 parts by mass •Resin (Resin A) 5.5 parts by mass • Compounds containing furan group (F1) 5.5 parts by mass • Radical polymerizable monomer (M1) 2.6 parts by mass •PGMEA Residual part

(The coloring compositions of Examples 2 to 23 and Comparative Examples 1 to 2) The pigment dispersion, photoradical polymerization initiator, resin, furan group-containing compound, and radical polymerizability were changed as described in Table 1 below. The types and contents (parts by mass) of monomers and solvents, and a coloring composition was prepared in the same manner as in Example 1. The solid content concentration of each coloring composition (mass %. It is described in the "solid content" column.) was adjusted by the blending amount of the solvent. In addition, Table 2 shows the M/I ratio (mass ratio), M/I _A1 ratio (mass ratio), and pigment concentration (mass %: the ratio of the content of the pigment to the solid content) for each coloring composition. .

<Preparation of cured film> Using a spin coater, each colored composition of Examples 1 to 23 was coated on a glass substrate so that the finished film thickness after drying became 2.0 μm, and then placed on a hot plate at 100°C It dried for 2 minutes. Then, using an ultra-high pressure mercury lamp, i-ray exposure was performed under ^the conditions of an exposure illuminance of 20 mW/cm ² and an exposure amount of 1 J/cm ² . Then, it heated on a 100 degreeC hotplate for 20 minutes, and after leaving to cool, the evaluation board|substrate with a cured film was obtained.

Using a spin coater, each coloring composition of Comparative Example 1 and Comparative Example 2 was coated on a glass substrate so that the finished film thickness after drying became 2.0 μm, and dried on a hot plate at 100°C for 2 minutes . Then, using an ultra-high pressure mercury lamp, i-ray exposure was performed under the conditions of an exposure illuminance of 20 mW/cm ² and an exposure amount of 50 mJ/cm ² . Then, it heated on a 100 degreeC hotplate for 20 minutes, and after leaving to cool, the evaluation board|substrate with a cured film was obtained.

In the production of the cured films of the above-mentioned Examples and Comparative Examples, the temperature of the substrate was in the range of 20-100°C in the entire process.

[Table 1] Pigment dispersion Photopolymerization initiator Resin Fluorine-containing compounds monomer Solvent Solid content Initiator ratio in solid content species content A1 content A2 content species content species content species content species content Example 1 PR 65 Initiator 1 2 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 2 PR 65 Initiator 1 2 - - Resin A 5.5 F2 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 3 PR 65 Initiator 1 2 - - Resin A 5.5 F1 6.5 M1 2.6 PGMEA 19.4 19.25 10.4% Example 4 PR 65 Initiator 1 2 - - Resin B 5.5 F1 5.5 M1 2.6 PGMEA 19.4 18.5 10.8% Example 5 PR 65 Initiator 1 2 - - Resin A 11 - - M1 2.6 PGMEA 19.4 19.6 10.2% Example 6 PR 65 Initiator 1 2 - - Resin B 11 - - M1 2.6 PGMEA 19.4 18.5 10.8% Example 7 PR 65 Initiator 1 2 - - A/B=5/5 5.5 F1 5.5 M1 2.6 PGMEA 19.4 18.775 10.7% Example 8 PR 65 Initiator 1 2 - - Resin A 5.5 F1 5.5 M1/M2=5/5 2.6 PGMEA 19.4 19.05 10.5% Example 9 PR 65 Initiator 1 2 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA/PGME =5/5 19.4 19.05 10.5% Example 10 PR 65 Initiator 2 2 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 11 PR 65 Initiator 3 2 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 12 PR 65 Starter 6 2 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 13 PR 65 Initiator 1 1 Initiator 4 1 Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 14 PR 65 Initiator 1 1 Starter 5 1 Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 15 PR 65 Initiator 7 1 Initiator 4 1 Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 16 PR 65 Initiator 1 1 Initiator 7 1 Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.4 19.05 10.5% Example 17 PG 50 Initiator 1 2 - - Resin B 9 F1 15 M1 4 PGMEA 20.4 18.8 10.6% Example 18 PB twenty three Initiator 1 2.2 - - Resin B 30 F1 16 M1 6 PGMEA 22.8 21.724 10.1% Example 19 PR 65 Initiator 1 3 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 18.4 20.05 15.0% Example 20 PR 65 Initiator 1 2.5 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 18.9 19.55 12.8% Example 21 PR 65 Initiator 1 1.5 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 19.9 18.55 8.1% Example 22 PR 65 Initiator 1 1 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 20.4 18.05 5.5% Example 23 PR 65 Initiator 1 0.6 - - Resin A 5.5 F1 5.5 M1 2.6 PGMEA 20.8 17.65 3.4% Comparative example 1 PR 65 Initiator 1 0.1 - - Resin A 6.5 F1 6.5 M1 2.6 PGMEA 19.3 17.65 0.6% Comparative example 2 PR 65 Initiator 1 0.1 - - Resin A 13 - - M1 2.6 PGMEA 19.3 18.3 0.5%

[Table 2] M/I ratio M/I _A1 ratio Pigment concentration Evaluation results stability Example 1 1.3 1.3 39.4% 5 Example 2 1.3 1.3 39.4% 5 Example 3 1.3 1.3 39.0% 5 Example 4 1.3 1.3 40.5% 4 Example 5 1.3 1.3 38.3% 4 Example 6 1.3 1.3 40.5% 4 Example 7 1.3 1.3 40.0% 5 Example 8 1.3 1.3 39.4% 5 Example 9 1.3 1.3 39.4% 5 Example 10 1.3 1.3 39.4% 5 Example 11 1.3 1.3 39.4% 5 Example 12 1.3 1.3 39.4% 5 Example 13 1.3 2.6 39.4% 5 Example 14 1.3 2.6 39.4% 5 Example 15 1.3 2.6 39.4% 4 Example 16 1.3 2.6 39.4% 4 Example 17 2.0 2.0 31.0% 5 Example 18 2.7 2.7 13.6% 5 Example 19 0.9 0.9 37.4% 5 Example 20 1.0 1.0 38.4% 5 Example 21 1.7 1.7 40.4% 4 Example 22 2.6 2.6 41.6% 3 Example 23 4.3 4.3 42.5% 2 Comparative example 1 26.0 26.0 42.5% 1 Comparative example 2 26.0 26.0 41.0% 1

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

(Photo-radical polymerization initiator) •Initiator 1: IRGACURE-OXE02 (manufactured by BASF, a compound with the following structure, the absorbance coefficient at 365 nm in methanol is 7749 mL/gcm. Corresponding to the photopolymerization initiator A1.) • Initiator 2: IRGACURE-OXE01 (manufactured by BASF, a compound with the following structure, the absorbance coefficient at a wavelength of 365 nm in methanol is 6969 mL/gcm. It corresponds to the photopolymerization initiator A1.) Initiator 3: Compound of the following structure (The absorbance coefficient of light with a wavelength of 365 nm in methanol is 18900 mL/gcm. It corresponds to the photopolymerization initiator A1.) • Initiator 4: IRGACURE-2959 (manufactured by BASF, the following structure The absorbance coefficient of the compound, methanol at a wavelength of 365nm is 48.93mL/gcm, and the absorbance coefficient at a wavelength of 254nm is 3.0×10 ⁴ mL/gcm. It corresponds to the photopolymerization initiator A2.) •Initiator 5: IRGACURE -184 (manufactured by BASF, a compound with the following structure, the absorption coefficient at a wavelength of 365 nm in methanol is 88.64 mL/gcm, and the absorption coefficient at a wavelength of 254 nm is 3.3×10 ⁴ mL/gcm. Corresponding to the photopolymerization initiator A2.) Initiator 6: A compound of the following structure (The absorption coefficient of light with a wavelength of 365 nm in methanol is 13200 mL/gcm. It corresponds to the photopolymerization initiator A1.) • Initiator 7: A compound of the following structure

[Chemical formula 31]

(Resin) • Resin A: It is a resin synthesized by the following method. A separate 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube, and a stirring device was charged with 70.0 parts by mass of cyclohexanone, and the temperature was raised to 80°C. After replacing the flask with nitrogen, In the dropping tube, 13.3 parts by mass of n-butyl methacrylate, 4.6 parts by mass of 2-hydroxyethyl methacrylate, 4.3 parts by mass of methacrylic acid, and p-cumylphenol ethylene oxide modified acrylic acid were added dropwise over 2 hours. A mixture of 7.4 parts by mass of ester (manufactured by TOAGOSEI CO., LTD., ARONIX M110) and 0.4 parts by mass of 2,2'-azobisisobutyronitrile. After the dropwise addition, the reaction was continued for another 3 hours to obtain a 30% by mass solution of resin A (Mw=26000).

• Resin B: It is a resin synthesized by the following method. Put 90.0 parts by mass of PGMEA in a reaction vessel equipped with a stirrer, a thermometer, a dripping device, a reflux cooler, and a gas introduction tube, and heat to 60°C while injecting nitrogen into the vessel, and heat it at the same temperature for 2 A mixture of 10.0 parts by mass of methacrylic acid, 45.0 parts by mass of methyl methacrylate, 45.0 parts by mass of n-butyl methacrylate, and 2.5 parts by mass of 2,2'-azobisisobutyronitrile was added dropwise and polymerization reaction . After the dripping was completed, the reaction was further carried out at 60°C for 1 hour, and then 0.5 parts by mass of 2,2'-azobisisobutyronitrile was dissolved in 10.0 parts by mass of PGMEA, and then stirring was continued at the same temperature The copolymer was obtained in 3 hours. After cooling to room temperature, it was diluted with PGMEA, thereby obtaining a solution of resin B containing an alkali-soluble functional group with a non-volatile content of 20% by mass. The weight average molecular weight of resin B is 27,000.

(Compounds containing furan group) • F1: It is a furyl-containing compound synthesized by the following method. Put 90.0 parts by mass of PGMEA in a reaction vessel equipped with a stirrer, a thermometer, a dripping device, a reflux cooler, and a gas introduction tube, and heat to 60°C while injecting nitrogen into the vessel, and heat it at the same temperature for 2 50.0 parts by mass of furfuryl methacrylate, 26.7 parts by mass of 2-methacryloxyethyl succinic acid, 23.3 parts by mass of 2-hydroxyethyl methacrylate, and 2,2'-azobis( 2,4-Dimethylvaleronitrile) 2.5 parts by mass of the mixture was polymerized. After the dropwise addition was completed, it was further reacted at 60°C for 1 hour, and 0.5 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and dissolved in 10.0 parts by mass of PGMEA Then, stirring was continued for 3 hours at the same temperature to obtain a copolymer. After cooling to room temperature, it was diluted with PGMEA, thereby obtaining a 20% by mass solution of furyl-containing compound F1 (Mw=52000).

• F2: It is a furyl-containing compound synthesized by the following method. Put 90.0 parts by mass of PGMEA in a reaction vessel equipped with a stirrer, a thermometer, a dripping device, a reflux cooler, and a gas introduction tube, and heat to 60°C while injecting nitrogen into the vessel, and heat it at the same temperature for 2 50.0 parts by mass of furfuryl methacrylate, 10 parts by mass of methacrylic acid, 40.0 parts by mass of methyl methacrylate, 5.0 parts by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) The mixture was polymerized. After the dropwise addition is completed, it is further reacted at 60°C for 1 hour, and then 1.0 part by mass of 2,2'-azobis(2,4-dimethylvaleronitrile) is dissolved in 10.0 part by mass of PGMEA. Then, stirring was continued for 3 hours at the same temperature to obtain a copolymer. After cooling to room temperature, it was diluted with PGMEA, thereby obtaining a 20% by mass solution of furyl-containing compound F2 (Mw=26000).

(Free radical polymerizable monomer) •M1: ARONIX M-402 (manufactured by TOAGOSEI CO., LTD., a mixture of dineopentaerythritol hexaacrylate and dineopentaerythritol pentaacrylate) •M2: the following structure Compound of (a+b+c=3) [Chemical formula 32]

(Solvent) •PGMEA: Propylene glycol monomethyl ether acetate •PGME: Propylene glycol methyl ether

(Examples 24 to 36 and Comparative Example 3) Using the coloring composition of the same composition as the coloring composition prepared in Example 1, the i-ray exposure was carried out under various exposure illuminance, exposure amount and environmental environment shown in Table 3. In addition, the "nitrogen environment" in the table is an environment in which the atmosphere is replaced with nitrogen until the oxygen concentration becomes 50 ppm or less. Then, it heated on a 100 degreeC hotplate for 20 minutes, and after leaving to cool, the evaluation board|substrate with a cured film was obtained. (Examples 24 to 36 and Comparative Example 3) In the production of the cured film of the above examples, the temperature of the substrate was 100° C. or less in the entire process.

[table 3] Exposure illuminance [mW/cm ² ] Exposure amount [mJ/cm ² ] Exposure environment Evaluation results stability Comparative example 3 20 50 atmosphere 1 Example 24 20 200 3 Example 25 20 800 4 Example 26 20 1000 5 Example 27 50 1000 5 Example 28 1000 1000 5 Example 29 2000 1000 5 Example 30 3000 1000 5 Example 31 1000 3000 5 Example 32 1000 6000 5 Example 33 1000 10000 5 Example 34 20 200 Nitrogen environment 4 Example 35 20 800 5 Example 36 20 1000 5

<Examples 37-41> Using the colored composition prepared by the following method, a cured film was prepared by the same method as in Example 1, and a substrate for evaluation (Example 37) was obtained. In addition, as described in Table 4 below, the content of the pigment derivative in Example 37 was changed, and a colored composition was prepared and a cured film was prepared by the same method as in Example 37 to obtain a substrate for evaluation (Example 38 ~41). In the production of the cured film of the foregoing embodiment, the temperature of the substrate is 100° C. or less in the entire process.

(Coloring composition of Example 37) A bead mill (zirconia beads with a diameter of 0.1 mm) was used to mix and disperse the following raw materials for 3 hours to prepare a pigment dispersion. Then, using a high-pressure dispersion machine NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism, the dispersion treatment was performed under the conditions of a pressure of 2000 kg/cm ³ and a flow rate of 500 g/min. This dispersion treatment was repeated all up to 10 times to obtain pigment dispersion liquid P-B2. Raw materials of pigment dispersion P-B2: • CI Pigment Blue 15: 6 (PB15: 6) 9.6 parts by mass • CI Pigment Violet 23 (PV23) 2.4 parts by mass • Pigment derivative 2B 1.0 parts by mass • Dispersant 2 4.7 parts by mass • PGMEA 82.3 parts by mass

•Pigment Derivative 2B: A compound having the following structure [Chemical formula 33]

• Dispersant 2: A compound with the following structure. The value attached to the main chain is the molar ratio of each repeating unit, and the value attached to the side chain is the repeating number of each repeating unit. [Chemical formula 34]

Next, after stirring and mixing the mixture of the following raw materials, it filtered using the nylon filter (made by Nihon Pall Ltd.) with a pore diameter of 0.45 micrometers, and the colored composition of Example 37 was obtained. Raw materials of the coloring composition of Example 37: •Pigment dispersion liquid P-B2 54.1 parts by mass • Resin 2 (40% by mass PGMEA solution) 1.0 parts by mass •Polymerizable monomer 2 0.9 parts by mass •Photopolymerization initiator 10 0.6 parts by mass • Surfactant 2 (1% by mass PGMEA solution) 4.2 parts by mass • Ultraviolet absorber 2 0.1 parts by mass •Epoxy resin 2 0.1 parts by mass •PGMEA 39.0 parts by mass

• Resin 2: A compound having the following structure. The numerical value attached to the main chain indicates the molar ratio of each repeating unit. [Chemical formula 35]

• Polymerizable monomer 2: A compound having the following structure [Chemical formula 36]

• Photopolymerization initiator 10: a compound having the following structure [Chemical formula 37]

• Surfactant 2: A mixture of two compounds each having the following structure (Mw=14000, written in mass %) [Chemical formula 38]

•Ultraviolet absorber 2: a compound having the following structure [Chemical formula 39]

•Epoxy resin 2: EHPE3150 (manufactured by Daicel Corporation, 1,2-epoxy-4-(2-oxiranyl)cyclohexane of 2,2'-bis(hydroxymethyl)-1-butanol) Adduct)

[Table 4] PB15:6 PV23 The content of pigment derivatives Evaluation results stability Example 37 9.6 2.4 1 3 Example 38 9.6 2.4 0.75 3 Example 39 9.6 2.4 0.5 4 Example 40 9.6 2.4 0.25 5 Example 41 9.6 2.4 0.1 5

<Examples 42 to 55> As described in Table 5 below, the types and contents of the pigment dispersion, photoradical polymerization initiator, resin, furan group-containing compound, radical polymerizable monomer, and solvent were changed as described in Table 5 below, and In the same manner as in Example 1, the colored compositions of Examples 42 to 55 were prepared. The solid content concentration of each coloring composition (mass %. It is described in the "solid content" column.) was adjusted by the blending amount of the solvent. In addition, in Table 6, the M/I ratio (mass ratio), M/I _A1 ratio (mass ratio), and pigment concentration are shown for each coloring composition. Then, using the colored composition prepared as described above, a cured film was produced by the same method as in Example 1 to obtain evaluation substrates (Examples 42 to 55). In the production of the cured film of the foregoing embodiment, the temperature of the substrate is 100° C. or less in the entire process.

[table 5] The first pigment dispersion The second pigment dispersion Photopolymerization initiator Resin Fluorine-containing compounds monomer additive Surfactant Solvent Solid content Initiator ratio in solid content species content species content A1 content A2 content species content species content species content species content species content species content Example 42 PX 65.00 - - Initiator 1 0.60 - - Resin A 5.50 F1 5.50 M1 2.60 - - - - PGMEA 20.80 18.95 3.2% Example 43 PY 65.00 - - Initiator 1 0.60 - - Resin A 5.50 F1 5.50 M1 2.60 - - - - PGMEA 20.80 18.95 3.2% Example 44 PZ 65.00 - - Initiator 1 0.60 - - Resin A 5.50 F1 5.50 M1 2.60 - - - - PGMEA 20.80 18.95 3.2% Example 45 PX 60.00 PZ 5.00 Initiator 1 0.60 - - Resin A 5.50 F1 5.50 M1 2.60 - - - - PGMEA 20.80 18.95 3.2% Example 46 PX 67.52 PZ 6.75 Initiator 1 0.58 - - Resin A 5.87 - - M1 0.36 E1 0.36 G1 0.09 PGMEA 18.48 18.00 3.2% Example 47 PX 67.52 PZ 6.75 Initiator 1 0.58 - - Resin B 8.80 - - M2 0.36 E1 0.36 G2 0.09 PGMEA 15.54 18.00 3.2% Example 48 PX 67.52 PZ 6.75 Initiator 1 0.58 - - Resin C 5.87 - - M2 0.36 E2 0.36 G1 0.09 PGMEA 18.48 18.00 3.2% Example 49 PX 67.52 PZ 6.75 Initiator 1 0.58 - - Resin PA-1 5.87 - - M3 0.36 E2 0.36 G2 0.09 PGMEA 18.48 18.00 3.2% Example 50 PX 47.26 PZ 4.73 Initiator 1 0.58 - - Resin PA-1 20.72 - - M3 0.36 E2 0.36 G2 0.09 PGMEA 25.90 18.00 3.2% Example 51 PX 75.66 PZ 7.56 Initiator 1 0.58 - - Resin PA-1 1.13 - - M3 0.18 E2 0.18 G2 0.09 PGMEA 14.67 18.00 3.2% Example 52 PY 60.77 PZ 13.50 Initiator 1 0.58 - - Resin A 2.81 - - M4 1.53 E1 0.18 G1 0.018 PGMEA 20.62 18.00 3.2% Example 53 PY 60.77 PZ 13.50 Initiator 1 0.58 - - Resin B 4.21 - - M5 1.53 E1 0.18 G2 0.018 PGMEA 19.22 18.00 3.2% Example 54 PY 60.77 PZ 13.50 Initiator 1 0.58 - - Resin C 2.81 - - M4/M5 =5/5 1.53 E2 0.18 G2 0.018 PGMEA 20.62 18.00 3.2% Example 55 PY 60.77 PZ 13.50 Initiator 1 0.58 - - Resin PA-1 2.81 - - M4/M5 =5/5 1.53 E2 0.18 G2 0.018 PGMEA 20.62 18.00 3.2%

[Table 6] M/I ratio M/I _A1 ratio Pigment concentration Evaluation results stability Example 42 4.3 4.3 45.7% 2 Example 43 4.3 4.3 45.7% 2 Example 44 4.3 4.3 45.7% 2 Example 45 4.3 4.3 45.7% 2 Example 46 0.6 0.6 55.0% 2 Example 47 0.6 0.6 55.0% 2 Example 48 0.6 0.6 55.0% 2 Example 49 0.6 0.6 55.0% 2 Example 50 0.6 0.6 38.5% 2 Example 51 0.3 0.3 61.6% 2 Example 52 2.7 2.7 55.0% 2 Example 53 2.7 2.7 55.0% 2 Example 54 2.7 2.7 55.0% 2 Example 55 2.7 2.7 55.0% 2 Example 56 2.7 2.7 55.0% 2

In the above Table 5, the specifications of the newly shown raw materials are as follows.

•樹脂PA-1：為與對上述顏料分散液進行說明之樹脂PA-1相同的溶液。(Resin) •Resin C: A solution obtained by dissolving a compound of the following structure (Mw=11000) in PGMEA. The solid content is 30% by mass. The numerical value attached to the main chain indicates the molar ratio of each repeating unit. [Chemical formula 40]

• Resin PA-1: It is the same solution as the resin PA-1 described above for the pigment dispersion.

•M4：具有下述結構之化合物 [化學式42]

•M5：具有下述結構之化合物 [化學式43]

(Radical polymerizable monomer) • M3: a compound having the following structure [Chemical formula 41]

•M4: A compound with the following structure [Chemical formula 42]

•M5: A compound with the following structure [Chemical formula 43]

(additive) • E1: EPICLON N-695 (manufactured by DIC Corporation) • E2: EHPE 3150 (made by Daicel Corporation) (Interface active agent) • G1: MEGAFACE F-781F (manufactured by DIC Corporation) • G2: KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd.)

<Examples 56 to 86> ＜＜Preparation of pigment dispersion＞＞ As shown in Table 7, after uniformly stirring and mixing the mixture of each composition, various pigment dispersion liquids were prepared by the same method as in the case of the pigment dispersion liquid P-R.

[Table 7] Dispersions The first colorant Second colorant 3rd colorant Pigment derivatives Dispersant Solvent species content species content species content species content species content species content P-R11 PR177 14.00 - - - - Pigment derivatives 3 1.40 Resin M 4.60 PGMEA 80.00 P-R12 PR254 10.50 PY139 4.5 - - Pigment derivatives 4 2.00 Resin M 5.50 PGMEA 77.50 P-K11 PY139 14.20 - - - - Pigment derivatives 3 1.42 Resin M 9.38 PGMEA 75.00 P-K12 PY150 12.00 - - - - Pigment derivatives 3 1.20 Resin M 6.80 PGMEA 80.00 P-G11 PG36 7.40 PY185 5.20 - - Pigment Derivative 2A 1.40 Resin N 4.86 PGMEA 81.14 P-G12 PG7 10.40 - - - - Pigment Derivative 2A 2.60 Resin N 6.50 PGMEA 80.50 P-G13 PG36 8.90 PG7 2.20 PY139 3.90 Pigment derivatives 3 1.50 Resin M 9.50 PGMEA 74.00 P-G14 PG36 12.60 - - - - Pigment Derivative 2A 1.26 Resin N 5.04 PGMEA 81.10 P-B11 PB15:6 9.50 PV23 5.00 - - - - Resin N 5.50 PGMEA 80.00 P-B12 PB15:6 12.00 PV23 3.00 - - Pigment Derivative 2A 2.70 Resin N 4.80 PGMEA 77.50 P-B13 PB15:6 20.00 - - - - - - Resin O Dispersant D 2.40 2.40 PGMEA 175.20

In Table 7 above, the specifications of the raw materials are as follows.

(Colorant) •PR177: C.I. Pigment Red 177 •PR254: C.I. Pigment Red 254 •PY139: C.I. Pigment Yellow 139 •PY150: C.I. Pigment Yellow 150 • PY185: C.I. Pigment Yellow 185 •PG7: C.I. Pigment Green 7 •PG36: C.I. Pigment Green 36 •PB15:6: C.I. Pigment Blue 15:6 •PV23: C.I. Pigment Violet 23

•顏料衍生物4：具有下述結構之化合物。 [化學式45]

(Pigment Derivatives) •Pigment Derivative 3: A compound having the following structure. [Chemical formula 44]

• Pigment Derivative 4: A compound with the following structure. [Chemical formula 45]

•樹脂N：具有下述結構之化合物。附屬於主鏈的括號之數值表示各重複單元的莫耳比，附屬於側鏈的括號之數值表示重複單元的重複數。重量平均分子量為24000。 [化學式47]

•樹脂O：具有下述結構之化合物。附屬於括號之數值表示各重複單元的莫耳比。重量平均分子量為11000。 [化學式48]

•分散劑D：DISPERBYK-161、BYK-Chemie GmbH製。(Dispersant) • Resin M: A compound with the following structure. The value attached to the parenthesis indicates the number of repeating units. [Chemical formula 46]

• Resin N: A compound having the following structure. The numerical value in the parentheses attached to the main chain indicates the molar ratio of each repeating unit, and the numerical value in the parentheses attached to the side chain indicates the repeating number of the repeating unit. The weight average molecular weight is 24,000. [Chemical formula 47]

• Resin O: A compound having the following structure. The values attached to parentheses indicate the molar ratio of each repeating unit. The weight average molecular weight is 11,000. [Chemical formula 48]

• Dispersant D: DISPERBYK-161, manufactured by BYK-Chemie GmbH.

＜＜Preparation of colored composition and production of cured film＞＞ After mixing and stirring the raw materials shown in the following Tables 8 to 10, they were filtered using a nylon filter (manufactured by Nihon Pall Ltd.) with a pore size of 0.45 μm, thereby preparing the colored compositions of Examples 56 to 86. The content in the table is shown in parts by mass. The solid content concentration of each coloring composition (mass %. It is described in the "solid content" column.) was adjusted by the blending amount of the solvent. In Table 11, the M/I ratio (mass ratio), M/IA1 ratio (mass ratio), and pigment concentration (mass %: the ratio of the content of the pigment to the solid content) are shown for each coloring composition. Then, using the colored composition prepared as described above, a cured film was produced by the same method as in Example 1 to obtain evaluation substrates (Examples 56 to 86). In the production of the cured film of the foregoing embodiment, the temperature of the substrate is 100° C. or less in the entire process.

[Table 8] The first pigment dispersion The second pigment dispersion The third pigment dispersion Photopolymerization initiator Resin Fluorine-containing compounds monomer Surfactant Solvent Solid content Initiator ratio in solid content species content species content species content A1 content A2 content species content species content species content species content species content Example 56 PX 58 PZ 16.5 - - Initiator 1 0.58 Initiator 4 0.62 Resin A 2.6 F1 3.9 M4 1.25 G1 0.008 PGMEA 16.5 18.92 6.3% Example 57 P-R11 64 P-K11 17.8 - - Initiator 1 0.74 Initiator 4 0.99 Resin A 4.4 F1 6.6 M4 2.29 G1 0.008 CyH 3.7 23.82 7.3% Example 58 P-R12 58 - - - - Initiator 1 1.14 Initiator 4 0.99 Resin A 6.4 F1 9.6 M4 2.42 G1 0.008 PGMEA 21.4 21.45 9.9% Example 59 P-G11 85 - - - - Initiator 1 1.04 Initiator 4 0.77 Resin A 0.9 F1 1.4 M4 2.04 G1 0.008 PGMEA 8.8 20.44 8.9% Example 60 P-G12 25 P-K12 43.9 P-G14 8.0 Initiator 2 2.00 Initiator 4 1.06 Resin A 5.3 F1 8 M4 5.50 G1 0.008 PGMEA 1.2 26.93 11.4% Example 61 P-G12 61 P-K12 28.3 - - Initiator 1 1.15 Initiator 4 0.86 Resin A 2.6 F1 3.9 M4 1.92 G1 0.008 PGMEA 0.3 23.05 8.7% Example 62 P-B11 51 - - - - Initiator 2 2.17 Initiator 4 0.83 Resin A 4.1 F1 6.2 M4 2.50 G2 0.008 BA 33.2 18.18 16.5% Example 63 P-B12 10 P-B13 15.8 - - Initiator 2 1.66 Initiator 4 1.07 Resin A 15.5 F1 23.2 M4 6.20 G1 0.008 PGMEA 26.6 22.44 12.2% Example 64 PX 58 PZ 16.5 - - Initiator 1 0.58 Initiator 4 0.62 Resin C 5.2 - - M4 1.25 G1 0.008 PGMEA 17.8 18.92 6.3% Example 65 PX 58 PZ 16.5 - - Initiator 1 0.58 Initiator 4 0.62 Resin D 5.2 - - M4 1.25 G1 0.008 PGMEA 17.8 18.92 6.3% Example 66 P-R11 64 P-K11 17.8 - - Initiator 1 0.74 Initiator 4 0.99 Resin C 8.8 - - M4 2.29 G1 0.008 CyH 5.9 23.82 7.3% Example 67 P-R11 64 P-K11 12.8 - - Initiator 1 0.74 Initiator 4 0.99 Resin C 12.7 - - M4 2.29 G1 0.008 CyH 6.5 23.84 7.3% Example 68 P-R12 58 - - - - Initiator 1 1.14 Initiator 4 0.99 Resin C 12.8 - - M4 2.42 G1 0.008 PGMEA 24.6 21.45 9.9%

[Table 9] The first pigment dispersion The second pigment dispersion The third pigment dispersion Photopolymerization initiator Resin Fluorine-containing compounds monomer Surfactant Solvent Solid content Initiator ratio in solid content species content species content species content A1 content A2 content species content species content species content species content species content Example 69 P-G11 85 - - - - Initiator 1 1.04 Initiator 4 0.77 Resin C 1.8 - - M4 2.04 G1 0.008 PGMEA 9.3 20.43 8.9% Example 70 P-G11 85 - - - - Initiator 1 1.04 Initiator 4 0.77 Resin C 1.8 - - M6 M4 1.02 1.02 G1 0.008 PGMEA 9.3 20.43 8.9% Example 71 P-G12 25 P-K12 4.39 P-G14 8.0 Initiator 2 2.00 Initiator 4 1.06 Resin C 10.6 - - M4 5.50 G1 0.008 PGMEA 3.9 26.92 11.4% Example 72 P-G12 61 P-K12 28.3 - - Initiator 1 1.15 Initiator 4 0.86 Resin C 5.2 - - M6 M4 0.58 1.34 G1 0.008 PGMEA 1.6 23.04 8.7% Example 73 P-G12 61 P-K12 28.3 - - Starter 2 Starter 3 0.80 0.35 Initiator 4 0.86 Resin C 5.2 - - M6 M4 0.58 1.34 G1 0.008 PGMEA 1.6 23.04 8.7% Example 74 P-G13 44 P-K11 12.6 - - Initiator 2 2.65 Initiator 4 1.27 Resin E 9.8 - - M6 M4 2.24 5.16 G1 0.008 PGMEA 22.3 28.86 13.6% Example 75 P-B11 51 - - - - Initiator 2 2.17 Initiator 4 0.83 Resin C 8.2 - - M6 M4 1.25 1.25 G2 0.008 PGMEA 35.3 18.17 16.5% Example 76 P-B11 51 - - - - Initiator 2 2.17 Initiator 4 0.83 Resin C 8.2 - - M6 M4 1.25 1.25 G2 0.008 BA 35.3 18.17 16.5% Example 77 P-B12 10 P-B13 15.8 - - Initiator 2 1.66 Initiator 4 1.07 Resin E 30.9 - - M6 M4 3.10 3.10 G1 0.008 PGMEA 34.4 22.42 12.2% Example 78 P-B12 5 P-B13 7.7 - - Initiator 2 0.85 Initiator 4 1.03 Resin E 39.8 - - M6 M4 3.10 3.10 G1 0.008 PGMEA 39.4 22.11 8.5% Example 79 P-B11 34 - - - - Initiator 2 2.00 Initiator 4 1.2 Resin E 24.7 - - M6 M4 3.10 3.10 G1 0.008 PGMEA 31.9 23.62 13.5% Example 80 P-B11 58 - - - - Initiator 2 2.35 Initiator 4 1.18 Resin E 9.2 - - M6 M4 3.10 3.10 G1 0.008 PGMEA 23.1 24.10 14.6%

[Table 10] The first pigment dispersion The second pigment dispersion The third pigment dispersion Photopolymerization initiator Resin Fluorine-containing compounds monomer Surfactant Solvent Solid content Initiator ratio in solid content species content species content species content A1 content A2 content species content species content species content species content species content Example 81 PX 58 PZ 16.5 - - Initiator 1 0.58 Initiator 4 0.62 Resin C 5.2 - - M4 M7 0.625 0.625 G1 0.008 PGMEA 17.8 18.92 6.3% Example 82 PX 58 PZ 16.5 - - Initiator 1 0.58 Initiator 4 0.62 Resin C 5.2 - - M4 M8 0.625 0.625 G1 0.008 PGMEA 17.8 18.92 6.3% Example 83 P-G11 85 - - - - Initiator 1 1.04 Initiator 4 0.77 Resin C 1.8 - - M6 M7 1.02 1.02 G1 0.008 PGMEA 9.3 20.43 8.9% Example 84 P-G11 85 - - - - Initiator 1 1.04 Initiator 4 0.77 Resin C 1.8 - - M6 M8 1.02 1.02 G1 0.008 PGMEA 9.3 20.43 8.9% Example 85 P-B11 51 - - - - Initiator 2 2.17 Initiator 4 0.83 Resin C 8.2 - - M6 M7 1.25 1.25 G2 0.008 PGMEA 35.3 18.17 16.5 Example 86 P-B11 51 - - - - Initiator 2 2.17 Initiator 4 0.83 Resin C 8.2 - - M6 M8 1.25 1.25 G2 0.008 PGMEA 35.3 18.17 16.5

[Table 11] M/I ratio M/I _A1 ratio Pigment concentration Evaluation results stability Example 56 1.0 2.2 52.5% 2 Example 57 1.3 3.1 47.9% 2 Example 58 1.1 2.1 40.6% 2 Example 59 1.1 2.0 52.4% 3 Example 60 1.8 2.8 33.0% 4 Example 61 1.0 1.7 42.3% 3 Example 62 0.8 1.2 40.7% 5 Example 63 2.3 3.7 13.7% 4 Example 64 1.0 2.2 52.5% 2 Example 65 1.0 2.2 52.5% 2 Example 66 1.3 3.1 47.9% 2 Example 67 1.3 3.1 45.2% 2 Example 68 1.1 2.1 40.6% 2 Example 69 1.1 2.0 52.4% 3 Example 70 1.1 2.0 52.4% 3 Example 71 1.8 2.8 33.0% 4 Example 72 1.0 1.7 42.3% 3 Example 73 1.0 1.7 42.3% 3 Example 74 1.9 2.8 29.1% 4 Example 75 0.8 1.2 40.7% 5 Example 76 0.8 1.2 40.7% 5 Example 77 2.3 3.7 13.7% 4 Example 78 3.3 7.3 6.9% 2 Example 79 1.9 3.1 20.9% 4 Example 80 1.8 2.6 34.9% 5 Example 81 1.0 2.2 52.5% 2 Example 82 1.0 2.2 52.5% 2 Example 83 1.1 2.0 52.4% 3 Example 84 1.1 2.0 52.4% 3 Example 85 0.8 1.2 40.7% 5 Example 86 0.8 1.2 40.7% 5

The raw materials described in Tables 8 to 10 are as follows.

(Photopolymerization initiator) • Initiators 1 to 4: are the same types of photo radical polymerization initiators as the initiators 1 to 4 described in Table 1, respectively.

•樹脂E：使下述結構的化合物（Mw=14000）溶於PGMEA而得之溶液。固體成分量為30質量%。附加在主鏈上之數值表示各重複單元的莫耳比。 [化學式50]

(Resin) • Resin A: It is the same type of resin as the resin A described in Table 1. • Resin C: It is the same type of resin as the resin C described in Table 5. • Resin D: A solution obtained by dissolving a compound of the following structure (Mw=12000) in PGMEA. The solid content is 30% by mass. The numerical value attached to the main chain indicates the molar ratio of each repeating unit. [Chemical formula 49]

• Resin E: A solution obtained by dissolving a compound of the following structure (Mw=14000) in PGMEA. The solid content is 30% by mass. The numerical value attached to the main chain indicates the molar ratio of each repeating unit. [Chemical formula 50]

(Compounds containing furan group) • F1: It is the same type of compound as the furyl-containing compound F1 described in Table 1.

•M7：3-乙基-3｛［（3-乙基氧雜環丁烷-3-基）甲氧基］甲基｝氧雜環丁烷（TOAGOSEI CO., LTD.製 OXT-221）。 •M8：（3-乙基氧雜環丁烷-3-基）甲基丙烯酸甲酯（Ube Industries, Ltd.製 ETERNACOLL OXMA）。(Radical polymerizable monomer) • M4: It is the same type of monomer as the radical polymerizable monomer M4 described in Table 5. • M6: A compound with the following structure. [Chemical formula 51]

•M7: 3-ethyl-3{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (OXT-221 manufactured by TOAGOSEI CO., LTD.) . • M8: (3-ethyloxetan-3-yl) methyl methacrylate (ETERNACOLL OXMA manufactured by Ube Industries, Ltd.).

(Interface active agent) • G1, G2: respectively the same type of surfactants as the surfactants G1 and G2 described in Table 5.

(Solvent) •PGMEA: Propylene glycol monomethyl ether acetate •CyH: Cyclohexanone •BA: Butyl acetate

＜Evaluation of the stability of spectral characteristics＞ The cured film was exposed to a high temperature and high humidity test at 85°C and 85% for 1000 hours, and the spectral transmittance before and after the test was measured. Then, in the wavelength range of 400 to 1100 nm, the change rate of the transmittance was calculated for each measurement wavelength, and the maximum value of the change rates was used as an index, and the evaluation was performed as described below. The evaluation results are shown in Tables 2 to 4 and Table 6. If the evaluation value is 2 or more, it can be said that the stability as a spectral characteristic is better than the conventional level. 5: The rate of change as an indicator is less than 1%. 4: The rate of change as an indicator is greater than 1% and less than 2%. 3: The rate of change as an indicator is greater than 2% and less than 3%. 2: The rate of change as an indicator is greater than 3% and less than 4%. 1: The rate of change as an indicator is greater than 4%.

As shown in the above-mentioned Tables 2 to 4, 6 and Table 11, the cured film formed using the coloring composition of the example has excellent stability of the spectral characteristics. As a result, for example, by incorporating a color filter formed using the coloring composition of the present invention into an organic electroluminescence display device, an organic electroluminescence display device having excellent stability of display performance can be obtained.

In addition, from the comparison of Example 2 and Example 4, it can be seen that it has a structure derived from the compound represented by the following formula (III). More specifically, the resin A having a p-cumylphenol group contributes more to the cured film The stability of the spectroscopic characteristics.

In addition, from the results of Example 13 and Example 14, it can be seen that even if the above-mentioned specific photopolymerization initiator A1 and the above-mentioned specific photopolymerization initiator A2 are used in combination, a composition with excellent stability of the spectral characteristics of the cured film can be obtained. Things.

In addition, from the results of Examples 37 to 40, it can be seen that by setting the content of the pigment derivative with respect to the pigment in the dispersion to 0.5 parts by mass or less, a composition with more excellent stability can be obtained.

Claims (21)

A coloring composition comprising a coloring agent, a radical polymerizable monomer and a photo radical polymerization initiator, wherein the content of the photo radical polymerization initiator in the total solid content of the coloring composition is 3% by mass As described above, the colored composition uses light having a wavelength greater than 350 nm and less than 380 nm, is exposed at an exposure amount of 200 mJ/cm ² or more, and is used to form a cured film at a temperature of 150° C. or less in the entire process. The colored composition as described in item 1 of the scope of patent application, wherein The content of the photo radical polymerization initiator is 9% by mass or more. Such as the coloring composition described in item 1 or item 2 of the scope of patent application, wherein The ratio M/I of the content M of the radical polymerizable monomer in the total solid content of the coloring composition to the content I of the photo radical polymerization initiator is 20 or less in mass ratio. Such as the coloring composition described in item 1 or item 2 of the scope of patent application, wherein The photoradical polymerization initiator contains an oxime compound. The coloring composition as described in item 4 of the scope of patent application, of which The content of the oxime compound is 10% by mass or more. The coloring composition described in item 1 or item 2 of the scope of patent application, wherein the photoradical polymerization initiator comprises a photopolymerization initiator with an absorption coefficient of 1.0×10 ³ mL/gcm or more in methanol at a wavelength of 365 nm The photopolymerization initiator A1 and the photopolymerization initiator A2 in which the absorption coefficient at a wavelength of 365 nm in methanol is 1.0×10 ² mL/gcm or less and the absorption coefficient at a wavelength of 254 nm is 1.0×10 ³ mL/gcm or more in methanol. The coloring composition as described in item 6 of the scope of patent application, wherein The content of the photopolymerization initiator A1 is 10% by mass or more. The coloring composition described in item 6 of the scope of patent application, wherein the ratio of the content M of the radical polymerizable monomer in the total solid content of the coloring composition to the content I _A1 of the photopolymerization initiator A1 M/I _A1 is 20 or less in mass ratio. The coloring composition as described in item 6 of the scope of patent application, wherein The photopolymerization initiator A1 contains an oxime compound containing a fluorine atom. The coloring composition as described in item 6 of the scope of patent application, wherein The photopolymerization initiator A2 contains a hydroxyalkylphenone compound. The coloring composition described in item 10 of the scope of patent application, wherein the hydroxyalkyl phenone compound is a compound represented by the following formula (V), formula (V):

In the formula, Rv ¹ represents a substituent, Rv ² and Rv ³ each independently represent a hydrogen atom or a substituent, Rv ² and Rv ³ may be bonded to each other to form a ring, and m represents an integer of 0-5. The coloring composition as described in item 6 of the scope of patent application, wherein The total content of the photopolymerization initiator A1 and the photopolymerization initiator A2 in the total solid content of the coloring composition is 5 to 15% by mass. The coloring composition described in item 1 or item 2 of the scope of the patent application, wherein the coloring composition further contains a resin containing a repeating unit derived from a compound represented by the following formula (I),

In the formula, X ¹ represents O or NH, R ¹ represents a hydrogen atom or a methyl group, L ¹ represents a divalent linking group, R ¹⁰ represents a substituent, m represents an integer of 0 to 2, and p represents an integer of 0 or more. The coloring composition described in item 1 or item 2 of the scope of the patent application further contains a furan group-containing compound. The coloring composition described in item 14 of the scope of patent application, wherein the furan group-containing compound is at least one selected from resins, and the resin includes a compound derived from the following formula (fur-1) and The repeating unit of the compound represented by the following formula (fur-1), formula (fur-1):

In the formula, Rf ¹ represents a hydrogen atom or a methyl group, and Rf ² represents a divalent linking group. A method for forming a hardened film, comprising: a process of coating the colored composition described in any one of items 1 to 15 in the scope of the patent application on a support to form a colored composition layer; and The exposure amount above cm ² irradiates the colored composition layer with light having a wavelength greater than 350 nm and less than 380 nm, thereby exposing the colored composition layer to an exposure process, which is obtained at a temperature below 150° C. in the entire process The film formed by curing the colored composition layer is also the cured film. The method for forming a cured film as described in item 16 of the scope of patent application, wherein the exposure amount in the exposure process is 1 J/cm ² or more. The method for forming a cured film as described in item 16 or item 17 of the scope of patent application, wherein the exposure illuminance in the exposure process is 1000 mW/cm ² or more. The method for forming a cured film as described in item 16 or item 17 of the scope of patent application, wherein In the whole process, the cured film is obtained at a temperature below 100°C. A method for manufacturing a color filter includes the method for forming a cured film described in any one of the 16th to 19th patent applications. A method of manufacturing a display device includes the method for forming a cured film described in any one of the 16th to 19th patent applications.