TW202406947A - Photosensitive composition, film, optical filter, solid-state imaging element and image display device - Google Patents

Abstract

This photosensitive composition comprises a coloring material, a polymerizable compound, and a photopolymerization initiator. The amount of coloring material contained in the total solid content of the photosensitive composition is 40% by mass or more. The polymerizable compound includes a polymerizable compound B1 having a weight-average molecular weight of 3000 or more. The amount of the polymerizable compound B1 contained in the total solid content of the polymerizable compound is 50% by mass or more. The photopolymerization initiator includes a compound represented by formula (1). The present invention also provides a film, an optical filter, a solid-state imaging element, and an image display device, each of which is produced using the photosensitive composition.

Description

Photosensitive compositions, films, optical filters, solid-state imaging devices and image display devices

The present invention relates to a photosensitive composition containing color materials. Furthermore, the present invention relates to a film, an optical filter, a solid-state imaging element, and an image display device using a photosensitive composition.

As described in Patent Document 1, a technology for manufacturing optical filters such as color filters using a photosensitive composition containing a color material, a photopolymerization initiator, and a polymerizable compound is being developed.

[Patent Document 1] Japanese Patent Application Publication No. 2012-189997

In recent years, there has been a strong demand for solid-state imaging elements to be miniaturized or thinned. Therefore, in recent years, there has been a demand for further thinning of films containing color materials such as color filters used in solid-state imaging elements. In order to maintain desired spectral performance and achieve thinning, it is necessary to increase the color material concentration of the photosensitive composition used for film formation.

However, as the color material concentration of the photosensitive composition becomes higher, the proportion of components other than the color material relatively decreases, so the curability tends to be insufficient. Therefore, when a photosensitive composition is used and pixels are formed by photolithography, as the color material concentration of the photosensitive composition becomes higher, the adhesion between the obtained pixel and the support tends to be insufficient.

Therefore, an object of the present invention is to provide a photosensitive composition capable of forming a film with excellent adhesion to a support. Furthermore, another object of the present invention is to provide a film, an optical filter, a solid-state imaging element, and an image display device.

Based on investigations, the inventors found that the above object can be achieved by the photosensitive composition described below, and completed the present invention. Accordingly, the present invention provides the following.

<1> A photosensitive composition containing a color material, a polymerizable compound, and a photopolymerization initiator, wherein the content of the color material in the total solid content of the photosensitive composition is 40% by mass or more, and the polymerizable The compound contains a polymerizable compound B1 with a weight average molecular weight of 3000 or more, the content of the polymerizable compound B1 in the total mass of the polymerizable compound is 50% by mass or more, and the photopolymerization initiator contains a compound represented by the formula (1) Compound, [Chemical Formula 1] In formula (1), X ¹ represents a bivalent linking group containing at least one selected from the group consisting of aromatic rings and heterocyclic rings, R ¹ represents a hydrogen atom or a hydroxyl group, and R ² represents an alkyl group or an aryl group. , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group, Alk ¹ and Alk ² each independently represent an alkyl group, R ³ and R ⁴ may be bonded to form a ring, Alk ¹ and Alk ² may be bonded to form a Ring, n represents 0 or 1. <2> The photosensitive composition according to <1>, wherein X ¹ in formula (1) is a group represented by any one of formulas (X-1) to (X-13), [Chemical Formula 2] In the formula, R ^X1 to R ^X9 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. <3> The photosensitive composition according to <2>, wherein X ¹ of formula (1) is a group represented by the above formula (X-2) or formula (X-6). <4> The photosensitive composition according to <1> or <2>, wherein the polymerizable compound B1 contains a repeating unit having a graft chain. <5> The photosensitive composition according to any one of <1> to <4>, wherein the polymerizable compound B1 contains a repeating unit having an ethylenically unsaturated bond-containing group in a side chain, and has The repeating unit of the graft chain. <6> The photosensitive composition according to <4> or <5>, wherein the graft chain contains at least 1 selected from the group consisting of a polyester structure, a polyether structure and a poly(meth)acrylic acid structure. repeating unit of a structure. <7> The photosensitive composition according to any one of <1> to <6>, wherein the content of the color material in the total solid content of the photosensitive composition is 50 mass % or more. <8> The photosensitive composition according to any one of <1> to <7>, wherein the color material contains colorimetric index Pigment Red 272. <9> The photosensitive composition according to any one of <1> to <8>, which further contains a polymerization inhibitor. <10> The photosensitive composition according to any one of <1> to <9>, which further contains a polysiloxane-based surfactant. <11> A film obtained using the photosensitive composition according to any one of <1> to <10>. <12> An optical filter having the film according to <11>. <13> An image display device having the film according to <11>. <14> A solid-state imaging element having the film according to <11>. [Effects of the invention]

According to the present invention, it is possible to provide a photosensitive composition capable of forming a film with excellent adhesion to a support. Furthermore, according to the present invention, it is possible to provide a film, an optical filter, a solid-state imaging element, and an image display device using a photosensitive composition.

Hereinafter, the contents of the present invention will be described in detail. In this specification, "～" is used in the sense that the numerical values described before and after it are included as the lower limit and the upper limit. Among the labels for groups (atomic groups) in this specification, the labels indicating unsubstituted and unsubstituted include groups (atomic groups) without substituents as well as groups (atomic groups) with substituents. For example, "alkyl" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include the bright line spectrum of a mercury lamp, actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light), X-rays, and electron beams represented by excimer lasers. In this specification, "(meth)acrylate" means both or either acrylate and methacrylate, "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid, and "(meth)acrylic acid" means both or either acrylic acid and methacrylic acid. "Meth)acrylyl" means both or either of acrylyl and methacrylyl. In this specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, the weight average molecular weight and the number average molecular weight are polystyrene-converted values measured by the GPC (gel permeation chromatography) method. In this specification, the total solid content refers to the total mass of components excluding solvents from all components of the composition. In this specification, pigments refer to color materials that are not easily soluble in solvents. In this specification, the term "step" includes not only independent steps, but also includes steps that cannot be clearly distinguished from other steps, as long as the expected effect of the step is achieved.

＜Photosensitive composition＞ The photosensitive composition of the present invention is characterized by containing: Color materials, polymerizable compounds and photopolymerization initiators, among which The content of the color material in the total solid content of the photosensitive composition is 40% by mass or more, The polymerizable compound contains polymerizable compound B1 with a weight average molecular weight of 3000 or more, and the content of polymerizable compound B1 in the total mass of the polymerizable compound is 50 mass % or more, The photopolymerization initiator contains a compound represented by formula (1).

When a photosensitive composition containing a large color material content is hardened by exposure, the exposure light tends to be less likely to reach the deep part of the film (support side). Therefore, especially in the deep part of the film, the hardening reaction during exposure tends to be low. If the hardening reaction in the deep part of the film is insufficient, the obtained film will tend to have insufficient adhesion to the support. However, even if the content of the color material in the total solid content of the photosensitive composition is 40% by mass or more, the photosensitive composition of the present invention can form a film having excellent adhesion to the support. The reason for this is not yet clear, but it is presumed that the hardening reaction can sufficiently proceed even in the deep part of the film due to an increase in the amount of generated radicals. Furthermore, it is presumed that the photosensitive composition of the present invention contains a polymerizable compound B1 having a weight average molecular weight of 3000 or more as a polymerizable compound, and the content of the polymerizable compound B1 in the total mass of the polymerizable compounds is 50% by mass. Therefore, the molecular weight of the polymerizable compound increases greatly due to the radical reaction during exposure, and the permeability of the developer can be suppressed, resulting in good adhesion. Therefore, it is presumed that the photosensitive composition of the present invention can form a film having excellent adhesion to the support.

Moreover, the film obtained using the photosensitive composition of this invention is also excellent in moisture resistance. It is presumed that the reason for this is that the molecular weight of the polymerizable compound increases significantly due to radical reaction during exposure. Furthermore, the photosensitive composition of the present invention also has excellent exposure sensitivity. In addition, the photosensitive composition of the present invention is also excellent in developability, and can form pixels with excellent linearity when patterning by photolithography to form pixels, and can also suppress the generation of residues between pixels.

The photosensitive composition of the present invention can be preferably used as a photosensitive composition for optical filters. Examples of the optical filter include a color filter, a near-infrared transmission filter, a near-infrared cutoff filter, and the like, and a color filter is preferred. Furthermore, the photosensitive composition of the present invention can be suitably used as a solid-state imaging element. More specifically, it can be preferably used as a photosensitive composition for optical filters used in solid-state imaging devices, and can be more preferably used as a photosensitive composition for forming colored pixels of color filters used in solid-state imaging devices. things.

Examples of the color filter include a filter having colored pixels that transmit light of a specific wavelength. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels. The colored pixels of the color filter can be formed using a photosensitive composition containing a color material.

The maximum absorption wavelength of the near-infrared cutoff filter is preferably in the range of 700 to 1800 nm, more preferably in the range of 700 to 1300 nm, and still more preferably in the range of 700 to 1000 nm. In addition, the transmittance of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. In addition, the transmittance at at least one location within the wavelength range of 700 to 1800 nm is preferably 20% or less. In addition, the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at the wavelength of 550 nm (absorbance Amax/absorbance A550) is preferably 20 to 500, more preferably 50 to 500, and 70 to 450. More preferably, 100 to 400 is particularly preferred. The near-infrared cut filter can be formed using a photosensitive composition containing a near-infrared absorbing color material.

The near-infrared transmission filter is a filter that transmits at least a part of near-infrared rays. The near-infrared transmission filter is preferably a filter that blocks at least part of visible light and transmits at least part of near-infrared rays. Preferable examples of the near-infrared transmission filter include those that have a maximum value of transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and at a wavelength of 400 to 640 nm. Filters with spectral characteristics such that the minimum value of transmittance in the range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). The near-infrared transmission filter is preferably a filter that satisfies the spectral characteristics of any one of the following (1) to (5). (1): The maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 800 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). (2): The maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 900 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). (3): The maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1000 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). (4): The maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1100 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). (5): The maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1200 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more).

The photosensitive composition of the present invention preferably has a solid content concentration of 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more. The upper limit is preferably 25 mass% or less, more preferably 20 mass% or less, and still more preferably 15 mass% or less.

Each component used in the photosensitive composition of this invention is demonstrated below.

＜＜Color＞＞ The photosensitive composition of the present invention contains a color material. Examples of color materials include white color materials, black color materials, chromatic color materials, and near-infrared absorbing color materials. Furthermore, in this specification, white color materials include not only pure white, but also light gray color materials that are close to white (such as off-white, light gray, etc.).

The color material preferably contains at least one selected from the group consisting of a color color material, a black color material and a near-infrared absorbing color material, and it is even more preferred that it contains a color color material.

When the photosensitive composition of the present invention is used as a color filter, it is preferable that the color material is substantially only a color color material. In addition, in this specification, when the color material is essentially only a color color material, it means that the content of the color color material in the color material is 99 mass % or more, preferably 99.9 mass % or more, and the color material is only a color color material. For the better.

The color material may be either a pigment or a dye, but it is preferably a pigment. The pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferred from the viewpoints of the amount of color variation, ease of dispersion, and safety. Furthermore, the pigment preferably contains at least one selected from the group consisting of color pigments and near-infrared absorbing pigments, and more preferably contains a color pigment.

The average primary particle size of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, and more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and still more preferably 100 nm or less. If the average primary particle diameter of the pigment is within the above range, the dispersion stability of the pigment in the photosensitive composition will be good. In addition, in the present invention, the primary particle diameter of the pigment can be determined from the photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the equivalent circle diameter corresponding thereto is calculated as the primary particle diameter of the pigment. In addition, the average primary particle diameter in the present invention is the arithmetic average of the primary particle diameters of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.

The crystallite size calculated from the half-value width of the peak of any crystal plane in the X-ray diffraction spectrum when the CuKα ray of the pigment is used as the X-ray source is preferably 0.1 to 100 nm, and more preferably 0.5 to 50 nm. The thickness is preferably 1 to 30 nm, and 5 to 25 nm is even more preferred.

The specific surface area of the pigment is preferably 1 to 300 m ² /g. The lower limit is preferably 10 m ² /g or more, and more preferably 30 m ² /g or more. The upper limit is preferably 250 m ² /g or less, and more preferably 200 m ² /g or less. The value of the specific surface area can be determined according to the BET (Brunauer, Emmett and Teller) method and according to DIN 66131: determination of the specific surface area of solids by gas adsorption (specific surface area of solids based on gas adsorption) (measurement).

As a preferred aspect, the color material is preferably one containing pigment red with a colorimetric index of 272.

(color material) Examples of the color material include those having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, yellow color materials, orange color materials, red color materials, green color materials, purple color materials, blue color materials, etc. can be cited. From the viewpoint of heat resistance, the color material is preferably a pigment (color pigment), more preferably a red pigment, a yellow pigment, and a blue pigment, and further preferably a red pigment and a blue pigment. Specific examples of color pigments include the following.

Examples of the red color material include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, formimine compounds, Kuchiyamaguchi star compounds, quinacridone compounds, perylene compounds, thioindigo compounds, and the like. , diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds are preferred, and diketopyrrolopyrrole compounds are more preferred. Moreover, it is preferable that the red color material is a pigment.

Specific examples of red color materials include C.I. (Color Index) 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, 295, 296, 297 and other red pigments. In addition, as the red color material, the compound described in paragraph 0034 of International Publication No. 2022/085485 and the brominated diketopyrrolopyrrole compound described in Japanese Patent Application Laid-Open No. 2020-085947 can also be used.

As the red color material, C.I. Pigment Red 122, 177, 254, 255, 264, 269, and 272 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, C.I. Pigment Red 254 and 272 are further preferred, and C.I. Pigment Red 272 is especially good.

Examples of green color materials include phthalocyanine compounds, squaraine compounds, and the like. Phthalocyanine compounds are preferred, and phthalocyanine pigments are more preferred. Furthermore, the green color material is preferably a pigment.

Specific examples of green color materials include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. In addition, as the green color material, it is also possible to use a halide zinc phthalocyanine pigment with an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms in one molecule of 8 to 12, and an average number of chlorine atoms in 2 to 5. . Specific examples include compounds described in International Publication No. 2015/118720. In addition, as the green color material, the compound described in paragraph 0029 of International Publication No. 2022/085485, the aluminum phthalocyanine compound described in Japanese Patent Application Laid-Open No. 2020-070426, etc. can also be used.

As a green color material, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred, and C.I. Pigment Green 36 and 58 are even more preferred.

Specific examples of the orange color material include C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73 and other orange pigments.

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

As the yellow color material, a nickel azobarbiturate complex having the following structure can also be used. [Chemical formula 3]

As the yellow color material, compounds described in paragraphs 0031 to 0033 of International Publication No. 2022/085485, methine dyes described in Japanese Patent Application Laid-Open No. 2019-073695, and Japanese Patent Application Laid-Open No. 2019-073696 can be used. The methine dye, the methine dye described in Japanese Patent Application Publication No. 2019-073697, the methine dye described in Japanese Patent Application Publication No. 2019-073698, the methine dye described in Japanese Patent Application Publication No. 2020-093994 Nitrogen compounds.

Specific examples of the purple color material include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

Specific examples of the blue color material include C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88 and other blue pigments. Furthermore, as the blue color material, an aluminum phthalocyanine compound having a phosphorus atom can also be used. Specific examples include compounds described in paragraphs 0022 to 0030 of Japanese Patent Application Laid-Open No. 2012-247591 and paragraph 0047 of Japanese Patent Application Laid-Open No. 2011-157478.

As the green color material or the blue color material, the diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used.

Regarding the preferred diffraction angles of various pigments, please refer to Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, Japanese Patent Publication No. 2020-026503, and Japanese Patent Publication No. 2020-033526. records, these contents are incorporated into this manual. In addition, as the pyrrolopyrrole pigment, it is better to use one whose crystallite size is 140 Å or less in the direction of the plane corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes of the lattice (±1±1±1). good. In addition, the physical properties of the pyrrolopyrrole pigment are preferably as described in paragraphs 0028 to 0073 of Japanese Patent Application Laid-Open No. 2020-097744.

As a pigment, from the viewpoint of improving spectral characteristics, it is also preferable to use a halide zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002. Furthermore, as the pigment, from the viewpoint of viscosity adjustment, it is also preferable to use the pigment with a controlled contact angle described in International Publication No. 2019/107166.

Dyes can also be used for colored materials. The dye is not particularly limited, and known dyes can be used. Examples include pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxocyanine series, pyrazotriazole azo series, Pyridone azo series, cyanine series, thiophene series, pyrrolopyrazole azomethine series, Kouyamaguchi galaxy, phthalocyanine series, benzopyran series, indigo series, pyrrromethylene series and other dyes .

Pigment polymers can also be used as color materials. It is preferable that the dye polymer is dissolved in a solvent and used. In addition, the dye multimer may form particles. When the pigment polymer is in the form of particles, it is usually used in a state of being dispersed in a solvent. The dye multimer in a particle state can be obtained by, for example, emulsion polymerization. Specific examples include the compound and the production method described in Japanese Patent Application Laid-Open No. 2015-214682. The pigment multimer has two or more pigment structures in one molecule, preferably three or more pigment structures. The upper limit is not particularly limited, but it can also be set to 100 or less. The plurality of pigment structures in one molecule may be the same pigment structure or may be different pigment structures. The weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000. It is more preferable that the lower limit is 3,000 or more, and it is further more preferable that it is 6,000 or more. It is more preferable that the upper limit is 30,000 or less, and it is further more preferable that it is 20,000 or less. The dye multimer can also be used as Japanese Patent Application Laid-Open Nos. 2011-213925, 2013-041097, 2015-028144, 2015-030742, and International Publication No. 2016/031442. Compounds described in etc.

As the color material, the triarylmethane dye polymer described in Korean Patent Publication No. 10-2020-0028160, the Yamaguchi star compound described in Japanese Patent Publication No. 2020-117638, and the International Publication No. 2020/174991 can be used. Phthalocyanine compounds described in Japanese Patent Application Laid-Open No. 2020-160279, isoindoline compounds or salts thereof, and compounds represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069442 , the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069730, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069070, Korean Patent Publication No. 10-2020 -The compound represented by Formula 1 described in Publication No. 0069067, the compound represented by Formula 1 described in Korean Patent Publication No. 10-2020-0069062, the halide zinc phthalocyanine pigment described in Japanese Patent No. 6809649, Japan Isoindoline compounds described in Japanese Patent Application Laid-Open No. 2020-180176, phenanthroline compounds described in Japanese Patent Application Publication No. 2021-187913, halogenated zinc phthalocyanine described in International Publication No. 2022/004261, International Publication No. Halogenated zinc phthalocyanine described in No. 2021/250883. The color material can be a rotaxane, and the pigment skeleton can be used for the ring structure of the rotaxane, the rod-shaped structure, or both structures. As the colorant, the quinoline compound represented by Formula 1 of Korean Patent Publication No. 10-2020-0030759, the polymer dye described in Korean Patent Publication No. 10-2020-0061793, and Japanese Patent Application Laid-Open can be used. The coloring agent described in the Publication No. 2022-029701, the isoindoline compound described in the International Publication No. 2022/014635, and the aluminum phthalocyanine compound described in the International Publication No. 2022/024926.

Color materials can be used in combination of two or more types. Moreover, when two or more kinds of color color materials are used in combination, black can be formed by the combination of two or more kinds of color color materials. Examples of such combinations include the following aspects (1) to (7). When the photosensitive composition contains two or more chromatic color materials and the combination of the two or more chromatic color materials produces black, the photosensitive composition of the present invention can be preferably used for forming a near-infrared transmission filter. Photosensitive composition. (1) Containing red color materials and blue color materials. (2) Containing red color materials, blue color materials and yellow color materials. (3) Containing red color materials, blue color materials, yellow color materials and purple color materials. (4) Containing red color materials, blue color materials, yellow color materials, purple color materials and green color materials. (5) Containing red color materials, blue color materials, yellow color materials and green color materials. (6) Containing red color materials, blue color materials and green color materials. (7) Containing yellow color materials and purple color materials.

(white color material) Examples of the white color material include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silicon dioxide, talc, mica, aluminum hydroxide, calcium silicate, Inorganic pigments (white pigments) such as aluminum silicate, hollow resin particles, and zinc sulfide. It is preferred that the white pigment is particles containing titanium atoms, and titanium oxide is even more preferred. Moreover, it is preferable that the white pigment is a particle whose refractive index with respect to light with a wavelength of 589 nm is 2.10 or more. The aforementioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.

As the white pigment, titanium oxide described in "Titanium Oxide: Physical Properties and Application Technology, Kiyono Gakusho, pp. 13 to 45, issued on June 25, 1991, published by GIHIDO SHUPPAN CO., Ltd." can also be used.

The white pigment may not only be composed of a single inorganic substance, but may also be composed of particles compounded with other materials. For example, particles with pores or other materials inside, particles with a plurality of inorganic particles attached to the core particles, and core-shell composites including core particles composed of polymer particles and shells composed of inorganic nanoparticles are used. Particles are better. As the core-shell composite particles including core particles composed of polymer particles and shell layers composed of inorganic nanoparticles, for example, the description in paragraphs 0012 to 0042 of Japanese Patent Application Laid-Open No. 2015-047520 can be referred to. are incorporated into this manual.

White pigments can also use hollow inorganic particles. Hollow inorganic particles refer to inorganic particles that have a hollow structure inside and are surrounded by a shell. Examples of the hollow inorganic particles include hollow inorganic particles described in Japanese Patent Application Publication No. 2011-075786, International Publication No. 2013/061621, Japanese Patent Application Publication No. 2015-164881, etc., and these contents are incorporated in this description.

(black color material) The black color material is not particularly limited, and known ones can be used. For example, examples of inorganic black color materials include inorganic pigments (black pigments) such as carbon black, titanium black, and graphite. Carbon black and titanium black are preferred, and titanium black is more preferred. Titanium black refers to black particles containing titanium atoms, preferably low-order titanium oxide or titanium oxynitride. The surface of titanium black can be modified if necessary for the purpose of improving dispersibility, inhibiting aggregation, etc. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide. Furthermore, it can also be treated with a water-repellent substance as shown in Japanese Patent Application Laid-Open No. 2007-302836. Examples of black pigments include C.I. Pigment Black 1, 7, and the like. It is preferable that each particle of titanium black has a small primary particle size and an average primary particle size. Specifically, the average primary particle diameter is preferably 10 to 45 nm. Titanium black can also be used as a dispersion. For example, a dispersion containing titanium black particles and silicon dioxide particles, and the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50. Regarding the above-mentioned dispersion, please refer to the description in paragraphs 0020 to 0105 of Japanese Patent Application Laid-Open No. 2012-169556, and this content is incorporated into this specification. Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, and 13M-T (trade name: Mitsubishi Materials Corporation), Tilack D (trade name: Mitsubishi Materials Corporation) Manufactured by Ako Kasei Co., Ltd.), etc.

Examples of organic black color materials include bisbenzofuranone compounds, methine azo compounds, perylene compounds, and azo compounds. Examples of the dibenzofuranone compound include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, etc., for example, it can be used as a dibenzofuranone compound manufactured by BASF Corporation. "Irgaphor Black" obtained. Examples of the perylene compound include the compounds described in paragraphs 0016 to 0020 of Japanese Patent Application Laid-Open No. 2017-226821, C.I. Pigment Black 31, 32, and the like. Examples of the azomethine compound include compounds described in Japanese Patent Application Laid-Open No. 01-170601, Japanese Patent Application Laid-Open No. 02-034664, etc., for example, compounds manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd. "CHROMO FINE BLACK A1103" was obtained. In addition, as the black color material, the black organic pigment described in Japanese Patent No. 6985715, Lumogen Black FK4280, and Paliogen Black S0084 (manufactured by BASF Corporation) can be used.

The color material used in the photosensitive composition of the present invention may only be the above-mentioned black color material, or may further contain a color color material. According to this aspect, it is easy to obtain a photosensitive composition capable of forming a film excellent in light-shielding properties in the visible region. When a black color material and a color color material are used together as a color material, the mass ratio of the two is black color material: color color material = 100:10 to 300 is preferred, and 100:20 to 200 is even more preferred.

Preferable combinations of black color materials and color color materials include the following, for example. (A-1) Contains organic black color materials and blue color materials. (A-2) Contains organic black color materials, blue color materials, and yellow color materials. (A-3) Containing organic black color materials, blue color materials, yellow color materials and red color materials. (A-4) Containing organic black color materials, blue color materials, yellow color materials and purple color materials.

In the aspect (A-1) above, the mass ratio of the organic black color material to the blue color material is organic black color material: blue color material = 100:1~70 is preferred, and 100:5~60 is more preferred. , 100:10～50 is further preferred. In the above aspect (A-2), the mass ratio of the organic black color material, blue color material and yellow color material is organic black color material: blue color material: yellow color material = 100:10～90:10～90 It is preferable, 100:15～85:15～80 is more preferable, and 100:20～80:20～70 is still more preferable. In the aspect (A-3) above, the mass ratio of the organic black color material, blue color material, yellow color material and red color material is organic black color material: blue color material: yellow color material: red color material = 100 :20～150:1～60: 10～100 is more preferable, 100:30～130:5～50:20～90 is more preferable, 100:40～120:10～40:30～80 is still more preferable . In the aspect (A-4) above, the mass ratio of the organic black color material, blue color material, yellow color material and purple color material is organic black color material: blue color material: yellow color material: purple color material = 100 :20～150:1～60: 10～100 is more preferable, 100:30～130:5～50:20～90 is more preferable, 100:40～120:10～40:30～80 is still more preferable .

(Near-infrared absorbing color material) The near-infrared absorbing color material is preferably a compound that has a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm. The near-infrared absorbing color material is preferably a compound with a maximum absorption wavelength in a range exceeding a wavelength of 700nm and below 1800nm, and a compound having a maximum absorption wavelength in a range exceeding a wavelength of 700nm and below 1400nm is more preferred. Furthermore, a compound having a maximum absorption wavelength in a range of 1,200 nm or less is more preferred, and a compound having a maximum absorption wavelength in a range exceeding a wavelength of 700 nm and not exceeding 1,000 nm is particularly preferred. Moreover, the ratio A ¹ /A ² of the absorbance A ¹ at a wavelength of 500 nm and the absorbance A ² at the maximum absorption wavelength of the near-infrared absorbing color material is preferably 0.08 or less, and more preferably 0.04 or less. Furthermore, the near-infrared absorbing color material is preferably a pigment, and more preferably an organic pigment.

Examples of the near-infrared absorbing color material include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, and quinonium compounds. Compounds, oxocyanine compounds, immonium compounds, dithiol compounds, triarylmethane compounds, pyrrromethylene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, disulfene metal azines compounds, metal oxides, metal borides, etc. Specific examples of these include compounds described in paragraph 0114 of International Publication No. 2022/065215. In addition, as the near-infrared absorbing color material, the compound described in paragraph 0121 of International Publication No. 2022/065215, the squaraine compound described in Japanese Patent Application Laid-Open No. 2020-075959, and Korean Patent Publication No. 10-2019 can also be used. The copper complex described in Japanese Patent Application Publication No. 2021-195515, the copper complex compound described in Japanese Patent Application Publication No. 2021-195515, and the near-infrared absorbing dye described in Japanese Patent Application Publication No. 2022-022070.

The content of the color material in the total solid content of the photosensitive composition is 40 mass% or more, preferably 50 mass% or more, and more preferably 55 mass% or more. The upper limit is preferably 80 mass% or less, more preferably 75 mass% or less, and still more preferably 70 mass% or less.

The content of the pigment in the total solid content of the photosensitive composition is preferably 40 mass% or more, more preferably 45 mass% or more, and still more preferably 50 mass% or more. The upper limit is preferably 80 mass% or less, more preferably 77.5 mass% or less, and still more preferably 75 mass% or less.

The content of the pigment in the color material is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and further preferably 70 to 100% by mass.

＜＜Polymerizable compounds＞＞ The photosensitive composition of the present invention contains a polymerizable compound. Examples of polymerizable compounds include compounds having a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include vinyl, (meth)allyl, (meth)acrylyl, (meth)acryloxy, and the like. The polymerizable compound is preferably a radical polymerizable compound.

(Polymerizable compound B1) In the photosensitive composition of the present invention, the polymerizable compound containing polymerizable compound B1 having a weight average molecular weight of 3,000 or more is used. The content of the polymerizable compound B1 in the total mass of the polymerizable compounds contained in the photosensitive composition is 50 mass% or more, preferably 60 mass% or more, and more preferably 70 mass% or more. The upper limit can be 100 mass% or less, 95 mass% or less, or 90 mass% or less.

The weight average molecular weight of the polymerizable compound B1 is 3,000 or more, preferably 3,000 to 300,000. The upper limit is preferably 200,000 or less, and 100,000 or less is even better. The lower limit is preferably 5,000 or more, and 10,000 or more is even better.

The group value (hereinafter, also referred to as C=C value) containing an ethylenically unsaturated bond of the polymerizable compound B1 is preferably 0.1 to 5.0 mmol/g. The upper limit is preferably 4.0 mmol/g or less, and more preferably 3.0 mmol/g or less. The lower limit is preferably 0.2 mmol/g or more, and more preferably 0.2 mmol/g or more. The C=C value of the polymerizable compound B1 is a numerical value indicating the molar amount of the group value containing an ethylenically unsaturated bond per 1 g of the solid content of the polymerizable compound B1. When it can be calculated from the structural formula of polymerizable compound B1, the value calculated from the structural formula is used. In addition, when it can be calculated from a structural formula and can be calculated from the raw material used for the synthesis of polymerizable compound B1, the value calculated from the added raw material is used. In addition, when the value of the group containing an ethylenically unsaturated bond of the polymerizable compound B1 cannot be calculated from the raw materials used for the synthesis of the polymerizable compound B1, the value measured by the hydrolysis method is used. Specifically, the component (a) containing the group moiety containing an ethylenically unsaturated bond was extracted from the polymerizable compound B1 by alkali treatment, and the content was measured by high performance liquid chromatography (HPLC). Calculate the formula. Moreover, when the said component (a) cannot be extracted from polymerizable compound B1 by alkali treatment, the value measured by NMR method (nuclear magnetic resonance) is used. Value of the group containing an ethylenically unsaturated bond of polymerizable compound B1 [mmol/g] = (content of component (a) [ppm]/molecular weight of component (a) [g/mol])/(polymerizable compound B1 Weighing value [g] × (solid content concentration of polymerizable compound B1 [mass %]/100) × 10)

It is also preferable that the polymerizable compound B1 is a compound containing an acid group. Examples of the acidic group include a carboxyl group, a sulfo group, and a phosphate group, with a carboxyl group being preferred. The acid value of the polymerizable compound B1 is preferably 20 to 200 mgKOH/g. The upper limit is preferably 150 mgKOH/g or less, and more preferably 100 mgKOH/g or less. The lower limit is preferably 30 mgKOH/g or more, and more preferably 35 mgKOH/g or more.

The polymerizable compound B1 is preferably a compound containing a repeating unit having a group containing an ethylenically unsaturated bond in a side chain. Examples of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain include a repeating unit represented by formula (b1-1). [Chemical formula 4]

In the formula, A ^b11 represents a trivalent linking group, L ^b11 represents a single bond or an n+1 valent linking group, Y ^b11 represents a group containing an ethylenically unsaturated bond, and n represents 1 or 2.

Examples of the trivalent linking group represented by A ^b11 include poly(meth)acrylic acid-based linking groups, polyalkyleneimine-based linking groups, polyester-based linking groups, polyurethane-based linking groups, and polyurea-based linking groups. , polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, etc., poly(meth)acrylic acid-based linking groups or polyalkyleneimine-based linking groups are preferred, poly(methyl) Acrylic linking groups are more preferred.

Examples of the n+1-valent linking group represented by L ^b11 include an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms) and an aromatic hydrocarbon group (preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms). ), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and groups combining two or more of these groups.

Examples of the group containing an ethylenically unsaturated bond represented by Y ^b11 include vinyl, (meth)allyl, (meth)acrylyl, (meth)acryloxy, (methyl) ) acryloxy group is preferred.

In the polymerizable compound B1, the content of the repeating unit having an ethylenically unsaturated bond in the side chain is preferably 1 mol% or more, and more preferably 1 to 80 mol% in the total repeating units of the polymerizable compound B1. good. The upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

It is preferable that the polymerizable compound B1 further contains a repeating unit having a graft chain in addition to a repeating unit having a group containing an ethylenically unsaturated bond in the side chain. That is, the polymerizable compound B1 is preferably a compound containing a repeating unit having a group containing an ethylenically unsaturated bond in a side chain and a repeating unit having a graft chain.

Furthermore, in this specification, a graft chain refers to a polymer chain branched and extended from the main chain of a repeating unit. As the graft chain, the number of atoms other than hydrogen atoms is preferably 40 to 10,000, the number of atoms other than hydrogen atoms is more preferably 50 to 2,000, and the number of atoms other than hydrogen atoms is still more preferably 60 to 500. .

The graft chain contains the repetition of at least one structure selected from the group consisting of polyester structure, polyether structure, poly(meth)acrylic acid structure, polystyrene structure, polyurethane structure, polyurea structure and polyamide structure. The unit is preferably a repeating unit containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, a poly(meth)acrylic acid structure and a polystyrene structure, and a repeating unit containing at least one structure selected from the group consisting of a polyester structure is preferred. The repeating unit of at least one structure in the group consisting of structure, polyether structure and poly(meth)acrylic acid structure is further preferred, and the repeating unit containing a polyester structure or a polyether structure is further preferred, and the repeating unit containing a poly(meth)acrylic acid structure is further preferred. Repeating units of an ester structure are particularly preferred.

Examples of the repeating unit of the polyester structure include repeating units of a structure represented by the following formula (G-1), formula (G-4) or formula (G-5). Examples of the repeating unit of the polyether structure include a repeating unit of a structure represented by the following formula (G-2). Examples of the repeating unit of the poly(meth)acrylic acid structure include a repeating unit of a structure represented by the following formula (G-3). Examples of the repeating unit of the polystyrene structure include a repeating unit of a structure represented by the following formula (G-6). [Chemical formula 5]

In the above formula, ^RG1 and ^RG2 each independently represent an alkylene group. The alkylene group represented by R ^G1 and R ^G2 is not particularly limited. A linear or branched alkylene group having 1 to 20 carbon atoms is preferred, and a linear or branched alkylene group having 2 to 16 carbon atoms is preferred. A chain alkylene group is more preferred, and a linear or branched alkylene group having 3 to 12 carbon atoms is still more preferred.

In the above formula, ^RG3 represents a hydrogen atom or a methyl group, Q ^G1 represents -O- or -NH-, ^LG1 represents a single bond or a bivalent linking group, and ^RG4 represents a hydrogen atom or a substituent. Examples of the bivalent linking group represented by L ^G1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms) and an alkyloxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms). ), oxyalkylenecarbonyl group (preferably oxyalkylenecarbonyl group with 1 to 12 carbon atoms), aryl group (preferably oxyalkylene carbonyl group with 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S- and groups combining two or more of these. Examples of the substituent represented by R ^G4 include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl sulfide group, and an aryl sulfide group. , Heterocyclic thioether group, etc.

^RG5 represents a hydrogen atom or a methyl group, ^{and RG6} represents an aryl group. The number of carbon atoms in the aryl group represented by R ^G6 is preferably 6 to 30, more preferably 6 to 20, and further preferably 6 to 12. The aryl group represented by R ^G6 may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl sulfide group, an aryl sulfide group, and a heterocyclic sulfide group. Key et al.

The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl sulfide group, an aryl sulfide group, and a heterocyclic sulfide group. Key et al. Among them, a group with a steric repulsion effect is preferred, and an alkyl group or alkoxy group having 5 to 24 carbon atoms is more preferred. The alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched are preferred.

The graft chain is represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a), formula (G-5a) or formula (G-6a) The structure is better, and the structure represented by formula (G-1a), formula (G-4a) or formula (G-5a) is even better. [Chemical formula 6]

In the above formula, R ^G1 and R ^G2 respectively represent an alkylene group, R ^G3 represents a hydrogen atom or a methyl group, Q ^G1 represents -O- or -NH-, L ^G1 represents a single bond or a divalent linking group, and R ^G4 represents hydrogen. Atoms or substituents, ^RG5 represents a hydrogen atom or a methyl group, ^RG6 represents an aryl group, W ¹⁰⁰ represents a hydrogen atom or a substituent, and n1 to n6 each independently represent an integer of 2 or more. ^RG1 to ^RG6 , Q ^G1 , and ^LG1 have the same meanings as ^RG1 to ^RG6 , Q ^G1 , and ^LG1 explained in the formulas (G-1) to (G-6), and the preferred ranges are also the same.

In formulas (G-1a) to (G-6a), W ¹⁰⁰ is preferably a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkyl sulfide group, an aryl sulfide group, and a heterocyclic sulfide group. Key et al. Among them, a group with a steric repulsion effect is preferred, and an alkyl group or alkoxy group having 5 to 24 carbon atoms is more preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched are preferred.

In formulas (G-1a) to (G-6a), n1 to n6 are each preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and still more preferably an integer of 8 to 60.

In formula (G-1a), when n1 is 2 or more, R ^G1 in each repeating unit may be the same or different. In addition, when ^RG1 contains two or more different repeating units, the arrangement of each repeating unit is not particularly limited, and may be any of random, alternating, and block. The same applies to Formula (G-2a) to Formula (G-6a). In addition, the graft chain is preferably a structure represented by Formula (G-1a), Formula (G-4a) or Formula (G-5a), and R ^G1 is preferably a structure containing two or more different repeating units.

Examples of the repeating unit having a graft chain include a repeating unit represented by formula (b1-2). [Chemical Formula 7]

In the formula, A ^b12 represents a trivalent linking group, L ^b12 represents a single bond or a divalent linking group, and Y ^b12 represents a graft chain.

Examples of the trivalent linking group represented by A ^b12 include poly(meth)acrylic acid-based linking groups, polyalkyleneimine-based linking groups, polyester-based linking groups, polyurethane-based linking groups, and polyurea-based linking groups. , polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, etc., poly(meth)acrylic acid-based linking groups or polyalkyleneimine-based linking groups are preferred, poly(methyl) Acrylic linking groups are more preferred.

Examples of the bivalent linking group represented by L ^b12 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an aryl group (preferably an aryl group having 6 to 20 carbon atoms), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and groups combining two or more of these groups.

Examples of the graft chain represented by Y ^b12 include the above-mentioned graft chains.

In the polymerizable compound B1, the weight average molecular weight of the repeating unit having a graft chain is preferably 1,000 or more, more preferably 1,000 to 10,000, and further preferably 1,000 to 7,500. In this specification, the weight average molecular weight of a repeating unit having a graft chain is a value calculated based on the weight average molecular weight of the raw material monomer used for polymerization of the repeating unit. For example, repeating units with grafted chains can be formed by polymerizing macromonomers. Here, the macromonomer refers to a polymer compound in which a polymerizable group is introduced at the end of the polymer. In the case where a macromonomer is used to form a repeating unit with a graft chain, the weight average molecular weight of the macromonomer is equivalent to the repeating unit with a graft chain.

When the polymerizable compound B1 contains a repeating unit having a graft chain, the content of the repeating unit having a graft chain is preferably 1 to 60 mol% in the total repeating units of the polymerizable compound B1. The upper limit is preferably 50 mol% or less, and more preferably 40 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

It is also preferable that the polymerizable compound B1 further contains a repeating unit having an acid group in addition to a repeating unit having an ethylenically unsaturated bond-containing group in the side chain. Examples of acidic groups include carboxyl groups, sulfo groups, phosphate groups, and the like.

Examples of the repeating unit having an acid group include a repeating unit represented by formula (b1-3). [Chemical formula 8]

In the formula, A ^b13 represents a trivalent linking group, L ^b13 represents a single bond or an n+1 valent linking group, Y ^b13 represents an acid group, and n represents 1 or 2.

Examples of the trivalent linking group represented by A ^b13 include poly(meth)acrylic acid-based linking groups, polyalkyleneimine-based linking groups, polyester-based linking groups, polyurethane-based linking groups, and polyurea-based linking groups. , polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, etc., poly(meth)acrylic acid-based linking groups or polyalkyleneimine-based linking groups are preferred, poly(methyl) Acrylic linking groups are more preferred.

Examples of the n+1-valent linking group represented by L ^b13 include an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 12 carbon atoms) and an aromatic hydrocarbon group (preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms). ), -NH-, -SO-, -SO ₂ -, -CO-, -O-, -COO-, OCO-, -S-, and groups combining two or more of these groups.

Examples of the acid group represented by Y ^b13 include a carboxyl group, a sulfo group, and a phosphate group.

When the polymerizable compound B1 contains a repeating unit having an acid group, the content of the repeating unit having an acid group in the total repeating units of the polymerizable compound B1 is preferably 1 to 80 mol%, and 5 to 80 mol% is More preferably, 10 to 80 mol% is still more preferably.

The polymerizable compound B1 may contain a repeating unit derived from a monomer component including a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may also be referred to as For "ether dimer".).

[Chemical formula 9]

In the formula (ED1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent. [Chemical formula 10] In formula (ED2), R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms. For details of the formula (ED2), please refer to the description of Japanese Patent Application Laid-Open No. 2010-168539, and this content is incorporated into this specification.

Regarding specific examples of the ether dimer, for example, the description in paragraph 0317 of Japanese Patent Application Laid-Open No. 2013-029760 can be referred to, and this content is incorporated into this specification.

The polymerizable compound B1 may contain a repeating unit derived from the compound represented by formula (X). [Chemical formula 11] In the formula, R ¹ represents a hydrogen atom or a methyl group, R ²¹ and R ²² each independently represent an alkylene group, and n represents an integer of 0 to 15. The number of carbon atoms in the alkylene group represented by R ²¹ and R ²² is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. n represents an integer of 0 to 15, and an integer of 0 to 5 is preferred, an integer of 0 to 4 is more preferred, and an integer of 0 to 3 is further preferred.

It is also preferable that the polymerizable compound B1 is a resin containing a repeating unit represented by formula (Ac-2). [Chemical formula 12] In formula (Ac-2), Ar ¹⁰ represents a group containing an aromatic carboxyl group, L ¹¹ represents -COO- or -CONH-, L ¹² represents a trivalent linking group, and P ¹⁰ represents a group containing (having ethylene on the side chain) Polymer chain of repeating units (groups of sexually unsaturated bonds).

Examples of the aromatic carboxyl group-containing group represented by Ar ¹⁰ in the formula (Ac-2) include a structure derived from an aromatic tricarboxylic anhydride, a structure derived from an aromatic tetracarboxylic anhydride, and the like. Examples of aromatic tricarboxylic acid anhydrides and aromatic tetracarboxylic acid anhydrides include compounds with the following structures. [Chemical formula 13]

In the above formula, Q ¹ represents a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C (CF ₃ ) ₂ -, and is represented by the following formula (Q-1) or a group represented by the following formula (Q-2). [Chemical formula 14]

The aromatic carboxyl group-containing group represented by Ar ¹⁰ may have an ethylenically unsaturated bond-containing group. Specific examples of the aromatic carboxyl group-containing group represented by Ar ¹⁰ include a group represented by formula (Ar-11), a group represented by formula (Ar-12), a group represented by formula (Ar-13) ) represents groups, etc. [Chemical formula 15]

In formula (Ar-11), n1 represents an integer from 1 to 4, 1 or 2 is preferred, and 2 is more preferred. In formula (Ar-12), n2 represents an integer of 1 to 8, and an integer of 1 to 4 is preferred, 1 or 2 is more preferred, and 2 is further preferred. In the formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4. An integer of 0 to 2 is preferred, 1 or 2 is more preferred, and 1 is further preferred. Among them, at least one of n3 and n4 is an integer greater than 1. In the formula (Ar-13), Q ¹ represents a single bond, -O-, -CO-, -COOCH ₂ CH ₂ OCO-, -SO ₂ -, -C (CF ₃ ) ₂ -. From the above formula (Q- The group represented by 1) or the group represented by the above formula (Q-2). In the formulas (Ar-11) to (Ar-13), *1 represents the bonding position with L ¹⁰ .

L ¹¹ in formula (Ac-2) represents -COO- or -CONH-, and -COO- is preferred.

Examples of the trivalent linking group represented by L ¹² in the formula (Ac-2) include hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and combinations thereof. A group consisting of 2 or more of them. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and further preferably 1 to 15. The aliphatic hydrocarbon group may be linear, branched, or cyclic. The number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include hydroxyl group and the like. The trivalent linking group represented by L ¹² is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2). [Chemical formula 16]

In formula (L12-1), L ^12b represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (Ac-2), and *2 represents the bonding position with L 11 of formula (Ac-2). P ¹⁰ bonding position. Examples of the trivalent linking group represented by L ^12b include a hydrocarbon group; a hydrocarbon group is obtained by combining a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. A group formed by a hydrocarbon group or a group formed by combining a hydrocarbon group and -O- is preferred.

In formula (L12-2), L ^12c represents a trivalent linking group, X ¹ represents S, *1 represents the bonding position with L ¹¹ of formula (Ac-2), and *2 represents the bonding position with L 11 of formula (Ac-2) P ¹⁰ bonding position. Examples of the trivalent linking group represented by L ^12c include a hydrocarbon group; a hydrocarbon group is obtained by combining a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. groups, etc., hydrocarbon groups are preferred.

P ¹⁰ in the formula (Ac-2) represents a polymer chain containing repeating units (having a group containing an ethylenically unsaturated bond in the side chain).

Examples of the polymer chain represented by P ¹⁰ include polyester structures, polyether structures, poly(meth)acrylic acid structures, polystyrene structures, polyurethane structures, polyurea structures, and polyamide structures. A polymer chain of repeating units of at least one structure in the group. Examples of the repeating unit of the polyester structure include repeating units of the structure represented by the above formula (G-1), formula (G-4) or formula (G-5). Examples of the repeating unit of the polyether structure include the repeating unit of the structure represented by the above formula (G-2). Examples of the repeating unit of the poly(meth)acrylic acid structure include the repeating unit of the structure represented by the above formula (G-3). Examples of the repeating unit of the polystyrene structure include the repeating unit of the structure represented by the above formula (G-6).

Examples of the repeating unit having a group containing an ethylenically unsaturated bond in the side chain of the polymer chain represented by P ¹⁰ include the repeating unit represented by the above formula (b1-1). The proportion of repeating units having a group containing an ethylenically unsaturated bond in the side chain among the total repeating units constituting ^P10 is preferably 1 mol% or more, and more preferably 1 to 80 mol%. The upper limit is preferably 70 mol% or less, and more preferably 60 mol% or less. The lower limit is preferably 2 mol% or more, and more preferably 5 mol% or more.

It is also preferred that the polymer chain represented by P ¹⁰ has a repeating unit containing an acid group. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, phenolic hydroxyl groups, and the like. Examples of the repeating unit having an acid group include the repeating unit represented by the above formula (b1-3). When the polymer chain represented by P ¹⁰ contains repeating units with acidic groups, the proportion of repeating units with acidic groups in the total repeating units constituting ^P10 is preferably 1 to 80 mol%, and 5 to 80 mol%. A molar % is more preferable, and a mole % of 10-80 mol% is further more preferable.

The weight average molecular weight of the polymer chain represented by P ¹⁰ is preferably 500 to 20,000. A lower limit of 1,000 or more is preferred. The upper limit is preferably 10,000 or less, more preferably 5,000 or less, and further preferably 3,000 or less.

(Polymerizable compound B2) The photosensitive composition of the present invention may further contain a polymerizable compound B2 having a molecular weight of less than 3,000.

The polymerizable compound B2 may be in any chemical form such as a monomer, a prepolymer, or an oligomer, but a monomer is preferred. The molecular weight of the polymerizable compound B2 is preferably 100 to 2,500. The upper limit is preferably 2,000 or less, and 1,500 or less is even better. The lower limit is preferably 150 or more, and 250 or more is even better.

From the viewpoint of storage stability of the photosensitive composition, the group value (C=C value) containing an ethylenically unsaturated bond of the polymerizable compound B2 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 still 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 still more preferably 8 mmol/g or less. The C=C value of B2 of the polymerizable compound is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.

The polymerizable compound B2 is preferably a compound containing three or more groups containing an ethylenically unsaturated bond, and more preferably a compound containing four or more groups containing an ethylenically unsaturated bond. From the viewpoint of storage stability of the photosensitive composition, the upper limit of the groups containing ethylenically unsaturated bonds is preferably 15 or less, more preferably 10 or less, and still more preferably 6 or less. In addition, the polymerizable compound B2 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, a 3- to 6-functional (meth)acrylate compound is particularly preferred. Specific examples of the polymerizable compound B2 include paragraphs 0095 to 0108 of Japanese Patent Application Laid-Open No. 2009-288705, paragraph 0227 of Japanese Patent Application Laid-Open No. 2013-029760, and paragraphs 0254 to 0257 of Japanese Patent Application Laid-Open No. 2008-292970. Paragraphs, Paragraphs 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224, Paragraph 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048367, Japanese Patent Publication No. 6057891, Japanese Patent Publication No. 6031807 Compounds described in , these contents are incorporated into this specification.

Examples of the polymerizable compound B2 include dipenterythritol tri(meth)acrylate (commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipenterythritol tetra(meth)acrylate base) acrylate (commercially available product, KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dineopenterythritol penta(meth)acrylate (commercially available product, KAYARAD D-310; Nippon Kayaku Co., Ltd.), dipenterythritol hexa(meth)acrylate (commercially available, KAYARAD DPHA; Nippon Kayaku Co., Ltd., NK ESTER A-DPH-12E; SHIN-NAKAMURA CHEMICAL Co., Ltd.) and compounds with structures in which the (meth)acrylyl groups are bonded via ethylene glycol and/or propylene glycol residues (for example, SR454 and SR499 commercially available from SARTOMER Company, Inc.) are Better. In addition, as the polymerizable compound, diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available as M-460; manufactured by TOAGOSEI CO., LTD.), neopentyl tetrahydrol Acrylate (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd., NK ESTER A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (Nippon Kayaku Co., Ltd.), ARONIX TO-2349 (TOAGOSEI CO., LTD.), NK Oligo UA-7200 (SHIN-NAKAMURA CHEMICAL Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (Made by KYOEISHA CHEMICAL Co., LTD.), 8UH-1006, 8UH-1012 (The above are manufactured by Taisei Fine Chemical Co., Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL Co., LTD.), etc.

Polymerizable compound B2 can also use trimethylolpropane tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, and trimethylolpropane ethylene oxide-modified tri(meth)acrylate. Trifunctional (meth)acrylate compounds such as (meth)acrylate, ethylene oxide isocyanurate modified tri(meth)acrylate, and neopentylerythritol tri(meth)acrylate are also relatively good. Commercially available products of trifunctional (meth)acrylate compounds include ARONIX M-309, M-310, M-321, M-350, M-360, M-313, M-315, M- 306, M-305, M-303, M-452, M-450 (manufactured by TOAGOSEI CO., LTD.), NK ESTER A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A -TMM-3L, A-TMM-3LM-N, A-TMPT, TMPT (manufactured by SHIN-NAKAMURA CHEMICAL Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 ( Manufactured by Nippon Kayaku Co., Ltd.), etc.

As the polymerizable compound B2, a compound having an acid group can also be used. Examples of the acidic group include a carboxyl group, a sulfo group, a phosphate group, and the like, with a carboxyl group being preferred. Examples of commercially available polymerizable compounds having an acid group include ARONIX M-510, M-520, ARONIX TO-2349 (manufactured by TOAGOSEI CO., LTD.), and the like. The preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH/g, more preferably 5 to 30 mgKOH/g.

As the polymerizable compound B2, a compound having a caprolactone structure can also be used. Examples of commercially available polymerizable compounds having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.).

As the polymerizable compound B2, a polymerizable compound having an alkyloxy group can also be used. The polymerizable compound having an alkyleneoxy group is preferably a polymerizable compound having an vinyloxy group and/or a propyleneoxy group, more preferably a polymerizable compound having an vinyloxy group, and a polymerizable compound having 4 to 20 vinyloxy groups. A 3- to 6-functional (meth)acrylate compound is further preferred. Examples of commercially available polymerizable compounds having an alkyleneoxy group include tetrafunctional (meth)acrylate SR-494 having four vinyloxy groups manufactured by Sartomer Company, Inc. and Nippon Kayaku Co., Ltd. .Preparation of KAYARAD TPA-330, a trifunctional (meth)acrylate with three isobutyleneoxy groups.

As the polymerizable compound B2, a polymerizable compound having a fluorine skeleton can also be used. The polymerizable compound having a fluorine skeleton is preferably a bifunctional polymerizable compound. Examples of the polymerizable compound having a fluorine skeleton include compounds having a partial structure represented by the following formula (Fr). [Chemical formula 17]

In the formula, wavy lines represent bonding bonds, R ^f1 and R ^f2 each independently represent a substituent, and m and n each independently represent an integer from 0 to 5. When m is 2 or more, m R ^f1 may be the same or different, and two R ^f1 among m R ^f1 may be bonded to each other to form a ring. When n is 2 or more, n R ^f2 may be the same or different, and two R ^f2 among n R ^f2 may be bonded to each other to form a ring. Examples of the substituent represented by R ^f1 and R ^f2 include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR ^f11 , -COR ^f12 , -COOR ^f13 , -OCOR ^f14 , -NR ^f15 R ^f16 , -NHCOR ^f17 , -CONR ^f18 R ^f19 , -NHCONR ^f20 R ^f21 , -NHCOOR ^f22 , -SR ^f23 , -SO ₂ R ^f24 , -SO ₂ OR ^f25 , -NHSO ₂ R ^f26 or -SO ₂ NR ^f27 R ^f28 . R ^f11 to R ^f28 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.

Specific examples of the polymerizable compound having a fluorine skeleton include compounds having the following structures. Examples of commercially available polymerizable compounds having a fluorine skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomer having a fluorine skeleton). wait. [Chemical formula 18]

As the polymerizable compound B2, it is also preferred to use a compound that does not substantially contain environmentally controlled substances such as toluene. Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and the like.

The content of the polymerizable compound in the total solid content of the photosensitive composition is preferably 5 to 50% by mass. The upper limit is preferably 45 mass% or less, and more preferably 40 mass% or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. In addition, the content of the above-mentioned polymerizable compound B1 in the total solid content of the photosensitive composition is preferably 5 to 50% by mass. The upper limit is preferably 45 mass% or less, and more preferably 40 mass% or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more. Moreover, the content of the polymerizable compound B1 is preferably 100 to 5000 parts by mass relative to 100 parts by mass of the specific oxime compound described below. The upper limit is preferably 3,000 parts by mass or less, and more preferably 2,000 parts by mass or less. The lower limit is preferably 200 parts by mass or more, and more preferably 300 parts by mass or more. When the photosensitive composition of the present invention contains the above-mentioned polymerizable compound B2, the content of the above-mentioned polymerizable compound B2 in the total solid content of the photosensitive composition is preferably 1 to 30 mass %. The upper limit is preferably 20 mass% or less, and more preferably 15 mass% or less. The lower limit is preferably 2 mass% or more, and more preferably 3 mass% or more. Moreover, the content of the polymerizable compound B2 is preferably 50 to 1,000 parts by mass relative to 100 parts by mass of the specific oxime compound described below. The upper limit is preferably 700 parts by mass or less, and more preferably 500 parts by mass or less. The lower limit is preferably 75 parts by mass or more, and more preferably 100 parts by mass or more. The photosensitive composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types of polymerizable compounds. When two or more types of polymerizable compounds are contained, the total amount is preferably within the above range.

＜＜Photopolymerization initiator＞＞ The photosensitive composition of the present invention contains a photopolymerization initiator. The photosensitive composition of the present invention contains a compound represented by formula (1) as a photopolymerization initiator. Hereinafter, the compound represented by formula (1) will also be called a specific oxime compound.

[Chemical formula 19] In formula (1), X ¹ represents a bivalent linking group containing at least one selected from the group consisting of aromatic rings and heterocyclic rings, R ¹ represents a hydrogen atom or a hydroxyl group, and R ² represents an alkyl group or an aryl group. , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group, Alk ¹ and Alk ² each independently represent an alkyl group, R ³ and R ⁴ may be bonded to form a ring, Alk ¹ and Alk ² may be bonded to form a Ring, n represents 0 or 1.

X ¹ in Formula (1) represents a bivalent linking group containing at least one selected from the group consisting of aromatic rings and heterocyclic rings. Examples of X ¹ include divalent aromatic ring groups, divalent heterocyclic groups, divalent groups in which two or more aromatic rings are bonded via a single bond or a linking group, and two or more heterocyclic groups. A bivalent group formed by connecting an aromatic ring and a heterocyclic ring through a single bond or a connecting group. Examples of the connecting group include -CH ₂ -, -O-, -CO-, -S-, -NR ^x -, groups combining these, and the like. R ^x represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

X ¹ in formula (1) is preferably a group represented by any one of formulas (X-1) to (X-13). Since a film with more excellent adhesion can be formed, the formula ( Groups represented by X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8) are more preferred, and are represented by formula (X-2) or formula ( A group represented by formula (X-6) is further preferred, and a group represented by formula (X-6) is particularly preferred. [Chemical formula 20] In the formula, R ^X1 to R ^X9 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group.

The number of carbon atoms in the alkyl group represented by R ^X1 to R ^X9 is preferably 1 to 15, more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heterocyclic group, and the like.

The carbon number of the alkenyl group represented by R ^X1 to R ^X9 is preferably 2 to 15, more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heterocyclic group, and the like.

The number of carbon atoms in the alkynyl group represented by R ^X1 to R ^X9 is preferably 2 to 15, more preferably 2 to 10. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, a heterocyclic group, and the like.

The number ^of carbon atoms in the aryl group represented by R ^X1 to R The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, and the like.

The heterocyclic group represented by R ^X1 to R ^X9 is preferably a 5-membered ring or a 6-membered ring. The heteroatoms having a heterocyclic group are preferably oxygen atoms, nitrogen atoms and sulfur atoms. The number of heteroatoms having a heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like.

R ¹ in the formula (1) represents a hydrogen atom or a hydroxyl group, preferably a hydroxyl group. The acyl group represented by R ¹ is preferably a group represented by -C(O)-R ¹⁰¹ . R ¹⁰¹ represents an aryl group or a heterocyclic group, with an aryl group being preferred.

The carbon number of the aryl group represented by R ¹⁰¹ is preferably 6 to 20, more preferably 6 to 12. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heterocyclic group, and the like. The aryl group represented by R ¹⁰¹ is preferably a phenyl group, a methylphenyl group or a naphthyl group, and more preferably a methylphenyl group or a naphthyl group.

The heterocyclic group represented by R ¹⁰¹ is preferably a 5-membered ring or a 6-membered ring. The heteroatoms having a heterocyclic group are preferably oxygen atoms, nitrogen atoms and sulfur atoms. The number of heteroatoms having a heterocyclic group is preferably 1 to 3. The heterocyclic group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and the like.

R ² in the formula (1) represents an alkyl group or an aryl group, and an alkyl group is preferred because of its high reactivity in generating radicals. The number of carbon atoms of the alkyl group represented by R ² is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be any one of straight chain, branched chain and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The alkyl group may have a substituent, but an unsubstituted alkyl group is preferred. The alkyl group represented by R ² is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. The aryl group represented by R ² preferably has a carbon number of 6 to 20, more preferably 6 to 12, further preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent, but an unsubstituted aryl group is preferred.

R ³ and R ⁴ in the formula (1) each independently represent a hydrogen atom or an alkyl group, preferably a hydrogen atom. The carbon number of the alkylene group represented by R ³ and R ⁴ is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be any one of straight chain, branched chain and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The alkyl group may have a substituent, but an unsubstituted alkyl group is preferred. R ³ and R ⁴ may be bonded to form a ring. The formed ring is preferably a 5- or 6-membered ring, and more preferably a 5- or 6-membered aliphatic hydrocarbon ring.

Alk ¹ and Alk ² in the formula (1) each independently represent an alkyl group. The carbon number of the alkylene group represented by R ³ and R ⁴ is preferably 1 to 15, more preferably 1 to 10, further preferably 1 to 5, and still more preferably 1 to 3. The alkyl group can be any one of straight chain, branched chain and cyclic. Straight chain or branched chain is preferred, and straight chain is more preferred. The alkyl group may have a substituent, but an unsubstituted alkyl group is preferred. Alk ¹ and Alk ² may be bonded to form a ring, and a ring is preferably formed. The formed ring is preferably a 5- or 6-membered ring, more preferably a 5- or 6-membered aliphatic hydrocarbon ring, and even more preferably a cyclopentane ring or a cyclohexane ring.

n in formula (1) represents 0 or 1, with 0 being preferred.

Specific examples of the specific oxime compound include compounds I-1 to I-21 described in the Examples described below, compounds described in paragraphs 0092 to 0096 of Japanese Patent Application Laid-Open No. 2012-113104, and Japanese Patent Application Laid-Open No. 2012- Compounds described in paragraph 0041 of Publication No. 189997, etc.

The content of the specific oxime compound in the total mass of the photopolymerization initiator contained in the photosensitive composition is preferably 50 mass% or more, more preferably 60 mass% or more, and still more preferably 70 mass% or more. The upper limit can be set to 100 mass% or less.

The photopolymerization initiator contained in the photosensitive composition of the present invention may be substantially only the above-mentioned specific oxime compound, or may further contain a photopolymerization initiator other than the above-mentioned specific oxime compound (hereinafter also referred to as Other photopolymerization initiators).

When the photopolymerization initiator is substantially only a specific oxime compound, it is preferable from the viewpoint of high exposure sensitivity. In addition, in this specification, the photopolymerization initiator is essentially only a specific oxime compound. It means that the specific oxime compound in the photopolymerization initiator is 99 mass % or more, preferably 99.9 mass % or more, and it is only the specific oxime compound. Compounds are better.

When the photopolymerization initiator further contains other photopolymerization initiators in addition to the specific oxime compound, the exposure sensitivity can be adjusted. When the photopolymerization initiator further contains other photopolymerization initiators in addition to the specific oxime compound, the content of the other photopolymerization initiator is preferably 5 to 50 parts by mass relative to 100 parts by mass of the specific oxime compound. The lower limit is preferably 10 parts by mass or more, and more preferably 15 parts by mass or more. The upper limit is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less.

Examples of other photopolymerization initiators include halogenated hydrocarbon derivatives (for example, compounds having a trioxadiazole skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbisimidazole compounds, oxime compounds, Organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the perspective of exposure sensitivity, photopolymerization initiators include trihalomethyltrifluoroethylene compounds, benzyldimethyl ketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, and oxidation compounds. Phosphine compounds, metallocene compounds, oxime compounds, hexaarylbisimidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethane compounds Preferred are ethadiazole compounds and 3-aryl substituted coumarin compounds, and compounds selected from the group consisting of oxime compounds, α-hydroxyketone compounds, α-aminoketone compounds and acylphosphine compounds are more preferred, and oxime compounds are more preferred. For further improvement. Examples of the photopolymerization initiator include compounds described in paragraphs 0065 to 0111 of Japanese Patent Application Laid-Open No. 2014-130173, compounds described in Japanese Patent Publication No. 6301489, and MATERIAL STAGE 37 to 60p, vol. 19 , the peroxide-based photopolymerization initiator described in No. 3, 2019, the photopolymerization initiator described in International Publication No. 2018/221177, the photopolymerization initiator described in International Publication No. 2018/110179 , the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-043864, the photopolymerization initiator described in Japanese Patent Application Publication No. 2019-044030, the peroxide system described in Japanese Patent Application Publication No. 2019-167313 Initiator, the aminoacetophenone-based initiator having an oxazolidinyl group described in Japanese Patent Application Laid-Open No. 2020-055992, the oxime-based photopolymerization initiator described in Japanese Patent Application Publication No. 2013-190459, The polymer described in Japanese Patent Application Publication No. 2020-172619, the compound represented by Formula 1 described in International Publication No. 2020/152120, the compound described in Japanese Patent Application Publication No. 2021-181406, Japanese Patent Application Publication No. 2022-013379 The photopolymerization initiator described in Japanese Patent Application Publication No. 2022-015747, the compound represented by formula (1) described in Japanese Patent Application Publication No. 2021-507058, the fluorine-containing fluorine-containing oxime ester photoinitiator described in Japanese Patent Application Publication No. 2021-507058 starter, etc.

Specific examples of hexaarylbisimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-di Phenyl-1,1'-bisimidazole, etc.

Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (the above products are manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (the above products are manufactured by BASF). manufactured by the company), etc. Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, and Omnirad 379EG (the above are manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, and Irgacure 379EG (the above are manufactured by IGM Resins B.V.). Manufactured by BASF Corporation), etc. Examples of commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (the above manufactured by IGM Resins B.V.), Irgacure 819, and Irgacure TPO (the above manufactured by BASF), and the like.

Examples of the oxime compound include compounds described in Japanese Patent Application Publication No. 2001-233842, compounds described in Japanese Patent Application Publication No. 2000-080068, compounds described in Japanese Patent Application Publication No. 2006-342166, and J.C.S. Perkin II ( Compounds described in J.C.S. Perkin II (1979, pp. 156-162), Journal of Photopolymer Science and Technology (1995, pp. 202-232) Compounds, compounds described in Japanese Patent Application Publication No. 2000-066385, compounds described in Japanese Patent Application Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, Japanese Patent Application Publication No. 2017-019766 Compounds described in, Compounds described in Japanese Patent Publication No. 6065596, Compounds described in International Publication No. 2015/152153, Compounds described in International Publication No. 2017/051680, Compounds described in Japanese Patent Publication No. 2017-198865 Compounds, compounds described in paragraphs 0025 to 0038 of International Publication No. 2017/164127, compounds described in International Publication No. 2013/167515, compounds represented by the general formula (1) of Japanese Patent Application Laid-Open No. 2021-173858 and compounds described in paragraphs 0022 to 0024, compounds represented by the general formula (1) of Japanese Patent Application Laid-Open No. 2021-170089, compounds described in paragraphs 0117 to 0120, and the like. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetyloxyiminobutan-2-one, and 3-propyloxyiminobutan-2-one. Aminobutan-2-one, 2-acetyloxyiminopentan-3-one, 2-acetyloxyiminopentan-1-one, 2-benzylpropan-1-one Oxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1 -Phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyl oxime), etc. Examples of commercially available products include Irgacure-OXE01, Irgacure-OXE02, and Irgacure-OXE03 (the above are manufactured by BASF), TR-PBG-301, TR-PBG-327 (manufactured by TRONLY), Adeka Optomer N-1919 ( Photopolymerization initiator 2) manufactured by ADEKA CORPORATION and described in Japanese Patent Application Publication No. 2012-014052. In addition, as the oxime compound, it is also preferable to use a non-coloring compound or a compound with high transparency and resistance to discoloration. Examples of commercially available products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (the above are manufactured by ADEKA CORPORATION).

As other photopolymerization initiators, oxime compounds having a fluorine ring can also be used. Specific examples of the oxime compound having a fluorine ring include the compounds described in Japanese Patent Application Laid-Open No. 2014-137466, the compounds described in Japanese Patent Publication No. 6636081, and the compounds described in Korean Patent Publication No. 10-2016-0109444. The compounds described are the benzylaminoketone photoinitiator described in Japanese Patent Publication No. 2020-507664, and the oxime ester compound described in International Publication No. 2021/023144.

As another photopolymerization initiator, an oxime compound having at least one benzene ring of a carbazole ring serving as the skeleton of a naphthalene ring can also be used. Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.

As another photopolymerization initiator, an oxime compound having a fluorine atom can also be used. Specific examples of the oxime compound having a fluorine atom include compounds described in Japanese Patent Application Publication No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and Japanese Patent Application Publication No. 2013- Compound (C-3) described in Publication No. 164471, etc.

As another photopolymerization initiator, 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 the oxime compound having a nitro group include compounds described in paragraphs 0031 to 0047 of Japanese Patent Application Laid-Open No. 2013-114249 and paragraphs 0008 to 0012 and 0070 to 0079 of Japanese Patent Application Laid-Open No. 2014-137466, The compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARKLS NCI-831 (manufactured by ADEKA CORPORATION).

As another photopolymerization initiator, an oxime compound having a benzofuran skeleton can also be used. Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.

As another photopolymerization initiator, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton can also be used. Examples of such photopolymerization initiators include compounds described in International Publication No. 2019/088055.

As another photopolymerization initiator, an oxime compound (hereinafter also referred to as an oxime compound OX) having an aromatic ring group Ar ^OX1 in which an electron-withdrawing group is introduced into the aromatic ring can also be used. Examples of the electron-withdrawing group of the aromatic ring group Ar ^OX1 include a hydroxyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, and an alkylsulfinyl group. Arylsulfonyl group, cyano group, acyl group and nitro group are preferred, acyl group is more preferred, and benzyl group is further preferred. The benzoyl group may have a substituent. As a substituent, halogen atom, cyano group, nitro group, hydroxyl group, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkenyl group, alkyl sulfanyl group (sulfanyl group) , arylthio group, acyl group or amine group is preferred, alkyl group, alkoxy group, aryl group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group or amine group is More preferably, an alkoxy group, an alkylthio group or an amino group is still more preferably.

Specific examples of the oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

As other photopolymerization initiators, bifunctional or trifunctional or higher photoradical polymerization initiators can be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained. Furthermore, when a compound with an asymmetric structure is used, the crystallinity decreases and the solubility in a solvent or the like increases, making it difficult to precipitate over time, thereby improving the storage stability of the photosensitive composition. Specific examples of the bifunctional or trifunctional or higher-functional photoradical polymerization initiator include Japanese Patent Application Publication No. 2010-527339, Japanese Patent Application Publication No. 2011-524436, International Publication No. 2015/004565, and Japanese Patent Application Publication No. 2015/004565. The dimer of the oxime compound described in paragraphs 0407 to 0412 of Table 2016-532675, paragraphs 0039 to 0055 of International Publication No. 2017/033680, the compound (E) described in Japanese Patent Publication No. 2013-522445, and Compound (G), Cmpd1 to 7 described in International Publication No. 2016/034963, oxime ester photoinitiator described in paragraph 0007 of Japanese Patent Application Publication No. 2017-523465, Japanese Patent Application Publication No. 2017-167399 The photoinitiator described in paragraphs 0020 to 0033, the photopolymerization initiator (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Laid-Open No. 2017-151342, the oxime ester photoinitiator described in Japanese Patent No. 6469669 starter, etc.

The content of the photopolymerization initiator in the total solid content of the photosensitive composition is preferably 0.5 to 20% by mass. The lower limit is preferably 1 mass % or more, more preferably 2 mass % or more, 3 mass % or more is still more preferably, and 3.5 mass % or more is still more preferably. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. The content of the specific oxime compound in the total solid content of the photosensitive composition is preferably 0.5 to 20% by mass. The lower limit is preferably 1 mass % or more, more preferably 2 mass % or more, 3 mass % or more is still more preferably, and 3.5 mass % or more is still more preferably. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. In the photosensitive composition of the present invention, only one type of photopolymerization initiator may be used, or two or more types of photopolymerization initiators may be used. When two or more types are used, the total amount is preferably within the above range.

＜＜Pigment Derivatives＞＞ The photosensitive composition of the present invention can contain a pigment derivative. When the color material used in the photosensitive composition of the present invention contains a pigment, it is preferred that the photosensitive composition of the present invention further contains a pigment derivative. Pigment derivatives can be used, for example, as dispersing aids. Examples of the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a tri-hydroxy structure and an acid group or a base.

Examples of the dye structure include a quinoline dye structure, a benzimidazolone dye structure, a benzoisoindole dye structure, a benzothiazole dye structure, an imine dye structure, a squaraine dye structure, and a ketone dye structure. Onium pigment structure, oxocyanine pigment structure, pyrrolopyrrole pigment structure, diketopyrrolopyrrole pigment structure, azo pigment structure, methimine pigment structure, phthalocyanine pigment structure, naphthalocyanine pigment structure, anthraquinone pigment structure , quinacridone pigment structure, di-isoindolinone pigment structure, quinacridone pigment structure, perylene pigment structure, thioindigo pigment structure, thioindigo pigment structure, isoindoline pigment structure, isoindolinone pigment structure, quinacridone pigment structure Phenozoline pigment structure, dithiol pigment structure, triarylmethane pigment structure, pyrromethane pigment structure, etc.

Examples of the acid group having a pigment derivative include a carboxyl group, a sulfo group, a phosphate group, a phosphonic acid group, a phenolic hydroxyl group, and the like.

Examples of the base having a pigment derivative include an amino group, a pyridyl group and a salt thereof, an ammonium group salt, and a phthalimide methyl group. Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonic acid ions, phenoxide ions, and the like.

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

Specific examples of the pigment derivatives include the compounds described in Paragraph 0124 of International Publication No. 2022/085485, the benzimidazolone compounds described in Japanese Patent Application Laid-Open No. 2018-168244, or their salts. As the pigment derivative, a compound having an isoindoline skeleton described in the general formula (1) of Japanese Patent No. 6996282 can be used.

The content of the pigment derivative is preferably 1 to 30 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 2 parts by mass or more, and more preferably 4 parts by mass or more. The upper limit is preferably 15 parts by mass or less, and more preferably 10 parts by mass or less. Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used in combination, the total amount is preferably within the above range.

＜＜Polyalkyleneimine＞＞ The photosensitive composition of the present invention may also contain polyalkyleneimine. Polyalkyleneimines are used, for example, as dispersion aids for pigments. Polyalkyleneimine refers to a polymer obtained by ring-opening polymerization of alkyleneimine, and is a polymer having at least a secondary amine group. In addition to the secondary amine group, the polyalkyleneimine may also contain a primary amine group or a tertiary amine group. The polyalkyleneimine is preferably a polymer having a branched chain structure containing primary amine groups, secondary amine groups and tertiary amine groups respectively. The number of carbon atoms in the alkylene imine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2. Specific examples of alkylene imine include ethylene imine, propylene imine, 1,2-butylene imine, 2,3-butylene imine, and the like. Preferred is propylene imine, and even more preferred is propylene imine.

The molecular weight of the polyalkyleneimine is preferably 200 or more, and more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less, and particularly preferably 2,000 or less. Furthermore, regarding the value of the molecular weight of the polyalkyleneimine, when the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, when the molecular weight of a specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. In addition, when it is impossible or difficult to measure using the boiling point elevation method, the value of the number average molecular weight measured using the viscometry method is used. In addition, when it is impossible or difficult to measure by viscometry, the polystyrene-converted number average molecular weight value measured by GPC (gel permeation chromatography) method is used.

The amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and still more preferably 15 mmol/g or more.

The polyalkyleneimine is particularly preferably polyethyleneimine. Relative to the total of primary amine groups, secondary amine groups and tertiary amine groups, polyethyleneimine preferably contains more than 10 mol% of primary amine groups, and more preferably contains more than 20 mol% of primary amine groups. , it is further preferred to contain more than 30 mol% of primary amine groups. Commercially available products of polyethyleneimine include EPOMIN SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (the above are manufactured by NIPPON SHOKUBAI CO., LTD.) wait.

The content of the polyalkyleneimine in the total solid content of the photosensitive composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and further preferably 1 mass% or more. The upper limit is preferably 4.5 mass% or less, more preferably 4 mass% or less, and still more preferably 3 mass% or less. In addition, the content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and more preferably 8 parts by mass or less. Only one type of polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

＜＜Resin＞＞ The photosensitive composition of the present invention may further contain resins other than the above-mentioned polymerizable compound B1. For example, the resin is blended for the purpose of dispersing pigments in a photosensitive composition and the purpose of a binder. In addition, resins mainly used to disperse pigments and the like in photosensitive compositions are also called dispersants. However, this use of the resin is an example, and the resin can be used for purposes other than such uses.

Examples of the resin include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, and polypropylene resin. Resin, polyether ester resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin , siloxane resin, etc. In addition, as the resin, the resin described in the Examples of International Publication No. 2016/088645, the resin described in Japanese Patent Application Laid-Open No. 2017-057265, the resin described in Japanese Patent Application Laid-Open No. 2017-032685, and the Japanese Patent Application Publication No. 2017-032685 can also be used. The resin described in Japanese Patent Application Publication No. 2017-075248, the resin described in Japanese Patent Application Publication No. 2017-066240, the resin described in Japanese Patent Application Publication No. 2017-167513, the resin described in Japanese Patent Application Publication No. 2017-173787 , the resin described in paragraphs 0041 to 0060 of Japanese Patent Application Publication No. 2017-206689, the resin described in paragraphs 0022 to 0071 of Japanese Patent Application Publication No. 2018-010856, and the block described in Japanese Patent Application Publication No. 2016-222891 Polyisocyanate resin, resin described in Japanese Patent Application Publication No. 2020-122052, resin described in Japanese Patent Application Publication No. 2020-111656, resin described in Japanese Patent Application Publication No. 2020-139021, Japanese Patent Application Publication No. 2017-138503 Resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in the publication, resin described in paragraphs 0199 to 0233 of Japanese Patent Application Laid-Open No. 2020-186373, Japanese Patent Application Laid-Open No. 2020 -Alkali-soluble resin described in Publication No. 186325, resin represented by Formula 1 described in Korean Patent Publication No. 10-2020-0078339, resin containing an epoxy group and an acid group described in International Publication No. 2022/030445 copolymer.

The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and even more preferably 500,000 or less. A lower limit of 4,000 or more is preferred, and a lower limit of 5,000 or more is even better.

As the resin, it is preferable to use a resin having an acid group. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, phenolic hydroxyl groups, and the like. When using a compound in which A ¹ of the formula (1) is a group containing a base as a specific compound described later, it is preferable to use a resin having an acidic group as the resin. According to this aspect, the storage stability of the photosensitive composition can be further improved.

The acid value of the resin with acid groups is preferably 30 to 500 mgKOH/g. It is more preferable that the lower limit is 40 mgKOH/g or more, and it is particularly preferable that it is 50 mgKOH/g or more. The upper limit is more preferably 400 mgKOH/g or less, more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less. The weight average molecular weight (Mw) of the resin having an acid group is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. In addition, the number average molecular weight (Mn) of the resin having an acidic group is preferably 1,000 to 20,000.

The resin having acidic groups preferably contains repeating units having acidic groups on the side chains, and it is more preferable that the resin contains 5 to 70 mol% of repeating units having acidic groups on the side chains of the total repeating units of the resin. The upper limit of the content of the repeating unit having an acid group on the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less. The lower limit of the content of the repeating unit having an acid group on the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.

Regarding the resin having an acid group, please refer to the description of paragraphs 0558 to 0571 of Japanese Patent Application Laid-Open No. 2012-208494 (corresponding to paragraphs 0685 to 0700 of US Patent Application Publication No. 2012/0235099) and Japanese Patent Application Laid-Open No. 2012-198408 The records in paragraphs 0076 to 0099 of the Gazette No. 1 are incorporated into this manual. In addition, commercially available resins having acidic groups can also be used. In addition, the method for introducing acid groups into the resin is not particularly limited, but an example thereof is the method described in Japanese Patent No. 6349629. Moreover, as a method of introducing an acid group into a resin, the method of making the hydroxyl group produced|generated by the ring-opening reaction of an epoxy group react with an acid anhydride, and introducing an acid group is also mentioned.

As the resin, a resin having a base can also be used. When using a compound in which A ¹ of the formula (1) is a group containing an acid group as a specific compound described later, it is preferable to use a resin having a basic group as the resin. According to this aspect, the storage stability of the photosensitive composition can be further improved.

The resin having a base is preferably a resin containing a repeating unit having a base on the side chain, and a copolymer having a repeating unit having a base on the side chain and a repeating unit without a base is even more preferred, and has Block copolymers having repeating units of bases and repeating units without bases on the side chains are further preferred. Resins with basic bases can also be used as dispersants. The amine value of the resin having a base is preferably 5 to 300 mgKOH/g. The lower limit is preferably 10 mgKOH/g or more, and more preferably 20 mgKOH/g or more. The upper limit is preferably 200 mgKOH/g or less, and more preferably 100 mgKOH/g or less.

Examples of commercially available resins having bases include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (the above are manufactured by BYK-Chemie GmbH), SOLSPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (the above are manufactured by Japan Lubrizol Corporation), Efka PX 4300, 4330, 4046, 4060, 4080 (the above are manufactured by BASF), etc. In addition, the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Application Laid-Open No. 2014-219665, and the block copolymer (B) described in paragraphs 0046 to 0076 of Japanese Patent Application Laid-Open No. 2018-156021 can also be used as the resin having a base. The block copolymer A1 and the vinyl resin having a base described in paragraphs 0150 to 0153 of Japanese Patent Application Laid-Open No. 2019-184763 are incorporated into this specification.

It is also preferable to use a resin having an acidic group or a resin having an alkali group as the resin. According to this aspect, the storage stability of the photosensitive composition can be further improved. When a resin having an acidic group and a resin having an alkali group are used together, the content of the resin having an alkali group is preferably 20 to 500 parts by mass, and 30 to 300 parts by mass relative to 100 parts by mass of the resin having an acidic group. Parts by mass are more preferably, and 50 to 200 parts by mass are still more preferably.

As the resin, it is also preferable to use a resin having an aromatic carboxyl group (hereinafter also referred to as resin Ac). In the resin Ac, the aromatic carboxyl group may be included in the main chain of the repeating unit or in the side chain of the repeating unit. It is preferred that the aromatic carboxyl group is included in the main chain of the repeating unit. In addition, in this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. Among the aromatic carboxyl groups, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.

As the resin, it is preferred to use at least one selected from the group consisting of graft polymers, star polymers, block copolymers, and resins in which at least one end of the polymer chain is terminated with an acid group. This resin can be preferably used as a dispersant.

Examples of the graft polymer include resins containing repeating units having graft chains. Examples of the graft chain include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic acid structure. The terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkyl sulfide group, and the like. Among them, from the viewpoint of improving the dispersibility of the pigment, a group having a steric repulsion effect is preferred, and an alkyl group or alkoxy group having 5 to 30 carbon atoms is preferred. The alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched are preferred.

Specific examples of the graft polymer include Paragraphs 0025 to 0094 of Japanese Patent Application Laid-Open No. 2012-255128, Paragraphs 0022 to 0097 of Japanese Patent Application Laid-Open No. 2009-203462, and Paragraphs 0102 of Japanese Patent Application Laid-Open No. 2012-255128. ~The resin described in paragraph 0166.

Examples of star-shaped polymers include resins having a structure in which a plurality of polymer chains are bonded to a core. Specific examples of the star polymer include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of Japanese Patent Application Laid-Open No. 2013-043962, and the like.

As a block copolymer, there is a block of a polymer having repeating units containing acidic groups or bases (hereinafter also referred to as block A) and a block of a polymer having repeating units containing no acidic groups or bases. (Hereinafter, also referred to as block B) block copolymer is preferred. As the block copolymer, the block copolymer (B) described in paragraphs 0063 to 0112 of Japanese Patent Application Laid-Open No. 2014-219665 and the block copolymer described in paragraphs 0046 to 0076 of Japanese Patent Application Laid-Open No. 2018-156021 can also be used. Item A1, which content is incorporated into this description.

Examples of the resin in which at least one end of the polymer chain is blocked by an acid group include a polymer chain containing at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic acid structure. A resin with a structure in which at least one end is blocked by an acid group. Examples of the acid group that blocks the end of the polymer chain include a carboxyl group, a sulfo group, and a phosphate group.

As the resin, a resin serving as a dispersant can also be used. Examples of the dispersant include acidic dispersants (acidic resins) and alkaline dispersants (basic resins). Here, the acidic dispersant (acidic resin) means a resin in which the amount of acid groups is greater than the amount of base groups. As an acidic dispersant (acidic resin), when the total amount of acid groups and base groups is 100 mol%, a resin having an acid group amount of 70 mol% or more is preferred. It is preferable that the acidic group of the acidic dispersant (acidic resin) is a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g. In addition, the alkaline dispersant (alkaline resin) means a resin in which the amount of base groups is greater than the amount of acid groups. As an alkaline dispersant (basic resin), when the total amount of acid groups and bases is 100 mol%, a resin in which the amount of bases exceeds 50 mol% is preferred. The alkaline dispersant preferably has an amine group as its base.

Dispersants are also available as commercial products, and specific examples thereof include the Disperbyk series manufactured by BYK-Chemie GmbH (for example, Disperbyk-111, 161, 2001, etc.) and the SOLSPERSE series manufactured by Lubrizol Japan Ltd. (for example, SOLSPERSE20000, 76500, etc.), Ajispar series manufactured by Ajinomoto Fine-Techno Co., Inc., A208F (manufactured by DKS Co. Ltd.), H-3606 (manufactured by DKS Co. Ltd.), SANDET ET (manufactured by SANYO KASEI CO., LTD. .manufacturing), etc. In addition, the products described in Paragraph 0129 of Japanese Patent Application Laid-Open No. 2012-137564 and the products described in Paragraph 0235 of Japanese Patent Application Laid-Open No. 2017-194662 can also be used as the dispersant.

The content of the resin in the total solid content of the photosensitive composition is preferably 1 to 50% by mass. The upper limit is preferably 40 mass% or less, and more preferably 30 mass% or less. The lower limit is preferably 5% by mass or more, and more preferably 10% by mass or more. The photosensitive composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resins are contained, the total amount is preferably within the above range.

＜＜Solvent＞＞ The photosensitive composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as it satisfies the solubility of each component or the coatability of the composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For details, please refer to paragraph 0223 of International Publication No. 2015/166779, which is incorporated into this specification. Furthermore, ester solvents in which a cyclic alkyl group is substituted and ketone solvents in which a cyclic alkyl group is substituted can also be suitably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, methylene chloride, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, and ethylcelusacetate. , Ethyl lactate, diglyme, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone , 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate , butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropylamide, 3-butoxy-N,N- Dimethylpropamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, cycloterine, anisole, 1,4-diethyloxy Butane, diethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol, etc. However, sometimes it is preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, it can be set to 50 mass based on the total amount of organic solvents). ppm (parts per million: parts per million) or less, it can also be set to 10 mass ppm or less, or it can be set to 1 mass ppm or less).

In the present invention, it is preferable to use an organic solvent with a small metal content. The metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less, for example. Organic solvents with a quality of ppt (parts per trillion: parts per trillion) level can be used as needed, and such organic solvents are provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter. The filter pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and further preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene or nylon.

Organic solvents can contain isomers (compounds with the same number of atoms but different structures). In addition, only one type of isomer may be contained, or a plurality of types of isomers may be contained.

It is preferable that the content rate of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that it contains substantially no peroxide.

The content of the solvent in the photosensitive composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and further preferably 30 to 90% by mass.

Moreover, from the viewpoint of environmental control, it is preferable that the photosensitive composition of the present invention substantially does not contain environmentally controlled substances. Furthermore, in the present invention, substantially no environmentally regulated substances means that the content of the environmentally regulated substances in the photosensitive composition is 50 mass ppm or less, preferably 30 mass ppm or less, and further preferably 10 mass ppm or less. , it is especially good if it is less than 1 mass ppm. Examples of environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzene such as chlorobenzene. These regulations are based on REACH (Registration Evaluation Authorization and Restriction of CHemicals: Chemical Registration, Evaluation, Authorization and Restriction) rules, PRTR (Pollutant Release and Transfer Register: Pollutant Release and Transfer Register) law, VOC (Volatile Organic Compounds: volatile Organic compounds) are registered as environmentally controlled substances, and their usage or disposal methods are strictly controlled. These compounds may be used as solvents when producing components used in the photosensitive composition, and may be mixed into the photosensitive composition as residual solvents. From the viewpoint of human safety and environmental considerations, it is better to reduce these substances as much as possible. An example of a method for reducing environmentally regulated substances is to heat or depressurize the system to a temperature above the boiling point of the environmentally regulated substances, and to distill and remove the environmentally regulated substances from the system. In addition, when removing a small amount of environmentally controlled substances by distillation, it is also useful to azeotrope the solvent with 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, in order to suppress cross-linking between molecules due to radical polymerization reaction during vacuum distillation removal, a polymerization inhibitor or the like may be added to perform vacuum distillation removal. These distillation removal methods can be performed at the raw material stage, at the stage of a product of the reaction of the raw materials (for example, a resin solution or a polyfunctional monomer solution after polymerization), or at the stage of a photosensitive composition produced by mixing these compounds, etc. in any stage.

＜＜Compounds with cyclic ether groups＞＞ The photosensitive composition of the present invention can further contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group, an oxetanyl group, and the like. The epoxy group may be an alicyclic epoxy group. In addition, the alicyclic epoxy group refers to a monovalent functional group having a cyclic structure formed by condensation of an epoxy ring and a saturated hydrocarbon ring. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of the epoxy compound include compounds having one or more epoxy groups per molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule. The upper limit of the epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the epoxy groups contained in the epoxy compound is preferably 2 or more. As the epoxy compound, Paragraphs 0034 to 0036 of Japanese Patent Application Laid-Open No. 2013-011869, Paragraphs 0147 to 0156 of Japanese Patent Application Laid-Open No. 2014-043556, and Paragraphs 0085 to 0092 of Japanese Patent Application Laid-Open No. 2014-089408 can also be used. Compounds described, compounds described in Japanese Patent Application Laid-Open No. 2017-179172, Kuchiyamaguchi star-shaped epoxy resin described in Japanese Patent Application Laid-Open No. 2021-195421, Kuchiyamaguchi star described in Japanese Patent Application Laid-Open No. 2021-195422 type epoxy resin.

The compound with a cyclic ether group can be a low molecular compound (for example, the molecular weight is less than 2000, and further, the molecular weight is less than 1000), or it can be a macromolecule compound (for example, the molecular weight is more than 1000, which is a polymer) In this case, the weight average molecular weight is 1000 or more). The weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000. The upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and still more preferably 3,000 or less.

Examples of commercially available compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, and G- 0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (the above are manufactured by NOF CORPORATION., polymers containing epoxy groups), etc. Moreover, as the compound which has a cyclic ether group, the compound described in the Example mentioned later can also be used.

The content of the compound having a cyclic ether group in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

＜＜Harding accelerator＞＞ The photosensitive composition of the present invention may contain a hardening accelerator. Examples of the hardening accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, and the like. Specific examples of the hardening accelerator include the compounds described in paragraph 0164 of International Publication No. 2022/085485, the compounds described in Japanese Patent Application Laid-Open No. 2021-181406, and the like. The content of the hardening accelerator in the total solid content of the photosensitive composition is preferably 0.3 to 8.9% by mass, and more preferably 0.8 to 6.4% by mass.

＜＜UV absorber＞＞ The photosensitive composition of the present invention can contain an ultraviolet absorber. Examples of the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl trisulfonate compounds, and indepine compounds. Indole compounds, tri-𠯤 compounds, etc. As specific examples of such compounds, the compound described in paragraph 0179 of International Publication No. 2022/085485, the reactive trifluoroethylene ultraviolet absorber described in Japanese Patent Application Laid-Open No. 2021-178918, and Japanese Patent Application Laid-Open No. 2022- can also be used. Ultraviolet absorbers described in Public Gazette No. 007884.

The content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, and more preferably 0.01 to 5% by mass. In the present invention, only one type of ultraviolet absorber may be used, or two or more types of ultraviolet absorbers may be used. When two or more types are used, the total amount is preferably within the above range.

＜＜Polymerization inhibitor＞＞ The photosensitive composition of the present invention can contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tertiary butyl-p-cresol, gallic acid, tertiary butylcatechol, benzoquinone, and 4,4'-thio Bis(3-methyl-6-tertiary butylphenol), 2,2'-methylenebis(4-methyl-6-tertiary butylphenol), N-nitrosophenylhydroxylamine salt ( Ammonium salt, first cerium salt, etc.). Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.0001 to 5% by mass. The polymerization inhibitor may be only one type or two or more types. When there are two or more types, the total amount is preferably within the above range.

＜＜Silane Coupling Agent＞＞ The photosensitive composition of the present invention can contain a silane coupling agent. In the present invention, a silane coupling agent refers to a silane compound having a hydrolyzable group and functional groups other than the hydrolyzable group. In addition, the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, a hydroxyl group, and the like, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acrylyl group, a mercapto group, an epoxy group, an oxetanyl group, and an amino group. , urea group, sulfide group, isocyanate group, phenyl group, etc., amine group, (meth)acrylyl group and epoxy group are preferred. Specific examples of the silane coupling agent include N-β-aminoethyl-γ-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N-β-aminoethyl-γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N-β-aminoethyl-γ-amine Propyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), γ-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name) KBM-903), γ-aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropylmethyldimethyl Oxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) etc. Specific examples of the silane coupling agent include the compounds described in paragraphs 0018 to 0036 of Japanese Patent Application Laid-Open No. 2009-288703 and the compounds described in paragraphs 0056 to 0066 of Japanese Patent Application Laid-Open No. 2009-242604. and other contents are incorporated into this manual. The content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.01 to 15.0 mass%, and more preferably 0.05 to 10.0 mass%. The silane coupling agent may be only one type or two or more types. When there are two or more types, the total amount is preferably within the above range.

＜＜Surfactant＞＞ The photosensitive composition of the present invention can contain a surfactant. As the surfactant, various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and polysiloxane surfactants can be used. The surfactant is preferably a polysiloxane-based surfactant or a fluorine-based surfactant. Regarding surfactants, please refer to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015/166779, and this content is incorporated into this specification.

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

As the fluorine-based surfactant, compounds described in paragraphs 0167 to 0169 of International Publication No. 2022/085485 can be used.

Block polymers can also be used as fluorine-based surfactants. The fluorine-based surfactant can also preferably use a fluorine-containing polymer compound that contains: a repeating unit derived from a (meth)acrylate compound having a fluorine atom; and a fluorine-containing polymer compound derived from a (meth)acrylate compound having 2 or more ( The repeating unit of a (meth)acrylate compound is preferably an alkyleneoxy group (preferably 5 or more) (preferably an vinyloxy group or a propyleneoxy group). In addition, the fluorine-containing surfactant described in paragraphs 0016 to 0037 of Japanese Patent Application Laid-Open No. 2010-032698 or the following compounds can also be exemplified as the fluorine-based surfactant used in the present invention. [Chemical formula 21] The weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000. In the above compounds, the percentage expressed as the proportion of repeating units is molar %.

As the fluorine-based surfactant, a fluorine-containing copolymer having a group containing an ethylenically unsaturated bond in the side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Laid-Open No. 2010-164965, and MEGAFACE RS-101, RS-102, RS-718K, and RS-72- manufactured by DIC Corporation. K et al. In addition, the compounds described in paragraphs 0015 to 0158 of Japanese Patent Application Laid-Open No. 2015-117327 and the fluorine-containing copolymer described in Japanese Patent Application Laid-Open No. 2022-000494 can also be used as the fluorine-based surfactant.

From the viewpoint of environmental control, it is also preferable to use the surfactant described in International Publication No. 2020/084854 as a substitute for the surfactant having a perfluoroalkyl group with a carbon number of 6 or more.

It is also preferable to use a fluoride-containing imine salt compound represented by formula (fi-1) as a surfactant. [Chemical formula 22] In formula (fi-1), m represents 1 or 2, n represents an integer from 1 to 4, a represents 1 or 2, X ^a+ represents a-valent metal ion, primary ammonium ion, secondary ammonium ion, tertiary ammonium ion, Quaternary ammonium ion or NH ₄ ⁺ .

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (for example, glycerol propoxylate, Glycerin ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene Glycol dilaurate, polyethylene glycol distearate, sorbitol 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 Japan Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILMWako 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 Industry Co., Ltd.), etc.

Examples of polysilicone-based surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (the above are manufactured by Dow Corning Toray Co., Ltd.), TSF- 4300, TSF-4445, TSF-4460, TSF-4452 (the above are manufactured by Momentive Performance Materials Inc.), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (the above are manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (the above are manufactured by BYK-Chemie GmbH), etc.

Moreover, the compound of the following structure can also be used as a polysiloxane surfactant. [Chemical formula 23]

The content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001 to 5.0 mass%, and more preferably 0.005 to 3.0 mass%. The surfactant may be only one type, or may be two or more types. When there are two or more types, the total amount is preferably within the above range.

＜＜Antioxidants＞＞ The photosensitive composition of the present invention can contain an antioxidant. Examples of antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like. As the phenolic compound, any phenolic compound known as a phenolic antioxidant can be used. Preferable phenol compounds include hindered phenol compounds. Compounds having a substituent at the position adjacent to the phenolic hydroxyl group (ortho position) are preferred. As the substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Moreover, it is also preferable that the antioxidant is a compound having a phenol group and a phosphite group in the same molecule. Moreover, as an antioxidant, a phosphorus-type antioxidant can also be suitably used. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphineheterocycloheptadien-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tertiary butyldibenzo[d,f] [1,3,2]dioxaphosphineheterocycloheptadien-2-yl)oxy]ethyl]amine, ethyl bis(2,4-di-tertiary butyl-6-methyl phosphite) phenyl) etc. Examples of commercially available antioxidants include ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, and ADEKA STAB AO-60G, ADEKA STAB AO-80, ADEKA STAB AO-330 (the above are manufactured by ADEKA CORPORATION), etc. In addition, the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compounds described in International Publication No. 2017/006600, the compounds described in International Publication No. 2017/164024, and Korean Patent Publication can also be used as antioxidants. Compounds described in Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20 mass%, and more preferably 0.3 to 15 mass%. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

＜＜Other ingredients＞＞ The photosensitive composition of the present invention may optionally contain sensitizers, hardening accelerators, fillers, thermal hardening accelerators, plasticizers and other auxiliaries (for example, conductive particles, defoaming agents, flame retardants, leveling agents, etc.) agents, peeling accelerators, fragrances, surface tension regulators, chain transfer agents, etc.). By appropriately containing these components, film physical properties and other properties can be adjusted. As these components, compounds described in paragraph 0182 of International Publication No. 2022/085485 can be used.

In order to adjust the refractive index of the obtained film, the photosensitive composition of this invention may contain a metal oxide. Examples of metal oxides include TiO ₂ , ZrO ₂ , Al ₂ O ₃ , SiO ₂ and the like. The primary particle diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and further preferably 5 to 50 nm. Metal oxides may have a core-shell structure. In addition, at this time, the core part may be hollow.

The photosensitive composition of the present invention may contain a light resistance improving agent. Examples of the light resistance improving agent include compounds described in paragraph 0183 of International Publication No. 2022/085485.

It is also preferable that the photosensitive composition of the present invention contains substantially no terephthalate. Here, "substantially free" means that the content of terephthalate ester in the total amount of the photosensitive composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably 0. The free metal content of the photosensitive composition of the present invention is preferably 100 ppm or less, and more preferably 50 ppm or less. Moreover, the free halogen content is preferably 100 ppm or less, and more preferably 50 ppm or less. Examples of methods for reducing free metals or halogens in the photosensitive composition include washing with ion-exchange water, filtration, ultrafiltration, and purification with ion-exchange resin.

From the viewpoint of environmental regulation, the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts is sometimes regulated. In the photosensitive composition of the present invention, when the content rate of the above-mentioned compound is reduced, perfluoroalkyl sulfonic acid (especially the carbon number of the perfluoroalkyl group is 6 to 8) relative to the total solid content of the photosensitive composition. The content rate of perfluoroalkylsulfonic acid) and its salts, and perfluoroalkylcarboxylic acid (especially perfluoroalkylcarboxylic acid with a perfluoroalkyl carbon number of 6 to 8) and its salts is 0.01 ppb ~ A range of 1,000 ppb is preferable, a range of 0.05 ppb to 500 ppb is more preferable, and a range of 0.1 ppb to 300 ppb is still more preferable. The photosensitive composition of the present invention may not substantially contain perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts. For example, by using compounds that can replace perfluoroalkyl sulfonic acid and its salts, and compounds that can replace perfluoroalkyl carboxylic acids and its salts, you can choose to be substantially free of perfluoroalkyl sulfonic acid and its salts, and photosensitive compositions of perfluoroalkylcarboxylic acids and their salts. Examples of compounds that can replace the regulated compounds include compounds that are excluded from the subject of regulation due to differences in the number of carbon atoms in the perfluoroalkyl group. Among them, the above content does not prevent the use of perfluoroalkyl sulfonic acid and its salts and perfluoroalkyl carboxylic acid and its salts. The photosensitive composition of the present invention may contain perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts within the maximum allowable range.

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

The photosensitive composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface shape (flatness, etc.), adjusting the film thickness, etc. The value of viscosity can be appropriately selected as needed. For example, 0.3mPa·s to 50mPa·s at 25°C is more preferred, and 0.5mPa·s to 20mPa·s is more preferred. As a method of measuring viscosity, for example, a cone and plate viscometer can be used to measure the viscosity in a state where the temperature is adjusted to 25°C.

＜＜Container＞＞ There is no particular limitation on the storage container for the photosensitive composition, and a known storage container can be used. In addition, as a storage container, in order to prevent impurities from being mixed into raw materials or photosensitive compositions, it is also preferable to use a multi-layered bottle with an inner wall composed of 6 types of 6-layer resins or a bottle with a 7-layer structure using 6 types of resins. . Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351. In addition, the inner wall of the container is preferably made of glass, stainless steel, etc. for the purpose of preventing metal from eluting from the inner wall of the container, improving the storage stability of the photosensitive composition, or suppressing deterioration of components.

＜Preparation method of photosensitive composition＞ The photosensitive composition of the present invention can be prepared by mixing the above-mentioned components. When preparing a photosensitive composition, all the components can be dissolved and/or dispersed in a solvent at the same time to prepare the photosensitive composition, or each component can be appropriately used as 2 or more parts of a solution or dispersion as necessary, and when used (coating When), these are mixed to prepare a photosensitive composition.

In addition, when preparing the photosensitive composition, it is preferable to include a process of dispersing pigments. In the process of dispersing pigments, examples of mechanical forces used to disperse pigments include compression, extrusion, impact, shearing, pitting, etc. Specific examples of these processes include bead milling, sand milling, roller milling, ball milling, paint stirring, micro-jet flow, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, and the like. In addition, when grinding the pigment in a sand mill (bead mill), it is preferable to perform the treatment under conditions that improve the grinding efficiency by using microbeads with small diameters, increasing the filling rate of microbeads, etc. In addition, after the grinding process, it is preferable to remove coarse particles by filtration, centrifugation, etc. In addition, regarding the process and dispersing machine for dispersing pigments, "Encyclopedia of Dispersion Technology, published by JOHOKIKO CO., LTD., July 15, 2005" or "Suspension (solid/liquid dispersion system)" can be preferably used. The Center's Comprehensive Data Collection on Dispersion Technology and Industrial Applications, published by the Publication Department of the Business Development Center, October 10, 1978", the process and dispersion machine described in paragraph 0022 of Japanese Patent Application Publication No. 2015-157893. In addition, in the process of dispersing pigments, the particles can be refined through a salt grinding step. Materials, equipment, processing conditions, etc. used in the salt grinding step can be referred to the descriptions of Japanese Patent Application Laid-Open No. 2015-194521 and Japanese Patent Application Laid-Open No. 2012-046629, for example. Examples of materials used for dispersed beads include zirconium dioxide, agate, quartz, titanium dioxide, tungsten carbide, silicon nitride, alumina, stainless steel and glass. In addition, an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads. The photosensitive composition may contain 1 to 10,000 ppm of the above beads.

When preparing a photosensitive composition, it is preferable to filter the photosensitive composition with a filter for the purpose of removing impurities or reducing defects. Examples of types of filters and filtration methods used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of International Publication No. 2022/085485.

＜Membrane＞ The film of the present invention is a film obtained from the photosensitive composition of the present invention described above. The film of the present invention can be used in filters such as color filters, near-infrared transmission filters, and near-infrared cutoff filters.

The film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. For example, the film thickness is preferably 20 μm or less, more preferably 10 μm or less, and still more preferably 5 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

When the film of the present invention is used as a color filter, it is preferred that the film of the present invention has a green, red, blue, cyan, magenta or yellow hue. Furthermore, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.

When the film of the present invention is used as a near-infrared cutoff filter, it is preferable that the maximum absorption wavelength of the film of the present invention exists in the range of wavelength 700 to 1800 nm, and it is more preferable that it exists in the range of wavelength 700 to 1300 nm. It is more preferable to have a wavelength in the range of 700 to 1000 nm. In addition, the transmittance of the film in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more. Moreover, it is preferable that the transmittance of at least one place within the wavelength range of 700 to 1800 nm of the film is 20% or less. Moreover, the ratio of the absorbance Amax at the maximum absorption wavelength and the absorbance A550 at the wavelength of 550 nm, that is, absorbance Amax/absorbance A550, is preferably 20 to 500, more preferably 50 to 500, and further preferably 70 to 450. 100 to 400 is especially good.

When the film of the present invention is used as a near-infrared transmission filter, it is preferable that the film of the present invention has any one of the following spectral characteristics (i1) to (i5), for example. (i1): The maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 800 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 640 nm, and can transmit light with a wavelength exceeding 750 nm. (i2): The maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 900 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 750 nm, and can transmit light with a wavelength exceeding 850 nm. (i3): The maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1000 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 830 nm, and can transmit light with a wavelength exceeding 950 nm. (i4): The maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1100 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 950 nm, and can transmit light with a wavelength exceeding 1050 nm. (i5): The maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less) and the transmittance in the wavelength range of 1200 to 1500 nm A filter with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more). A film with such spectroscopic characteristics can block light with a wavelength in the range of 400 to 1050 nm, and can transmit light with a wavelength exceeding 1150 nm.

＜Optical filter＞ The optical filter of the present invention has the above-mentioned film of the present invention. Examples of types of optical filters include color filters, near-infrared cutoff filters, near-infrared transmission filters, and the like, with color filters being preferred. It is preferable that the color filter has the film of the present invention as its pixel, and it is more preferable that it has the film of the present invention as the colored pixel.

In the optical filter, the film thickness of the film of the present invention can be appropriately adjusted depending on the purpose. The film thickness of the pixels included in the filter is preferably 5 μm or less, more preferably 1 μm or less, and further preferably 0.6 μm or less. The lower limit of the film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and still more preferably 0.3 μm or more.

The width of the pixels included in the filter is preferably 0.4 to 10.0 μm. The lower limit is preferably 0.4 μm or more, more preferably 0.5 μm or more, and still more preferably 0.6 μm or more. The upper limit is preferably 5.0 μm or less, more preferably 2.0 μm or less, further preferably 1.0 μm or less, and still more preferably 0.8 μm. In addition, the Young's modulus of the pixel is preferably 0.5 to 20 GPa, and more preferably 2.5 to 15 GPa.

The optical filter may be provided with a protective layer on the surface of the film of the present invention. By providing a protective layer, various functions can be provided, such as blocking oxygen oxidation, making it low-reflective, making it hydrophilic and hydrophobic, and blocking light of specific wavelengths (ultraviolet, near-infrared, etc.). The thickness of the protective layer is preferably 0.01 to 10 μm, and more preferably 0.1 to 5 μm. Examples of methods for forming the protective layer include a method of applying a resin composition for forming a protective layer, a chemical vapor deposition method, a method of attaching a molded resin with an adhesive material, and the like. Examples of components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polystyrene resin, polyetherstyrene resin, and polyphenylene resin. Polyarylene ether phosphine oxide resin, polyimide resin, polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin , melamine resin, urethane resin, polyarylamine resin, polyamide resin, alkyd resin, epoxy resin, modified polysiloxane resin, fluorine resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ₂ O ₃ , Mo, SiO ₂ , Si ₂ N ₄ , etc. may contain two or more of these components. For example, in the case of a protective layer with the purpose of blocking oxygen oxidation, it is preferable that the protective layer contains polyol resin, SiO ₂ and Si ₂ N ₄ . In addition, in the case of a protective layer for the purpose of low reflection, the protective layer preferably contains (meth)acrylic resin and fluororesin.

When the resin composition is applied to form a protective layer, known methods such as spin coating, casting, screen printing, and inkjet can be used as a method for coating the photosensitive composition. As the organic solvent contained in the photosensitive composition, a known organic solvent (for example, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used. When the protective layer is formed by the chemical vapor deposition method, as the chemical vapor deposition method, a known chemical vapor deposition method (thermal chemical vapor deposition method, plasma chemical vapor deposition method, photochemical vapor deposition method) can be used Law).

If necessary, the protective layer may contain organic/inorganic particles, absorbers for specific wavelengths of light (for example, ultraviolet, near-infrared, etc.), refractive index adjusters, antioxidants, adhesives, surfactants and other additives. Examples of organic/inorganic fine particles include polymer fine particles (for example, polysilicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, Titanium nitride, titanium oxynitride, magnesium fluoride, hollow silicon dioxide, silicon dioxide, calcium carbonate, barium sulfate, etc. As an absorber for light of a specific wavelength, a known absorber can be used. The content of these additives can be appropriately adjusted, but relative to the total mass of the protective layer, 0.1 to 70 mass % is more preferred, and 1 to 60 mass % is further more preferred.

In addition, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Laid-Open No. 2017-151176 can also be used.

The optical filter may have a structure in which each pixel is embedded in a space divided by partition walls into, for example, a grid shape.

The optical filter of the present invention can be used in optical sensors such as solid-state imaging devices, image display devices, and the like.

＜How to manufacture optical filters＞ The manufacturing method of the optical filter preferably includes the following steps: forming a photosensitive composition layer on a support using the photosensitive composition of the present invention; exposing the photosensitive composition layer in a pattern; and developing The step of removing the unexposed portion of the photosensitive composition layer to form a pattern (pixel). If necessary, a step of baking the photosensitive composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) can be provided.

In the step of forming the photosensitive composition layer, the photosensitive composition layer of the present invention is used to form the photosensitive composition layer on the support. The support is not particularly limited and can be appropriately selected depending on the use. For example, a glass substrate, a silicon substrate, etc. are mentioned, and a silicon substrate is preferable. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may also be formed on the silicon substrate. In addition, a black matrix is sometimes formed on the silicon substrate to isolate each pixel. Furthermore, the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing diffusion of substances, or flattening the surface of the substrate. The surface contact angle of the base layer is preferably 20 to 70° when measured with diiodomethane. In addition, when measuring with water, 30 to 80° is preferred.

As a coating method of the photosensitive composition, a known method can be used. For example, the coating method described in paragraph 0207 of International Publication No. 2022/085485 can be used.

The photosensitive composition layer formed on the support may be dried (prebaked). When the film is manufactured by a low-temperature process, pre-baking is not required. When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and further preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Prebaking can be performed using a heating plate, oven, etc.

Next, the photosensitive composition layer formed on the support is exposed in a pattern. For example, the photosensitive composition layer can be exposed in a pattern by using a stepper exposure machine, a scanning exposure machine, etc. through a mask having a predetermined mask pattern. Thereby, the exposed portion can be hardened.

Examples of radiation (light) that can be used during exposure include g-rays, i-rays, and the like. 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 KrF rays (wavelength: 248 nm) are preferred. In addition, a long-wavelength light source of 300 nm or more can also be used. As a light source, it is possible to use electrodeless UV lamp systems, mixed curing of UV and infrared rays.

In addition, during exposure, light may be continuously irradiated for exposure, or pulse irradiation may be performed for exposure (pulse exposure). In addition, pulse exposure refers to an exposure method in which light is irradiated and paused repeatedly to perform exposure in a short period of time (for example, milliseconds or less).

For example, the irradiation amount (exposure amount) is preferably 0.03 to 2.5 J/cm ² , and more preferably 0.05 to 1.0 J/cm ² . The oxygen concentration during exposure can be appropriately selected. In addition to performing it in the atmosphere, for example, it can also be performed in a low-oxygen environment with an oxygen concentration of 19 volume % or less (for example, 15 volume %, 5 volume %, or substantially no oxygen). Exposure can also be carried out in a high oxygen environment with an oxygen concentration exceeding 21 volume % (for example, 22 volume %, 30 volume % or 50 volume %). In addition, the exposure illuminance can be appropriately set, and can usually be selected from the range of 1000W/m ² to 100000W/m ² (for example, 5000W/m ² , 15000W/m ² or 35000W/m ² ). The conditions of oxygen concentration and exposure illuminance can be combined appropriately. For example, the oxygen concentration can be 10 volume % and the illuminance is 10000 W/m ² , the oxygen concentration can be 35 volume % and the illuminance is 20000 W/m ² , etc.

Next, the unexposed portion of the photosensitive composition layer is removed by development to form a pattern (pixel). The unexposed portion of the photosensitive composition layer can be removed by development using a developing solution. Thereby, the photosensitive composition layer in the unexposed portion in the exposure step is dissolved into the developer, and only the photohardened portion remains. For example, the temperature of the developer is preferably 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, in order to improve the residue removal performance, the step of shaking off the developer every 60 seconds and supplying new developer may be repeated several times.

Examples of the developer include organic solvents, alkali developers, and the like, and an alkali developer is preferably used. Regarding the developer and the cleaning (rinsing) method after development, the developer or the cleaning method described in paragraph 0214 of International Publication No. 2022/085485 can be used.

After development, it is preferable to perform additional exposure processing or heat processing (post-baking) after drying. The additional exposure process or post-baking is a hardening process after development for complete hardening. The heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C. In order to achieve the above conditions, heating mechanisms such as heating plates, convection ovens (hot air circulation dryers), and high-frequency heating machines can be used to post-bake the developed film in a continuous or intermittent manner. When performing additional exposure processing, it is preferable that the light used for exposure is light with a wavelength of 400 nm or less. In addition, the additional exposure process can be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

＜Solid-state imaging device＞ The solid-state imaging element of the present invention has the above-mentioned film of the present invention. The structure of the solid-state imaging element is not particularly limited as long as it is provided with the film of the present invention and functions as a solid-state imaging element. For example, the following structures can be cited.

A solid-state imaging device has a structure in which a plurality of photodiodes constituting the light-receiving area of a solid-state imaging device (CCD (Charge Coupled Device) image sensor, CMOS (Complementary Metal Oxide Semiconductor) image sensor, etc.) are provided on a substrate. The transmission electrode is composed of silicon and polysilicon, and has a light-shielding film on the photodiode and the transmission electrode that opens only the light-receiving part of the photodiode. The light-shielding film has a light-shielding film formed in such a manner as to cover the entire light-shielding film and the light-receiving part of the photodiode. The element protective film composed of silicon nitride, etc. has a color filter on the element protective film. Furthermore, a light condensing mechanism (for example, a microlens, etc.; the same applies below) may be provided on the element protection film and below the color filter (closer to the substrate), or a light condensing mechanism may be provided on the color filter. wait. Moreover, the color filter may have a structure in which each pixel is embedded in a space divided by partition walls into a grid shape, for example. At this time, it is preferable that the refractive index of the partition wall is lower than that of each colored pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. 2018/043654. Furthermore, as shown in Japanese Patent Application Publication No. 2019-211559, an ultraviolet absorbing layer can be provided in the structure of the solid-state imaging element to improve light resistance. The imaging device equipped with the solid-state imaging element of the present invention can be used not only as a digital camera or an electronic device (mobile phone, etc.) with an imaging function, but also as a driving recorder or a surveillance camera.

<Image display device> The image display device of the present invention has the film of the present invention described above. Examples of the image display device include a liquid crystal display device, an organic electroluminescence display device, and the like. The definition of an image display device or the details of each image display device are described in, for example, "Electronic Display Devices (by Akio Sasaki, published by Kogyo Chosakai Publishing Co., Ltd., 1990)" and "Display Devices (Jun Ibuki)" Chapter book, Sangyo Tosho Publishing Co., Ltd., released in 1989)" and so on. Further, the liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosakai Publishing Co., Ltd., 1994)". The liquid crystal display device to which the present invention can be applied is not particularly limited. For example, it can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology". [Example]

Hereinafter, an Example is given and this invention is demonstrated more concretely. The materials, usage amounts, proportions, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

＜Manufacture of dispersion＞ The materials listed in the table below were mixed to obtain a mixed liquid. The obtained mixed liquid was dispersed using a nanomill manufactured by KOTOBUKI KOGYOU.CO., LTD. as a circulating dispersion device (bead mill) to produce a dispersion. The unit of the added amount values in the table is parts by mass.

[Table 1] Pigments Dispersion aid Resin Solvent Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Green dispersion 1 PG58 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Green dispersion 2 PG58 10.67 Syn-2 1.19 B-2 4.15 D-1 84 Green dispersion 3 PG7 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Green dispersion 4 PG36 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Green dispersion 5 PG59 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Green dispersion 6 PG63 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Green dispersion 7 PG7 10.67 Syn-2 1.19 B-2 4.15 D-1 84 Green dispersion 8 PG36 10.67 Syn-2 1.19 B-2 4.15 D-1 84 Green dispersion 9 PG59 10.67 Syn-2 1.19 B-2 4.15 D-1 84 Green dispersion 10 PG63 10.67 Syn-2 1.19 B-2 4.15 D-1 84 Green dispersion 11 PG58 10.67 Syn-3 1.19 B-4 4.15 D-1 84 Green dispersion 12 PG36 10.67 Syn-3 1.19 B-4 4.15 D-1 84 Green dispersion 13 PG63 10.67 Syn-3 1.19 B-4 4.15 D-1 84 Yellow dispersion 1 PY185 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Yellow dispersion 2 PY139 10.67 Syn-1 1.19 B-2 4.15 D-1 84 Yellow dispersion 3 PY129 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Yellow dispersion 4 PY150 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Yellow dispersion 5 PY138 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Yellow dispersion 6 PY215 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Yellow dispersion 7 PY231 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Yellow dispersion 8 PY233 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Yellow dispersion 9 PY185 10.67 Syn-3 1.19 B-4 4.15 D-1 84 Yellow dispersion 10 PY139 10.67 Syn-3 1.19 B-4 4.15 D-1 84 Yellow dispersion 11 PY150 10.67 Syn-3 1.19 B-4 4.15 D-1 84 Yellow dispersion 12 PY138 10.67 Syn-3 1.19 B-4 4.15 D-1 84

[Table 2] Pigments Dispersion aid Resin Solvent Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Red dispersion 1 PR254 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Red dispersion 2 PR254/PR272= (50/50 mass ratio) 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Red dispersion 3 PR272 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Red dispersion 4 PR177 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Red dispersion 5 PR264 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Red dispersion 6 PR291 10.67 Syn-1 1.19 B-1 4.15 D-1 84 Red dispersion 7 PR254 10.67 Syn-4 1.19 B-4 4.15 D-1 84 Red dispersion 8 PR272 10.67 Syn-7 1.19 B-4 4.15 D-1 84 Red dispersion 9 PR272 10.67 Syn-8 1.19 B-4 4.15 D-1 84 Red dispersion 10 PR254 10.67 Syn-1 1.19 B-3 4.15 D-1 84 blue dispersion 1 PB15:6 10.67 Syn-5 1.19 B-1 4.15 D-1 84 Blue dispersion 2 PB15:4 10.67 Syn-5 1.19 B-1 4.15 D-1 84 Blue dispersion 3 PB15:3 10.67 Syn-5 1.19 B-1 4.15 D-1 84 Blue dispersion 4 PB16 10.67 Syn-5 1.19 B-1 4.15 D-1 84 Blue dispersion 5 PB15:6 10.67 Syn-5 1.19 B-4 4.15 D-1 84 Blue dispersion 6 PB15:4 10.67 Syn-5 1.19 B-4 4.15 D-1 84 Blue dispersion 7 PB15:3 10.67 Syn-5 1.19 B-4 4.15 D-1 84 Blue dispersion 8 PB16 10.67 Syn-5 1.19 B-4 4.15 D-1 84 Blue dispersion 9 PB15:6 10.67 Syn-5 1.19 B-1 4.15 D-1 D-2 D-3 58.8 21 4.2 Purple dispersion 1 PV23 10.67 Syn-6 1.19 B-1 4.15 D-1 84 Purple dispersion 2 PV23 10.67 Syn-6 1.19 B-4 4.15 D-1 84 Purple dispersion 3 PV23 10.67 Syn-6 1.19 B-1 4.15 D-1 D-2 D-3 58.8 21 4.2 IR dispersion 1 P-23 10.67 Syn-1 1.19 B-1 4.15 D-1 84 IR dispersion 2 P-24 10.67 Syn-1 1.19 B-1 4.15 D-1 84

Details of the materials listed in the above table are as follows. In addition, resins B-1 to B-4 are materials corresponding to polymerizable compounds having a weight average molecular weight of 3,000 or more.

(Pigment) PG7: CI Pigment Green 7 (green pigment) PG36: CI Pigment Green 36 (green pigment) PG58: CI Pigment Green 58 (green pigment) PG59: CI Pigment Green 59 (green pigment) PG63: CI Pigment Green 63 ( Green pigment) PY129: CI Pigment Yellow 129 (yellow pigment) PY138: CI Pigment Yellow 138 (yellow pigment) PY139: CI Pigment Yellow 139 (yellow pigment) PY150: CI Pigment Yellow 150 (yellow pigment) PY185: CI Pigment Yellow 185 ( Yellow pigment) PY215: CI Pigment Yellow 215 (yellow pigment) PY231: CI Pigment Yellow 231 (yellow pigment) PY233: CI Pigment Yellow 233 (yellow pigment) PR177: CI Pigment Red 177 (red pigment) PR254: CI Pigment Red 254 ( Red pigment) PR264: CI Pigment Red 264 (red pigment) PR272: CI Pigment Red 272 (red pigment) PR291: CI Pigment Red 291 (red pigment) PB15:3: CI Pigment Blue 15:3 (blue pigment) PB15: 4: CI Pigment Blue 15:4 (blue pigment) PB15:6: CI Pigment Blue 15:6 (blue pigment) PB16: CI Pigment Blue 16 (blue pigment) PV23: CI Pigment Violet 23 (purple pigment) P -23: Compound with the following structure (pyrrolopyrrole compound, near-infrared absorbing pigment) P-24: Compound with the following structure (squaraine compound, near-infrared absorbing pigment) [Chemical Formula 24]

(Dispersion aid) Syn-1: Compound with the following structure (pigment derivative) [Chemical Formula 25] Syn-2: Polyethyleneimine (EPOMINSP-006 (manufactured by NIPPON SHOKUBAI CO., LTD.)) Syn-3: A compound with the following structure (pigment derivative) [Chemical Formula 26] Syn-4: Compound with the following structure (pigment derivative) [Chemical Formula 27] Syn-5: Compound with the following structure (pigment derivative) [Chemical Formula 28] Syn-6: Compound with the following structure (pigment derivative) [Chemical Formula 29] Syn-7: Compound with the following structure (pigment derivative) [Chemical Formula 30] Syn-8: Compound with the following structure (pigment derivative) [Chemical Formula 31]

(Resin) B-1: Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3,000 or more. The value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. The weight average molecular weight is 20,000, Acid value 66.6mgKOH/g) [Chemical formula 32] B-2: Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3,000 or more. The value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. The weight average molecular weight is 23,000, and the acid value is 59.6 mgKOH/g) [Chemical formula 33] B-3: Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3,000 or more. The value marked on the main chain is the molar ratio, and the value marked on the side chain is the number of repeating units. Weight average molecular weight: 16,000, acid value: 67 mgKOH /g) [Chemical formula 34] B-4: Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3000 or more. Weight average molecular weight of 18000, acid value of 82.1 mgKOH/g) [Chemical Formula 35]

(solvent) D-1: Propylene glycol monomethyl ether acetate D-2: cyclopentanone D-3: Propylene glycol monomethyl ether

＜Manufacture of photosensitive composition＞ The materials listed in the following table were mixed to produce a photosensitive composition. The unit of the added amount values in the table is parts by mass.

[table 3] Dispersions Dispersions polymeric compound Resin Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 1 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 2 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 3 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 4 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 5 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 6 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 7 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 8 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 9 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 10 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 11 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 12 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 13 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 14 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.10 Example 15 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.10 Example 16 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.10 Example 17 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.10 Example 18 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 19 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 20 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 21 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 22 Green dispersion 3 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 23 Green dispersion 4 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 24 Green dispersion 5 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 25 Green dispersion 6 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 26 Green dispersion 7 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 27 Green dispersion 8 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 28 Green dispersion 9 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 29 Green dispersion 10 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 30 Green dispersion 2 59.06 Yellow dispersion 2 25.31 M-4 0.75 C-1 0.13 Example 31 Green dispersion 2 59.06 Yellow dispersion 3 25.31 M-4 0.75 C-1 0.13 Example 32 Green dispersion 2 59.06 Yellow dispersion 4 25.31 M-4 0.75 C-1 0.13 Example 33 Green dispersion 2 59.06 Yellow dispersion 5 25.31 M-4 0.75 C-1 0.13 Example 34 Green dispersion 2 59.06 Yellow dispersion 6 25.31 M-4 0.75 C-1 0.13 Example 35 Green dispersion 2 59.06 Yellow dispersion 7 25.31 M-4 0.75 C-1 0.13 Example 36 Green dispersion 2 59.06 Yellow dispersion 8 25.31 M-4 0.75 C-1 0.13 Example 37 Green dispersion 4 59.06 Yellow dispersion 2 25.31 M-4 0.75 C-1 0.13 Example 38 Green dispersion 4 59.06 Yellow dispersion 3 25.31 M-4 0.75 C-1 0.13 Example 39 Green dispersion 4 59.06 Yellow dispersion 4 25.31 M-4 0.75 C-1 0.13 Example 40 Green dispersion 4 59.06 Yellow dispersion 5 25.31 M-4 0.75 C-1 0.13 Example 41 Green dispersion 4 59.06 Yellow dispersion 6 25.31 M-4 0.75 C-1 0.13 Example 42 Green dispersion 4 59.06 Yellow dispersion 7 25.31 M-4 0.75 C-1 0.13 Example 43 Green dispersion 4 59.06 Yellow dispersion 8 25.31 M-4 0.75 C-1 0.13 Example 44 Green dispersion 2 39.38 Yellow dispersion 1 16.88 M-4 0.75 C-1 4.63 Example 45 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-4 0.75 C-1 2.38 [Table 4] Photopolymerization initiator surfactant polymerization inhibitor additives Solvent Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 1 I-1 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 2 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 3 I-3 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 4 I-4 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 5 I-5 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 6 I-6 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 7 I-7 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 8 I-8 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 9 I-9 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 10 I-10 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 11 I-11 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 12 I-12 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 13 I-13 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 14 I-2 0.60 W-1 0.01 Q-1 0.01 S-1 0.03 D-1 14.13 Example 15 I-2 0.60 W-1 0.01 Q-1 0.01 S-2 0.03 D-1 14.13 Example 16 I-2 0.60 W-1 0.01 Q-1 0.01 S-3 0.03 D-1 14.13 Example 17 I-2 0.60 W-1 0.01 Q-1 0.01 S-4 0.03 D-1 14.13 Example 18 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 19 I-5 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 20 I-11 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 21 I-13 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 22 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 23 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 24 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 25 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 26 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 27 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 28 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 29 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 30 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 31 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 32 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 33 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 34 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 35 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 36 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 37 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 38 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 39 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 40 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 41 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 42 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 43 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 44 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 37.75 Example 45 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94

[table 5] Dispersions Dispersions polymeric compound Resin Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 46 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-1 0.75 C-1 0.15 Example 47 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-2 0.75 C-1 0.13 Example 48 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-3 0.75 C-1 0.13 Example 49 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-1/M-4 =50/50 0.75 C-1 0.13 Example 50 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 51 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 52 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 53 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 54 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 55 Green dispersion 2 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 56 Green dispersion 11 59.06 Yellow dispersion 9 25.31 M-1 0.75 C-2 0.13 Example 57 Green dispersion 12 59.06 Yellow dispersion 11 25.31 M-1 0.75 C-2 0.13 Example 58 Green dispersion 13 59.06 Yellow dispersion 9 25.31 M-1 0.75 C-2 0.13 Example 59 Green dispersion 13 59.06 Yellow dispersion 11 25.31 M-1 0.75 C-2 0.13 Example 60 Green dispersion 13 59.06 Yellow dispersion 12 25.31 M-1 0.75 C-2 0.13 Example 61 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-1 0.75 C-1 2.08 Example 62 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-1 0.75 C-1 1.78 Example 63 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-1 0.75 C-1 2.53 Example 64 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-1 0.75 C-1 2.68 Example 65 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-1 1.13 C-1 2.01 Example 66 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-1 1.50 C-1 1.63 Example 67 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-4 2.25 C-1 0.88 Example 68 Green dispersion 2 49.22 Yellow dispersion 1 21.09 M-4 2.85 C-1 0.28 Example 69 Red dispersion 1 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 70 Red dispersion 1 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 71 Red dispersion 1 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 72 Red dispersion 1 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 73 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 74 Red dispersion 3 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 75 Red dispersion 4 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 76 Red dispersion 5 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 77 Red dispersion 6 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 78 Red dispersion 1 59.06 Yellow dispersion 5 25.31 M-1 0.75 C-1 0.13 Example 79 Red dispersion 2 59.06 Yellow dispersion 5 25.31 M-1 0.75 C-1 0.13 Example 80 Red dispersion 7 59.06 Yellow dispersion 10 25.31 M-1 0.75 C-2 0.13 [Table 6] Photopolymerization initiator surfactant polymerization inhibitor additives Solvent Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 46 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 15.83 Example 47 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 48 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 49 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 50 I-2/I-5=30/70 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 51 I-2/I-5=50/50 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 52 1-2/1-5=70/30 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 53 I-11/I-13=30/70 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 54 I-11/I-13=50/50 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 55 I-11/I-13=70/30 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 56 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 57 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 58 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 59 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 60 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 61 I-2 0.90 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94 Example 62 I-2 1.20 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94 Example 63 I-2 0.45 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94 Example 64 I-2 0.30 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94 Example 65 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94 Example 66 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94 Example 67 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94 Example 68 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 25.94 Example 69 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 70 I-5 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 71 I-11 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 72 I-13 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 73 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 74 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 75 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 76 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 77 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 78 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 79 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 80 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13

[Table 7] Dispersions Dispersions polymeric compound Resin Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 81 Red dispersion 8 59.06 Yellow dispersion 10 25.31 M-1 0.75 C-2 0.13 Example 82 Red dispersion 9 59.06 Yellow dispersion 10 25.31 M-1 0.75 C-2 0.13 Example 83 Red dispersion 10 59.06 Yellow dispersion 10 25.31 M-1 0.75 C-2 0.13 Example 84 blue dispersion 1 59.06 Purple dispersion 1 25.31 M-2 0.75 C-1 0.13 Example 85 blue dispersion 1 59.06 Purple dispersion 1 25.31 M-2 0.75 C-1 0.13 Example 86 blue dispersion 1 59.06 Purple dispersion 1 25.31 M-2 0.75 C-1 0.13 Example 87 blue dispersion 1 59.06 Purple dispersion 1 25.31 M-2 0.75 C-1 0.13 Example 88 Blue dispersion 2 59.06 Purple dispersion 1 25.31 M-2 0.75 C-1 0.13 Example 89 Blue dispersion 3 59.06 Purple dispersion 1 25.31 M-2 0.75 C-1 0.13 Example 90 Blue dispersion 4 59.06 Purple dispersion 1 25.31 M-2 0.75 C-1 0.13 Example 91 Blue dispersion 5 59.06 Purple dispersion 2 25.31 M-2 0.75 C-2 0.13 Example 92 Blue dispersion 6 59.06 Purple dispersion 2 25.31 M-2 0.75 C-2 0.13 Example 93 Blue dispersion 7 59.06 Purple dispersion 2 25.31 M-2 0.75 C-2 0.13 Example 94 Blue dispersion 8 59.06 Purple dispersion 2 25.31 M-2 0.75 C-2 0.13 Example 95 IR dispersion 1 84.38 - 0.00 M-3 0.75 C-1 0.13 Example 96 IR dispersion 2 84.38 - 0.00 M-3 0.75 C-1 0.13 Example 97 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 98 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 99 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 100 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 101 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 102 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 103 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 104 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 105 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 106 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 107 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 108 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 109 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 110 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 111 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 112 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 113 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 114 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 115 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 [Table 8] Photopolymerization initiator surfactant polymerization inhibitor additives Solvent Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 81 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 82 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 83 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 84 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 85 I-5 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 86 I-11 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 87 I-13 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 88 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 89 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 90 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 91 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 92 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 93 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 94 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 95 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 96 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 97 I-14 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 98 I-15 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 99 I-16 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 100 I-17 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 101 I-18 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 102 I-19 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 103 I-20 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 104 I-21 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 105 I-14 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 106 I-15 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 107 I-16 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 108 I-17 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 109 I-18 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 110 I-19 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 111 I-20 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 112 I-21 0.6 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13 Example 113 I-2 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13 Example 114 I-14 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13 Example 115 I-15 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13

[Table 9] Dispersions Dispersions polymeric compound Resin Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 116 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 117 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 118 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 119 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 120 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 121 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 122 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-4/M-5=50/50 0.75 C-1 0.13 Example 123 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 124 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 125 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 126 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 127 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 128 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 129 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 130 Green dispersion 1 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 Example 131 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 132 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 [Table 10] Photopolymerization initiator surfactant polymerization inhibitor additives Solvent Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 116 I-16 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13 Example 117 I-17 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13 Example 118 I-18 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13 Example 119 I-19 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13 Example 120 I-20 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13 Example 121 I-21 0.3 W-1 0.01 Q-1 0.01 E-1 0.3 D-1 14.13 Example 122 I-19 0.3 W-1 0.01 Q-1 0.01 E-1/E-2=50/50 0.3 D-1 14.13 Example 123 I-1 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1/D-5=50/50 14.13 Example 124 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1/D-5=50/50 14.13 Example 125 I-3 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1/D-5=50/50 14.13 Example 126 I-4 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1/D-5=50/50 14.13 Example 127 I-1 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-2/D-5=50/50 14.13 Example 128 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-2/D-5=50/50 14.13 Example 129 I-3 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-2/D-5=50/50 14.13 Example 130 I-4 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-2/D-5=50/50 14.13 Example 131 I-1 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1/D-5=50/50 14.13 Example 132 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1/D-5=50/50 14.13

[Table 11] Dispersions Dispersions polymeric compound Resin Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 133 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 134 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 135 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 136 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 137 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 138 Red dispersion 2 59.06 Yellow dispersion 2 25.31 M-1 0.75 C-1 0.13 Example 139 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-3/M-5=50/50 0.75 C-1 0.13 Example 140 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-3/M-5=50/50 0.75 C-1 0.13 Example 141 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-3/M-5=50/50 0.75 C-1 0.13 Example 142 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-3/M-5=50/50 0.75 C-1 0.13 Example 143 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-3/M-5=50/50 0.75 C-1 0.13 Example 144 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-3/M-5=50/50 0.75 C-1 0.13 Example 145 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-3/M-5=50/50 0.75 C-1 0.13 Example 146 Blue dispersion 9 59.06 Purple dispersion 3 25.31 M-3/M-5=50/50 0.75 C-1 0.13 Comparative example 1 Green dispersion 4 59.06 Yellow dispersion 1 25.31 M-4 0.75 C-1 0.13 [Table 12] Photopolymerization initiator surfactant polymerization inhibitor additives Solvent Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Kind Adding amount Example 133 I-3 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1/D-5=50/50 14.13 Example 134 I-4 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1/D-5=50/50 14.13 Example 135 I-1 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-2/D-5=50/50 14.13 Example 136 I-2 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-2/D-5=50/50 14.13 Example 137 I-3 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-2/D-5=50/50 14.13 Example 138 I-4 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-2/D-5=50/50 14.13 Example 139 I-1 0.30 W-1 0.01 Q-1 0.01 E-1 0.30 D-1/D-5=50/50 14.13 Example 140 I-2 0.30 W-1 0.01 Q-1 0.01 E-1 0.30 D-1/D-5=50/50 14.13 Example 141 I-3 0.30 W-1 0.01 Q-1 0.01 E-1 0.30 D-1/D-5=50/50 14.13 Example 142 I-4 0.30 W-1 0.01 Q-1 0.01 E-1 0.30 D-1/D-5=50/50 14.13 Example 143 I-1 0.30 W-1 0.01 Q-1 0.01 E-1 0.30 D-4/D-5=50/50 14.13 Example 144 I-2 0.30 W-1 0.01 Q-1 0.01 E-1 0.30 D-4/D-5=50/50 14.13 Example 145 I-3 0.30 W-1 0.01 Q-1 0.01 E-1 0.30 D-4/D-5=50/50 14.13 Example 146 I-4 0.30 W-1 0.01 Q-1 0.01 E-1 0.30 D-4/D-5=50/50 14.13 Comparative example 1 IC-1 0.60 W-1 0.01 Q-1 0.01 - 0.00 D-1 14.13

Details of the materials listed in the above table are as follows. In addition, resins C-1 and C-2 are materials corresponding to polymerizable compounds having a weight average molecular weight of 3,000 or more.

(Dispersions) Green dispersion 1 to 13: the above Green dispersion 1 to 13 Yellow dispersion 1 to 12: the above Yellow dispersion 1 to 12 Red dispersion 1 to 10: the above Red dispersion 1 to 10 Blue dispersion 1 to 9: the above Blue dispersion 1 to 9 Violet dispersion 1～3: Violet dispersion 1～3 mentioned above IR dispersion 1, 2: IR dispersion 1, 2 mentioned above

(Polymerizable compound) M-1: A mixture of compounds with the following structure (compound on the left: compound on the right = 7:3 (mol ratio)) [Chemical Formula 36] M-2: Compound with the following structure [Chemical Formula 37] M-3: Compound with the following structure [Chemical Formula 38] M-4: Compound with the following structure [Chemical Formula 39] M-5: ARONIX M-521 (polyacid-modified acrylic oligomer, manufactured by TOAGOSEI CO., LTD.)

(Resin) C-1: Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3,000 or more. The numerical value indicated on the main chain is the molar ratio. The weight average molecular weight is 11,000, and the acid value is 69.2 mgKOH/g) [Chemical Formula 40] C-2: Resin with the following structure (a polymerizable compound with a weight average molecular weight of 3,000 or more. The numerical value indicated on the main chain is the molar ratio. The weight average molecular weight is 21,000, and the acid value is 80 mgKOH/g) [Chemical Formula 41]

(Photopolymerization initiator) I-1 to I-21: Compounds with the following structures [Chemical Formula 42] [Chemical formula 43] [Chemical formula 44] IC-1: Compound with the following structure [Chemical Formula 45]

(surfactant) W-1: KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., polysilicone-based surfactant)

(polymerization inhibitor) Q-1: p-methoxyphenol

(Additive) S-1: Karenz MTBD1 (manufactured by SHOWA DENKO K.K., multifunctional thiol compound) S-2: Karenz MTPE1 (manufactured by SHOWA DENKO K.K., multifunctional thiol compound) S-3: Karenz MTNR1 (manufactured by SHOWA DENKO K.K., multifunctional thiol compound) S-4: Karenz MTTPMB (manufactured by SHOWA DENKO K.K., multifunctional thiol compound) E-1: 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2’-bis(hydroxymethyl)-1-butanol E-2: PIONIN D-6112-W (manufactured by Takemoto Oil & Fat Co., Ltd., nonionic surfactant)

(solvent) D-1: Propylene glycol monomethyl ether acetate D-2: cyclopentanone D-4: Butyl acetate D-5: Propylene glycol diacetate

<Performance evaluation> (Evaluation of exposure sensitivity, adhesion, and residue) Each photosensitive composition obtained above was coated on an 8-inch (203.2mm) silicon wafer with a primer layer by spin coating. , so that the film thickness after coating reaches 0.4 μm, and then heated at 100° C. for 2 minutes using a hot plate to form a composition layer. Next, using a KrF scanning exposure machine, ^the obtained composition layer was irradiated with ^light of a wavelength of 248nm ( KrF line) were exposed. Next, the exposed composition layer was spray developed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. After that, pure water is used and rinsed by rotating spray to form pixels. The obtained pixels were observed using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation) at a magnification of 20,000 times. Based on the observed images, the adhesion and residue were evaluated according to the following criteria.

-Evaluation criteria for exposure sensitivity- The exposure amount required to achieve a pattern line width of 0.7 μm was calculated, and the exposure sensitivity was evaluated based on the following criteria. 5: Exposure amount is 60mJ/ ^cm2 or less 4: Exposure amount exceeds 60mJ/ ^cm2 and is less than 100mJ/ ^cm2 3: Exposure amount exceeds 100mJ/ ^cm2 and is less than 150mJ/ ^cm2 2: Exposure amount exceeds 150mJ/cm2 ² and less than 200mJ/cm ² 1: Exposure exceeds 200mJ/cm ²

-Adhesion evaluation- About the obtained pixels, 1071 × 1071 parts among the parts exposed at an exposure dose of 100 mJ/cm ² were observed with an optical microscope, and the number of peeled pixels was counted. Based on the number of peeled pixels, the adhesion was determined based on the following criteria. 5: The number of peeled pixels is 10 or less. 4: The number of peeled pixels is more than 10 and less than 20. 3: The number of peeled pixels is more than 20 and less than 50. 2: The number of peeled pixels is more than 50 and less than 200. Less than 1: The number of stripped pixels exceeds 200

-Evaluation criteria for residues- Regarding the pixels after development, residues were evaluated based on the following criteria. 5: The linearity of pixels is good and there is less residue between pixels. 4: Since the residue pattern at the periphery of the pixel is slightly less linear, there is less residue between pixels. 3: Due to poor linearity of the residue pattern around the pixels, there is less residue between pixels. 2: Due to the poor linearity of the residue pattern around the pixels, there is also a lot of residue between pixels. 1: The pixels are not developed and cannot form pixels.

(Evaluation of Moisture Resistance) On a silicon wafer having a grid structure with a pitch of 0.7 μm, a grid width of 120 nm, and a grid height of 0.4 μm, each photosensitivity obtained above was applied by spin coating. The composition was applied so that the film thickness after coating was 0.4 μm, and then heated at 100° C. for 2 minutes using a hot plate to form a composition layer. Next, the obtained composition layer was irradiated with light of a wavelength of 248 nm (KrF line) using a KrF scanning exposure machine at an illumination intensity of 35000 W/m ² and an exposure amount of 100 mJ/cm ² through a mask having a 0.5 μm square pattern. ) were exposed. Next, the exposed composition layer was spray developed at 23° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. After that, pure water was used and rinsed by rotating spray, and an evaluation substrate with a pattern embedded in the grid was produced. This evaluation substrate was maintained for 168 hours under conditions of 110° C. and 85% humidity using a highly accelerated life (HAST) testing machine (HAST CHAMBER EHS221 manufactured by ESPEC CORP.). The substrate after the moisture resistance test was cut, the cross-sectional shape was observed with a scanning electron microscope (SEM) S-4800 (manufactured by Hitachi High-Tech Corporation), and the moisture resistance was evaluated based on the following criteria. 5: The pattern is embedded in the grid, and no void is observed. 4: The pattern is embedded in the grid, but there are slight gaps. 3: The pattern is embedded in the grid, but there are gaps. 2: The pattern is embedded within the grid but peeled off from it. 1: The pattern is completely peeled off and does not exist within the grid.

[Table 13] exposure sensitivity Tightness residue Moisture resistance Example 1 3 4 4 4 Example 2 4 4 4 5 Example 3 3 4 4 4 Example 4 3 4 4 4 Example 5 4 4 4 5 Example 6 3 3 4 4 Example 7 3 3 3 3 Example 8 3 3 3 3 Example 9 3 3 3 3 Example 10 3 5 4 4 Example 11 5 5 5 5 Example 12 3 5 4 4 Example 13 5 5 5 5 Example 14 5 5 3 5 Example 15 5 5 3 5 Example 16 5 5 3 5 Example 17 5 5 3 5 Example 18 4 4 4 5 Example 19 4 4 4 5 Example 20 5 5 5 5 Example 21 5 5 5 5 Example 22 4 4 4 5 Example 23 4 4 4 5 Example 24 4 4 4 5 Example 25 4 4 4 5 Example 26 4 4 4 5 Example 27 4 4 4 5 Example 28 4 4 4 5 Example 29 4 4 4 5 Example 30 4 4 4 5 Example 31 4 4 4 5 Example 32 4 4 4 5 Example 33 4 4 4 5 Example 34 4 4 4 5 Example 35 4 4 4 5 Example 36 4 4 4 5 Example 37 4 4 4 5 Example 38 4 4 4 5 Example 39 4 4 4 5 Example 40 4 4 4 5

[Table 14] exposure sensitivity Tightness residue Moisture resistance Example 41 4 4 4 5 Example 42 4 4 4 5 Example 43 4 4 4 5 Example 44 4 4 4 5 Example 45 4 4 4 5 Example 46 4 4 3 5 Example 47 4 4 3 5 Example 48 4 4 3 5 Example 49 4 4 4 5 Example 50 4 5 5 5 Example 51 4 5 5 5 Example 52 4 4 4 5 Example 53 5 5 5 5 Example 54 5 5 5 5 Example 55 5 5 4 5 Example 56 4 4 4 5 Example 57 4 4 4 5 Example 58 4 4 4 5 Example 59 4 4 4 5 Example 60 4 4 4 5 Example 61 4 4 4 5 Example 62 5 4 4 5 Example 63 4 3 4 5 Example 64 3 3 4 5 Example 65 4 4 4 5 Example 66 4 4 4 5 Example 67 4 4 3 5 Example 68 4 3 3 5 Example 69 4 4 4 5 Example 70 4 4 4 5 Example 71 5 5 4 5 Example 72 5 5 4 5 Example 73 4 4 4 5 Example 74 4 4 4 5 Example 75 4 4 4 5 Example 76 4 4 4 5 Example 77 4 4 4 5 Example 78 4 4 4 5 Example 79 4 4 4 5 Example 80 4 4 4 5

[Table 15] exposure sensitivity Tightness residue Moisture resistance Example 81 4 4 4 5 Example 82 4 4 4 5 Example 83 4 4 4 5 Example 84 4 4 4 5 Example 85 4 4 4 5 Example 86 5 5 4 5 Example 87 5 5 5 5 Example 88 4 4 4 5 Example 89 4 4 4 5 Example 90 4 4 4 5 Example 91 4 4 4 5 Example 92 4 4 4 5 Example 93 4 4 4 5 Example 94 4 4 4 5 Example 95 4 4 4 5 Example 96 4 4 4 5 Example 97 5 5 5 5 Example 98 5 5 5 5 Example 99 5 5 5 5 Example 100 5 5 5 5 Example 101 5 5 5 5 Example 102 5 5 5 5 Example 103 5 5 5 5 Example 104 5 5 5 5 Example 105 5 5 5 5 Example 106 5 5 5 5 Example 107 5 5 5 5 Example 108 5 5 5 5 Example 109 5 5 5 5 Example 110 5 5 5 5 Example 111 5 5 5 5 Example 112 5 5 5 5 Example 113 5 5 5 5 Example 114 5 5 5 5 Example 115 5 5 5 5 Example 116 5 5 5 5 Example 117 5 5 5 5 Example 118 5 5 5 5 Example 119 5 5 5 5 Example 120 5 5 5 5

[Table 16] exposure sensitivity Tightness residue Moisture resistance Example 121 5 5 5 5 Example 122 5 5 5 5 Example 123 3 4 4 4 Example 124 4 4 4 5 Example 125 3 4 4 4 Example 126 3 4 4 4 Example 127 3 4 4 4 Example 128 4 4 4 5 Example 129 3 4 4 4 Example 130 3 4 4 4 Example 131 3 4 4 4 Example 132 4 4 4 5 Example 133 3 4 4 4 Example 134 3 4 4 4 Example 135 3 4 4 4 Example 136 4 4 4 5 Example 137 3 4 4 4 Example 138 3 4 4 4 Example 139 3 4 4 4 Example 140 4 4 4 5 Example 141 3 4 4 4 Example 142 3 4 4 4 Example 143 3 4 4 4 Example 144 4 4 4 5 Example 145 3 4 4 4 Example 146 3 4 4 4 Comparative example 1 1 1 2 2

As shown in the table above, the colored compositions of the Examples can form pixels excellent in moisture resistance and adhesion.

In each Example, the same effect was obtained even if surfactant W-1 was changed to surfactant W-2 to W-45 shown below. W-2: FZ-2122 (manufactured by Dow Corning Toray Co., Ltd., polysilicone-based surfactant) W-3: BYK-322 (manufactured by BYK-Chemie GmbH, polysilicone surfactant) W-4: BYK-323 (manufactured by BYK-Chemie GmbH, polysilicone-based surfactant) W-6: BYK-3760 (manufactured by BYK-Chemie GmbH, polysilicone-based surfactant) W-7: BYK-UV3510 (manufactured by BYK-Chemie GmbH, polysilicone-based surfactant) W-8: KF-6001 (Shin-Etsu Chemical Co., Ltd., polysilicone-based surfactant) W-9: MEGAFACE F-477 (DIC Corporation, fluorine-based surfactant) W-10: MEGAFACE F-554 (DIC Corporation, fluorine-based surfactant) W-11: MEGAFACE F-555-A (DIC Corporation, fluorine-based surfactant) W-12: MEGAFACE F-556 (DIC Corporation, fluorine-based surfactant) W-13: MEGAFACE F-557 (DIC Corporation, fluorine-based surfactant) W-14: MEGAFACE F-558 (DIC Corporation, fluorine-based surfactant) W-15: MEGAFACE F-559 (DIC Corporation, fluorine-based surfactant) W-16: MEGAFACE F-560 (DIC Corporation, fluorine-based surfactant) W-17: MEGAFACE F-561 (DIC Corporation, fluorine-based surfactant) W-18: MEGAFACE F-563 (DIC Corporation, fluorine-based surfactant) W-19: MEGAFACE F-565 (DIC Corporation, fluorine-based surfactant) W-20: MEGAFACE F-568 (DIC Corporation, fluorine-based surfactant) W-21: MEGAFACE F-575 (DIC Corporation, fluorine-based surfactant) W-22: MEGAFACE R-01 (DIC Corporation, fluorine-based surfactant) W-23: MEGAFACE R-40 (DIC Corporation, fluorine-based surfactant) W-24: MEGAFACE R-40-LM (DIC Corporation, fluorine-based surfactant) W-25: MEGAFACE R-41 (DIC Corporation, fluorine-based surfactant) W-26: MEGAFACE R-41-LM (DIC Corporation, fluorine-based surfactant) W-27: MEGAFACE R-94 (DIC Corporation, fluorine-based surfactant) W-28: MEGAFACE DS-21 (DIC Corporation, fluorine-based surfactant) W-29: MEGAFACE RS-43 (DIC Corporation, fluorine-based surfactant) W-30: MEGAFACE RS-72-K (DIC Corporation, fluorine-based surfactant) W-31: MEGAFACE RS-90 (DIC Corporation, fluorine-based surfactant) W-32: MEGAFACE TF-1956 (DIC Corporation, fluorine-based surfactant) W-33: Futurgent 208G (NEOS COMPANY LIMITED, fluorine-based surfactant) W-34: Futurgent 215M (NEOS COMPANY LIMITED, fluorine-based surfactant) W-35: Futurgent 245F (NEOS COMPANY LIMITED, fluorine-based surfactant) W-36: Futurgent 601AD (NEOS COMPANY LIMITED, fluorine-based surfactant) W-37: Futurgent 601ADH2 (NEOS COMPANY LIMITED, fluorine-based surfactant) W-38: Futurgent 602A (NEOS COMPANY LIMITED, fluorine-based surfactant) W-39: Futurgent 610FM (NEOS COMPANY LIMITED, fluorine-based surfactant) W-40: Futurgent 710FL (NEOS COMPANY LIMITED, fluorine-based surfactant) W-41: Futurgent 710FM (NEOS COMPANY LIMITED, fluorine-based surfactant) W-42: Futurgent 710FS (NEOS COMPANY LIMITED, fluorine-based surfactant) W-43: Futurgent FTX-218 (NEOS COMPANY LIMITED, fluorine-based surfactant) W-44: PF-6320 (manufactured by OMNOVA Solutions Inc., fluorine-based surfactant) W-45: BYK-330 (manufactured by BYK-Chemie GmbH, polysilicone surfactant)

without.

Claims (14)

A photosensitive composition containing a color material, a polymerizable compound and a photopolymerization initiator, wherein the content of the color material in the total solid content of the photosensitive composition is 40% by mass or more, and the polymerizable compound contains The polymerizable compound B1 with an average molecular weight of 3000 or more, the content of the polymerizable compound B1 in the total mass of the polymerizable compound is 50 mass % or more, the photopolymerization initiator contains a compound represented by formula (1), In formula (1), X ¹ represents a bivalent linking group containing at least one selected from the group consisting of aromatic rings and heterocyclic rings, R ¹ represents a hydrogen atom or a hydroxyl group, and R ² represents an alkyl group or an aryl group. , R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group, Alk ¹ and Alk ² each independently represent an alkyl group, R ³ and R ⁴ may be bonded to form a ring, Alk ¹ and Alk ² may be bonded to form a Ring, n represents 0 or 1. The photosensitive composition according to claim 1, wherein X ¹ in formula (1) is a group represented by any one of formulas (X-1) to (X-13), In the formula, R ^X1 to R ^X9 each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group or a heterocyclic group. The photosensitive composition according to claim 2, wherein X ¹ in formula (1) is a group represented by the aforementioned formula (X-2) or formula (X-6). The photosensitive composition as described in claim 1 or claim 2, wherein The polymerizable compound B1 contains a repeating unit having a graft chain. The photosensitive composition as described in claim 1 or claim 2, wherein The polymerizable compound B1 contains a repeating unit having a group containing an ethylenically unsaturated bond in a side chain, and a repeating unit having a graft chain. The photosensitive composition as described in claim 4, wherein The aforementioned graft chain contains a repeating unit of at least one structure selected from the group consisting of a polyester structure, a polyether structure, and a poly(meth)acrylic acid structure. The photosensitive composition as described in claim 1 or claim 2, wherein The content of the color material in the total solid content of the photosensitive composition is 50% by mass or more. The photosensitive composition as described in claim 1 or claim 2, wherein The aforementioned color material contains colorimetric index Pigment Red 272. The photosensitive composition according to Claim 1 or Claim 2, which further contains a polymerization inhibitor. The photosensitive composition according to claim 1 or claim 2, which further contains a polysiloxane surfactant. A film obtained using the photosensitive composition according to Claim 1 or Claim 2. An optical filter having the film described in claim 11. An image display device having the film according to claim 11. A solid-state imaging element having the film according to claim 11.