Dispersion resin, colored composition for color filter, color filter, and solid-state imaging element

Abstract

According to one embodiment of the present invention, provided are a dispersion resin mixed with a pigment for use, a colored composition for a color filter, a color filter, and a solid-state imaging element. The dispersion resin includes: a first portion having an affinity with a pigment; and a second part that functions so as to prevent the particles of the pigment from agglomerating with each other. The refractive index of the dispersion resin at a wavelength of 594 nm is 1.54 or more. According to the embodiment, the refractive index of the color filter can be improved, and the sensitivity characteristic of the solid-state imaging element can be improved.

Description

Technical Field

[0001] The present invention relates to a dispersion resin, a coloring composition for a color filter, a color filter, and a solid-state imaging element. Background Art

[0002] As the unit pixel of a solid-state imaging element becomes smaller, its size is gradually becoming smaller than 1.0 μmY (a square with a side length of 1 μm when the unit pixel is viewed from above). In addition, due to the miniaturization and thinning of electronic devices (smartphones, digital cameras, etc.) equipped with solid-state imaging elements, it is necessary to ensure and further improve the sensitivity characteristics.

[0003] In order to improve the sensitivity characteristics of a solid-state imaging element, it is necessary to reduce the thickness of the color filter in the longitudinal direction (shrink in the three-dimensional direction) by thinning the color filter in accordance with the miniaturization of the unit pixel (shrink in the two-dimensional direction).

[0004] In particular, in a small camera module in which a solid-state imaging element is integrated with an optical lens, light incident on the edge of the solid-state imaging element becomes oblique incident light, so that sensitivity characteristics of the solid-state imaging element deteriorate, and sensitivity shading tends to deteriorate significantly.

[0005] Patent Document 1 discloses a technique of providing a partition wall having a refractive index lower than that of a color filter and forming a color filter in an opening of the partition wall, thereby improving the sensitivity characteristics of a solid-state imaging element and reducing color mixing.

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] [Patent Document 1] International Publication No. 2019 / 064993 Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] According to the research conducted by the present inventors, in order to further improve the sensitivity characteristics of the solid-state imaging element, it is effective to increase the refractive index of the color filter.

[0011] Therefore, in view of the above situation, the present invention focuses on the dispersion resin used for dispersing the pigment, and provides a dispersion resin with an improved refractive index, a coloring composition for a color filter with a high refractive index, a color filter, and a solid-state imaging element with improved sensitivity characteristics.

[0012] [Technical means to solve the problem]

[0013] According to one embodiment of the present invention, a dispersion resin is provided for use in combination with a pigment. The dispersion resin includes: a first portion having affinity with the pigment; and a second portion functioning to prevent the aggregation of pigment particles. The refractive index of the dispersion resin at a wavelength of 594 nm is greater than 1.54.

[0014] According to the above-described embodiment, the refractive index of the color filter can be increased, thereby improving the sensitivity characteristics of the solid-state imaging element. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 It is a perspective view showing a camera module.

[0016] Figure 2 It is a longitudinal sectional view showing the structure of the camera body.

[0017] Figure 3 Yes Figure 2 A diagram showing an enlarged portion of a portion.

[0018] Explanation of symbols

[0019] 1: Camera body

[0020] 2: Solid-state imaging element

[0021] 3: Optical system

[0022] 4: Joint

[0023] 21: Light receiving substrate

[0024] 22: Bonding substrate

[0025] 23: Cover substrate

[0026] 24: Spacer

[0027] 31: Frame

[0028] 32: First convex lens

[0029] 33: Second convex lens

[0030] 34: Infrared cut filter

[0031] 35: Joint

[0032] 100: Camera module

[0033] 210: Unit pixel

[0034] 211: Base plate (base)

[0035] 212: Photodiode (photoelectric conversion element)

[0036] 213: Insulation film

[0037] 215: Color filter

[0038] 215R: Red filter unit (color filter unit, filter unit)

[0039] 215G: Green filter unit (color filter unit, filter unit)

[0040] 215B: Blue filter unit (color filter unit, filter unit)

[0041] 216: Separation Wall

[0042] 217: Microlens

[0043] 221: Substrate

[0044] 222: Through hole (conductive part)

[0045] 223: Connecting terminal

[0046] 311: Opening

[0047] 2171: Convex surface

[0048] B: Flexible wiring board

[0049] C: Connector

[0050] H: Height (thickness)

[0051] T B , T G , T R :Thickness (thickest part)

[0052] W: Width DETAILED DESCRIPTION

[0053] Hereinafter, the dispersion resin, the coloring composition for color filters, the color filter, and the solid-state imaging element of the present invention will be described in detail based on the preferred embodiments shown in the drawings.

[0054] In addition, the following description is intended to illustrate the present invention and does not limit the scope of the present invention. Of course, other embodiments may also fall within the scope of the present invention as long as they conform to the gist of the present invention.

[0055] For example, in the present invention, "process" refers not only to a process that can be distinguished and identified from other processes, but also to a process combined with other operations, a process that is actually dispersed in multiple processes, a process that includes other process elements in the "process", and a process that can combine and implement multiple processes in one process. As long as it conforms to the main purpose of the invention, it can fall within the scope of the present invention.

[0056] Definition of terms used in this specification. The refractive index is a value measured when a film with a thickness of 1 μm is formed. A graft copolymer is a polymer having a structure in which a polymer chain with a side chain is bonded to the main chain. A dispersion resin is a dispersant for a polymer.

[0057] <Camera modules and solid-state imaging devices>

[0058] Figure 1 It is a perspective view showing a camera module. Figure 2 It is a longitudinal sectional view showing the structure of the camera body. Figure 3 Yes Figure 2 In the following description, Figure 2 and Figure 3 The upper side in the description is also referred to as “upper” or “above”, and the lower side is also referred to as “lower” or “below”.

[0059] Figure 1 The camera module 100 shown includes a camera body 1 having a solid-state imaging element, a connector C, and a flexible wiring board B that electrically connects the camera body 1 and the connector C. In addition, a rigid wiring board may be used instead of the flexible wiring board B.

[0060] like Figure 2 As shown, the camera body 1 includes a solid-state imaging element 2 and an optical system 3 bonded to the upper side of the solid-state imaging element 2 via a bonding portion 4 .

[0061] The solid-state imaging element 2 includes a light receiving substrate 21 , a bonding substrate 22 formed in close contact with the lower side of the light receiving substrate 21 , and a cover substrate 23 bonded to the upper side of the light receiving substrate 21 via a spacer 24 .

[0062] Here, a silicon substrate is used as the bonding substrate 22, for example. A logic circuit substrate may also be formed (laminated) on the silicon substrate. Furthermore, the logic circuit substrate formed as the bonding substrate 22 may also be a multi-layer laminated substrate including a dynamic random access memory (DRAM) substrate or the like.

[0063] The light receiving substrate 21 will be described in detail later.

[0064] The bonding substrate 22 includes a substrate 221 , a wiring layer (not shown) formed on the surface and / or inside of the substrate 221 , a plurality of through holes (conductive portions) 222 penetrating the substrate 221 , and connection terminals 223 provided corresponding to and electrically connected to the through holes 222 .

[0065] The substrate 221 is made of, for example, a hard resin material, an insulating material such as a ceramic material, etc. The through holes 222 and the connection terminals 223 are each made of, for example, a conductive material.

[0066] The spacer 24 includes various adhesive materials, and if necessary, spacer particles may be mixed in. In addition, the spacer 24 may also include a frame formed of a metal material, a ceramic material, or the like.

[0067] The cover substrate 23 is made of a light-transmitting material such as a glass material (including quartz) or a resin material.

[0068] The optical system 3 includes a frame 31 having an opening 311 , a first convex lens 32 and a second convex lens 33 disposed in the frame 31 , and an infrared cut filter 34 bonded to the lower side of the frame 31 via a bonding portion 35 .

[0069] The bonding portion 35 and the bonding portion 4 may each include, for example, an acrylic resin adhesive, an epoxy resin adhesive, a vinyl chloride resin adhesive, or the like.

[0070] The frame 31 is made of a black or dark material or a light-shielding material to ensure light-shielding properties inside the camera body 1 .

[0071] The first convex lens 32 and the second convex lens 33 both have convex surfaces protruding downward. Figure 2 As shown, incident light passing through the opening 311 of the frame body 31 is diffused when passing through the first convex lens 32 and the second convex lens 33 , and then enters the solid-state imaging element 2 .

[0072] like Figure 3 As shown, the light receiving substrate 21 includes a substrate 211, a plurality of photodiodes (photoelectric conversion elements) 212, an insulating film 213, a partition wall 216, a color filter 215, and a microlens 217. Figure 3 In the drawings, hatching indicating cross sections is omitted from the viewpoint of preventing the drawings from becoming difficult to see.

[0073] The light that has passed through the microlens 217 and the color filter 215 is incident on and received by the photodiode 212. That is, the solid-state imaging element 2 includes the color filter 215 and a plurality of photodiodes 212 that receive the light that has passed through the color filter 215.

[0074] The substrate (base) 211 may include, for example, a silicon substrate, an InGaAs substrate, etc. In addition, a base layer may be formed on the surface of the substrate 211 for the purpose of improving adhesion, preventing diffusion of substances, improving flatness, etc.

[0075] In addition, the substrate 211 may be formed integrally with the substrate 221 of the bonding substrate 22 by, for example, plasma bonding or the like. In such a case, the solid-state imaging element 2 is also referred to as a back-illuminated solid-state imaging element.

[0076] A plurality of photodiodes 212 are provided on the upper surface (one surface) side of the substrate 211. The plurality of photodiodes 212 may be formed integrally with the substrate 211, or may be arranged (mounted) on the upper surface of the substrate 211.

[0077] The photodiode 212 may include, for example, a silicon photodiode, an InGaAs photodiode, a single layer of an organic photoelectric conversion layer or an inorganic photoelectric conversion layer, and a stack containing an organic photoelectric conversion layer or an inorganic photoelectric conversion layer, a single layer of a photoelectric conversion layer containing quantum dots, and a stack containing a photoelectric conversion layer containing quantum dots, etc.

[0078] Here, in Figure 2 The lower left corner of FIG. 1 shows an enlarged plan view of a portion of the light receiving substrate 21 surrounded by a dotted line.

[0079] In this specification, when the light receiving substrate 21 is viewed from above, the photodiode 212 and a region including the photodiode 212 to the center of a partition wall 216 formed between adjacent photodiodes 212 are defined as a “unit pixel 210 ”.

[0080] The size of the photodiode 212 in a plan view is not particularly limited, but is preferably about 0.8 μmY, and can be larger or smaller as necessary.

[0081] An insulating film 213 is provided on the plurality of photodiodes 212 .

[0082] The insulating film 213 may include, for example, a silicon oxide film, a silicon nitride oxide film, a hafnium oxide film, an aluminum oxide film, a zirconium oxide film, a tantalum oxide film, a titanium oxide (TiO 2 ) film, or the like.

[0083] A partition wall 216 is provided on the insulating film 213 (ie, on the upper surface side of the substrate 211). The partition wall 216 is provided upright on the upper surface of the insulating film 213 along the gap so as to divide the plurality of photodiodes 212.

[0084] The color filter 215 is provided so as to fill the space defined by the partition wall 216 and cover the upper surface (the surface on the opposite side to the substrate 211 ) of the partition wall 216 .

[0085] The color filter 215 includes red filter units 215R, green filter units 215G, and blue filter units 215B provided respectively corresponding to the plurality of photodiodes 212. Each of the filter units 215R, 215G, and 215B is formed of a coloring composition for a color filter described later.

[0086] That is, the color filter 215 includes a plurality of color filter units 215R, 215G, and 215B formed of a coloring composition for a color filter filled in at least a space partitioned by the partition wall 216 .

[0087] The red filter unit 215R preferably has a high transmittance for light having a wavelength of about 580 nm or more, and has a transmittance as low as possible for light having other wavelengths.

[0088] The green filter unit 215G preferably has a high transmittance for light having a wavelength of approximately 480 nm or more and 600 nm or less, and has a transmittance as low as possible for light having other wavelengths.

[0089] The blue filter unit 215B preferably has a high transmittance for light having a wavelength of approximately 400 nm or more and 500 nm or less, and has a transmittance as low as possible for light having other wavelengths.

[0090] In addition, in addition to the red filter unit 215R, the green filter unit 215G and the blue filter unit 215B, the color filter 215 may also have a yellow filter unit, a cyan filter unit, a magenta filter unit, a transparent filter unit that is substantially transparent under visible light, a dimming filter unit whose spectral transmittance of visible light is approximately constant (flat), a near-infrared absorption filter unit, a near-infrared transmitting filter unit, etc.

[0091] A microlens 217 is provided on the color filter 215 (on the side opposite to the substrate 211). The microlens 217 has a plurality of convex curved surfaces 2171 protruding toward the upper side (on the side opposite to the color filter 215).

[0092] The microlens 217 may include, for example, styrene-acrylic copolymer resin, silicon nitride, or the like.

[0093] Furthermore, an anti-reflection layer may be additionally provided between the microlens 217 and the color filter 215 .

[0094] Thickness (thickest part) of the red filter unit 215R R It is preferable that the thickness (thickest part) of the green filter unit 215G is equal to T G and the thickness (thickest part) of the blue filter unit 215B T BGenerally speaking, it is difficult to make the thickness T of the red filter unit 215R R Than the thickness T of the green filter unit 215G G and the thickness T of the blue filter unit 215B B Thin, but can be achieved by using the red composition described later.

[0095] According to the above structure, the color filter 215 can be made thinner, the light receiving substrate 21 (solid-state imaging element 2) can be made thinner, and its sensitivity characteristics can be further improved.

[0096] The thickness T of the red filter unit 215R R , the thickness T of the green filter unit 215G G and the thickness T of the blue filter unit 215B B The maximum value of is preferably 0.55 μm or less, more preferably 0.5 μm or less, and further preferably 0.45 μm or less. The light receiving substrate 21 (solid-state imaging element 2) including such a thin color filter 215 can be sufficiently thinned.

[0097] The lower limit of the maximum value is not particularly limited, but is preferably 0.2 μm or more, more preferably 0.25 μm or more, and further preferably 0.3 μm or more. Thus, the color filter 215 can exhibit necessary and sufficient spectral characteristics. As a result, the solid-state imaging element 2 can obtain high-quality images.

[0098] Especially the thickness T R In the red filter unit 215R of 0.55 μm, the transmittance of light with a wavelength of 620 nm is preferably 80% or more, the transmittance of light with a wavelength of 530 nm is preferably 10% or less, and the refractive index relative to light with a wavelength of 650 nm is preferably 1.8 or more. The red filter unit 215R exhibits excellent light-gathering properties and can further improve the sensitivity of the solid-state imaging element 2.

[0099] The transmittance of the light having a wavelength of 620 nm of the red filter unit 215R is more preferably 85% or more, and further preferably 90% or more.

[0100] The transmittance of the red filter unit 215R for light of a wavelength of 530 nm is more preferably 8% or less, and further preferably 6% or less.

[0101] The refractive index of the red filter unit 215R with respect to light having a wavelength of 650 nm is more preferably 1.85 or more, and further preferably 1.9 or more.

[0102] In addition, the refractive index of the red filter unit 215R with respect to light of a wavelength of 650 nm is n. R, the refractive index of the green filter unit 215G with respect to light of wavelength 550nm is set to n G , the refractive index of the blue filter unit 215B with respect to light of wavelength 450nm is set to n B When n R >n G ≧ B Thus, when the red light having a smaller focusing angle in the microlens 217 enters the red filter unit 215R, it can be refracted (focused) at a larger angle. Therefore, more light can reach the photodiode 212. As a result, better sensitivity characteristics can be obtained at the end of the light receiving substrate 21.

[0103] When the refractive indices of filter unit 215R, filter unit 215G, and filter unit 215B are set to the above relationship, the composition of the coloring resin composition used to form filter unit 215R, filter unit 215G, and filter unit 215B can be adjusted by, for example, selecting the type and amount of the pigment (pigment) used, the type and amount of the pigment's binder, the type and amount of the dispersed resin, etc.

[0104] Refractive index n R The specific value of is not particularly limited, but is preferably 1.7 or more, more preferably 1.75 or more, and further preferably 1.8 or more.

[0105] Refractive index n G The specific value of is not particularly limited, but is preferably 1.6 or more, more preferably 1.63 or more, and further preferably 1.7 or more.

[0106] In addition, the refractive index n B The specific value of is not particularly limited, but is preferably 1.6 or more, more preferably 1.63 or more, and further preferably 1.64 or more.

[0107] The entire partition wall 216 includes a portion of the red filter element 215R having a refractive index n R , the refractive index n of the green filter unit 215G G and the refractive index n of the blue filter unit 215B B A low refractive index portion.

[0108] According to the structure, due to the total reflection effect of light (preventing light from passing through), the light passing through the filter unit 215R, the filter unit 215G, and the filter unit 215B is reflected by the isolation wall 216 and guided to the photodiode 212, so that the sensitivity characteristics of the light receiving substrate 21 (solid-state imaging element 2) are further improved.

[0109] If the difference between the refractive index of the filter unit 215R, the filter unit 215G, and the filter unit 215B and the refractive index of the partition wall 216 is further increased, the critical angle can be reduced. Therefore, the sensitivity characteristics of the light receiving substrate 21 can be further improved.

[0110] In addition, the refractive index (n R 、n G 、n B ) and the refractive index difference between the partition wall 216 and the partition wall 216 is preferably 0.01 or more, more preferably 0.1 or more, and further preferably 0.2 or more. In this case, the critical angle can be further reduced, and the total reflection characteristics of light of the partition wall 216 can be further improved.

[0111] The specific value of the refractive index of the partition wall 216 is not particularly limited, but the refractive index with respect to light of a wavelength of 450 nm is preferably 1.44 or less, more preferably 1.42 or less, and still more preferably 1.4 or less.

[0112] like Figure 3 As shown, the width W of the isolation wall 216 is preferably 50 nm to 300 nm, more preferably 50 nm to 280 nm, and further preferably 50 nm to 260 nm. In this case, the degradation of the total reflection effect of light can be prevented or suppressed, and a good pixel size (size of the photodiode 212) can be ensured while maintaining the mechanical strength of the isolation wall 216.

[0113] In addition, if Figure 3 As shown in FIG. 1 , the height (thickness) H of the partition wall 216 is formed to be larger than the thickness (T R , T G , T B ) is thinner, preferably less than 0.52 μm. In this way, the partition wall 216 is formed thinner than the color filter 215, and the color filter 215 covers the upper surface of the partition wall 216, thereby suppressing the mixing of white light passing through the partition wall 216, and also making the light receiving substrate 21 sufficiently thin.

[0114] As a constituent material of the partition wall 216, a composition including a resin material and inorganic particles can be preferably used.

[0115] Examples of the resin material include at least one selected from silicone resins, fluorine-based resins, and the like.

[0116] Inorganic particles include, for example, at least one selected from SiO particles, SiOC particles, hollow silica particles, metal fillers, carbon particles (e.g., carbon black), etc. Among these, silica particles can be preferably used among inorganic particles from the viewpoint of improving the strength of the partition wall 216. Among these, hollow silica particles can be particularly preferably used among inorganic particles because they can improve the strength of the partition wall 216 and reduce the refractive index.

[0117] The thickness of the color filter 215 may be set to be substantially equal to or slightly smaller than the height of the partition wall 216. In this case, the light receiving substrate 21 (solid-state imaging element 2) can be made thinner (lower in height).

[0118] The color filter 215 is formed (configured) using the coloring composition for color filter of the present invention (hereinafter, also simply referred to as “coloring composition”).

[0119] The coloring composition contains at least a pigment and a dispersion resin (the dispersion resin of the present invention).

[0120] <<Pigment>>

[0121] As a pigment, it is preferred that the particle size is as small as possible. Considering the dispersibility in the coloring composition and the handling of the pigment, the average particle size of the pigment is preferably 0.001 μm or more and 0.1 μm or less, and more preferably 0.005 μm or more and 0.05 μm or less. In addition, the pigment preferably contains particles having a particle size within the range of 0.01 μm ± 0.005 μm in an amount of 75% by mass or more relative to the total mass of the pigment.

[0122] Here, the average particle size refers to the particle size (D50) at which the volume ratio of particles with smaller particle sizes is 50%. The average particle size can be measured using a general particle size distribution meter, such as a dynamic light scattering particle size distribution meter.

[0123] As the pigment, either an inorganic pigment or an organic pigment can be used.

[0124] Examples of the inorganic pigment include metal oxides and metal compounds such as metal complex salts, etc. Specific examples thereof include metal oxides containing metals such as aluminum, iron, cobalt, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides containing these metals.

[0125] On the other hand, examples of organic pigments include: Color Index (hereinafter referred to as "CI") Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199; CI Pigment Orange 36, 38, 43, 71; CI Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270; CI Pigment Violet 19, 23, 32, 39; CI Pigment Blue CI Pigment Green: 7, 36, 37, 58, 59, 62, 63; CI Pigment Brown: 25, 28, etc.

[0126] The organic pigment may be used alone or in combination of two or more in order to improve the color purity.

[0127] Specifically, as the red pigment, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments can be used alone, or at least one of them can be used in combination with a disazo yellow pigment, isoindoline yellow pigment, quinophthalone yellow pigment, perylene red pigment, or the like.

[0128] For example, an anthraquinone-based pigment includes CI Pigment Red 177, perylene-based pigments include CI Pigment Red 155 and CI Pigment Red 224, and diketopyrrolopyrrole-based pigments include CI Pigment Red 254.

[0129] In addition, the red pigment is preferably used in combination with a yellow pigment such as CI Pigment Yellow 138 or CI Pigment Yellow 139 from the viewpoint of color reproducibility.

[0130] In this case, the mass ratio of the red pigment to the yellow pigment is preferably 100:5 to 100:50, more preferably 100:10 to 100:30. If the mass ratio is within the above range, the light transmittance of the red filter unit 215R can be suppressed and the color purity can be improved.

[0131] When different types of red pigments are used in combination, their mass ratio can be adjusted together with the chromaticity.

[0132] As the green pigment, a halogenated phthalocyanine pigment may be used alone or in combination with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment.

[0133] Green pigments are preferably CI Pigment Green 7, 36, 37, 58, 59, 62, 63, etc. In addition, these green pigments are preferably used in combination with yellow pigments such as CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI Pigment Yellow 185.

[0134] In this case, the mass ratio of the green pigment to the yellow pigment is preferably 100:5 or more and 100:150 or less, and more preferably 100:30 or more and 100:120 or less. If the mass ratio is within the above range, the transmittance of light with a wavelength of 400 nm or more and 450 nm or less in the green filter unit 215G can be suppressed, thereby improving color purity.

[0135] As the blue pigment, a phthalocyanine-based pigment may be used alone or in combination with a dioxazine-based violet pigment.

[0136] As a blue pigment, for example, CI Pigment Blue 15:6 and CI Pigment Violet 23 are preferably used in combination.

[0137] In this case, the mass ratio of the blue pigment to the violet pigment is preferably 100:0 or more and 100:30 or less, and more preferably 100:0 or more and 100:10 or less.

[0138] The pigment is preferably mixed with other raw materials after being subjected to micronization treatment.

[0139] Examples of the method for the micronization process include wet milling, dry milling, and dissolution separation.

[0140] Among these, the method of the micronization treatment is preferably a salt milling treatment using a kneading method which is a type of wet milling.

[0141] The salt milling treatment is a treatment in which a mixture of a pigment, a water-soluble inorganic salt and a water-soluble organic solvent is mechanically kneaded with heating using a kneading machine, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water.

[0142] As the kneading machine, for example, a batch kneading machine or a continuous kneading machine such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer can be preferably used.

[0143] The water-soluble inorganic salt is a compound that functions as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling.

[0144] By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0145] Examples of the water-soluble inorganic salt include sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. Among these, the water-soluble inorganic salt is available at low cost, and therefore sodium chloride (common salt) is preferred.

[0146] The amount of the water-soluble inorganic salt used is preferably 50 parts by mass or more and 2,000 parts by mass or less, and more preferably 300 parts by mass or more and 1,000 parts by mass or less, based on 100 parts by mass of the pigment, in terms of both treatment efficiency and production efficiency.

[0147] The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt.

[0148] As the water-soluble organic solvent, it is preferable to use a compound which is soluble (mixable) in water and does not substantially dissolve the water-soluble inorganic salt.

[0149] The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120° C. or higher from the viewpoint of being difficult to volatilize due to the temperature rise during salt milling.

[0150] Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol.

[0151] The amount of the water-soluble organic solvent used is preferably 5 parts by mass or more and 1,000 parts by mass or less, and more preferably 50 parts by mass or more and 500 parts by mass or less, relative to 100 parts by mass of the pigment.

[0152] When salt milling the pigment, resin can be added as needed.

[0153] The type of resin is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified from natural resins, and the like can be used.

[0154] The resin is solid at room temperature, preferably water-insoluble, and further preferably partially soluble in the organic solvent.

[0155] The amount of the resin used is preferably 5 parts by mass or more and 200 parts by mass or less relative to 100 parts by mass of the pigment.

[0156] Furthermore, by finely dispersing the pigment in, for example, an acrylic resin, a maleic resin, a vinyl chloride-vinyl acetate copolymer, an ethyl cellulose resin, etc. to produce a powdered processed pigment, a coloring composition having excellent dispersibility and dispersion stability can be obtained.

[0157] The coloring composition can be preferably used in the form of powder, paste, granules or the like.

[0158] <<Dispersion resin>>

[0159] The dispersion resin is mixed with the above-mentioned pigment and used. The dispersion resin includes a first part and a second part, and the first part has a higher affinity for the pigment than the second part.

[0160] Therefore, the dispersion resin is coordinated with respect to the pigment particles in such a manner that the first site is the pigment particle side and the second site is the side opposite to the pigment particles (solvent side). Thus, the second site functions as a steric repulsion site, and the pigment particles can be prevented from agglomerating with each other, thereby obtaining a coloring composition with excellent dispersion stability.

[0161] That is, the dispersion resin includes a first portion having affinity for the pigment and a second portion that functions to prevent aggregation of pigment particles.

[0162] The refractive index of the dispersion resin at a wavelength of 594 nm is 1.54 or more. By using the dispersion resin having a high refractive index, a color filter 215 (particularly a red filter unit 215R) with a high refractive index can be formed. Therefore, even if the thickness is reduced (the height is reduced), a solid-state imaging element with excellent sensitivity characteristics can be obtained.

[0163] As long as the refractive index of the dispersed resin at a wavelength of 594nm is more than 1.54, it is preferably more than 1.54 and less than 1.65, more preferably more than 1.55 and less than 1.63. In this case, the effect can be further improved. In addition, the dispersed resin with a refractive index exceeding the upper limit value sometimes reduces the dispersibility of the pigment.

[0164] The refractive index of the dispersion resin can be adjusted by appropriately designing the molecular structure of the dispersion resin. According to the research of the present inventors, the refractive index of the dispersion resin containing an aromatic ring in particular tends to be higher.

[0165] Here, the aromatic ring includes an aromatic aliphatic ring and an aromatic heterocyclic ring, which may be monocyclic or polycyclic. In addition, the polycyclic aromatic ring may be a bonding type in which multiple aromatic rings are bonded (e.g., a biphenyl ring, etc.), or a condensation type in which multiple aromatic rings are condensed (e.g., a naphthalene ring, etc.).

[0166] The proportion of aromatic rings in the total mass of the dispersed resin is preferably 25% by mass or more, more preferably 30% by mass or more and 80% by mass or less, and further preferably 35% by mass or more and 75% by mass or less. By including aromatic rings in the above proportion, the refractive index of the dispersed resin can be set to the above range. In addition, there is a trade-off relationship between the proportion of aromatic rings exceeding the above upper limit and the dispersibility of the pigment.

[0167] The proportion of aromatic rings in the total mass of the dispersed resin. In this specification, the molecular weight of the aromatic ring can be calculated by defining benzene (C6H6) as about 78. First, the proportion of aromatic rings in the monomer having an aromatic ring (first value) is calculated from the ratio of the molecular weight of the aromatic ring to the molecular weight of the monomer. Next, the proportion of the monomer having an aromatic ring in the dispersed resin (second value) is calculated from the charge amount (mass) of the monomer constituting the dispersed resin (polymer). Thereafter, the proportion of the aromatic ring in the total mass of the dispersed resin is calculated by accumulating the first value and the second value.

[0168] The dispersion resin may contain an aromatic ring only in the first part, may contain an aromatic ring only in the second part, or may contain an aromatic ring in both the first part and the second part. However, the dispersion resin preferably contains an aromatic ring mainly in the second part. Thus, the affinity of the dispersion resin for the pigment can be prevented or suppressed from decreasing, while the refractive index of the dispersion resin is fully increased. In addition, it also shows a tendency to improve the function of preventing the aggregation of the pigment particles.

[0169] The proportion of the aromatic ring in the mass of the second part is preferably 20% by mass or more, more preferably 25% by mass or more and 70% by mass or less, and further preferably 27% by mass or more and 65% by mass or less. By including the aromatic ring in the above proportion, the refractive index of the dispersed resin can be set to the above range. If the proportion of the aromatic ring is less than 20% by mass, the desired refractive index cannot be obtained.

[0170] The proportion of the aromatic ring in the mass of the second part, the molecular weight of the aromatic ring can be calculated by defining benzene (C6H6) as about 78. First, the proportion of the aromatic ring in the monomer having an aromatic ring (first value) is calculated by the ratio of the molecular weight of the aromatic ring to the molecular weight of the monomer. Next, the proportion of the monomer having an aromatic ring in the second part (second value) is calculated from the charge amount (mass) of the monomer constituting the second part (polymer). Thereafter, the proportion of the aromatic ring in the mass of the second part is calculated by accumulating the first value and the second value.

[0171] The weight average molecular weight of the dispersion resin is preferably 5,000 to 50,000, more preferably 6,000 to 40,000, and still more preferably 7,000 to 25,000. The dispersion resin having such a weight average molecular weight can highly exert the function of preventing the aggregation of pigment particles.

[0172] The weight average molecular weight is a value measured by gel permeation chromatography (GPC method) in terms of polystyrene.

[0173] Dispersed resins include, for example, graft copolymers (hereinafter, also described as "graft copolymers") in which the second part branches and extends from the first part, block copolymers (hereinafter, also described as "block copolymers") in which the first part and the second part are bonded to each other at the ends, random copolymers in which the first part and the second part are randomly bonded, etc. Among these, the dispersed resin is preferably a graft copolymer or a block copolymer. If it is a dispersed resin of the molecular structure, the effect of affinity with the pigment based on the first part and the effect of being a stereo repulsive part based on the second part can be well balanced.

[0174] Graft copolymer

[0175] The graft copolymer preferably has an acidic group (e.g., carboxyl, phosphoric acid, sulfonic acid) at the first site, and more preferably contains an aromatic ring directly bonded with a total of 3 or more carboxyl groups or carboxyl residues at the first site. In this case, the first site of the graft copolymer contains an acidic group (especially a carboxyl group) having a property of a strong acid, and thus can show extremely high affinity for particles of pigments showing alkaline properties on the surface. Such a graft copolymer can also be called an acidic dispersing resin.

[0176] Furthermore, part or all of the aromatic ring may be substituted by another aromatic ring to which two carboxyl residues are directly bonded. Examples of the other aromatic ring include naphthalene-type aromatic rings, bisphenol A-type aromatic rings, and biphenyl-type aromatic rings.

[0177] In addition, the structural unit of the first part of the graft copolymer is preferably a polyester connected by an ester bond. The first part containing an ester bond is formed by the reaction of a compound (monomer) having a carboxyl group (or anhydride group) and a compound (monomer) having a hydroxyl group. The reaction can be relatively easy to produce, and the compound used for the reaction can also be relatively easy to obtain, so it is preferred.

[0178] If the second part of the graft copolymer can function as a steric repulsion site, its molecular structure is not particularly limited, but is preferably a polymer site of a monomer having an ethylenically unsaturated bond. With respect to the polymer site, its chain length (weight average molecular weight) can be adjusted relatively easily. In addition, it also has the following advantages: it is easy to introduce a substituent (side chain) corresponding to the purpose such as polymerizability (e.g., photopolymerizability) and alkali solubility into the polymer site. The monomer having an ethylenically unsaturated bond (hereinafter, also recorded as "unsaturated monomer") preferably uses a monomer having a base containing a double bond, a monomer having a (meth)acryloyl group, etc.

[0179] Here, in the present specification, when expressed as “(meth)acryloyl”, “(meth)acrylic acid”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide”, unless otherwise specified, it means “acryloyl and / or methacryloyl”, “acrylic acid and / or methacrylic acid”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively.

[0180] Regarding such a graft copolymer, for example, there can be mentioned (I) a method of reacting at least one acid anhydride selected from the group consisting of tetracarboxylic anhydride and tricarboxylic anhydride with a separately synthesized vinyl polymer having a hydroxyl group near the terminal, or (II) a method of reacting a hydroxyl-containing thiol with the acid anhydride and then forming a vinyl polymer part by a polymerization reaction starting from the thiol group of the thiol.

[0181] In other words, the graft copolymer is a resin (polymer) composed of a polyester part (first part) having a carboxyl group and a vinyl polymer part (second part).

[0182] As tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example.

[0183] Specific examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuranyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, and bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetrahydrofurantetracarboxylic dianhydride.

[0184] Specific examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, ethylene glycol trimellitic anhydride, propylene glycol trimellitic anhydride, butanediol trimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-diphenyl sulfone tetracarboxylic dianhydride, ,4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether Dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride, and the like.

[0185] Examples of the aromatic tetracarboxylic dianhydride include compounds represented by the following general formula (1) or (2).

[0186] General formula (1):

[0187] [Chemistry 1]

[0188]

[0189] [In the general formula (1), k is 1 or 2]

[0190] General formula (2):

[0191] [Chemistry 2]

[0192]

[0193] [In the general formula (2), Q1 is a direct bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following general formula (3), or a group represented by the following general formula (4)]

[0194] General formula (3):

[0195] [Chemistry 3]

[0196]

[0197] General formula (4):

[0198] [Chemistry 4]

[0199]

[0200] Among these, from the viewpoint of excellent adsorption property to a pigment, as tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride is preferred, and tetracarboxylic dianhydride having two or more aromatic rings is more preferred.

[0201] Aromatic tetracarboxylic dianhydride may be used in combination with aliphatic tetracarboxylic dianhydride.

[0202] Examples of the tricarboxylic anhydride include benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenyl ethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride.

[0203] Among these, as the tricarboxylic anhydride, trimellitic anhydride is preferred.

[0204] In the present invention, the unsaturated monomer used is preferably an unsaturated monomer having an aromatic ring.

[0205] Examples of the unsaturated monomer having an aromatic ring include (meth)acrylates such as benzyl (meth)acrylate, phenylene (meth)acrylate, phenoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and 3-methyl-3-oxetanyl (meth)acrylate; phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate; (Poly)alkylene glycol (meth)acrylates such as acrylates, p-cumylphenoxyethyl (meth)acrylate, p-cumylphenoxyethylene glycol (meth)acrylate, p-cumylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate; styrenes such as styrene and α-methylstyrene (vinyl toluene); carbazoles such as vinyl carbazole, etc.

[0206] Furthermore, as the unsaturated monomer, other unsaturated monomers may be used in addition to the unsaturated monomer having an aromatic ring.

[0207] Other unsaturated monomers include, for example, linear or branched alkyl (meth)acrylates; cyclic alkyl (meth)acrylates; (meth)acrylates having a hydroxyl group; (poly)alkylene glycol monoalkyl ether (meth)acrylates; (meth)acrylates having an alkoxysilyl group; (meth)acrylate fluoroalkyl esters; (meth)acryloyloxy-modified polydimethylsiloxanes (silicone macromolecular monomers); vinyl ethers; fatty acid vinyl esters, etc.

[0208] Examples of the linear or branched alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate.

[0209] Examples of the cyclic alkyl (meth)acrylate include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate.

[0210] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxypropyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 5-hydroxy-3-methylpentyl (meth)acrylate, neopentyl glycol mono(meth)acrylate, and cyclohexanediol mono(meth)acrylate.

[0211] Examples of the (poly)alkylene glycol monoalkyl ether (meth)acrylate include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, polyethylene glycol monostearyl ether (meth)acrylate, and octyloxy polyethylene glycol-polypropylene glycol (meth)acrylate.

[0212] Examples of the (meth)acrylate having an alkoxysilyl group include 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane.

[0213] Examples of the fluoroalkyl (meth)acrylate include trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate.

[0214] Examples of the vinyl ether include ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether.

[0215] Examples of fatty acid vinyl esters include vinyl acetate and vinyl propionate.

[0216] The hydroxyl group-containing thiol is preferably a compound having two hydroxyl groups and one thiol group.

[0217] Examples of the hydroxyl-containing thiol include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethylenediol, 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0218] The equivalent ratio of the anhydride group in the acid anhydride to the hydroxyl group in the hydroxyl-containing thiol is preferably anhydride group / hydroxyl group = 0.15 to 1.25, more preferably 0.3 to 1. This further improves the dispersion stability of the pigment based on the graft copolymer.

[0219] The weight average molecular weight of the vinyl polymer part in the graft copolymer is preferably 1,000 to 20,000, more preferably 3,000 to 15,000. When the vinyl polymer part has an appropriate weight average molecular weight, the dispersion stability of the pigment based on the graft copolymer is further improved.

[0220] The proportion of the vinyl polymer part (second part) in the total mass of the graft copolymer is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more and 80% by mass or less. This can prevent the affinity of the graft copolymer for the pigment from being reduced, while giving full play to the steric repulsion based on the second part of the graft copolymer.

[0221] The acid value of the graft copolymer is preferably 5 mgKOH / g to 200 mgKOH / g, more preferably 10 mgKOH / g to 170 mgKOH / g, and even more preferably 20 mgKOH / g to 150 mgKOH / g. The graft copolymer has an appropriate acid value, and the dispersion stability of the pigment based on the graft copolymer is further improved.

[0222] Block copolymers

[0223] The block copolymer preferably has a basic group at the first site, and more preferably contains one or more selected from the group consisting of a tertiary amino group and a quaternary ammonium group at the first site. In this case, the first site of the block copolymer contains a tertiary amino group or a quaternary ammonium group having a property of being a base, and thus can show extremely high affinity to particles of pigments showing acidic properties on the surface. Such a block copolymer may also be referred to as a basic dispersion resin.

[0224] The first part and the second part of the block copolymer are not particularly limited in their molecular structure as long as they can respectively function as a part showing affinity with the pigment and a steric repulsion part, but are preferably polymer parts of monomers (unsaturated monomers) having ethylenically unsaturated bonds. The polymer part can relatively easily adjust its chain length (weight average molecular weight). Unsaturated monomers preferably use monomers having a base containing a double bond, monomers having a (meth)acryloyl group, etc.

[0225] The block copolymer is the same as the graft copolymer except that the molecular structure of the first part is different and the molecular structure is linear as a whole. That is, the molecular structure of the second part is the same in the graft copolymer and the block copolymer.

[0226] The block copolymer is preferably an AB block polymer or a BAB block polymer synthesized by living radical polymerization.

[0227] For example, an AB block polymer can be produced by first synthesizing A (the first site), and then synthesizing B (the second site). Alternatively, a BAB block polymer can be produced by first synthesizing B (the second site), then synthesizing A (the first site), and then synthesizing B (the second site). Of course, the order of synthesizing A (the first site) and B (the second site) is arbitrary.

[0228] The first site preferably includes at least one selected from the group consisting of structural units (repeating units) represented by the following general formulae (5) to (7).

[0229] General formula (5):

[0230] [Chemistry 5]

[0231]

[0232] [In the general formula (5), R1 to R3 each independently represent a hydrogen atom, or a chain or cyclic hydrocarbon group which may have a substituent, and two or more of R1 to R3 may be bonded to each other to form a cyclic structure; R4 represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y - represents the counter anion]

[0233] General formula (6):

[0234] [Chemistry 6]

[0235]

[0236] [In the general formula (6), R5 and R6 each independently represent a hydrogen atom, or a chain or cyclic hydrocarbon group which may have a substituent, and R5 and R6 may be bonded to each other to form a cyclic structure; R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group]

[0237] General formula (7):

[0238] [Chemistry 7]

[0239]

[0240] [In the general formula (7), R7 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxy radical, or OR 12 , R 12 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, and R8, R9, R 10 , R 11 each independently represents a methyl group, an ethyl group, or a phenyl group; R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group]

[0241] R1 to R3 in the general formula (5) are preferably, for example, an alkyl group having 1 to 4 carbon atoms which may have a substituent or an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and more preferably a methyl group, an ethyl group, a propyl group, a butyl group or a benzyl group.

[0242] R5 and R6 in the general formula (6) are preferably, for example, an alkyl group having 1 to 4 carbon atoms which may have a substituent, and more preferably a methyl group, an ethyl group, a propyl group, or a butyl group.

[0243] In R7 of the general formula (7), the alkyl group having 1 to 18 carbon atoms may be a linear, branched or cyclic alkyl group, and specific examples thereof include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-hexyl, cyclohexyl, n-octyl and hexadecyl groups.

[0244] Examples of the aryl group having 6 to 20 carbon atoms include phenyl, 1-naphthyl, and 2-naphthyl.

[0245] Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specific examples thereof include benzyl, phenethyl, α-methylbenzyl, and 2-phenylpropane-2-yl.

[0246] Examples of the acyl group include an alkanoyl group and an aroyl group having 2 to 8 carbon atoms, and specific examples thereof include an acetyl group and a benzoyl group.

[0247] Among these, R7 in the general formula (7) is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an oxy radical, more preferably a hydrogen atom or a methyl group, and still more preferably a methyl group.

[0248] In the general formulae (5) to (7), the divalent linking group X includes, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R13 -、-COO-R 14 -(where R 13 and R 14 Each of them is independently a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group), etc., preferably -COO-R 14 -.

[0249] In the general formula (5), the counter anion Y - For example, Cl - Br - ,I - 、ClO4 - 、BF4 - 、CH3COO - PF6 - wait.

[0250] Examples of monomers that form the structural unit represented by the general formula (5) include: quaternary ammonium salts of alkyl (meth)acrylates such as (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, and (meth)acryloyloxyethylmethylmorpholinammonium chloride; quaternary ammonium salts of alkyl (meth)acryloylamides such as (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, and (meth)acryloylaminoethyldimethylbenzylammonium chloride; dimethyldiallylammonium methylsulfate; trimethylvinylphenylammonium chloride, and the like.

[0251] Examples of monomers forming the structural unit represented by the general formula (6) include (meth)acrylates having a tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate; and (meth)acrylamides having a tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide.

[0252] Examples of monomers that form the structural unit represented by the general formula (7) include compounds represented by the following structural formulas. In the following structural formulas, R4 represents a hydrogen atom or a methyl group.

[0253] [Chemistry 8]

[0254]

[0255] Among the above compounds, the monomer forming the structural unit represented by the general formula (7) is preferably 2,2,6,6-tetramethylpiperidinyl methacrylate or 1,2,2,6,6-pentamethylpiperidinyl methacrylate, and more preferably 1,2,2,6,6-pentamethylpiperidinyl methacrylate.

[0256] The structural units represented by the general formulae (5) to (7) may be contained alone or in combination of two or more, and may be contained in any form of random copolymerization, block copolymerization or graft copolymerization, and are preferably contained in the form of block copolymerization.

[0257] Structural units other than the structural units represented by the general formulae (5) to (7) may be contained.

[0258] In the formation of monomer units other than the structural units represented by the general formulae (5) to (7) in the first site of the block copolymer and in the synthesis of the second site, monomers that can be used for the synthesis of the vinyl polymer site can be used.

[0259] The radical polymerization initiator used when producing the block copolymer by living radical polymerization is preferably, for example, an azo compound or a peroxide.

[0260] Examples of the azo compound include 2,2'-azobisisobutyronitrile, 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(methyl isobutyrate), 1,1'-azobis(cyclohexane-1-carbonitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethyl-4-methoxyvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobis(2-hydroxymethylpropionitrile), and 2,2'-azobis[2-(2-imidazolin-2-yl)propane].

[0261] Examples of the peroxide include benzoyl peroxide, tert-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di(2-ethoxyethyl) peroxydicarbonate, tert-butyl peroxyneodecanoate, tert-butyl peroxytrimethylacetate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide.

[0262] The above-mentioned polymerization initiators may be used alone or in combination of two or more.

[0263] The reaction temperature during the polymerization reaction is preferably 40°C or higher and 150°C or lower, more preferably 50°C or higher and 110°C or lower.

[0264] The reaction time is preferably 3 hours to 30 hours, more preferably 5 hours to 20 hours.

[0265] Living radical polymerization can be carried out by a known polymerization method, preferably RAFT polymerization (reversible addition fragmentation chain transfer polymerization).

[0266] RAFT polymerization is a method of radically polymerizing monomers in the presence of a RAFT agent, and has an advantage that the molecular weight and molecular weight distribution of the obtained polymer or copolymer can be easily controlled.

[0267] The RAFT agent is a compound having a chain transfer effect and a polymerization initiation effect, and examples of the RAFT agent include dithiobenzoate-type compounds, trithiocarbonate-type compounds, dithiocarbamate-type compounds, xanthate-type compounds, and disulfide-type compounds that are precursors of these.

[0268] Examples of the dithiobenzoate-type compound include 2-cyano-2-propyl dithiobenzoate, 4-cyano-4-(thiobenzoylthio)pentanoic acid, and 2-phenyl-2-propyl benzodithioate.

[0269] Examples of trithiocarbonate-type compounds include 4-[(2-carboxyethylthiothiocarbonyl)thio]-4-cyanovaleric acid, 2-{[(2-carboxyethyl)thiothiocarbonyl]thio}propionic acid, 4-cyano-4-[(dodecylthiothiocarbonyl)thio]pentanoic acid, 2-cyano-2-[(dodecylthiothiocarbonyl)thio]propionic acid, 2-[(dodecylthiothiocarbonyl)thio]propionic acid, 4-cyano-4-[(dodecylthiothiocarbonyl)thio]pentanoic acid methyl ester, 2-methyl -2-[(dodecylthiothiocarbonyl)thio]propionic acid, S,S-dibenzyl trithiocarbonic acid, trithiocarbonic acid = bis[4-(allyloxycarbonyl)benzyl], trithiocarbonic acid = bis[4-(2,3-dihydroxypropoxycarbonyl)benzyl], trithiocarbonic acid = bis{4-[ethyl-(2-acetoxyethyl)carbamoyl]benzyl}, trithiocarbonic acid bis{4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl}, trithiocarbonic acid = bis[4-(2-hydroxyethoxycarbonyl)benzyl], etc.

[0270] Examples of dithiocarbamate-type compounds include 2'-cyanobutane-2'-yl 4-chloro-3,5-dimethylpyrazole-1-dithiocarboxylate, 2'-cyanobutane-2'-yl 3,5-dimethylpyrazole-1-dithiocarboxylate, cyanomethyl 3,5-dimethylpyrazole-1-dithiocarboxylate, and cyanomethyl N-methyl-N-phenyldithiocarbamate.

[0271] Examples of the disulfide-type compound include bis(dodecylthiothiocarbonyl)disulfide and bis(thiobenzoyl)disulfide.

[0272] The RAFT agent described above is preferably used in the production of AB block polymers.

[0273] Among these, from the viewpoint of easy reaction control during synthesis, the RAFT agent is preferably a trithiocarbonate type compound, and more preferably 4-cyano-4-[(dodecylthiothiocarbonyl)thio]pentanoic acid, 2-cyano-2-[(dodecylthiothiocarbonyl)thio]propionic acid, 4-cyano-4-[(dodecylthiothiocarbonyl)thio]pentanoic acid methyl ester, bis{4-[ethyl-(2-hydroxyethyl)carbamoyl]benzyl} trithiocarbonate, and bis(dodecylthiothiocarbonyl)disulfide.

[0274] The amount of the RAFT agent used is preferably 0.1 parts by mass or more and 10 parts by mass or less relative to 100 parts by mass of the monomer.

[0275] The synthesis of the block copolymer is preferably carried out using an organic solvent. Examples of the organic solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, and diethylene glycol monobutyl ether acetate.

[0276] The organic solvent may be used alone or in combination of two or more.

[0277] The proportion of the second part in the total mass of the block copolymer is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more and 45% by mass or less. Thus, the reduction of the steric repulsion of the second part of the block copolymer can be prevented, while the excellent affinity of the block copolymer to the pigment is brought into play.

[0278] The amine value of the block copolymer is preferably 10 mgKOH / g or more and 200 mgKOH / g or less, more preferably 20 mgKOH / g or more and 150 mgKOH / g or less, and further preferably 30 mgKOH / g or more and 100 mgKOH / g or less. The block copolymer having an appropriate amine value has improved affinity (adsorption) for the pigment and solubility in the solvent, and the dispersion stability of the pigment is further improved.

[0279] In the non-volatile components of the coloring composition, the content of the dispersion resin is preferably 3% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and further preferably 10% by mass or more and 25% by mass or less. By using an appropriate amount of the dispersion resin, the resistance to the stripping solution of the dry etching process and the refractive index are excellent, and the dispersion stability of the coloring composition is further improved.

[0280] Furthermore, the basic dispersion resin can also be synthesized as a graft copolymer by designing the structure of the monomer used.

[0281] <<Pigment derivatives>>

[0282] The coloring composition may contain a pigment derivative as necessary.

[0283] The pigment derivative is a compound having an acidic group, a basic group, a neutral group or the like in an organic pigment residue.

[0284] Examples of the pigment derivatives include compounds having an acidic group such as a sulfonic group, a carboxyl group, or a phosphoric group, or amine salts thereof, compounds having a sulfonamide group, a basic group such as a tertiary amino group at the terminal, and compounds having a neutral group such as a phenyl group or a phthalimide alkyl group.

[0285] Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, reduced pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0286] As the pigment derivative, the above compounds may be used alone or in combination of two or more.

[0287] The amount of the coloring matter derivative used is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and still more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the organic pigment.

[0288] By adding a pigment derivative to an organic pigment and subjecting it to a micronizing treatment such as acid gelatinization, acid slurrying, dry grinding, salt grinding, or solvent salt grinding, the pigment derivative is adsorbed on the surface of the organic pigment, and the organic pigment can be dispersed finely compared to the case where no pigment derivative is added.

[0289] <<Organic ingredients>>

[0290] The coloring composition may further contain an organic component.

[0291] When filter unit 215R, filter unit 215G, and filter unit 215B are formed by dry etching, that is, when a cured product of a coloring composition is processed by dry etching, the coloring composition preferably comprises a copolymer containing a first structural unit (first repeating unit) having a polymerizable group in a side chain and a second structural unit (second repeating unit) having an acidic group or a basic group in a side chain as an organic component.

[0292] The coloring composition may be a composition that cures by heat and / or light, but is preferably a composition that cures by at least heat (hereinafter also referred to as a "coloring thermosetting composition") from the viewpoint of uniformity of curing or improvement of the content of the pigment in the coloring composition.

[0293] Hereinafter, a copolymer having the first constitutional unit and the second constitutional unit is also referred to as a "curable copolymer".

[0294] By including the first structural unit, curability can be imparted to the curable copolymer, and by including the second structural unit, the dispersibility of the curable copolymer to the pigment can be improved.

[0295] Therefore, the amount of components other than the pigment (dispersant, thermosetting compound, curing agent, etc.) used can be reduced, and a coloring composition containing a large amount of pigment can be obtained. In addition, by using the coloring composition to form the filter unit 215R, the filter unit 215G, and the filter unit 215B, further thin film can be achieved.

[0296] The method of introducing a polymerizable group into a curable copolymer is preferably a form in which a compound having a polymerizable group is added to a copolymer having an acidic group or a hydroxyl group in a side chain by reaction.

[0297] Examples of the polymerizable group include an allyl group, a vinyl group, a styryl group, an acryloyl group, and a methacryloyl group, and an acryloyl group and a methacryloyl group are preferred.

[0298] Examples of the monomer having a polymerizable group include acrylic acid, methacrylic acid, allyl methacrylate, allyl acrylate, vinyl methacrylate, vinyl acrylate, 2-(vinyloxy)ethyl methacrylate, p-vinyloxystyrene, p-{2-(vinyloxy)ethyl}styrene, etc. Among these, acrylic acid and methacrylic acid are preferred.

[0299] The method of introducing an acidic group or a basic group into the curable copolymer is preferably a form of copolymerizing a monomer having an acidic group or a basic group.

[0300] The "acidic group or basic group" (hereinafter also referred to as a "dispersing group") can be selected from various functional groups.

[0301] Examples of the acidic group include a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among these, the acidic group is preferably a carboxyl group or a phosphoric acid group, and more preferably a carboxyl group, from the viewpoint of dispersion stability of the pigment.

[0302] Examples of the monomer having an acidic group include acrylic acid, methacrylic acid, itaconic acid, aspartic acid, and sulfonic acid, and acrylic acid, methacrylic acid, and aspartic acid are preferred.

[0303] As a monomer which has a hydroxyl group, 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, etc. are mentioned, for example.

[0304] Examples of the basic group include an amino group, a guanidine group, an imidazole group, a secondary amino group, a tertiary amino group, a quaternary ammonium group (including forms such as quaternary ammonium cations and salts), and the like.

[0305] The monomer having a basic group is preferably, for example, N,N-dimethyllaurylamine or N,N-dimethylpalmitamine, and more preferably N,N-dimethylpalmitamine.

[0306] When the pigment has an acidic group on the surface, a curable copolymer containing a basic group (e.g., primary to tertiary amino groups) is preferred, and when the pigment has a basic group on the surface, a curable copolymer containing an acidic group (e.g., carboxyl groups) is preferred.

[0307] From the above point of view, the copolymer is more preferably a copolymer comprising an allyl group and a pigment adsorption group (dispersible group). With regard to the allyl group, polymerization (hardening) can be performed by heat. According to the thermal hardening method, it is easy to harden the coloring composition uniformly, and an initiator is not required, so it is preferred. In addition, it is easy to increase the content of the pigment in the non-volatile component (total non-volatile component) of the coloring composition.

[0308] Here, the "non-volatile component (total non-volatile component) of the coloring composition" refers to all components after removing the solvent from the coloring composition.

[0309] In addition, as a form in which a compound having a polymerizable group is added to a copolymer having an acidic group or a basic group in a side chain by reaction, the following method is also preferred: a copolymer of a monomer having an acidic group or a basic group and a monomer having a reactive functional group such as a hydroxyl group or a carboxyl group is synthesized, and then reacted with a monomer having a reactive functional group that reacts with the reactive functional group.

[0310] Examples of such methods include a method of reacting 2-methacryloyloxyethyl isocyanate with a copolymer having a hydroxyl group, and a method of reacting glycidyl methacrylate with a copolymer having a carboxyl group.

[0311] The weight average molecular weight of the curable copolymer is preferably 3,000 or more and 300,000 or less, more preferably 5,000 or more and 100,000 or less, and still more preferably 7,000 or more and 70,000 or less.

[0312] The ratio of the polymerizable group to the dispersible group (polymerizable group / dispersible group) is preferably 95 / 5 to 5 / 95, more preferably 85 / 15 to 15 / 85, and even more preferably 75 / 25 to 25 / 75 in terms of molar ratio.

[0313] The content of the curable copolymer in the nonvolatile component of the coloring composition slightly varies depending on the type of the curable copolymer and is not particularly limited, but is preferably 50 mass % or less, more preferably 0.1 mass % to 45 mass % or less, and further preferably 0.5 mass % to 40 mass % or less.

[0314] In the coloring composition, in addition to the curable copolymer, a thermosetting compound described below may be used as an optional component. In this case, the total content of the curable copolymer and the thermosetting compound in the coloring composition is preferably 50% by mass or less, more preferably 0.2% by mass or more and 50% by mass or less, and further preferably 1% by mass or more and 30% by mass or less in the non-volatile component (mass) of the coloring composition.

[0315] From the perspective of improving the ease of adjusting the thickness of the coating film (liquid film) of the coloring composition, the organic component may include a binder other than the curable copolymer in addition to the curable copolymer. In the present embodiment (dry etching application), the binder does not need to be alkali-soluble, as long as it is soluble in an organic solvent.

[0316] Examples of the binder include polymers having a carboxyl group in a side chain such as methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, and partially esterified maleic acid copolymers, and acidic cellulose derivatives having carboxylic acid introduced in a side chain.

[0317] In addition to the above, useful binders include adducts obtained by adding acid anhydride to a polymer having a hydroxyl group, polyhydroxystyrene resins, polysiloxane resins, poly(2-hydroxyethyl (meth)acrylate), polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, and the like.

[0318] In addition, a hydrophilic monomer may be copolymerized. Examples of the monomer include alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, (meth)acrylamide, N-hydroxymethylacrylamide, secondary alkyl acrylamide or tertiary alkyl acrylamide, dialkylaminoalkyl (meth)acrylate, morpholine (meth)acrylate, N-vinyl pyrrolidone, N-vinyl caprolactam, vinylimidazole, vinyltriazole, methyl (meth)acrylate, ethyl (meth)acrylate, branched or linear propyl (meth)acrylate, branched or linear butyl (meth)acrylate, phenoxyhydroxypropyl (meth)acrylate, and the like.

[0319] Among these, as the binder, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymers are preferred from the viewpoint of heat resistance, and acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred from the viewpoint of control of developability.

[0320] Examples of acrylic resins include copolymers containing monomers selected from benzyl (meth)acrylate, (meth)acrylic acid, hydroxyethyl (meth)acrylate, (meth)acrylamide, etc. The copolymers are preferably, for example, benzyl methacrylate / methacrylic acid copolymers, benzyl methacrylate / benzylmethacrylamide copolymers, KS Resist-106 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (manufactured by Daicel), etc.

[0321] The weight average molecular weight of the binder is preferably 1,000 or more and 2×10 5 less than 2,000, more preferably not less than 1×10 5 less than 5,000, and more preferably 5×10 4 the following.

[0322] The coloring composition disperses a high content of a pigment in a curable copolymer (and optionally a binder) to impart adhesion to a base layer etc. when forming a cured film, and also contributes to film-forming properties during spin coating or slit coating.

[0323] In the case of this form (dry etching application), the monomer (polymerizable compound) or photopolymerization initiator, which is an essential component in the photolithography method, does not necessarily need to be added to the coloring composition. Therefore, the non-volatile component (total non-volatile component) of the coloring composition, in other words, the content of the pigment in the filter unit 215R, the filter unit 215G, and the filter unit 215B, which is the cured product of the coloring composition, can be set to 65% by mass or more. As a result, the spectral characteristics of the filter unit 215R, the filter unit 215G, and the filter unit 215B can be improved.

[0324] In the non-volatile component of the coloring composition, the content of the pigment in the coloring composition is preferably 65% ​​by mass or more and less than 100% by mass, more preferably 70% by mass or more and 98% by mass or less, and further preferably 75% by mass or more and 95% by mass or less. In this case, the filter unit 215R, the filter unit 215G, and the filter unit 215B have high spectral characteristics and color reproducibility, and the curability of the coloring composition can be good.

[0325] <<Other ingredients>>

[0326] The coloring composition may contain other components besides the above components.

[0327] ·dye

[0328] In the coloring composition, a dye may also be used together with the pigment.

[0329] Examples of the dye include triphenylmethane dyes, anthraquinone dyes, benzylidene dyes, oxonol dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, and indigo dyes.

[0330] Thermosetting compounds

[0331] The thermosetting compound may supplementarily include a thermosetting compound. The thermosetting compound is not particularly limited as long as it can be cured by heating, and examples thereof include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and blocked isocyanate compounds. Among these, epoxy compounds, oxetane compounds, melamine compounds, and blocked isocyanate compounds are preferred, and epoxy compounds are more preferred.

[0332] (Epoxides)

[0333] Examples of epoxy compounds include polycondensates of glycerol polyglycidyl ether, sorbitol polyglycidyl ether, bisphenols (bisphenol A, bisphenol F, bisphenol S, bisphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, o-phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.); polycondensates of phenol and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropylbenzene, etc.); Polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyl dimethanol, α,α,α',α'-biphenyl dimethanol, etc.); polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethyl biphenyl, etc.); polycondensates of bisphenols and various aldehydes; glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins, etc. obtained by glycidylating alcohols, etc.

[0334] Examples of commercially available epoxy compounds include: EPICOAT 807, 815, 825, 827, 828, 190P, 191P manufactured by Oil Shell Epoxy, TECHMORE VG3101L manufactured by Mitsui Chemicals, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku, EPICOAT 1004, 1256, JER 1032H60, 157S65, 157S70, 152, 154 manufactured by Nippon Epoxy, CELLOXIDE 2021, EHPE-3150, Epolead GT401 manufactured by Daicel, and Nagase Chemicals. Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by ChemteX, TEPIC-L, H, S manufactured by Nissan Chemical Industry, EPICLON 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, HP-9500, etc. manufactured by DIC.

[0335] From the viewpoint of high temperature and high humidity resistance and solvent resistance, the epoxy compound is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0336] The epoxy equivalent of the epoxy compound is preferably 50 g / eq or more and 400 g / eq or less, and more preferably 100 g / eq or more and 200 g / eq or less. The epoxy equivalent is defined as the mass of the epoxy compound containing 1 equivalent of epoxy groups.

[0337] The thermosetting compound can be used alone or in combination of two or more.

[0338] The content of the thermosetting compound in 100% by mass of the nonvolatile component of the photosensitive composition is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 15% by mass or less.

[0339] Photopolymerization initiator

[0340] The coloring composition may auxiliary contain a photopolymerization initiator.

[0341] Examples of the photopolymerization initiator include benzophenone compounds, acetophenone compounds, oxime ester compounds, acylphosphine compounds, quinone compounds, borate compounds, and carbazole compounds.

[0342] As for commercially available products of photopolymerization initiators, acetophenone compounds include Omnirad 907, 369E, 379EG, 127, 184, 1173, and 2959 manufactured by IGM Resins; acylphosphine compounds include Omnirad 819 and TPO manufactured by IGM Resins; and oxime ester compounds include BASF Japan. Japan), IRGACURE OXE-01, 02, 03, 04, ADEKA N-1919, NCI-730, 831, 930, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057, IGM Resins Omnirad 1312, 1314, 1316, SAMYANG CORPORATION SPI-02, 03, 04, 05, 06, 07, Daito Chemix DFI-020, 306, EOX-01, etc.

[0343] Among these, oxime ester compounds are preferred in terms of photocurability, and compounds represented by the following general formula (6) and compounds represented by the following general formula (7) are preferred in terms of further improving heat resistance and pattern shape.

[0344] [Chemistry 9]

[0345]

[0346] In the general formula (6), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.

[0347] In the general formula (7), X1 and X2 each independently represent a carbonyl bond (-CO-) or a single bond. R4 represents an alkyl group having 1 to 20 carbon atoms, and R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R7 and R8 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.

[0348] In the general formula (6), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.

[0349] The alkyl group having 1 to 8 carbon atoms may be linear, branched, cyclic, or a combination of these groups, and examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, and cyclohexylmethyl. Among them, linear alkyl groups having 3 to 8 carbon atoms are preferred, and linear alkyl groups having 4 to 6 carbon atoms are more preferred.

[0350] In the general formula (6), R3 represents a hydrogen atom or an arbitrary monovalent substituent.

[0351] Examples of the monovalent substituent include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl groups; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy groups; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; benzoyl groups which may have a substituent; and thenoyl groups which may have a substituent. Examples of the substituents that the benzoyl group or thenoyl group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, hydrogen atoms and nitro groups are preferred from the viewpoint of free radical generation efficiency, and hydrogen atoms are more preferred.

[0352] Examples of methods for producing the compound represented by general formula (6) include methods described in JP-A-2019-507108 and JP-A-2019-528331.

[0353] Specific examples of the compound represented by the general formula (6) are shown below, but the present invention is not limited to these.

[0354] [Chemistry 10]

[0355]

[0356] In general formula (7), X1 and X2 each independently represent a carbonyl bond (-CO-) or a single bond. From the viewpoint of solubility in an organic solvent, at least one of X1 and X2 is preferably a carbonyl bond (-CO-), and both are more preferably carbonyl bonds (-CO-).

[0357] In the general formula (7), R4 represents an alkyl group having 1 to 20 carbon atoms.

[0358] The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic, or a combination thereof, and may be an alkyl group substituted with a halogen atom, an amino group, a nitro group, or the like. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, and cyclohexylmethyl. Among these, ethyl, propyl, and isopropyl are preferred.

[0359] In the general formula (7), R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.

[0360] The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic or a combination thereof, and may also be an alkyl group substituted with a halogen atom, an amino group, a nitro group or the like. Examples thereof include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, hexadecyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, etc. Among these, pentyl, hexyl, heptyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, and cyclohexylmethyl are preferred.

[0361] Examples of the heterocyclic group having 2 to 30 carbon atoms include pyridyl, pyrimidinyl, furanyl, tetrahydrofuranyl, dioxolanyl, imidazolidinyl, oxazolidinyl, piperidinyl and morpholinyl.

[0362] Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, and the like. The aryl group may be substituted with a halogen atom, an amino group, a nitro group, or the like.

[0363] Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl. The arylalkyl group may be substituted with a halogen atom, an amino group, a nitro group, or the like.

[0364] Among these, R5 and R6 are more preferably a linear alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group having 1 to 20 carbon atoms.

[0365] In the general formula (7), R7 and R8 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.

[0366] The alkyl group having 1 to 20 carbon atoms may be any of a linear, branched, cyclic or a combination thereof, and may be an alkyl group substituted with a halogen atom, an amino group, a nitro group or the like. Examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclopentylmethyl group, and a cyclohexyl group. Among these, from the viewpoint of reactivity, a methyl group, an ethyl group, a propyl group, and an isopropyl group are preferred.

[0367] Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuranyl group, a dioxolanyl group, an imidazolidinyl group, an oxazolidinyl group, a piperidinyl group, and a morpholinyl group.

[0368] Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, etc., and may be substituted with a halogen atom, amino group, nitro group, etc. Among these, phenyl is preferred from the viewpoint of reactivity.

[0369] Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl. The arylalkyl group may be substituted with a halogen atom, an amino group, a nitro group, or the like.

[0370] Among these, from the viewpoint of reactivity, R7 and R8 are preferably a methyl group, an ethyl group or a phenyl group, and more preferably a methyl group or an ethyl group.

[0371] The method for producing the compound represented by the general formula (7) can be, for example, the method described in Japanese Patent Publication No. 2017-523465.

[0372] Specific examples of the compound represented by the general formula (7) are shown below. However, the present invention is not limited to these.

[0373] [Chemistry 11]

[0374]

[0375] The content of the photopolymerization initiator in 100% by mass of the nonvolatile component of the colored composition is preferably 0.5% by mass or more and 20% by mass or less.

[0376] When a photopolymerization initiator is used, a sensitizer or a photostabilizer may be used together.

[0377] Specific examples thereof include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone, 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-tert-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2-methoxyxanthone, 2-ethoxyxanthone, thioxanthone, 2,4-diethylthioxanthone, acridone, 10-butyl-2-chloroacridone, benzyl, dibenzylacetone, p-(dimethylamino)benzene, phenyl ketone, p-(dimethylamino)phenyl-p-methylphenyl ketone, benzophenone, p-(dimethylamino)benzophenone (or Mitchler's ketone), p-(diethylamino)benzophenone, benzanthrone, benzothiazole compounds, 5-(2H-benzotriazol-2-yl)-4-hydroxy-3-tert-butylbenzenepropionic acid methyl ester (Tinuvin 1130), 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol (Tinuvin 400), etc.

[0378] Examples of other photopolymerization initiators include vicinal polyketol aldonyl compounds, α-carbonyl compounds, acyloin ethers, α-hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, a combination of triallylimidazole dimer / p-aminophenyl ketone, and a combination of benzothiazole compounds / trihalomethyl-s-triazine compounds.

[0379] Hardener

[0380] When an epoxy resin is used as the thermosetting compound, it is preferable to add a curing agent to the coloring composition.

[0381] Specific examples of the curing agent include diethylenetriamine, m-phenylenediamine, tris(dimethylaminomethyl)phenol, phthalic anhydride, polyamide resin, polysulfide resin, boron trifluoride-monoethylamine complex, phenol resin, dicyandiamide, and the like.

[0382] These curing agents are compounds that react with epoxy groups by heating and polymerize to increase the crosslinking density and cure. In order to form a thin film, the content of the curing agent in the coloring composition is preferably as small as possible, preferably 35% by mass or less, more preferably 30% by mass or less, and further preferably 25% by mass or less relative to the thermosetting compound.

[0383] Hardening catalyst

[0384] The coloring composition may contain a hardening catalyst.

[0385] When an epoxy resin is used as the curing compound, the curing catalyst preferably includes, for example, imidazole compounds, boron trifluoride complexes (particularly amine complexes), tertiary amines (guanidine, biguanidine), titanate esters, phosphine derivatives, and the like.

[0386] The amount of the curing catalyst used is preferably 1 / 10 to 1 / 1,000, more preferably 1 / 20 to 1 / 500, and still more preferably 1 / 30 to 1 / 250, based on the mass ratio of the epoxy resin having an epoxy equivalent of 150 to 200.

[0387] There is no particular limitation on commercially available curing catalysts, and examples thereof include imidazole silane series "IS-1000", "IS-1000D", "IM-1000", "SP-1000", "IA-1000A", "IA-100P", "IA-100F", "IA-100AD", "IA-100FD", "IM-100F", "IS-3000", "IS-4000" (all manufactured by Nippon Energy), "1B2PZ", "SFZ" (all manufactured by Shikoku Chemical), etc.

[0388] Solvent

[0389] The coloring composition may contain at least one solvent.

[0390] The solvent is preferably selected in consideration of the solubility of each component, the coating properties and safety of the coloring composition, and the like.

[0391] Examples of the solvent include ketones, aromatic hydrocarbons, esters, and ethers.

[0392] Examples of the ketone include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.

[0393] Examples of the aromatic hydrocarbon include toluene and xylene.

[0394] Esters include, for example, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, 3-methoxypropionate ethyl 2-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, and the like.

[0395] Examples of the ether include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, and propylene glycol monopropyl ether acetate.

[0396] Dispersants

[0397] In order to improve the dispersibility of the pigment, a dispersant may be added to the coloring composition as an auxiliary.

[0398] Examples of the dispersant include cationic surfactants, fluorine-based surfactants, polymer dispersants, etc. The dispersants may be used alone or in combination of two or more.

[0399] For example, a graft copolymer having a monomer containing a specific acid amide group and a quaternary ammonium salt monomer residue in the main chain can be used as a dispersant because it has an excellent effect of microdispersing the pigment. By using a graft copolymer, the pigment can be finely dispersed while reducing the consumption of energy or time. In addition, the dispersed pigment will not condense or settle even after a period of time, and the long-term dispersion stability can be maintained.

[0400] The content of the dispersant in the coloring composition is usually preferably 0.1 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the pigment.

[0401] <Method for preparing coloring composition>

[0402] Next, an example of a method for preparing a coloring composition is described.

[0403] In addition, hereinafter, the curable copolymer (and the binder as needed) may be referred to as a "curable resin".

[0404] The coloring composition can be preferably prepared using a pigment dispersion in which a pigment is dispersed in the presence of a curable resin.

[0405] As a method for dispersing the pigment, it is preferred to use a method in which the pigment particles are micronized and the particle size distribution is sharpened. Specifically, it is preferred to use a method in which the pigment particles contain 75% by mass or more of pigment particles having an average particle diameter of about 0.01 μm and a particle diameter in the range of 0.01 μm ± 0.005 μm.

[0406] The dispersion method for adjusting the particle size distribution of the pigment to the above range includes, for example, a dispersion method that combines dry dispersion (mixing and dispersing treatment) in a high viscosity state using a kneader or a double roll mill, and wet dispersion (micro-dispersing treatment) in a relatively low viscosity state using a triple roll mill or a bead mill, etc. In the dispersion method, it is also preferred to co-disperse two or more pigments, or to use no solvent or to minimize the amount of solvent used during the mixing and dispersing treatment.

[0407] In addition, it is preferred to add the curable resin separately during the kneading and dispersion treatment and during the micro-dispersion treatment (two-division use) to mitigate the impact of the solvent. In addition, it is also preferred to use a curable resin with excellent solubility to prevent the re-agglomeration of pigment particles when transferring from the kneading and dispersion treatment to the micro-dispersion treatment. Furthermore, it is also effective to use high-hardness ceramics or beads with small particle sizes for the beads of the bead mill used in the micro-dispersion treatment.

[0408] It is particularly preferable to use a pigment obtained by using two or more pigments and dispersing the two or more pigments in a high viscosity state of 50,000 mPa·s or more and then dispersing them in a low viscosity state of 1,000 mPa·s or less.

[0409] Generally speaking, these pigments are supplied after being dried by various methods after synthesis. Usually, they are supplied as powders after being dried from an aqueous medium, but since water drying requires a large latent heat of evaporation, a large amount of heat energy is imparted when drying and powdering. Therefore, the pigments usually form aggregates (secondary particles) composed of primary particles.

[0410] In the method for preparing a coloring composition, it is preferred that a pigment dispersion liquid in which a pigment is dispersed in a curable resin is first prepared.

[0411] Specifically, the pigment is preferably kneaded and dispersed so that the viscosity of the curable resin after kneading and dispersion becomes a relatively high viscosity of 50,000 mPa·s or more (preferably 50,000 mPa·s or more and 100,000 mPa·s or less).

[0412] Here, the kneading and dispersing treatment may be high-viscosity dispersion or dry dispersion.

[0413] Then, it is preferred to further add a curable resin or other dispersant to the pigment dispersion after kneading and dispersion treatment as necessary, and to perform fine dispersion treatment so that the viscosity after fine dispersion treatment becomes a relatively low viscosity of 1,000 mPa·s or less (preferably 100 mPa·s or less).

[0414] Furthermore, the fine dispersion treatment may be low-viscosity dispersion or wet dispersion.

[0415] In the mixing and dispersing process, the ratio of the solvent is preferably more than 0 mass % and less than 20 mass % relative to the dispersed material. In this way, if the solvent is not too used to disperse, the wetting of the surface of the particles of the pigment and the constituent components based on the resin component of the carrier can be promoted. Therefore, the interface formed by the particle surface of the pigment can be transformed into the solid / solution interface of the particle of the pigment and the carrier solution from the solid / gas interface of the particle of the pigment and the air. If the interface formed by the surface of the particle of the pigment is transformed into solution and mixed and stirred from air, the pigment can be dispersed to the micro state close to the primary particle.

[0416] Thus, in order to make the pigment highly dispersed, it is effective to transform the interface formed by the particle surface of the pigment from air to solution. The transformation requires strong shearing force or compression. Therefore, in the mixing and dispersing process, it is preferred to use a mixer that can exert strong shearing force or compression, using a high-viscosity material as the mixed material.

[0417] In addition, during the microdispersion treatment, it is preferably mixed and stirred with a fine particle dispersion medium of glass or ceramic. Furthermore, the ratio of the solvent during the microdispersion treatment is preferably 20% by mass or more and 90% by mass or less of the dispersed material.

[0418] In the microdispersion treatment, the pigment particles need to be uniformly and stably distributed in a microscopic state, and therefore it is preferred to use a disperser that can impart impact force and shear force to the aggregated pigment particles and to use a low-viscosity substance as the dispersed substance.

[0419] A curing catalyst or a curing agent, or a thermosetting compound, may be added to the pigment dispersion liquid obtained in this way as needed, and a solvent may be further added as needed, thereby preparing a coloring composition.

[0420] When the filter unit 215R, the filter unit 215G, and the filter unit 215B are formed using photolithography, an alkali-soluble resin is used as the binder.

[0421] <<Alkali-soluble resin>>

[0422] The molecular weight of the alkali-soluble resin is not particularly limited, but the weight average molecular weight (Mw) is preferably 5000 or more and 100,000 or less. The number average molecular weight (Mn) is preferably 1,000 or more and 20,000 or less.

[0423] Examples of the alkali-soluble resin include resins having at least one group that promotes alkali solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain).

[0424] As the alkali-soluble resin, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred from the viewpoint of heat resistance, and acrylic resins, acrylamide resins, and acrylic acid / acrylamide copolymer resins are preferred from the viewpoint of control of developability.

[0425] Examples of groups that promote alkali solubility (hereinafter also referred to as "acid groups") include carboxyl groups, phosphoric acid groups, sulfonic acid groups, phenolic hydroxyl groups, etc. The acid groups are preferably groups that are soluble in organic solvents and can be developed by weak alkaline aqueous solutions, and are preferably groups derived from (meth)acrylic acid. These acid groups may be one or more.

[0426] In the production of the alkali-soluble resin, for example, a method based on a radical polymerization method can be applied. When producing the alkali-soluble resin by a radical polymerization method, polymerization conditions such as temperature, pressure, type and amount of a radical initiator, and type of a solvent can be appropriately set.

[0427] As the alkali-soluble resin, a polymer having a carboxylic acid in a side chain is preferred, and examples thereof include methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenolic resins such as novolac-type resins, acidic cellulose derivatives having a carboxyl group in a side chain, and those obtained by adding an acid anhydride to a polymer having a hydroxyl group.

[0428] In particular, a copolymer of (meth)acrylic acid and other monomers copolymerizable therewith is preferred as the alkali-soluble resin. Examples of other monomers copolymerizable with (meth)acrylic acid include alkyl (meth)acrylates, aryl (meth)acrylates, and vinyl compounds.

[0429] Examples of the alkyl (meth)acrylate and the aryl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, toluene (meth)acrylate, naphthyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0430] Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomers, polymethyl methacrylate macromonomers, N-phenylmaleimide, and N-cyclohexylmaleimide.

[0431] Furthermore, these other monomers copolymerizable with (meth)acrylic acid may be used alone or in combination of two or more.

[0432] In addition, in order to improve the crosslinking efficiency of the coloring composition, an alkali-soluble resin having a polymerizable group may also be used. Examples of the polymerizable group include (meth)allyl and (meth)acryloyl groups. Useful alkali-soluble resins having a polymerizable group include alkali-soluble resins containing a polymerizable group in a side chain.

[0433] Examples of the alkali-soluble resin containing a polymerizable group include: Dianal NR series (manufactured by Mitsubishi Rayon), Photomer 6173 (manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry), Cyclomer P series, Placcel CF200 series (all manufactured by Daicel), Ebecryl 3800 (manufactured by Daicel UCB), Acrycure RD-F8 (manufactured by Nippon Catalyst), etc.

[0434] Among the alkali-soluble resins, multi-component copolymers such as benzyl (meth)acrylate / (meth)acrylic acid copolymers, benzyl (meth)acrylate / (meth)acrylic acid / 2-hydroxyethyl (meth)acrylate copolymers, and benzyl (meth)acrylate / (meth)acrylic acid / other monomer copolymers can be preferably used.

[0435] In addition, among the alkali-soluble resins, polymers obtained by copolymerizing 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymers, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymers, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymers, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymers, and the like can also be preferably used.

[0436] Moreover, as a commercial item of an alkali-soluble resin, FF-426 (made by Fujikura Chemical Industry Co., Ltd.) etc. are mentioned, for example.

[0437] The acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 500 mgKOH / g, more preferably 40 mgKOH / g to 400 mgKOH / g, further preferably 50 mgKOH / g to 200 mgKOH / g, particularly preferably 60 mgKOH / g to 150 mgKOH / g, and most preferably 50 mgKOH / g to 120 mgKOH / g.

[0438] In the non-volatile component (total non-volatile component) of the coloring composition, the content of the alkali-soluble resin in the coloring composition is preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.5% by mass or more and 18% by mass or less, further preferably 1% by mass or more and 15% by mass or less, particularly preferably 2% by mass or more and 12% by mass or less, and most preferably 3% by mass or more and 10% by mass or less.

[0439] The coloring composition may contain only one alkali-soluble resin or two or more alkali-soluble resins. When two or more alkali-soluble resins are contained, the total content thereof is preferably adjusted to fall within the above range.

[0440] In the present specification, the content of all resins including the dispersion resin and the binder in the coloring composition is preferably 3% by mass or more and 35% by mass or less, and more preferably 10% by mass or more and 30% by mass or less.

[0441] In addition, when the filter unit 215R, the filter unit 215G, and the filter unit 215B are formed using a photolithography method, the coloring composition may further contain a polymerizable compound and a photopolymerization initiator.

[0442] <<Polymerizable compounds>>

[0443] As the polymerizable compound, a monomer or oligomer having a polymerizable unsaturated group can be used.

[0444] The polymerizable compound is preferably a compound having two or more polymerizable unsaturated groups. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)acryloyl group, and a (meth)allyl group.

[0445] Examples of polymerizable compounds include: linear or branched alkyl (meth)acrylates; cyclic alkyl (meth)acrylates; fluoroalkyl (meth)acrylates; (meth)acryloyloxy-modified polydimethylsiloxanes (silicone macromonomers); (meth)acrylates having heterocyclic rings; (meth)acrylates having aromatic rings; (poly)alkylene glycol monoalkyl ether (meth)acrylates; (meth)acrylates having carboxyl groups; (meth)acrylates having hydroxyl groups; (poly)alkylene glycol di(meth)acrylates; di(meth)acrylates; (meth)acrylates having tertiary amino groups; trifunctional or higher polyfunctional (meth)acrylates; epoxy (meth)acrylates; (meth)acryloyl-modified resin oligomers; vinyls; vinyl ethers; amides; acrylonitrile, etc.

[0446] The polymerizable compound may be used alone or in combination of two or more.

[0447] Examples of the linear or branched alkyl (meth)acrylate include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate.

[0448] Examples of the cyclic alkyl (meth)acrylate include cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate.

[0449] Examples of the fluoroalkyl (meth)acrylate include trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate.

[0450] Examples of the (meth)acrylate having a heterocyclic ring include tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate.

[0451] Examples of the (meth)acrylate having an aromatic ring include benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, p-cumylphenoxyethyl (meth)acrylate, p-cumylphenoxypolyethylene glycol (meth)acrylate, and nonylphenoxypolyethylene glycol (meth)acrylate.

[0452] Examples of the (poly)alkylene glycol monoalkyl ether (meth)acrylate include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, tripropylene glycol mono(meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, and polyethylene glycol monostearyl ether (meth)acrylate.

[0453] Examples of the (meth)acrylate having a carboxyl group include (meth)acrylic acid, acrylic acid dimer, 2-(meth)acryloxyethyl phthalate, 2-(meth)acryloxypropyl phthalate, 2-(meth)acryloxyethyl hexahydrophthalate, 2-(meth)acryloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth)acrylate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate.

[0454] Examples of (meth)acrylates having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth)phthalate, diethylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, polyethylene glycol mono(meth)acrylate, propylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polytetramethylene glycol mono(meth)acrylate, poly(ethylene glycol-propylene glycol) mono(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) mono(meth)acrylate, poly(propylene glycol-tetramethylene glycol) mono(meth)acrylate, and glycerol (meth)acrylate.

[0455] Examples of the (poly)alkylene glycol di(meth)acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol-propylene glycol) di(meth)acrylate, poly(ethylene glycol-tetramethylene glycol) di(meth)acrylate, poly(propylene glycol-tetramethylene glycol) di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3-tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, and 2-ethyl, 2-butyl-propylene glycol di(meth)acrylate.

[0456] Examples of the di(meth)acrylate include dimethyloldicyclopentane di(meth)acrylate, hydroxypivalate neopentyl glycol di(meth)acrylate, stearic acid-modified pentaerythritol di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, tetramethylene oxide-modified bisphenol A di(meth)acrylate, ethylene oxide-modified bisphenol F di(meth)acrylate, propylene oxide-modified bisphenol F di(meth)acrylate, tetramethylene oxide-modified bisphenol F di(meth)acrylate, zinc diacrylate, ethylene oxide-modified phosphoric acid triacrylate, and glycerol di(meth)acrylate.

[0457] Examples of the (meth)acrylate having a tertiary amino group include dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and diethylaminopropyl (meth)acrylate.

[0458] Specific examples of trifunctional or higher polyfunctional (meth)acrylates include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.

[0459] Examples of epoxy (meth)acrylates include glycerol triglycidyl ether-(meth)acrylic acid adducts, glycerol diglycidyl ether-(meth)acrylic acid adducts, polyglycerol polyglycidyl ether-(meth)acrylic acid adducts, 1,6-butanediol diglycidyl ether-(meth)acrylic acid adducts, alkyl glycidyl ether-(meth)acrylic acid adducts, allyl glycidyl ether-(meth)acrylic acid adducts, phenyl glycidyl ether-(meth)acrylic acid adducts, styrene oxide-(meth)acrylic acid adducts, bisphenol A diglycidyl ether-(meth)acrylic acid adducts, and propylene oxide-modified bisphenol A diglycidyl ether-(meth)acrylic acid adducts. adducts, bisphenol F diglycidyl ether-(meth)acrylic acid adducts, epichlorohydrin-modified phthalic acid-(meth)acrylic acid adducts, epichlorohydrin-modified hexahydrophthalic acid-(meth)acrylic acid adducts, ethylene glycol diglycidyl ether-(meth)acrylic acid adducts, polyethylene glycol diglycidyl ether-(meth)acrylic acid adducts, propylene glycol diglycidyl ether-(meth)acrylic acid adducts, polypropylene glycol diglycidyl ether-(meth)acrylic acid adducts, phenol novolac type epoxy resin-(meth)acrylic acid adducts, cresol novolac type epoxy resin-(meth)acrylic acid adducts, other epoxy resin-(meth)acrylic acid adducts, etc.

[0460] Examples of the (meth)acryl-modified resin oligomer include (meth)acryl-modified isocyanurate, (meth)acryl-modified polyurethane, (meth)acryl-modified polyester, (meth)acryl-modified melamine, (meth)acryl-modified silicone, (meth)acryl-modified polybutadiene, and (meth)acryl-modified rosin.

[0461] Examples of the vinyl group include styrene, α-methylstyrene, vinyl acetate, vinyl (meth)acrylate, and allyl (meth)acrylate.

[0462] Examples of the vinyl ether include hydroxyethyl vinyl ether, ethylene glycol divinyl ether, and pentaerythritol trivinyl ether.

[0463] Examples of the amide include (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, and N-vinylformamide.

[0464] The content of the polymerizable compound in the nonvolatile component of the coloring composition is preferably 1 mass % to 30 mass %, more preferably 3 mass % to 25 mass %, further preferably 5 mass % to 20 mass %.

[0465] The above-mentioned polymerizable compounds may be used alone or in combination of two or more.

[0466] When the colored composition is used in combination with a photolithography method, the colored composition preferably contains the polymerizable compound. However, when the colored composition is used in combination with a dry etching method, the colored composition preferably does not contain the polymerizable compound.

[0467] <<Photopolymerization initiator>>

[0468] The photopolymerization initiator is as described above.

[0469] From the viewpoint of improving the spectral characteristics and refractive index corresponding to the solid-state imaging element 2 , the pigment used for preparing the coloring composition is preferably a compound having an aromatic ring.

[0470] The pigment used in the preparation of the coloring composition may be used alone, or two or more kinds thereof may be used in combination in order to improve color purity.

[0471] The preferred ratio when two or more pigments are used in combination is as described above.

[0472] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63 , 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 1 75, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 2 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, etc. Among these, CI Pigment Red 177, 254, and 269, which are pigments having an aromatic ring, are preferred as red pigments because of their excellent refractive index, light resistance, heat resistance, and transparency.

[0473] Examples of yellow pigments include CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 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, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119 , 120, 123, 126, 127, 128, 129, 138, 139, 147, 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, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, etc. Among these, CI Pigment Yellow (Pigment Yellow) 138, 139, 150, 185, 231, 233, which are pigments having an aromatic ring, are preferred as yellow pigments. Furthermore, since the refractive index is high, it is particularly preferable to contain CI Pigment Yellow 139 or 185.

[0474] Green pigments are preferably CI Pigment Green 7, 36, 37, 58, 59, 62, 63, etc. In addition, these green pigments are preferably used in combination with yellow pigments such as CI Pigment Yellow 83, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 180, or CI Pigment Yellow 185.

[0475] As the blue pigment, a phthalocyanine-based pigment may be used alone or in combination with a dioxazine-based violet pigment.

[0476] As a blue pigment, for example, CI Pigment Blue 15:6 and CI Pigment Violet 23 are preferably used in combination.

[0477] The content of the pigment in the nonvolatile component of the coloring composition is preferably 50 mass % to 95 mass %, more preferably 60 mass % to 90 mass %. When the content of the pigment is within the above range, the refractive index of the color filter 215 is further increased.

[0478] The coloring composition forming the color filter 215 preferably contains 50% by mass or more and 95% by mass or less of pigment and 3% by mass or more and 50% by mass or less of resin in the non-volatile component. The content of the pigment is more preferably 60% by mass or more and 93% by mass or less, and further preferably 65% ​​by mass or more and 90% by mass or less. In addition, the content of the resin is more preferably 7% by mass or more and 50% by mass or less, and further preferably 10% by mass or more and 40% by mass or less.

[0479] The coloring composition preferably contains 80% by mass or more, more preferably 90% by mass or more, of the aromatic ring-containing compound in its nonvolatile content. The aromatic ring-containing compound includes resins, pigments, pigment derivatives, and other additives.

[0480] When the color filter 215 is formed by dry etching using a coloring composition, it is preferably a composition containing a pigment, a dispersion resin, etc. In addition, the dispersion resin preferably contains a thermally crosslinkable group.

[0481] When the color filter 215 is formed by photolithography, a composition including a pigment, a dispersion resin, an alkali-soluble resin, a photopolymerization initiator, a polymerizable compound, and the like is preferably used.

[0482] The green composition in the coloring composition described above preferably contains a green pigment selected from CI Pigment Green 36, CI Pigment Green 58 and CI Pigment Green 63, and a yellow pigment selected from CI Pigment Yellow 150, CI Pigment Yellow 138, CI Pigment Yellow 231 and CI Pigment Yellow 185 as a pigment, and when a sample with a thickness of 0.6 μm is prepared, the absorbance at the maximum absorption wavelength of 400 nm to 500 nm is 1 or more, and the absorbance at the maximum absorption wavelength of 600 nm to 700 nm is 1 or more.

[0483] From the viewpoint of increasing the refractive index of the color filter 215, a filler (e.g., titanium dioxide particles) having a high refractive index is sometimes added to the coloring composition. In this case, if the amount of filler added is large, the coloring degree of the color filter is reduced, and the function as a color filter is damaged. On the other hand, if the amount of filler added is reduced, the refractive index of the color filter cannot be increased, and the sensitivity characteristics of the solid-state imaging element are degraded. In particular, if the solid-state imaging element is thinned (the color filter is filmized), the undesirable situation becomes more significant. That is, when using a filler, it is difficult to increase the refractive index while maintaining the coloring degree of the color filter. Therefore, a color filter made using a coloring composition to which a filler is added cannot meet the characteristics.

[0484] On the other hand, in the present invention, since a dispersion resin having a high refractive index is used, it is not necessary to use a filler, or even if used, only a small amount can be used, so the above-mentioned inconvenience can be prevented.

[0485] Furthermore, in the present invention, the addition of a filler to the coloring composition is not excluded as long as the refractive index can be increased while maintaining the coloring degree of the color filter.

[0486] As mentioned above, although the dispersion resin, the coloring composition for color filters, the color filter, and the solid-state imaging element were described, the present invention is not limited thereto.

[0487] For example, the dispersion resin, coloring composition for color filter, color filter and solid-state imaging element of the present invention can be replaced with any structure that performs the same function, or a structure that performs any target function can be added. In addition, the dispersion resin of this specification can also be used for inkjet inks and resin molded bodies.

[0488] The camera module 100 can be mounted on electronic devices such as smartphones, digital cameras, tablets, and personal computers. In addition, the solid-state imaging element 2 can be directly manufactured into the electronic device. In this case, the electronic device corresponds to the electronic device of the present invention.

[0489] Furthermore, it can also be provided in the various forms described below.

[0490] (1) A dispersion resin for use in combination with a pigment, the dispersion resin comprising: a first portion having an affinity for the pigment; and a second portion functioning to prevent aggregation of the pigment particles, the dispersion resin having a refractive index of 1.54 or greater at a wavelength of 594 nm.

[0491] (2) The dispersion resin according to (1) above, wherein the dispersion resin contains an aromatic ring, and the ratio of the aromatic ring to the total mass of the dispersion resin is 25% by mass or more.

[0492] (3) The dispersion resin according to (2), wherein the dispersion resin mainly contains the aromatic ring in the second portion.

[0493] (4) The dispersion resin according to (2) or (3), wherein the dispersion resin is a graft copolymer in which the second site branches and extends from the first site, or a block copolymer in which the first site and the second site are bonded to each other at their ends.

[0494] (5) The dispersion resin according to (4), wherein the graft copolymer includes an aromatic ring to which a total of three or more carboxyl groups or carboxyl residues are directly bonded in the first portion.

[0495] (6) The dispersion resin according to (4) or (5) above, wherein the structural units of the first portion of the graft copolymer are polyesters connected by ester bonds.

[0496] (7) The dispersion resin according to any one of (4) to (6) above, wherein the second portion of the graft copolymer is a polymer portion of a monomer having an ethylenically unsaturated bond.

[0497] (8) The dispersion resin according to any one of (4) to (7) above, wherein the proportion of the second part in the total mass of the graft copolymer is 50% by mass or more.

[0498] (9) The dispersion resin according to (4), wherein the block copolymer includes at the first site one or more selected from the group consisting of a tertiary amino group and a quaternary ammonium group.

[0499] (10) The dispersion resin according to (9) above, wherein in the block copolymer, both the first site and the second site are polymer sites of a monomer having an ethylenically unsaturated bond.

[0500] (11) The dispersion resin according to (9) or (10) above, wherein the proportion of the second segment in the total mass of the block copolymer is 30% by mass or more.

[0501] (12) The dispersion resin according to any one of (1) to (11) above, wherein the weight average molecular weight of the dispersion resin is 5,000 or more and 50,000 or less.

[0502] (13) A coloring composition for a color filter, comprising at least a pigment and the dispersion resin according to any one of (1) to (12).

[0503] (14) The coloring composition for color filters according to (13) above, further comprising a polymerizable compound and a photopolymerization initiator.

[0504] (15) The coloring composition for color filter according to (13) or (14), wherein the green composition as the coloring composition for color filter contains a green pigment selected from CI Pigment Green 36, CI Pigment Green 58 and CI Pigment Green 63, and a yellow pigment selected from CI Pigment Yellow 150, CI Pigment Yellow 138, CI Pigment Yellow 231 and CI Pigment Yellow 185 as the pigments, and when a sample with a thickness of 0.6 μm is prepared, the absorbance at the maximum absorption wavelength of 400 nm to 500 nm is 1 or more, and the absorbance at the maximum absorption wavelength of 600 nm to 700 nm is 1 or more.

[0505] (16) A color filter including a plurality of filter units filled at least in spaces partitioned by partition walls and comprising the coloring composition for color filter according to any one of (13) to (15).

[0506] (17) A solid-state imaging element comprising: the color filter according to (16); and a plurality of photodiodes for receiving light that has passed through the color filter.

[0507] Of course, it is not limited to this.

[0508] Finally, various embodiments of the present disclosure are described, but they are provided as examples and are not intended to limit the scope of the invention. The novel embodiments can be implemented in various other forms, and various omissions, substitutions, and changes can be made without departing from the scope of the invention. The embodiments and their variations are included in the scope or spirit of the invention, and are included in the invention described in the claims and their equivalents.

[0509] [Example]

[0510] Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to the examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass".

[0511] First, the methods for measuring the average primary particle size and dispersed particle size of the pigment, the weight average molecular weight (Mw) of the dispersion resin, the acid value of the dispersion resin, and the nonvolatile content of the dispersion resin are described.

[0512] 1. Determination method

[0513] (Average primary particle size of pigment)

[0514] The average primary particle diameter of the pigment is determined by a general method of measuring the size of the primary particles directly from a transmission electron microscope (TEM) photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment are measured, and the average is set as the particle diameter of the pigment particles. Next, for more than 100 pigment particles, the volume (weight) of each particle is approximated with a rectangular parallelepiped of the obtained particle diameter, and the volume average particle diameter is set as the average primary particle diameter.

[0515] (Dispersed particle size)

[0516] The microtrac UPA-EX150 of Nikkiso Co., Ltd. using dynamic light scattering (fast Fourier transform (FFT) power spectrum method) was used, and the particle permeability was set to absorption mode, the particle shape was set to non-spherical, and the D50 was rounded off to an average diameter in units of 5 nm. The dilution solvent used for the measurement was the solvent used in the dispersion, and the measurement was performed immediately after the sample was adjusted for the sample after ultrasonic treatment.

[0517] (Weight average molecular weight of dispersion resin (Mw))

[0518] The weight average molecular weight (Mw) of the dispersed resin is the following weight average molecular weight, that is, the weight average molecular weight converted to polystyrene measured using a TSK gel column (manufactured by Tosoh) and a GPC (manufactured by Tosoh, HLC-8120GPC) equipped with a refractive index (RI) detector, using tetrahydrofuran (THF) as the developing solvent.

[0519] (Acid value of dispersion resin)

[0520] 80 mL of acetone and 10 mL of water were added to 0.5 g or more and 1 g or less of the dispersion resin solution and stirred to make it uniformly dissolved, and a 0.1 mol / L KOH aqueous solution was used as a titrant and titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Industry) to measure the acid value of the dispersion resin solution. In addition, the acid value per unit non-volatile component of the dispersion resin was calculated based on the acid value of the dispersion resin solution and the non-volatile component concentration of the dispersion resin solution.

[0521] The acid value (mgKOH / g) was determined as the value of the dispersed resin in a dry state by the following formula.

[0522] Acid value (mgKOH / g) = {(5.611×α×F) / S} / (non-volatile content concentration / 100)

[0523] Where, S: the amount of sample collected (g)

[0524] α: Consumption of 0.1 mol / L potassium hydroxide·ethanol solution (mL)

[0525] F: Titer of 0.1 mol / L potassium hydroxide ethanol solution

[0526] (Non-volatile components of dispersion resin)

[0527] The conditions for determining the nonvolatile content of the dispersed resin were as follows: the mass of the sample was set to about 1 g, the drying condition was set to 200° C., and the drying time was set to 10 minutes.

[0528] 2. Preparation of dispersion resin solution

[0529] 2-1. Production of graft copolymer

[0530] (Example 1: Preparation of a solution of dispersion resin X1)

[0531] 75.0 parts of benzyl methacrylate, 20.0 parts of benzyl acrylate, 5.0 parts of methacrylic acid and 25.0 parts of propylene glycol methyl ether acetate (PGMAc) were placed in a reaction container equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, and the atmosphere was replaced with nitrogen.

[0532] The reaction container was heated and stirred to 50° C., and 6.0 parts of 3-mercapto-1,2-propanediol was added.

[0533] The temperature in the reaction container was raised to 90° C., and a solution prepared by adding 0.1 parts of 2,2′-azobisisobutyronitrile to 45.7 parts of PGMAc was added and reacted for 7 hours. The nonvolatile content was measured, and it was confirmed that 95% of the reaction had proceeded.

[0534] Next, 9.7 parts of pyromellitic dianhydride, 31.5 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120° C. for 5 hours. The acid value was measured by sampling, and it was confirmed that 96% of the acid anhydride had reacted.

[0535] Next, 9.0 g of 3-methoxybutanol was added and reacted at 120° C. for 3 hours. Sampling was performed to measure the acid value, and it was confirmed that 98% or more of the acid anhydride had reacted, and the reaction was terminated. After cooling to room temperature, PGMAc was added and prepared so that the non-volatile component was 40% by mass, thereby obtaining a solution of dispersed resin X1 having an acid value of 98.5 mgKOH / g and a weight average molecular weight of 8500.

[0536] Here, the molecular weight of benzyl methacrylate is about 176, the molecular weight of benzyl acrylate is about 162, and the molecular weight of methacrylic acid is about 86. In addition, regarding the molecular weight of the aromatic ring, benzene (C6H6) is set to about 78.

[0537] The charged amounts of the monomers constituting the second part of the dispersion resin X1 were 75.0 parts of benzyl methacrylate, 20.0 parts of benzyl acrylate, and 5.0 parts of methacrylic acid (100.0 parts in total).

[0538] Therefore, the ratio of the aromatic ring to the mass of the second site ("aromatic ring ratio of the second site" in Table 1) is calculated as (78 / 176×75.0 / 100.0+78 / 162×20.0 / 100.0)×100≈43%.

[0539] The same calculation was performed for the dispersion resins shown below.

[0540] (Example 2 to Example 9, Comparative Examples 1 and 2: Preparation of Solutions of Dispersion Resins X2 to X9, and Comparative Dispersion Resins Y1 and Y2)

[0541] Solutions of dispersion resins X2 to X9 and comparative dispersion resins Y1 to Y2 were obtained in the same manner as the solution of dispersion resin X1 except that the raw materials and blending amounts were as shown in Table 1. The blending amounts in the table are parts.

[0542] (Example 10: Preparation of Dispersed Resin X10 Solution)

[0543] Into a reaction container equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 95 parts of benzyl methacrylate, 5 parts of methacrylic acid, and 45.4 parts of PGMAc were placed, and the atmosphere was replaced with nitrogen.

[0544] The reaction container was heated to 70°C, 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 parts of AIBN (azo isobutyronitrile) was added, and the mixture was reacted for 12 hours. The nonvolatile content was measured, and it was confirmed that 95% of the reaction had progressed.

[0545] Next, 19.2 parts of trimellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the mixture was reacted at 120° C. for 7 hours. The acid value was measured to confirm that 98% or more of the anhydride was half-esterified, and the reaction was terminated.

[0546] PGMAc was added to adjust the nonvolatile content to 40%. In this way, a dispersion resin X10 solution having an acid value of 90 mgKOH / g, a weight average molecular weight of 9,000, a poly(meth)acrylate skeleton and aromatic carboxyl groups was obtained.

[0547] (Example 11: Preparation of Dispersed Resin X11 Solution)

[0548] Into a reaction container equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 95 parts of benzyl methacrylate, 5 parts of methacrylic acid, and 45.4 parts of PGMAc were placed, and the atmosphere was replaced with nitrogen.

[0549] The reaction container was heated to 70° C., 2 parts of 3-mercapto-1,2-propanediol were added, and 0.12 parts of AIBN (azobisisobutyronitrile) were added, and the mixture was reacted for 12 hours. The nonvolatile content was measured, and it was confirmed that 95% of the reaction had proceeded.

[0550] Next, 3.2 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added and reacted at 120° C. for 7 hours. The acid value was measured to confirm that 98% or more of the anhydride was half-esterified, and the reaction was terminated.

[0551] PGMAc was added to adjust the nonvolatile content to 40%. In this way, a dispersion resin X11 solution having an acid value of 47 mgKOH / g, a weight average molecular weight of 18,000, a poly(meth)acrylate skeleton and aromatic carboxyl groups was obtained.

[0552] (Example 12: Preparation of Dispersed Resin X12 Solution)

[0553] 100 parts of benzyl methacrylate and 25.0 parts of PGMAc were placed in a reaction container equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, and the atmosphere was replaced with nitrogen.

[0554] The reaction vessel was heated to 50°C, and 6.0 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution prepared by dissolving 0.1 parts of 2,2'-azobisisobutyronitrile in 45.7 parts of PGMAc was added, and the mixture was reacted for 10 hours. The nonvolatile content was measured, and it was confirmed that 95% of the reaction had occurred.

[0555] Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120° C. for 5 hours. Then, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120° C. for 3 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated.

[0556] After the reaction was completed, PGMAc was added to prepare the mixture so that the nonvolatile content was 40% by mass, thereby obtaining a dispersion resin X12 solution having an acid value of 95 mgKOH / g and a weight average molecular weight of 9,500.

[0557] (Example 13: Preparation of Dispersed Resin X13 Solution)

[0558] Into a reaction container equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 10 parts of OXE-30 ((3-ethyloxetan-3-yl)methyl methacrylate) manufactured by Osaka Organic Chemical Industry, 5 parts of methacrylic acid, 20 parts of tert-butyl methacrylate, 65 parts of benzyl methacrylate, and 45.4 parts of PGMAc were charged, and the atmosphere was replaced with nitrogen.

[0559] The reaction container was heated to 70° C., 6 parts of 3-mercapto-1,2-propanediol was added, and 0.12 parts of AIBN (azobisisobutyronitrile) was added, and the mixture was reacted for 12 hours. The nonvolatile content was measured, and it was confirmed that 95% of the reaction had proceeded.

[0560] Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added and reacted at 120° C. for 7 hours. The acid value was measured to confirm that 98% or more of the anhydride was half-esterified, and the reaction was terminated.

[0561] PGMAc was added to adjust the nonvolatile content to 40%. In this way, a dispersion resin X13 solution having an acid value of 75 mgKOH / g, a weight average molecular weight of 9,000, a poly(meth)acrylate skeleton and aromatic carboxyl groups was obtained.

[0562] [Table 1]

[0563]

[0564] [Table 2]

[0565]

[0566] The abbreviations in the table are as follows.

[0567] BzMA: benzyl methacrylate

[0568] BzA: Benzyl acrylate

[0569] MMA: Methyl Methacrylate

[0570] EA: Ethyl acrylate

[0571] MAA: Methacrylic acid

[0572] t-BA: tert-butyl acrylate

[0573] 2MTA: 2-Methoxyethyl acrylate

[0574] 4ClSt: 4-chlorostyrene

[0575] MPD: 3-Mercapto-1,2-propanediol

[0576] RUVA93: Polymeric UV absorber (manufactured by Otsuka Chemical)

[0577] AIBN: 2,2'-azobisisobutyronitrile

[0578] PGMAc: Propylene glycol monomethyl ether acetate

[0579] PMA: Pyromellitic anhydride

[0580] TMA: trimellitic anhydride

[0581] DBU: 1,8-diazabicyclo-[5.4.0]-7-undecene

[0582] 3MB: 3-methoxybutanol

[0583] PGME: Propylene glycol monomethyl ether

[0584] DAA: diacetone alcohol

[0585] HPMA: Hydroxypropyl Methacrylate

[0586] MOI: 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko)

[0587] (Example 14: Preparation of Dispersed Resin X14 Solution)

[0588] Into a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6 parts of 1-thioglycerol, 9.7 parts of pyromellitic anhydride, 36.9 parts of PGMAc (methoxypropyl acetate), and 0.2 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) were placed, and after replacing with nitrogen, the reaction was carried out at 120° C. for 5 hours (first step). By measuring the acid value, it was confirmed that 95% or more of the anhydride was half-esterified.

[0589] Next, 20 parts of 2-hydroxypropyl methacrylate, 75 parts of benzyl methacrylate, 5 parts of methacrylic acid, and 66.3 parts of PGMAc were added, the reaction vessel was heated to 80°C, 0.12 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). The nonvolatile content was measured, and it was confirmed that 95% of the reaction had occurred.

[0590] Finally, 21.6 parts of 2-methacryloyloxyethylisocyanate (MOI) and 0.1 parts of hydroquinone were added, and the reaction was continued until the isocyanate group-derived wavelength at 2270 cm was observed by IR. -1 The peak value disappears (third process).

[0591] After confirming that the peak disappeared, the reaction solution was cooled and the nonvolatile component was adjusted with PGMAc to obtain a dispersion resin X13 solution with a nonvolatile component of 40%. The acid value of the obtained dispersant was 68 mgKOH / g, the unsaturated double bond equivalent was 1593, and the weight average molecular weight was 10000. In addition, since the dispersion resin X14 has a methacryloyl group, it has thermosetting properties and photocuring properties.

[0592] (Example 15: Preparation of Dispersed Resin X15 Solution)

[0593] 6 parts of 3-mercapto-1,2-propanediol, 14.5 parts of PMA, and 70.8 parts of PGMAc were added to a reaction vessel including a gas inlet pipe, a thermometer, a condenser, and a stirrer, and replaced with nitrogen. The reaction vessel was heated to 100°C and reacted for 5 hours. Then, 12.1 g of 3-methoxybutanol was added and reacted at 120°C for 3 hours. After confirming that more than 98% of the anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, 100 parts of benzyl methacrylate were added, and 38.0 parts of PGMAc dissolved with 0.1 parts of 2,2'-azobisisobutyronitrile were added and reacted for 10 hours. By measuring the non-volatile component, it was confirmed that the polymerization was 95% and the reaction was terminated. After the reaction was completed, PGMAc was added to prepare the mixture so that the nonvolatile content was 40% by mass, thereby obtaining a dispersion resin X15 solution having an acid value of 93 mgKOH / g and a weight average molecular weight of 10,800.

[0594] (Example 16: Preparation of Dispersed Resin X16 Solution)

[0595] Into a reaction container equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 12 parts of 3-mercapto-1,2-propanediol, 12 parts of PMA, 11 parts of trimellitic anhydride, and 35 parts of PGMAc were placed, and the atmosphere was replaced with nitrogen.

[0596] The reaction vessel was heated to 100°C and allowed to react for 7 hours. After confirming that more than 98% of the anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, 160 parts of benzyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 20 parts of 2-hydroxypropyl methacrylate were added, and 200 parts of a PGMAc solution in which 0.5 parts of 2,2'-azobisisobutyronitrile was dissolved was added, and the reaction was allowed to react for 10 hours. By measuring the non-volatile component, it was confirmed that the polymerization was 95% and the reaction was terminated.

[0597] PGMAc was added to adjust the nonvolatile content to 40%, thereby obtaining a dispersion resin X16 solution having an acid value of 53 mgKOH / g and a weight average molecular weight of 10,000.

[0598] (Example 17: Preparation of Dispersed Resin X17 Solution)

[0599] Into a reaction container equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 12 parts of 3-mercapto-1,2-propanediol, 15 parts of PMA, 11 parts of neopentyl glycol, 14 parts of trimellitic anhydride, and 52 parts of PGMAc were placed, and the atmosphere was replaced with nitrogen.

[0600] The reaction vessel was heated to 100°C and allowed to react for 7 hours. After confirming that 98% or more of the anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, 180 parts of benzyl methacrylate and 20 parts of 2-hydroxypropyl methacrylate were added, and 200 parts of a PGMAc solution in which 0.5 parts of 2,2'-azobisisobutyronitrile was dissolved was added, and the reaction was allowed to react for 10 hours. By measuring the non-volatile component, it was confirmed that the polymerization had proceeded by 95%, and the reaction was terminated.

[0601] PGMAc was added to adjust the nonvolatile content to 40%, thereby obtaining a dispersion resin X17 solution having an acid value of 63 mgKOH / g and a weight average molecular weight of 9,000.

[0602] [Table 3]

[0603]

[0604] 2-2. Production of block copolymer

[0605] (Example 18: Preparation of Dispersed Resin X18 Solution)

[0606] 80 parts of benzyl methacrylate, 1.0 part of methyl 4-cyano-4-[(dodecylthiothiocarbonyl)thio]pentanoate, and 80 parts of PGMAc were placed in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and heated and stirred to 70° C. while nitrogen was flowing. 0.11 parts of 2,2'-azobis(isobutyric acid)dimethyl was added thereto to start polymerization of the first block.

[0607] After 6 hours and 8 hours from the start of polymerization, 0.01 parts of 2,2'-azobis(isobutyric acid)dimethyl was added, and then the polymerization solution was sampled 1 hour later for nonvolatile content measurement. The polymerization conversion rate was confirmed to be 95% or more based on the nonvolatile content, and the polymerization of the first block was completed.

[0608] Next, 20 parts of dimethylaminoethyl methacrylate and 23 parts of PGMAc were added to the reaction tank, stirred at 70°C under a nitrogen atmosphere, and 0.09 parts of 2,2'-azobis(isobutyric acid)dimethyl were added to start the polymerization of block A. 0.01 parts of 2,2'-azobis(isobutyric acid)dimethyl were added 2 hours and 3 hours after the start of the polymerization, and then the polymerization solution was sampled after 1 hour to measure the non-volatile component. The polymerization conversion rate was confirmed to be 95% or more based on the non-volatile component, thus completing the polymerization of the second block.

[0609] PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40 mass %, thereby obtaining a dispersion resin X18 solution having an amine value per nonvolatile content of 71.4 mgKOH / g, a weight average molecular weight of 20,000, and a nonvolatile content of 40 mass %.

[0610] (Example 19: Preparation of Dispersed Resin X19 Solution)

[0611] 80 parts of benzyl methacrylate and 13.2 parts of tetramethylethylenediamine were placed in a reaction apparatus equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and stirred at 50° C. for 1 hour while nitrogen was flowing to replace the interior of the system with nitrogen.

[0612] Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cupric chloride, and 133 parts of PGMAc were added, and the temperature was raised to 110° C. under a nitrogen stream to start polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled for nonvolatile content measurement, and the polymerization conversion rate was confirmed to be 98% or more based on the nonvolatile content.

[0613] Next, 61 parts of PGMAc and 25.0 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride ("DMC-80" manufactured by Sanyo Chemical Co., Ltd., non-volatile content 80%) as a monomer of the second block were added to the reaction apparatus, and the reaction was continued while stirring at 110° C. in a nitrogen atmosphere. After 2 hours from the addition of methacryloyloxyethyltrimethylammonium chloride, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second site was 98% or more based on the non-volatile content. The reaction solution was cooled to room temperature to stop the polymerization.

[0614] PGMAc was added to the previously synthesized block copolymer solution so that the nonvolatile content was 40 mass %, thereby obtaining a dispersion resin X19 solution having a quaternary ammonium salt value of 29.4 mgKOH / g per nonvolatile content and a weight average molecular weight of 9800 (Mw).

[0615] (Example 20: Preparation of Dispersing Resin X20 Solution)

[0616] 60 parts of benzyl methacrylate, 1.0 part of methyl 4-cyano-4-[(dodecylthiothiocarbonyl)thio]pentanoate, and 80 parts of PGMAc were placed in a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, and heated and stirred to 70° C. while nitrogen was flowing. 0.11 parts of 2,2'-azobis(isobutyric acid)dimethyl was added thereto to start polymerization of the first block.

[0617] After 6 hours and 8 hours from the start of polymerization, 0.01 parts of 2,2'-azobis(isobutyric acid)dimethyl was added, and then the polymerization solution was sampled 1 hour later for nonvolatile content measurement. The polymerization conversion rate was confirmed to be 95% or more based on the nonvolatile content, and the polymerization of the first block was completed.

[0618] Next, 40 parts of dimethylaminoethyl methacrylate and 23 parts of PGMAc were placed in the reaction vessel, and stirred while maintaining at 70° C. under a nitrogen atmosphere. 0.09 parts of 2,2′-azobis(isobutyric acid)dimethyl was added to start polymerization of the second block.

[0619] After 2 hours and 3 hours from the start of polymerization, 0.01 parts of 2,2'-azobis(isobutyric acid)dimethyl was added, and then the polymerization solution was sampled 1 hour later for nonvolatile content measurement. The polymerization conversion rate was confirmed to be 95% or more based on the nonvolatile content, and the polymerization of the second block was completed.

[0620] In this way, a precursor solution of a block copolymer having an amine value per nonvolatile component of 145.0 mgKOH / g and a weight average molecular weight of 24,000 was obtained.

[0621] Furthermore, 2.0 parts of benzyl chloride was added to the reaction apparatus, and the mixture was stirred for 3 hours at 70° C. in a nitrogen atmosphere to form a pigment affinity site. The mixture was then cooled, and finally PGMAC was added so that the nonvolatile content was 40% by mass.

[0622] Thus, a dispersion resin X20 solution having an amine value of 120 mgKOH / g per unit of nonvolatile matter, a quaternary ammonium salt value of 18.0 mgKOH / g, and a nonvolatile matter content of 40% by mass was obtained.

[0623] [Table 4]

[0624]

[0625] The abbreviations in the table are as follows.

[0626] DM: Dimethylaminoethyl methacrylate

[0627] DMCMA: Methacryloyloxyethyltrimethylammonium chloride

[0628] BzCl: benzyl chloride

[0629] (Refractive index of dispersion resin)

[0630] The obtained dispersion resin was applied to a 100 μm thick easy-adhesion treated polyester film ("COSMOSHINE A4100" manufactured by Toyobo) as a transparent substrate using a No. 20 bar coater to a dry thickness of 2.0 μm, and then dried at 100° C. for 10 minutes to prepare a test film.

[0631] The refractive index of the obtained test film at 594 nm was determined using “prism coupler model 2010” manufactured by Metricon, and evaluated based on the following criteria.

[0632] ○:1.55 or more

[0633] △: 1.53 or more and less than 1.55

[0634] ×: less than 1.53

[0635] [Table 5]

[0636] Table 5 Refractive Index evaluate X1 1.56 ○ X2 1.57 ○ X3 1.55 ○ X4 1.58 ○ X5 1.57 ○ X6 1.55 ○ X7 1.57 ○ X8 1.57 ○ X9 1.57 ○ X10 1.55 ○ X11 1.56 ○ X12 1.57 ○ X13 1.54 △ X14 1.54 △ X15 1.57 ○ X16 1.56 ○ X17 1.56 ○ X18 1.55 ○ X19 1.55 ○ X20 1.54 △ Y1 1.51 × Y2 1.51 ×

[0637] 3. Preparation of Binder Resin Solution

[0638] 70.0 parts of PGMAc was placed in a separable four-necked flask (reaction container) equipped with a thermometer, a cooling tube, a nitrogen inlet tube, and a stirring device, and the temperature was raised to 80° C. to replace the interior of the reaction container with nitrogen.

[0639] Then, polymerization was carried out while a mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of p-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei) and 0.4 parts of 2,2′-azobisisobutyronitrile was added dropwise from a dropper over 2 hours.

[0640] After the addition was completed, the reaction was continued for 3 hours to terminate the reaction. After cooling to room temperature, about 2 g of the solution was sampled, heated and dried at 180° C. for 20 minutes, and the non-volatile component was measured. Then, PGMAc was added in a manner that the non-volatile component was 20% by mass to prepare an alkali-soluble resin, i.e., a binder resin solution. In addition, the weight average molecular weight (Mw) of the resin was 26,000.

[0641] 4. Preparation of pigment dispersion

[0642] (Preparation of raw materials)

[0643] ((pigment))

[0644] PR254 (CI Pigment Red 254): "Irgaphor Red B-CF" manufactured by BASF Japan

[0645] PB15:6 (CI Pigment Blue 15:6): "LIONOL BLUE ESP-S" manufactured by TOYOCOLOR

[0646] PG36 (CI Pigment Green 36): "Green 8G" manufactured by CLARIANT

[0647] PG58 (CI Pigment Green 58): "FASTOGEN GREEN A110" manufactured by DIC

[0648] PY138 (CI Pigment Yellow 138): ("Paliotol Yellow K 0961HD" manufactured by BASF)

[0649] · PY150 (CI Pigment Yellow 150): (“Hostaperm Yellow HN4G” manufactured by CLARIANT)

[0650] PY185 (CI Pigment Yellow 185): ("Paliotol Yellow D 1155" manufactured by BASF)

[0651] PY139 (CI Pigment Yellow 139): ("Paliotol Yellow L 2146HD" manufactured by BASF)

[0652] ((Pigment derivatives))

[0653] Pigment derivative 1:

[0654] [Chemistry 12]

[0655]

[0656] Pigment derivative 2:

[0657] [Chemistry 13]

[0658]

[0659] Pigment derivative 3:

[0660] [Chemistry 14]

[0661]

[0662] (Production of Pigment Dispersion 1)

[0663] 11.7 parts of PR254, 1.3 parts of basic derivative 1, 17.5 parts of a solution of dispersion resin X1, and 78.25 parts of PGMAc were stirred and mixed so as to become uniform.

[0664] Next, the obtained mixture was dispersed for 3 hours using zirconia beads having a diameter of 0.5 mm using an eiger mill (manufactured by Eiger Japan, "mini model M-250MKII").

[0665] Then, the obtained dispersion was filtered using a filter having a pore size of 5.0 μm to obtain a pigment dispersion 1 having a nonvolatile content of 20% by mass.

[0666] (Manufacturing of Pigment Dispersions 2 to 26)

[0667] Pigment dispersions 2 to 26 were obtained in the same manner as in pigment dispersion 1 except that the raw materials and the charged amounts were set as shown in Table 6.

[0668] [Table 6]

[0669]

[0670] 5. Production of photosensitive coloring composition

[0671] (Preparation of raw materials)

[0672] (Polymerizable compound)

[0673] A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (manufactured by Toa Gosei Chemical, "Aronix M-402")

[0674] (Photopolymerization Initiator)

[0675] Ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], 1-(O-acetyl oxime) (manufactured by BASF Japan, "IRGACURE OXE02")

[0676] (Sensitizer)

[0677] 4,4'-Bis(diethylamino)benzophenone (manufactured by Hodogaya Chemical, "EAB-F")

[0678] (Example 21)

[0679] First, 60.0 parts of the pigment dispersion 1, 1.0 part of the polymerizable compound, 0.25 parts of the photopolymerization initiator, 0.05 parts of the sensitizer, and 38.7 parts of propylene glycol monomethyl ether acetate (PGMAc) were stirred and mixed so as to become uniform.

[0680] Then, the obtained mixture was filtered using a filter having a pore size of 1 μm, thereby obtaining a coloring composition 1.

[0681] (Example 22 to Example 47)

[0682] Except that the formulation of Example 21 was changed to the materials and formulation amounts described in Table 7, the same procedure as Example 21 was carried out to obtain Examples 22 to 47, respectively.

[0683] [Table 7]

[0684]

[0685] 6. Evaluation of dispersion resin and coloring composition

[0686] Each test was conducted using the following method.

[0687] <Filterability>

[0688] A pressure of 0.05 MPas was applied to 60 g of the obtained colored composition using a 1.5 μm disk filter (Tomsic, “Titan 3 PTFE FILTER”) for a certain period of time, and the amount of liquid passing through the disk filter during this period was evaluated. The larger the amount of liquid, the better the filterability.

[0689] Then, the filterability was evaluated according to the following evaluation criteria.

[0690] ○: The amount of liquid that passed through the filter was 45 g or more (good)

[0691] △: The amount of liquid that passed through the filter is 30 g or more and less than 45 g (practical)

[0692] ×: The amount of liquid that passed through the filter is less than 30 g (defective)

[0693] <Viscosity stability>

[0694] The viscosity stability of the obtained coloring composition was evaluated by the following method: The initial viscosity on the second day after the preparation of the coloring composition and the viscosity after aging for one week at 40°C were measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo) at 25°C and 50 rpm.

[0695] The viscosity change rate over time was calculated from the values ​​of these initial viscosity and viscosity over time by the following formula. The obtained results were evaluated by the following criteria.

[0696] [Change rate of viscosity over time] = |([initial viscosity] - [viscosity over time]) / [initial viscosity]| × 100

[0697] [Evaluation criteria]

[0698] ○: Change rate is less than 5% (good)

[0699] △: Change rate is 5% or more and less than 10% (practical)

[0700] ×: Change rate 10% or more (defective)

[0701] <Foreign matter evaluation>

[0702] The obtained colored composition was applied onto a glass substrate on which a black matrix was previously formed by a spin coating method, and then dried in a clean oven at 70° C. for 20 minutes.

[0703] Next, after the substrate was cooled to room temperature, ultraviolet light exposure was performed using an ultra-high pressure mercury lamp through a photomask. Then, the substrate was spray-developed for 30 seconds using a 0.2 mass % sodium carbonate aqueous solution at 23°C, and then washed and dried using ion exchange water. Furthermore, a heat treatment was performed at 230°C for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate. The prepared colored pixel layer was heat-treated at 230°C for 30 minutes to obtain a test substrate with a thickness of 2.0 μm.

[0704] The obtained test substrate was used to measure the number of foreign matter in the colored pixels. For evaluation, the surface was observed using a metal microscope "BX60" manufactured by Olympus System. The magnification was set to 500 times, and the number of foreign matter that could be observed in any five fields of view during perspective was measured.

[0705] Then, foreign matter evaluation was performed according to the following evaluation criteria.

[0706] [Evaluation criteria]

[0707] ◎: The number of foreign matter is less than 3 (extremely good)

[0708] ○: The number of foreign matter is 3 or more and less than 20 (good)

[0709] △: The number of foreign objects is 21 or more and less than 100 (practical)

[0710] ×: The number of foreign matter is 100 or more (defective)

[0711] <Refractive Index>

[0712] The test substrate produced in the above-mentioned foreign matter evaluation was used to evaluate the refractive index using "prism coupler model 2010" manufactured by Metricon.

[0713] <Redissolution>

[0714] The obtained colored composition was applied onto a glass substrate by spin coating and pre-baked at 100° C. for 3 minutes to obtain a test substrate having a thickness of 2.0 μm. The obtained test substrate was immersed in PGMAc for 5 minutes.

[0715] Then, the dissolved state was visually observed according to the following evaluation criteria, and the solubility was evaluated according to the following criteria.

[0716] ○: Dissolved (good)

[0717] ×: Peeling (bad)

[0718] [Table 8]

[0719] Table 8 Filterability Stability over time Refractive Index foreign body Resolubility Embodiment 21 ○ ○ 1.78 ○ ○ Embodiment 22 ○ ○ 1.71 ○ ○ Embodiment 23 ○ ○ 1.92 ○ ○ Embodiment 24 ○ ○ 1.73 ○ ○ Embodiment 25 ○ ○ 1.96 ○ ○ Embodiment 26 ○ ○ 1.43 ○ ○ Embodiment 27 ○ ○ 1.60 ○ ○ Embodiment 28 ○ ○ 1.59 △ △ Embodiment 29 ○ ○ 1.60 ○ ○ Embodiment 30 ○ ○ 1.60 ○ ○ Embodiment 31 ○ ○ 1.61 ○ ○ Embodiment 32 ○ ○ 1.60 ○ ○ Embodiment 33 ○ ○ 1.60 ○ ○ Embodiment 34 ○ ○ 1.60 ○ ○ Embodiment 35 ○ ○ 1.60 ○ ○ Embodiment 36 ○ ○ 1.61 ○ ○ Embodiment 37 ○ ○ 1.60 ○ ○ Embodiment 38 ○ ○ 1.60 ○ ○ Embodiment 39 ○ ○ 1.60 ○ ○ Embodiment 40 ○ ○ 1.60 ○ ○ Embodiment 41 ○ ○ 1.60 ○ ○ Embodiment 42 ○ ○ 1.60 ○ ○ Embodiment 43 ○ ○ 1.60 ○ ○ Embodiment 44 ○ ○ 1.60 ○ ○ Embodiment 45 ○ ○ 1.62 ◎ ○ Embodiment 46 ○ ○ 1.62 ◎ ○ Embodiment 47 ○ ○ 1.61 ◎ ○

[0720] According to the results in Table 5, the refractive index of the dispersion resin of the example is good, while the refractive index of the comparative dispersion resin of the comparative example is low.

[0721] According to the results of Table 8, the colored compositions of Examples were good in filterability, storage stability, foreign matter evaluation, re-dissolution properties, and refractive index.

[0722] On the other hand, the results of the colored compositions of Comparative Examples showed differences in refractive index.

Claims

1. A dispersion resin, mixed with a pigment and containing an aromatic ring, comprising: A first part having affinity with the pigment; as well as The second part functions to prevent the pigment particles from agglomerating with each other. The ratio of the aromatic ring to the mass of the second part is 20 mass % or more, The refractive index of the dispersion resin at a wavelength of 594 nm is 1.54 or more.

2. The dispersion resin according to claim 1, wherein The ratio of the aromatic ring to the total mass of the dispersion resin is 25 mass % or more.

3. The dispersion resin according to claim 2, wherein The dispersion resin mainly includes the aromatic ring in the second portion.

4. The dispersion resin according to claim 2, wherein The dispersion resin is a graft copolymer in which the second site branches and extends from the first site, or a block copolymer in which the first site and the second site are bonded to each other at the end portions.

5. The dispersion resin according to claim 4, wherein The graft copolymer includes an aromatic ring to which a total of three or more carboxyl groups or carboxyl residues are directly bonded at the first site.

6. The dispersion resin according to claim 4, wherein The structural units of the first part of the graft copolymer are polyesters connected by ester bonds.

7. The dispersion resin according to claim 4, wherein The second part of the graft copolymer is a polymer part of a monomer having an ethylenically unsaturated bond.

8. The dispersion resin according to claim 4, wherein The ratio of the second part to the total mass of the graft copolymer is 50 mass % or more.

9. The dispersion resin according to claim 4, wherein The block copolymer includes at the first site one or more selected from the group consisting of a tertiary amino group and a quaternary ammonium group.

10. The dispersion resin according to claim 9, wherein In the block copolymer, both the first site and the second site are polymer sites of monomers having ethylenically unsaturated bonds.

11. The dispersion resin according to claim 9, wherein The ratio of the second part to the total mass of the block copolymer is 30 mass % or more.

12. The dispersion resin according to claim 1, wherein The weight average molecular weight of the dispersion resin is 5,000 or more and 50,000 or less.

13. A coloring composition for a color filter, comprising at least A pigment, and a dispersion resin as claimed in any one of claims 1 to 12.

14. The coloring composition for color filter according to claim 13, further comprising A polymerizable compound and a photopolymerization initiator.

15. The coloring composition for color filter according to claim 13, wherein The green composition as the coloring composition for the color filter contains a green pigment selected from CI Pigment Green 36, CI Pigment Green 58 and CI Pigment Green 63, and a yellow pigment selected from CI Pigment Yellow 150, CI Pigment Yellow 138, CI Pigment Yellow 231 and CI Pigment Yellow 185 as the pigment, and when a sample with a thickness of 0.6 μm is prepared, the absorbance at the maximum absorption wavelength of 400 nm to 500 nm is 1 or more, and the absorbance at the maximum absorption wavelength of 600 nm to 700 nm is 1 or more.

16. A color filter comprising a plurality of filter units, The plurality of filter units are composed of the coloring composition for color filter according to claim 13 filled at least in spaces partitioned by partition walls.

17. A solid-state imaging element, comprising: The color filter as claimed in claim 16; as well as A plurality of photodiodes receive light that has passed through the color filter.

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