WO2023243414A1 - Composition de résine, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image - Google Patents

Composition de résine, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image Download PDF

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Publication number
WO2023243414A1
WO2023243414A1 PCT/JP2023/020455 JP2023020455W WO2023243414A1 WO 2023243414 A1 WO2023243414 A1 WO 2023243414A1 JP 2023020455 W JP2023020455 W JP 2023020455W WO 2023243414 A1 WO2023243414 A1 WO 2023243414A1
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Prior art keywords
group
resin composition
resin
compounds
pigment
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PCT/JP2023/020455
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English (en)
Japanese (ja)
Inventor
俊佑 柳
憲晃 佐藤
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富士フイルム株式会社
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Publication of WO2023243414A1 publication Critical patent/WO2023243414A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials

Definitions

  • the present invention relates to a resin composition containing a coloring material.
  • the present invention also relates to a film, an optical filter, a solid-state image sensor, and an image display device using the resin composition.
  • optical filters such as color filters are manufactured using a resin composition containing a coloring material and a resin.
  • an object of the present invention is to provide a resin composition with excellent storage stability. Further, an object of the present invention is to provide a film, an optical filter, a solid-state image sensor, and an image display device.
  • the present invention provides the following.
  • a coloring material containing a pigment, resin and A compound represented by formula (1) which has a maximum molar extinction coefficient of 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less in the wavelength range of 400 to 700 nm, and has a molecular weight of 475 or less.
  • a resin composition comprising;
  • a 1 represents a group containing an acid group or a basic group
  • X 1 represents a urea group, thiourea group, urethane group, thiourethane group or amide group
  • L 1 represents an n-valent group
  • n represents an integer from 1 to 4.
  • ⁇ 2> The resin composition according to ⁇ 1>, wherein X 1 in the above formula (1) is a urea group.
  • ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein A 1 in the above formula (1) is a group containing a basic group.
  • ⁇ 4> The resin composition according to ⁇ 1> or ⁇ 2>, wherein A 1 in formula (1) is a group represented by formula (A20); A20 - L20 -...(A20) In formula (A20), A 20 represents a basic group, and L 20 represents an alkylene group.
  • n in the above formula (1) is 1, L 1 is a polycyclic aromatic ring group, an aliphatic hydrocarbon group having 2 or more carbon atoms, or a monocyclic aromatic hydrocarbon group having an electron-withdrawing group or an electron-donating group as a substituent, ⁇
  • the pigment is any one of ⁇ 1> to ⁇ 6>, including at least one selected from the group consisting of diketopyrrolopyrrole pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, and azo pigments.
  • the resin composition described in . ⁇ 8> A film obtained using the resin composition according to any one of ⁇ 1> to ⁇ 7>.
  • An optical filter comprising the film according to ⁇ 8>.
  • a solid-state imaging device comprising the film according to ⁇ 8>.
  • An image display device including the film according to ⁇ 8>.
  • a resin composition with excellent storage stability can be provided. Furthermore, a film, an optical filter, a solid-state image sensor, and an image display device can be provided.
  • ⁇ is used to include the numerical values described before and after it as a lower limit and an upper limit.
  • the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the term "alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
  • EUV light extreme ultraviolet rays
  • (meth)acrylate” represents acrylate and/or methacrylate
  • (meth)acrylic represents both acrylic and/or methacrylic
  • (meth)acrylate” represents acrylic and/or methacrylate.
  • Acryloyl refers to acryloyl and/or methacryloyl.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Ph represents a phenyl group.
  • the weight average molecular weight and number average molecular weight are polystyrene equivalent values measured by GPC (gel permeation chromatography).
  • the total solid content refers to the total mass of all components of the composition excluding the solvent.
  • pigment means a coloring material that is difficult to dissolve in a solvent.
  • the term "process” is used not only to refer to an independent process, but also to include a process in which the intended effect of the process is achieved even if the process cannot be clearly distinguished from other processes. .
  • the resin composition of the present invention is A coloring material containing a pigment, resin and A compound represented by formula (1), which has a maximum molar extinction coefficient of 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less in the wavelength range of 400 to 700 nm, and has a molecular weight of 475 or less ( (hereinafter also referred to as a specific compound), It is characterized by including.
  • the resin composition of the present invention can improve the dispersibility of the pigment in the resin composition and suppress the increase in viscosity of the resin composition over time. Therefore, the resin composition of the present invention has excellent storage stability. It is presumed that the reason why such an effect is obtained is as follows.
  • the above-mentioned specific compound contains a functional group selected from a urea group, a thiourea group, a urethane group, a thiourethane group, and an amide group, so this functional group and the pigment interact through hydrogen bonding, and the specific compound is formed on the surface of the pigment. It is assumed that the specific compound is strongly adsorbed and exists near the pigment in the resin composition.
  • the specific compound since the specific compound further has a group containing an acid group or a basic group, it is assumed that these groups included in the specific compound interact with the resin. Therefore, a strong network structure between the pigment, the specific compound, and the resin is formed in the resin composition, which suppresses aggregation of the pigment, and as a result, increases in the viscosity of the resin composition over time. It is presumed that this is because it was able to be suppressed.
  • the resin composition of the present invention can suppress pigment aggregation with the above-mentioned specific compound, it also has excellent pigment dispersibility and can also suppress the generation of coarse particles.
  • the resin composition of the present invention When a pattern is formed by photolithography using the resin composition of the present invention, generation of development residues can also be suppressed.
  • the reason for this effect is that the above-mentioned specific compounds are strongly adsorbed on the surface of the pigment through hydrogen bonding, which enhances the emulsifying effect of the pigment during development and efficiently removes the resin composition in the unexposed areas. It is assumed that this is because it could not be removed by development. For these reasons, the resin composition of the present invention can also suppress the generation of development residues.
  • the resin composition of the present invention has excellent developability, and furthermore, since the above-mentioned specific compound contained in the resin composition has excellent transparency, the resin composition of the present invention can be used on a support on which pixels are formed.
  • the resin composition of the present invention is preferably used as a resin composition for optical filters.
  • the optical filter include color filters, near-infrared transmission filters, near-infrared cut filters, etc., and color filters are preferred.
  • the resin composition of the present invention is preferably used for solid-state imaging devices. More specifically, it is preferably used as a resin composition for an optical filter used in a solid-state imaging device, and more preferably used as a resin composition for forming colored pixels in a color filter used in a solid-state imaging device.
  • color filters include filters that have colored pixels that transmit light of a specific wavelength.
  • colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc., and red pixels are more preferable.
  • the colored pixels of the color filter can be formed using a resin composition containing a chromatic coloring material.
  • the maximum absorption wavelength of the near-infrared cut filter preferably exists in a wavelength range of 700 to 1800 nm, more preferably exists in a wavelength range of 700 to 1300 nm, and even more preferably exists in a wavelength range of 700 to 1000 nm.
  • the transmittance of the near-infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more.
  • the transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less.
  • the ratio of the absorbance Amax at the maximum absorption wavelength of the near-infrared cut filter to the absorbance A550 at a wavelength of 550 nm is preferably 20 to 500, more preferably 50 to 500. , more preferably from 70 to 450, particularly preferably from 100 to 400.
  • the near-infrared cut filter can be formed using a resin composition containing a near-infrared absorbing coloring material.
  • a near-infrared transmission filter is a filter that transmits at least a portion of near-infrared rays.
  • the near-infrared transmitting filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of near-infrared rays.
  • the near-infrared transmission filter has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and a transmittance in the wavelength range of 1100 to 1300 nm.
  • Preferred examples include filters that satisfy spectral characteristics with a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more).
  • the near-infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
  • the maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1500 nm is 20% or less (preferably 15% or less, more preferably 10% or less).
  • 70% or more preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1200 to 1500 nm is 70% or more (preferably 75% or more, more preferably 80% or more).
  • the resin composition of the present invention can also be used for light-shielding films and the like.
  • the solid content concentration of the resin composition of the present invention is preferably 5 to 30% by mass.
  • the lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
  • the resin composition of the present invention contains a coloring material.
  • coloring materials include white coloring materials, black coloring materials, chromatic coloring materials, and near-infrared absorbing coloring materials.
  • the white coloring material includes not only pure white but also a light gray coloring material close to white (for example, grayish white, light gray, etc.).
  • the coloring material contained in the resin composition of the present invention is one containing a pigment.
  • the pigment may be either an inorganic pigment or an organic pigment, but organic pigments are preferable from the viewpoints of large color variations, ease of dispersion, safety, and the like. Further, the pigment preferably contains at least one selected from chromatic pigments and near-infrared absorbing pigments, and more preferably contains chromatic pigments.
  • the average primary particle diameter of the pigment is preferably 1 to 200 nm.
  • the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
  • the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
  • the average primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment using a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circular equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 pigment primary particles.
  • the primary particles of pigment refer to independent particles without agglomeration.
  • the crystallite size determined from the half-value width of the peak derived from any crystal plane in the X-ray diffraction spectrum when the CuK ⁇ ray of the pigment is used as the X-ray source is preferably 0.1 to 100 nm, and preferably 0.1 to 100 nm. It is more preferably from 5 to 50 nm, even more preferably from 1 to 30 nm, and particularly preferably from 5 to 25 nm.
  • the specific surface area of the pigment is preferably 1 to 300 m 2 /g.
  • the lower limit is preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more.
  • the upper limit is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less.
  • the value of the specific surface area is determined according to DIN 66131: determination of the specific surface area of solids by gas adsorption according to the BET (Brunauer, Emmett and Teller) method. (Measurement of specific surface area of solids).
  • the colorant is selected from the group consisting of phthalocyanine pigments, dioxazine pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments, pyrrolopyrrole pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, azo pigments and azomethine pigments. It preferably contains at least one kind, and more preferably contains at least one kind selected from the group consisting of diketopyrrolopyrrole pigments, isoindoline pigments, pteridine pigments, quinophthalone pigments, and azo pigments.
  • the coloring material contained in the resin composition of the present invention may further contain a dye.
  • a dye When a dye is included, the content of the dye is preferably 10 to 100 parts by weight per 100 parts by weight of the pigment.
  • the upper limit is preferably 80 parts by mass or less, more preferably 70 parts by mass or less.
  • the lower limit is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and even more preferably 40 parts by mass or more. Only one type of dye may be used, or two or more types may be used in combination. Further, it is also preferable that the coloring material contained in the resin composition of the present invention is substantially free of dye. According to this aspect, a film with excellent light resistance and heat resistance can be formed. "Substantially free of dye” means that the content of dye in the coloring material is 0.1% by mass or less, preferably 0.01% by mass or less, and more preferably no content. .
  • chromatic coloring materials include coloring materials having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. Examples include yellow coloring material, orange coloring material, red coloring material, green coloring material, purple coloring material, blue coloring material, and the like.
  • the chromatic color material is preferably a pigment (chromatic pigment), more preferably a red pigment, a yellow pigment, and a blue pigment, and still more preferably a red pigment and a blue pigment. Specific examples of chromatic pigments include those shown below.
  • red colorants examples include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, thioindigo compounds, etc. It is preferably a compound, and more preferably a diketopyrrolopyrrole compound. Moreover, it is preferable that the red coloring material is a pigment.
  • red coloring materials include C. I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 269, 270, 272, Examples include red pigments such as 279, 291, 294, 295, 296, 297, and the like.
  • red coloring material a compound described in paragraph number 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A No. 2020-085947 can also be used.
  • C. I. Pigment Red 122, 177, 254, 255, 264, 269, 272 are preferred, and C.I. I. Pigment Red 254, 264, and 272 are more preferred, and C.I. I. Pigment Red 254 and 272 are more preferred.
  • the green coloring material examples include phthalocyanine compounds and squarylium compounds, preferably phthalocyanine compounds, and more preferably phthalocyanine pigments. Moreover, it is preferable that the green coloring material is a pigment.
  • a specific example of the green coloring material is C. I.
  • examples include green pigments such as Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66.
  • halogenated zinc phthalocyanine has an average number of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule.
  • Pigments can also be used.
  • Specific examples include compounds described in International Publication No. 2015/118720.
  • the compound described in paragraph number 0029 of International Publication No. 2022/085485, the aluminum phthalocyanine compound described in JP 2020-070426, etc. can also be used.
  • C. I. Pigment Green 7, 36, 58, 62, 63 are preferred; I. Pigment Green 36 and 58 are more preferred. used.
  • a specific example of the orange coloring material is C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, etc. orange pigments.
  • yellow colorants examples include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds.
  • Specific examples of yellow colorants include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166
  • an azobarbituric acid nickel complex having the following structure can also be used.
  • a specific example of the purple coloring material is C. I.
  • Examples include purple pigments such as Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
  • C. I. Pigment Blue 1 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, 88, etc.
  • examples include pigments.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue coloring material. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A No. 2012-247591 and paragraph number 0047 of JP-A No. 2011-157478.
  • Diarylmethane compounds described in Japanese Patent Publication No. 2020-504758 can also be used as the green coloring material or the blue coloring material.
  • Pyrrolopyrrole pigments include those whose crystallite size in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight ( ⁇ 1 ⁇ 1 ⁇ 1) crystal lattice planes is 140 ⁇ or less. It is also preferable to use Further, the physical properties of the pyrrolopyrrole pigment are also preferably set as described in paragraph numbers 0028 to 0073 of JP-A-2020-097744.
  • the pigment it is also preferable to use a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6744002 from the viewpoint of improving spectral characteristics. Further, as the pigment, it is also preferable to use a dioxazine pigment with a controlled contact angle described in International Publication No. 2019/107166 from the viewpoint of viscosity adjustment.
  • Dyes can also be used as chromatic coloring materials. There are no particular restrictions on the dye, and known dyes can be used. For example, pyrazole azo series, anilinoazo series, triarylmethane series, anthraquinone series, anthrapyridone series, benzylidene series, oxonol series, pyrazolotriazole azo series, pyridone azo series, cyanine series, phenothiazine series, pyrrolopyrazole azomethine series, xanthene series, Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyrromethene-based dyes.
  • a pigment multimer can also be used as a chromatic coloring material.
  • the dye multimer is preferably a dye that is dissolved in a solvent. Further, the dye multimer may form particles. When the dye multimer is in the form of particles, it is usually used in a state of being dispersed in a solvent.
  • the dye multimer in a particle state can be obtained, for example, by emulsion polymerization, and specific examples include the compound and manufacturing method described in JP-A No. 2015-214682.
  • the dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
  • the plurality of dye structures contained in one molecule may be the same dye structure or may be different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
  • the lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • Dye multimers are described in JP 2011-213925, JP 2013-041097, JP 2015-028144, JP 2015-030742, WO 2016/031442, etc. Compounds can also be used.
  • triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638, and International Publication No. 2020/174991 are also used.
  • the phthalocyanine compound described in JP-A No. 2020-160279 or a salt thereof, the compound represented by formula 1 described in Korean Published Patent No. 10-2020-0069442, Korean Published Patent No. 10 Compounds represented by formula 1 described in -2020-0069730, compounds represented by formula 1 described in Korean published patent No. 10-2020-0069070, Korean published patent No. 10-2020-0069067 Compounds represented by formula 1 described in Korean Patent Publication No.
  • chromatic coloring material may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, the rod-like structure, or both structures.
  • a chromatic coloring agent As a chromatic coloring agent, a quinophthalone compound represented by formula 1 of Korean Patent Publication No. 10-2020-0030759, a polymer dye described in Korean Publication Patent No. 10-2020-0061793, and Japanese Patent Application Publication No. 2022-029701. You may use the coloring agent described in WO 2022/014635, the isoindoline compound described in WO 2022/024926, and the aluminum phthalocyanine compound described in WO 2022/024926.
  • Two or more chromatic color materials may be used in combination. Furthermore, when two or more chromatic coloring materials are used in combination, black may be formed by a combination of two or more chromatic coloring materials. Examples of such combinations include the following embodiments (1) to (7).
  • the resin composition of the present invention can be used to form a near-infrared transmission filter. It can be preferably used as a resin composition for. (1) Embodiment containing a red coloring material and a blue coloring material. (2) An embodiment containing a red coloring material, a blue coloring material, and a yellow coloring material.
  • An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a purple coloring material An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, a purple coloring material, and a green coloring material.
  • An embodiment containing a red coloring material, a blue coloring material, a yellow coloring material, and a green coloring material An embodiment containing a red coloring material, a blue coloring material, and a green coloring material.
  • An embodiment containing a yellow coloring material and a purple coloring material An embodiment containing a yellow coloring material and a purple coloring material.
  • White coloring materials include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples include hollow resin particles and inorganic pigments (white pigments) such as zinc sulfide.
  • the white pigment is preferably particles containing titanium atoms, and more preferably titanium oxide.
  • the white pigment is a particle having a refractive index of 2.10 or more with respect to light with a wavelength of 589 nm.
  • the above-mentioned refractive index is preferably 2.10 to 3.00, more preferably 2.50 to 2.75.
  • titanium oxide described in "Titanium oxide physical properties and applied technology, Manabu Seino, pages 13-45, published June 25, 1991, published by Gihodo Publishing" can also be used.
  • the white pigment is not only made of a single inorganic substance, but also particles made of a composite with other materials may be used. For example, particles with pores or other materials inside, particles with a core particle attached to a large number of inorganic particles, and core/shell composite particles with a core particle made of polymer particles and a shell layer made of inorganic nanoparticles are used. It is preferable.
  • the core and shell composite particles consisting of a core particle consisting of a polymer particle and a shell layer consisting of an inorganic nanoparticle for example, the description in paragraphs 0012 to 0042 of JP 2015-047520A can be referred to, This content is incorporated herein.
  • Hollow inorganic particles can also be used as the white pigment.
  • a hollow inorganic particle is an inorganic particle having a structure that has a cavity inside, and is an inorganic particle having a cavity surrounded by an outer shell.
  • Examples of hollow inorganic particles include hollow inorganic particles described in JP2011-075786A, WO2013/061621A, JP2015-164881A, etc., the contents of which are not incorporated herein. It will be done.
  • the black coloring material is not particularly limited, and any known material can be used.
  • examples of the inorganic black coloring material include inorganic pigments (black pigments) such as carbon black, titanium black, and graphite, with carbon black and titanium black being preferred, and titanium black being more preferred.
  • Titanium black is black particles containing titanium atoms, and lower titanium oxide and titanium oxynitride are preferable.
  • the surface of titanium black can be modified as necessary for the purpose of improving dispersibility, suppressing agglomeration, and the like. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Furthermore, treatment with a water-repellent substance as disclosed in JP-A No.
  • 2007-302836 is also possible.
  • a black pigment C. I. Pigment Black 1, 7, etc.
  • the titanium black has a small primary particle size and an average primary particle size of each particle. Specifically, it is preferable that the average primary particle diameter is 10 to 45 nm.
  • Titanium black can also be used as a dispersion. For example, there may be mentioned a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50.
  • titanium blacks examples include Titanium Black 10S, 12S, 13R, 13M, 13MC, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D ( Product name: Ako Kasei Co., Ltd.).
  • organic black coloring materials include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds.
  • bisbenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, and Japanese Patent Application Publication No. 2012-515234, and for example, as "Irgaphor Black” manufactured by BASF. available.
  • perylene compounds include compounds described in paragraph numbers 0016 to 0020 of JP-A No. 2017-226821, C.I. I. Pigment Black 31, 32 and the like.
  • Examples of the azomethine compound include compounds described in JP-A-01-170601 and JP-A-02-034664, and are available as "Chromofine Black A1103" manufactured by Dainichiseika Kaisha, Ltd., for example. Further, as a black coloring material, a black organic pigment described in Japanese Patent No. 6985715, Lumogen Black FK4280, Paliogen Black S0084 (manufactured by BASF) may be used.
  • the coloring material used in the resin composition of the present invention may be only the above-mentioned black coloring material, or may further include a chromatic coloring material. According to this aspect, it is easy to obtain a resin composition that can form a film with excellent light-shielding properties in the visible region.
  • Preferred combinations of black coloring materials and chromatic coloring materials include, for example, the following.
  • the ratio is preferably 100:15 to 85:15 to 80, even more preferably 100:20 to 80:20 to 70.
  • the near-infrared absorbing coloring material is preferably a compound having a maximum absorption wavelength on the longer wavelength side than the wavelength of 700 nm.
  • the near-infrared absorbing coloring material is preferably a compound having a maximum absorption wavelength in a range of more than 700 nm and 1800 nm, more preferably a compound having a maximum absorption wavelength in a range of more than 700 nm and 1400 nm.
  • a compound having a maximum absorption wavelength in a range of more than 700 nm and 1200 nm or less is more preferable, and a compound having a maximum absorption wavelength in a range of more than 700 nm and 1000 nm or less is particularly preferable.
  • the ratio A 1 /A 2 between the absorbance A 1 at a wavelength of 500 nm and the absorbance A 2 at the maximum absorption wavelength of the near-infrared absorbing coloring material is preferably 0.08 or less, and more preferably 0.04 or less. preferable.
  • the near-infrared absorbing coloring material is preferably a pigment, and more preferably an organic pigment.
  • Near-infrared absorbing coloring materials include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, and pyrromethene compounds. , azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, metal borides, and the like. Specific examples of these include compounds described in paragraph number 0114 of International Publication No. 2022/065215.
  • the compound described in paragraph number 0121 of International Publication No. 2022/065215 the compound described in paragraph number 0121 of International Publication No. 2022/065215, the squarylium compound described in JP 2020-075959, Korean Published Patent No. 10-2019-0135217 Copper complexes described in the publication, croconic acid compounds described in JP 2021-195515, and near-infrared absorbing dyes described in JP 2022-022070 can also be used.
  • the content of the coloring material in the total solid content of the resin composition is preferably 20% by mass or more, more preferably 30% by mass or more, even more preferably 40% by mass or more, and 50% by mass. It is particularly preferable that it is above.
  • the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and even more preferably 70% by mass or less.
  • the content of pigment in the total solid content of the resin composition is preferably 30% by mass or more, more preferably 45% by mass or more, and even more preferably 55% by mass or more.
  • the upper limit is preferably 80% by mass or less, more preferably 77.5% by mass or less, and even more preferably 75% by mass or less. According to the resin composition of the present invention, even when the pigment content is high, the storage stability is excellent, so that the effects of the present invention are more prominently exhibited when the pigment content is high.
  • the content of pigment in the coloring material is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.
  • the resin composition of the present invention contains a resin.
  • the resin is blended, for example, for dispersing pigments in a resin composition or for use as a binder.
  • a resin used mainly for dispersing pigments and the like in a resin composition is also referred to as a dispersant.
  • this use of the resin is just an example, and the resin can also be used for purposes other than this use.
  • the resin examples include (meth)acrylic resin, epoxy resin, (meth)acrylamide resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, and polyarylene.
  • examples include ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.
  • the resins include the resin described in the examples of International Publication No.
  • Polyisocyanate resin resin described in JP 2020-122052, resin described in JP 2020-111656, resin described in JP 2020-139021, JP 2017-138503 Resin containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain described in JP-A-2020-186373, resin described in paragraphs 0199 to 0233 of JP-A No. 2020-186325 Alkali-soluble resins described in the publication, resins represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339, copolymers containing epoxy groups and acid groups described in International Publication No. 2022/030445 You can also use
  • the weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
  • the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 5000 or more.
  • the resin it is preferable to use a resin having acid groups.
  • the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
  • a resin having an acid group it is preferable to use a resin having an acid group as the resin. According to this aspect, the storage stability of the resin composition can be further improved.
  • the acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g.
  • the lower limit is more preferably 40 mgKOH/g or more, particularly preferably 50 mgKOH/g or more.
  • the upper limit is more preferably 400 mgKOH/g or less, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
  • the weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, more preferably 5,000 to 50,000. Further, the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
  • the resin having an acid group preferably contains a repeating unit having an acid group in its side chain, and more preferably contains 5 to 70 mol% of repeating units having an acid group in its side chain based on the total repeating units of the resin.
  • the upper limit of the content of repeating units having acid groups in their side chains is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of repeating units having acid groups in their side chains is preferably 10 mol% or more, more preferably 20 mol% or more.
  • a resin having a basic group can also be used.
  • a 1 in formula (1) is a group containing an acid group as the specific compound described later, it is preferable to use a resin having a basic group as the resin. According to this aspect, the storage stability of the resin composition can be further improved.
  • the resin having a basic group is preferably a resin containing a repeating unit having a basic group in its side chain, and a resin having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group.
  • a polymer is more preferable, and a block copolymer having a repeating unit having a basic group in its side chain and a repeating unit not containing a basic group is even more preferable.
  • a resin having a basic group can also be used as a dispersant.
  • the amine value of the resin having a basic group is preferably 5 to 300 mgKOH/g.
  • the lower limit is preferably 10 mgKOH/g or more, more preferably 20 mgKOH/g or more.
  • the upper limit is preferably 200 mgKOH/g or less, more preferably 100 mgKOH/g or less.
  • resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (manufactured by BYK Chemie), Solsperse 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 385 00, 39000, 53095, 56000, 7100 (all manufactured by Japan Lubrizol), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like.
  • the resin having a basic group is the block copolymer (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and the block copolymer (B) described in paragraphs 0046 to 0076 of JP2018-156021A. It is also possible to use block copolymer A1, a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A No. 2019-184763, the contents of which are incorporated herein.
  • the storage stability of the resin composition can be further improved.
  • the content of the resin having a basic group is preferably 20 to 500 parts by mass per 100 parts by mass of the resin having an acid group.
  • the amount is preferably 30 to 300 parts by weight, more preferably 50 to 200 parts by weight.
  • the resin is derived from a monomer component containing a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer”). It is also preferable to use a resin containing repeating units.
  • R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • R 1 represents a hydrogen atom or a methyl group
  • R 21 and R 22 each independently represent an alkylene group
  • n represents an integer of 0 to 15.
  • the alkylene group represented by R 21 and R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly 2 or 3 carbon atoms.
  • n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 3.
  • Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol.
  • Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
  • the resin it is also preferable to use a resin having a crosslinkable group.
  • the crosslinkable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • the ethylenically unsaturated bond-containing group include a vinyl group, a styrene group, a (meth)allyl group, and a (meth)acryloyl group.
  • the cyclic ether group include an epoxy group and an oxetanyl group, with an epoxy group being preferred.
  • the epoxy group may be a cycloaliphatic epoxy group. Note that the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • the resin it is also preferable to use a resin having an aromatic carboxy group (hereinafter also referred to as resin Ac).
  • the aromatic carboxy group may be included in the main chain of the repeating unit, or may be included in the side chain of the repeating unit.
  • the aromatic carboxy group is preferably contained in the main chain of the repeating unit.
  • an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
  • the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.
  • the resin Ac is preferably a resin containing at least one type of repeating unit selected from a repeating unit represented by formula (Ac-1) and a repeating unit represented by formula (Ac-2).
  • Ar 1 represents a group containing an aromatic carboxy group
  • L 1 represents -COO- or -CONH-
  • L 2 represents a divalent linking group
  • Ar 10 represents a group containing an aromatic carboxy group
  • L 11 represents -COO- or -CONH-
  • L 12 represents a trivalent linking group
  • P 10 represents a polymer Represents a chain.
  • Examples of the group containing an aromatic carboxy group represented by Ar 1 in formula (Ac-1) include a structure derived from an aromatic tricarboxylic acid anhydride, a structure derived from an aromatic tetracarboxylic acid anhydride, and the like.
  • Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds having the following structures.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, represented by the following formula (Q-1) or a group represented by the following formula (Q-2).
  • the aromatic carboxy group-containing group represented by Ar 1 may have a crosslinkable group.
  • the crosslinkable group is preferably an ethylenically unsaturated bond-containing group and a cyclic ether group, and more preferably an ethylenically unsaturated bond-containing group.
  • Specific examples of the group containing an aromatic carboxy group represented by Ar 1 include a group represented by formula (Ar-11), a group represented by formula (Ar-12), and a group represented by formula (Ar-13). Examples include groups such as
  • n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.
  • n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.
  • n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and preferably 1. More preferred. However, at least one of n3 and n4 is an integer of 1 or more.
  • Q 1 is a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2 -, -C(CF 3 ) 2 -, the above formula (Q- Represents a group represented by 1) or a group represented by the above formula (Q-2).
  • *1 represents the bonding position with L 1 .
  • L 1 represents -COO- or -CONH-, and preferably represents -COO-.
  • the divalent linking group represented by L 2 includes an alkylene group, an arylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these. Examples include groups combining two or more of the following.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the number of carbon atoms in the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
  • the alkylene group and arylene group may have a substituent.
  • the divalent linking group represented by L 2 is preferably a group represented by -L 2a -O-.
  • L 2a is an alkylene group; an arylene group; a group combining an alkylene group and an arylene group; at least one selected from an alkylene group and an arylene group, and -O-, -CO-, -COO-, -OCO-, Examples include a group combining at least one selected from -NH- and -S-, and an alkylene group is preferred.
  • the alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and even more preferably 1 to 15 carbon atoms.
  • the alkylene group may be linear, branched, or cyclic.
  • the alkylene group and arylene group may have a substituent. Examples of the substituent include a hydroxy group.
  • the aromatic carboxy group-containing group represented by Ar 10 in formula (Ac-2) has the same meaning as Ar 1 in formula (Ac-1), and the preferred range is also the same.
  • L 11 represents -COO- or -CONH-, preferably -COO-.
  • the trivalent linking group represented by L 12 includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and these two groups. Examples include groups that combine more than one species.
  • the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic.
  • the aromatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 10 carbon atoms.
  • the hydrocarbon group may have a substituent. Examples of the substituent include a hydroxy group.
  • the trivalent linking group represented by L 12 is preferably a group represented by formula (L12-1), and more preferably a group represented by formula (L12-2).
  • L 12b represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents formula ( It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group, and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-.
  • a hydrocarbon group or a group consisting of a hydrocarbon group and -O- is preferable.
  • L 12c represents a trivalent linking group
  • X 1 represents S
  • *1 represents the bonding position with L 11 of formula (Ac-2)
  • *2 represents formula ( It represents the bonding position of Ac-2) with P10 .
  • the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one kind selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-.
  • a hydrocarbon group is preferable.
  • P 10 represents a polymer chain.
  • the polymer chain represented by P 10 preferably has at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure.
  • the weight average molecular weight of the polymer chain P 10 is preferably 500 to 20,000.
  • the lower limit is preferably 1000 or more.
  • the upper limit is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less. If the weight average molecular weight of P 10 is within the above range, the pigment will have good dispersibility in the composition.
  • the resin having an aromatic carboxyl group is a resin having a repeating unit represented by formula (Ac-2), this resin is preferably used as a dispersant.
  • the polymer chain represented by P 10 may contain a crosslinkable group.
  • the crosslinkable group include ethylenically unsaturated bond-containing groups and cyclic ether groups.
  • At least one type of resin selected from graft polymers, star polymers, block copolymers, and resins in which at least one end of a polymer chain is capped with an acid group.
  • Such resins are preferably used as dispersants.
  • Examples of the graft polymer include a resin having a repeating unit having a graft chain and a resin having a repeating unit represented by the above-mentioned formula (Ac-2).
  • Examples of the graft chain include a graft chain containing at least one structure selected from a polyester structure, a polyether structure, a polystyrene structure, and a poly(meth)acrylic structure.
  • the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkylthioether group, and the like.
  • alkyl groups or alkoxy groups having 5 to 30 carbon atoms are preferred.
  • the alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
  • graft polymers include paragraph numbers 0025 to 0094 of JP2012-255128A, paragraphs 0022 to 0097 of JP2009-203462A, and paragraphs 0102 to 0166 of JP2012-255128A. Mention may be made of the resins mentioned.
  • star-shaped polymers include resins with a structure in which a plurality of polymer chains are bonded to a core portion.
  • Specific examples of star-shaped polymers include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962.
  • the block copolymers include a polymer block having a repeating unit containing an acid group or a basic group (hereinafter also referred to as block A), and a polymer block having a repeating unit not containing an acid group or a basic group. (hereinafter also referred to as block B) is preferably a block copolymer.
  • the block copolymers include block copolymers (B) described in paragraph numbers 0063 to 0112 of JP2014-219665A, and blocks described in paragraph numbers 0046 to 0076 of JP2018-156021A. Copolymers A1 can also be used, the contents of which are incorporated herein.
  • the resin in which at least one end of the polymer chain is capped with an acid group is a resin in which at least one end of the polymer chain contains at least one type of structure selected from a polyester structure, a polyether structure, and a poly(meth)acrylic structure.
  • examples include resins with a structure sealed with acid groups.
  • acid groups that block the ends of polymer chains include carboxy groups, sulfo groups, and phosphoric acid groups.
  • a resin as a dispersant can also be used.
  • the dispersant include acidic dispersants (acidic resins) and basic dispersants (basic resins).
  • the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
  • the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol % or more when the total amount of acid groups and basic groups is 100 mol %.
  • the acid group that the acidic dispersant (acidic resin) has is preferably a carboxy group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g.
  • the basic dispersant refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
  • the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and basic groups is 100 mol%.
  • the basic group that the basic dispersant has is preferably an amino group.
  • Dispersants are also available as commercial products, and specific examples include the Disperbyk series manufactured by Byk Chemie (for example, Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajisper series manufactured by Ajinomoto Fine Techno Co., Ltd., A208F (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), H-3606 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), Sandet Examples include ET (manufactured by Sanyo Chemical Industries, Ltd.). Further, the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.
  • Disperbyk series manufactured by Byk Chemie for example, Disperbyk-111, 161, 2001, etc.
  • the content of the resin in the total solid content of the resin composition is preferably 1 to 50% by mass.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the resin composition of the present invention may contain only one type of resin, or may contain two or more types of resin. When two or more types of resin are included, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention is a compound represented by formula (1), and has a maximum molar extinction coefficient of 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less in the wavelength range of 400 to 700 nm, and Includes compounds with a molecular weight of 475 or less (hereinafter also referred to as specific compounds). Certain compounds are used as dispersion aids.
  • a dispersion aid is a material for improving the dispersibility of pigments in a coloring composition.
  • a 1 represents a group containing an acid group or a basic group
  • X 1 represents a urea group, thiourea group, urethane group, thiourethane group or amide group
  • L 1 represents an n-valent group
  • n represents an integer from 1 to 4.
  • a 1 in formula (1) represents a group containing an acid group or a basic group, and is preferably a group containing a basic group.
  • Examples of the acid group contained in the group represented by A1 include a carboxy group, a sulfo group, a phosphoric acid group, a phosphonic acid group, and a phenolic hydroxy group.
  • a carboxy group or a sulfo group is more preferable.
  • a 1 is a group containing an acid group
  • the number of acid groups contained in A 1 is preferably 1 to 4, more preferably 1 or 2, and 1. is even more preferable.
  • the group represented by A 1 preferably does not contain a basic group.
  • Examples of the basic group contained in the group represented by A 1 include an amino group, a pyridinyl group and its salt, a salt of an ammonium group, and a phthalimidomethyl group, and an amino group is preferable.
  • Examples of the atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • Examples of the amino group include a group represented by -NR x11 R x12 and a cyclic amino group.
  • R x11 and R x12 each independently represent a hydrogen atom, an alkyl group, or an aryl group.
  • R x11 and R x12 are each independently an alkyl group or an aryl group.
  • one of R x11 and R x12 is an alkyl group and the other is an alkyl group or an aryl group, and it is more preferable that R x11 and R x12 are each independently an alkyl group.
  • the alkyl group may be straight chain, branched, or ring, but is preferably straight chain or branched, and more preferably straight chain.
  • the alkyl group may have a substituent.
  • Examples of the substituent include a hydroxy group, an acyl group, a nitro group, an alkoxy group, an aryloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkyl group, an aryl group, a halogen atom, and a polymerizable group.
  • Examples of the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
  • the number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
  • the aryl group may have a substituent.
  • substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group, Examples include halogen atoms and polymerizable groups.
  • the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
  • Examples of the cyclic amino group include a pyrrolidine ring group, a piperidine ring group, a morpholine ring group, a pyrrole ring group, an imidazole ring group, a pyrazole ring group, a pyrazolidine group, an imidazolin(di)ine ring group, a succinimide group, a 2-oxazolidone ring group, Examples include hydantoin ring group, phenothiazine ring group, phenoxazine ring group, and tetrazole ring group.
  • a 1 is a group containing a basic group
  • the number of basic groups contained in A 1 is preferably 1 to 4, more preferably 1 or 2, and more preferably 1 or 2. It is even more preferable that there be.
  • the group represented by A 1 does not contain an acid group.
  • a 1 in formula (1) is preferably a group represented by formula (A10).
  • (A 10 ) p -L 10 - (A10) In formula (A10), A 10 represents an acid group or a basic group, L 10 represents a single bond or an aliphatic hydrocarbon group, and p represents an integer of 1 to 4.
  • Examples of the acid group and basic group represented by A 10 include the above-mentioned acid groups and basic groups.
  • a 10 is preferably a basic group, more preferably a group represented by -NR x11 R x12 or a cyclic amino group.
  • the aliphatic hydrocarbon group represented by L 10 preferably has 1 to 15 carbon atoms.
  • the upper limit is preferably 10 or less, more preferably 8 or less.
  • the lower limit is preferably 2 or more, more preferably 3 or more.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, and preferably linear or branched.
  • the aliphatic hydrocarbon group may have a substituent.
  • substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group,
  • substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group,
  • the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
  • L 10 is an aliphatic hydrocarbon group.
  • a 1 in formula (1) is preferably a group represented by formula (A20). According to this aspect, the storage stability of the resin composition can be further improved.
  • the acid group and basic group represented by A 10 include the above-mentioned basic groups, and are preferably a group represented by -NR x11 R x12 or a cyclic amino group.
  • the alkylene group represented by L 10 preferably has 1 to 15 carbon atoms.
  • the upper limit is preferably 10 or less, more preferably 8 or less.
  • the lower limit is preferably 2 or more, more preferably 3 or more.
  • the alkylene group may be linear, branched, or cyclic, and preferably linear or branched.
  • the alkylene group may have a substituent.
  • substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group,
  • substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group,
  • the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
  • X 1 in formula (1) represents a urea group, a thiourea group, a urethane group, a thiourethane group, or an amide group, preferably a urea group, a thiourea group, a urethane group, or a thiourethane group; It is more preferably a urethane group, even more preferably a urea group or a thiourea group, and particularly preferably a urea group.
  • L 1 in formula (1) represents an n-valent group.
  • the n-valent group represented by L 1 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic heterocyclic group, and a combination of two or more of these groups.
  • the number of carbon atoms in the aliphatic hydrocarbon group is 1 or more, and is 2 or more because it can further improve the pigment adsorption property through hydrophobic interaction and further improve the storage stability of the resin composition. It is preferably 3 or more, more preferably 5 or more, even more preferably 8 or more.
  • the upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched because it can further improve the storage stability of the resin composition. It is more preferable that there be.
  • the aliphatic hydrocarbon group may have a substituent.
  • substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group,
  • substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group,
  • the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
  • the aliphatic hydrocarbon group has no substituent
  • the aromatic hydrocarbon group and the aromatic heterocyclic group may be monocyclic or polycyclic.
  • the heteroatom constituting the ring of the aromatic heterocyclic group preferably contains at least one selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a nitrogen atom.
  • the number of heteroatoms constituting the ring of the aromatic heterocyclic group is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1 or 2.
  • the aromatic hydrocarbon group is polycyclic, the number of ring structures contained in the aromatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 8, and 2 to 5. It is even more preferable.
  • the number of ring structures contained in the aromatic heterocyclic group is preferably 2 to 10, more preferably 2 to 8, and 2 to 5. It is even more preferable.
  • the aromatic hydrocarbon group and the aromatic heterocyclic group may have a substituent.
  • the substituent is preferably an electron-withdrawing group or an electron-donating group.
  • an electron-withdrawing group is a substituent that is more likely to attract electrons to the bonded atom compared to a hydrogen atom
  • an electron-donating group is a substituent that is more likely to attract electrons to the bonded atom than a hydrogen atom.
  • electron-withdrawing groups include halogen atoms, halogenated alkyl groups, alkoxycarbonyl groups, cyano groups, nitro groups, carboxy groups, and sulfonyl groups. It is preferable that there be.
  • electron-donating group include an alkyl group, an alkoxy group, a hydroxy group, an amino group, etc., and preferably an alkoxy group, a hydroxy group, or an amino group.
  • the pigment adsorption property can be further improved by the ⁇ - ⁇ interaction, and the storage stability of the resin composition can be further improved.
  • the aromatic hydrocarbon group has an electron-withdrawing group or an electron-donating group as a substituent, it is possible to further improve pigment adsorption by changing the electronic state of the X 1 part in formula (1). Therefore, the storage stability of the resin composition can be further improved.
  • n in formula (1) represents an integer from 1 to 4.
  • n in formula (1) is an embodiment in which n is 1.
  • Another preferred embodiment of n in formula (1) includes an embodiment in which n is an integer of 2 to 4. In this embodiment, n is preferably 2 or 3, more preferably 2.
  • L 1 is a polycyclic aromatic ring group, an aliphatic hydrocarbon group having 2 or more carbon atoms, or an electron-withdrawing group or an electron-donating group substituted.
  • a monocyclic aromatic hydrocarbon group is preferable.
  • the polycyclic aromatic ring group may be a polycyclic aromatic hydrocarbon group or a polycyclic aromatic heterocyclic group.
  • a polycyclic aromatic hydrocarbon group is preferred because it can further improve the storage stability of the resin composition.
  • the number of ring structures contained in the polycyclic aromatic ring group is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 5.
  • polycyclic aromatic ring group examples include naphthalene ring group, anthracene ring group, acenaphthene ring group, acenaphthylene ring group, phenalene ring group, phenanthrene ring group, fluorene ring group, pyrene ring group, quinoline ring group, and isoquinoline ring group.
  • examples include ring groups, quinoxaline ring groups, pentacene ring groups, benzopyrene ring groups, chrysene groups, triphenylene groups, corannulene ring groups, coronene groups, and obalene ring groups.
  • the polycyclic aromatic ring group may have a substituent or not have a substituent. Examples of the substituent include electron-withdrawing groups and electron-donating groups.
  • the number of carbon atoms in the aliphatic hydrocarbon group is preferably 3 or more, more preferably 5 or more, and even more preferably 8 or more.
  • the upper limit is preferably 30 or less, more preferably 20 or less, and even more preferably 15 or less.
  • the aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched because it can further improve the storage stability of the resin composition. It is more preferable that Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, an alkynyl group, etc., and an alkyl group is preferable, and a straight-chain alkyl group is more preferable.
  • the aliphatic hydrocarbon group may have a substituent or not have a substituent.
  • substituents include hydroxy group, aldehyde group, carbonyl group, acyl group, nitro group, alkoxy group, aryloxy group, aryloxycarbonyl group, alkoxycarbonyl group, acyloxy group, ether group, ester group, alkyl group, aryl group, Examples include halogen atoms and polymerizable groups.
  • the polymerizable group include a vinyl group, a styrene group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.
  • the aliphatic hydrocarbon group has no substituent.
  • Examples of the monocyclic aromatic hydrocarbon group include a benzene ring group.
  • Examples of the electron-withdrawing group possessed by the monocyclic aromatic hydrocarbon group include the above-mentioned electron-withdrawing groups.
  • the monocyclic aromatic hydrocarbon group preferably has an electron-withdrawing group at the para position of the aromatic hydrocarbon group. According to this aspect, the storage stability of the resin composition can be further improved.
  • the monocyclic aromatic hydrocarbon group and the monocyclic aromatic heterocyclic group may have two or more electron-withdrawing groups.
  • Examples of the electron-donating group possessed by the monocyclic aromatic hydrocarbon group include the electron-donating groups described above.
  • the monocyclic aromatic hydrocarbon group may have two or more electron-donating groups.
  • L 1 is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic heterocyclic group, or a combination of two or more of these groups.
  • An aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a combination of two or more of these groups is preferred.
  • the preferred ranges of the aliphatic hydrocarbon group, aromatic hydrocarbon group, and aromatic heterocyclic group are the same as described above.
  • the maximum value of the molar extinction coefficient of the specific compound in the wavelength range of 400 to 700 nm is 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, preferably 1000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, and 100 L ⁇ mol It is more preferably -1 ⁇ cm -1 or less, and even more preferably 10 L ⁇ mol -1 ⁇ cm -1 or less.
  • the molecular weight of the specific compound is 475 or less, preferably 465 or less, and more preferably 460 or less.
  • the lower limit is preferably 150 or more, more preferably 200 or more, and even more preferably 250 or more.
  • Specific examples of the specific compound include compounds having the structures shown in the dispersion aids M-1 to M-53 described in Examples below.
  • the content of the specific compound in the total solid content of the resin composition is preferably 0.01 to 15% by mass.
  • the upper limit is preferably 12% by mass or less, more preferably 10% by mass or less.
  • the lower limit is preferably 0.05% by mass or more, more preferably 1% by mass or more.
  • the total content with the specific compound is preferably 1 to 30 parts by weight per 100 parts by weight of the pigment.
  • the lower limit is preferably 2 parts by mass or more, more preferably 4 parts by mass or more.
  • the upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less.
  • the resin composition of the present invention may contain only one type of specific compound, or may contain two or more types of specific compounds. When two or more types of resin are included, the total amount thereof is preferably within the above range.
  • the resin composition of the present invention can contain a pigment derivative.
  • Pigment derivatives are used, for example, as dispersion aids.
  • the pigment derivative include compounds having at least one structure selected from the group consisting of a pigment structure and a triazine structure, and an acid group or a basic group.
  • the above dye structures include quinoline dye structure, benzimidazolone dye structure, benzisoindole dye structure, benzothiazole dye structure, iminium dye structure, squarylium dye structure, croconium dye structure, oxonol dye structure, pyrrolopyrrole dye structure, diketo Pyrrolopyrrole dye structure, azo dye structure, azomethine dye structure, phthalocyanine dye structure, naphthalocyanine dye structure, anthraquinone dye structure, quinacridone dye structure, dioxazine dye structure, perinone dye structure, perylene dye structure, thiazine indigo dye structure, thioindigo dye structure, isoindoline dye structure, isoindolinone dye structure, quinophthalone dye structure, dithiol dye structure, triarylmethane dye structure, pyrromethene dye structure, etc.
  • Examples of acid groups possessed by pigment derivatives include carboxy groups, sulfo groups, phosphoric acid groups, phosphonic acids, and phenolic hydroxy groups.
  • Examples of the basic group that the pigment derivative has include an amino group, a pyridinyl group and its salts, an ammonium group salt, and a phthalimidomethyl group.
  • Examples of atoms or atomic groups constituting the salt include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
  • a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative) can also be used.
  • the maximum molar extinction coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is preferably 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less, and preferably 1000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less. is more preferable, and even more preferably 100 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
  • the lower limit of ⁇ max is, for example, 1 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, and may be 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
  • pigment derivatives include compounds described in JP-A-56-118462, compounds described in JP-A-63-264674, compounds described in JP-A-01-217077, and JP-A-03-1999.
  • Compounds described in JP-A-03-026767, compounds described in JP-A-03-153780, compounds described in JP-A-03-045662, JP-A-04-285669 Compounds described in JP-A No. 06-145546, compounds described in JP-A No. 06-212088, compounds described in JP-A No. 06-240158, compounds described in JP-A No.
  • the total content of the pigment derivative and the above-mentioned specific compound is preferably 1 to 30 parts by weight based on 100 parts by weight of the pigment.
  • the lower limit is preferably 2 parts by mass or more, more preferably 4 parts by mass or more.
  • the upper limit is preferably 15 parts by mass or less, more preferably 10 parts by mass or less.
  • the content of the pigment derivative is preferably 10 to 90 parts by weight, more preferably 15 to 85 parts by weight, and even more preferably 20 to 80 parts by weight based on 100 parts by weight of the above-mentioned specific compound. Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types are used in combination, it is preferable that the total amount is within the above range.
  • the resin composition of the present invention does not substantially contain a pigment derivative.
  • the content of the pigment derivative in the total solid content of the resin composition is 0.1% by mass or less, and 0.05% by mass. It is more preferable that it is at most % by mass, and even more preferably that it does not contain a pigment derivative.
  • the resin composition of the present invention contains a polymerizable compound.
  • the polymerizable compound include compounds having an ethylenically unsaturated bond-containing group.
  • the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group.
  • the polymerizable compound used in the present invention is preferably a radically polymerizable compound.
  • the polymerizable compound may be in any chemical form such as a monomer, prepolymer, or oligomer, but monomers are preferred.
  • the molecular weight of the polymerizable compound is preferably 100 to 2,500.
  • the upper limit is preferably 2000 or less, more preferably 1500 or less.
  • the lower limit is preferably 150 or more, more preferably 250 or more.
  • the ethylenically unsaturated bond-containing group value (hereinafter referred to as C ⁇ C value) of the polymerizable compound is preferably 2 to 14 mmol/g from the viewpoint of storage stability of the resin composition.
  • the lower limit is preferably 3 mmol/g or more, more preferably 4 mmol/g or more, and even more preferably 5 mmol/g or more.
  • the upper limit is preferably 12 mmol/g or less, more preferably 10 mmol/g or less, and even more preferably 8 mmol/g or less.
  • the C ⁇ C value of a polymerizable compound is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.
  • the polymerizable compound is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, and more preferably a compound containing four or more ethylenically unsaturated bond-containing groups.
  • the upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less from the viewpoint of storage stability of the resin composition.
  • the polymerizable compound is preferably a trifunctional or higher functional (meth)acrylate compound, more preferably a trifunctional to 15 functional (meth)acrylate compound, and a trifunctional to 10 functional (meth)acrylate compound.
  • polymerizable compounds include paragraph numbers 0095 to 0108 of JP 2009-288705, paragraph 0227 of JP 2013-029760, paragraph 0254 to 0257 of JP 2008-292970, and The compounds described in paragraph numbers 0034 to 0038 of JP 2013-253224, paragraph 0477 of JP 2012-208494, JP 2017-048367, JP 6057891, and JP 6031807 are , the contents of which are incorporated herein.
  • polymerizable compounds examples include dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and modified products of these compounds.
  • modified product examples include compounds having a structure in which the (meth)acryloyl groups of the above compounds are bonded via an alkyleneoxy group, such as ethoxylated dipentaerythritol hexa(meth)acrylate.
  • Specific examples include compounds represented by formula (Z-4) and compounds represented by formula (Z-5).
  • E is each independently -((CH 2 ) y CH 2 O)-, or -((CH 2 ) y CH(CH 3 )O)- , each y independently represents an integer of 0 to 10, and each X independently represents a (meth)acryloyl group, a hydrogen atom, or a carboxy group.
  • the total number of (meth)acryloyl groups is 3 or 4
  • each m independently represents an integer of 0 to 10
  • the total of each m is an integer of 0 to 40.
  • the total number of (meth)acryloyl groups is 5 or 6
  • each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60.
  • m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to 4. Further, the sum of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
  • a form in which the side end is bonded to X is preferable.
  • polypentaerythritol poly(meth)acrylate as shown in the following formula (Z-6) can also be used.
  • X 1 to X 6 each independently represent a hydrogen atom or a (meth)acryloyl group, and n represents an integer of 1 to 10. However, at least one of X 1 to X 6 is a (meth)acryloyl group.
  • the polymerizable compound used in the present invention is at least one selected from the group consisting of dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol poly(meth)acrylate, and modified products thereof. Preferably it is a seed.
  • Commercially available products include KAYARAD D-310, DPHA, DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.), NK Ester A-DPH-12E, and TPOA-50 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). Can be mentioned.
  • polymerizable compounds examples include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercial product: M-460; manufactured by Toagosei), pentaerythritol tetra(meth)acrylate (manufactured by Shin-Nakamura Chemical Co., Ltd., NK ester) A-TMMT), 1,6-hexanediol diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) ), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyo
  • Polymerizable compounds include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide modified tri(meth)acrylate, trimethylolpropane ethylene oxide modified tri(meth)acrylate, isocyanuric acid ethylene oxide modified tri(meth)acrylate, and pentaerythritol. It is also preferable to use trifunctional (meth)acrylate compounds such as tri(meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305.
  • M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.
  • a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group can also be used.
  • Commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.
  • a compound having a caprolactone structure can also be used.
  • the description in paragraphs 0042 to 0045 of JP-A No. 2013-253224 can be referred to, the contents of which are incorporated herein.
  • Examples of compounds having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, and DPCA-120, which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth)acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound that does not substantially contain environmentally controlled substances such as toluene.
  • environmentally controlled substances such as toluene.
  • Commercially available products of such compounds include KAYARAD DPHA LT, KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.), and the like.
  • Examples of the polymerizable compound include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Publication No. 02-032293, and Japanese Patent Publication No. 02-016765; Urethane compounds having an ethylene oxide skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238.
  • the polymerizable compounds include UA-7200 (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, Commercially available products such as T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
  • the content of the polymerizable compound in the total solid content of the resin composition is preferably 1 to 35% by mass.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less, even more preferably 20% by mass or less, and particularly preferably 10% by mass or less.
  • the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more.
  • the resin composition of the present invention may contain only one kind of polymerizable compound, or may contain two or more kinds of polymerizable compounds. When two or more types of polymerizable compounds are included, it is preferable that the total amount thereof falls within the above range.
  • the resin composition of the present invention can contain a photopolymerization initiator.
  • the resin composition of the present invention contains a polymerizable compound, it is preferable that the resin composition of the present invention further contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet to visible range are preferred.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and the like.
  • halogenated hydrocarbon derivatives e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.
  • acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and the like.
  • photopolymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylbylene compounds.
  • imidazole compounds onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, ⁇ -hydroxyketones
  • the compound is more preferably a compound selected from a compound, an ⁇ -aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.
  • photopolymerization initiators compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No.
  • hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole, etc. can be mentioned.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 117. 3, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company).
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure 36.
  • Irgacure 369E Irgacure 379EG (all manufactured by BASF) (manufactured by).
  • Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.
  • Examples of oxime compounds include the compounds described in JP-A No. 2001-233842, the compounds described in JP-A No. 2000-080068, the compounds described in JP-A No. 2006-342166, and the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660); C. S. Compounds described in Perkin II (1979, pp. 156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A-2000-0 Compounds described in Publication No. 66385, Compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Application Publication No. 2006-342166, compounds described in Japanese Patent Application Publication No.
  • oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
  • an oxime compound having a fluorene ring can also be used.
  • oxime compounds having a fluorene ring include compounds described in JP-A No. 2014-137466, compounds described in Japanese Patent No. 6636081, compounds described in Korean Patent Publication No. 10-2016-0109444, Examples include fluorenylaminoketone photoinitiators described in Japanese Patent Publication No. 2020-507664 and oxime ester compounds described in International Publication No. 2021/023144.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring is also possible.
  • Specific examples of such oxime compounds include compounds described in International Publication No. 2013/083505.
  • an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
  • oxime compounds having a fluorine atom include compounds described in JP-A No. 2010-262028, compounds 24, 36 to 40 described in Japanese Patent Application Publication No. 2014-500852, and compounds described in JP-A No. 2013-164471. Examples include compound (C-3).
  • an oxime compound having a nitro group can be used as the photopolymerization initiator. It is also preferable that the oxime compound having a nitro group is in the form of a dimer.
  • Specific examples of oxime compounds having a nitro group include compounds described in paragraph numbers 0031 to 0047 of JP 2013-114249, paragraphs 0008 to 0012, and 0070 to 0079 of JP 2014-137466, Examples include compounds described in paragraph numbers 0007 to 0025 of Japanese Patent No. 4223071, and Adeka Arcles NCI-831 (manufactured by ADEKA Corporation).
  • an oxime compound having a benzofuran skeleton can also be used.
  • Specific examples include OE-01 to OE-75 described in International Publication No. 2015/036910.
  • photopolymerization initiator it is also possible to use an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton.
  • photopolymerization initiators include compounds described in International Publication No. 2019/088055.
  • oxime compound OX an oxime compound having an aromatic ring group Ar OX1 (hereinafter also referred to as oxime compound OX) in which an electron-withdrawing group is introduced into the aromatic ring.
  • Examples of the electron-withdrawing group possessed by the aromatic ring group Ar OX1 include an acyl group, a nitro group, a trifluoromethyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a cyano group, An acyl group and a nitro group are preferred, an acyl group is more preferred, and a benzoyl group is even more preferred.
  • the benzoyl group may have a substituent.
  • substituents include halogen atoms, cyano groups, nitro groups, hydroxy groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, It is preferably an acyl group or an amino group, and more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, or an amino group. More preferably, it is a sulfanyl group or an amino group.
  • oxime compound OX examples include compounds described in paragraph numbers 0083 to 0105 of Japanese Patent No. 4,600,600.
  • oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g/L.
  • the photopolymerization initiator it is also preferable to use a combination of Irgacure OXE01 (manufactured by BASF) and/or Irgacure OXE02 (manufactured by BASF) and Omnirad 2959 (manufactured by IGM Resins B.V.).
  • a difunctional, trifunctional or more functional photoradical polymerization initiator may be used as the photopolymerization initiator.
  • a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time and improving the storage stability of the resin composition.
  • Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
  • the content of the photopolymerization initiator in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less.
  • only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the resin composition of the present invention contains a solvent.
  • the solvent include organic solvents.
  • the type of solvent is basically not particularly limited as long as it satisfies the solubility of each component and the coatability of the composition.
  • the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.
  • paragraph number 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein.
  • Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
  • organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
  • aromatic hydrocarbons benzene, toluene, xylene, ethylbenzene, etc.
  • organic solvents for environmental reasons (for example, 50 mass ppm (parts) based on the total amount of organic solvents). per million), 10 mass ppm or less, and 1 mass ppm or less).
  • an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content. It is preferable that the metal content of the organic solvent is, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015). .
  • Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.
  • the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
  • the content of peroxide in the organic solvent is 0.8 mmol/L or less, and it is more preferable that the organic solvent contains substantially no peroxide.
  • the content of the solvent in the resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
  • the resin composition of the present invention does not substantially contain environmentally regulated substances.
  • "not substantially containing environmentally controlled substances” means that the content of environmentally controlled substances in the resin composition is 50 mass ppm or less, preferably 30 mass ppm or less. , more preferably 10 mass ppm or less, particularly preferably 1 mass ppm or less.
  • environmentally controlled substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • REACH Registration Evaluation Authorization and Restriction of CHemicals
  • PRTR Policy Release and It is registered as an environmentally regulated substance under the Transfer Register Act
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • methods for reducing environmentally controlled substances include a method of heating or reducing pressure in the system to raise the temperature above the boiling point of the environmentally controlled substance to distill off the environmentally controlled substances from the system.
  • distillation methods can be used at the stage of raw materials, at the stage of products obtained by reacting raw materials (for example, resin solution or polyfunctional monomer solution after polymerization), or at the stage of resin compositions prepared by mixing these compounds. This is possible at any stage.
  • the resin composition of the present invention can contain a thermal crosslinking agent as a component other than the above-mentioned resin and polymerizable compound.
  • the thermal crosslinking agent include compounds having a cyclic ether group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • the epoxy group may be a cycloaliphatic epoxy group. Note that the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
  • Examples of the epoxy compound include compounds having one or more epoxy groups in one molecule, and preferably compounds having two or more epoxy groups.
  • the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
  • the upper limit of the epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less.
  • the lower limit of the epoxy groups contained in the epoxy compound is preferably two or more.
  • Examples of epoxy compounds include those described in paragraph numbers 0034 to 0036 of JP2013-011869, paragraphs 0147 to 0156 of JP2014-043556, and paragraphs 0085 to 0092 of JP2014-089408.
  • Compounds, compounds described in JP 2017-179172, xanthene type epoxy resins described in JP 2021-195421, and xanthene epoxy resins described in JP 2021-195422 can also be used.
  • the compound having a cyclic ether group may be a low-molecular compound (e.g., molecular weight less than 2,000, further, molecular weight less than 1,000), or a macromolecule (e.g., molecular weight 1,000 or more, in the case of a polymer, a weight average molecular weight may be 1000 or more).
  • the weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.
  • cyclic ether group Commercially available compounds having a cyclic ether group include, for example, EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, and G-0130SP. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all of which are epoxy group-containing polymers manufactured by NOF Corporation). Further, as a compound having a cyclic ether group, compounds described in Examples described later can also be used.
  • the content of the thermal crosslinking agent in the total solid content of the resin composition is preferably 0.1 to 20% by mass.
  • the lower limit is, for example, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more.
  • the upper limit is, for example, more preferably 15% by mass or less, and even more preferably 10% by mass or less. Only one type of thermal crosslinking agent may be used, or two or more types may be used. When two or more types are used, it is preferable that their total amount falls within the above range.
  • the resin composition of the present invention may also contain a curing accelerator.
  • the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidine salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds, and the like.
  • Specific examples of the curing accelerator include compounds described in paragraph numbers 0094 to 0097 of International Publication No. 2018/056189, compounds described in paragraph numbers 0246 to 0253 of JP 2015-034963, and JP 2013-041165. Compounds described in paragraph numbers 0186 to 0251 of JP-A No.
  • the content of the curing accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
  • the resin composition of the present invention can contain an ultraviolet absorber.
  • the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and the like. Specific examples of such compounds include the compound described in paragraph number 0179 of International Publication No. 2022/085485, the reactive triazine ultraviolet absorber described in JP 2021-178918, and JP 2022-007884. It is also possible to use the ultraviolet absorbers described in .
  • the content of the ultraviolet absorber in the total solid content of the resin composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
  • only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention can contain a polymerization inhibitor.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), Examples include 2,2'-methylenebis(4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Among them, p-methoxyphenol is preferred.
  • the content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass.
  • the number of polymerization inhibitors may be one, or two or more. In the case of two or more types, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention can contain a silane coupling agent.
  • the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
  • the term "hydrolyzable group" refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, ureido groups, sulfide groups, and isocyanate groups. , phenyl group, etc., and amino group, (meth)acryloyl group and epoxy group are preferable.
  • silane coupling agents include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-602), N- ⁇ -aminoethyl- ⁇ -amino Propyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-602), ⁇ -Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-
  • silane coupling agent examples include compounds described in paragraph numbers 0018 to 0036 of JP-A No. 2009-288703 and compounds described in paragraph numbers 0056 to 0066 of JP-A-2009-242604. , the contents of which are incorporated herein.
  • the content of the silane coupling agent in the total solid content of the resin composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. Only one type of silane coupling agent may be used, or two or more types may be used. In the case of two or more types, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention can contain a surfactant.
  • a surfactant various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.
  • the surfactant is preferably a silicone surfactant or a fluorine surfactant.
  • the fluorine content in the fluorine surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid saving, and also has good solubility in the resin composition.
  • fluorine-based surfactant compounds described in paragraph numbers 0167 to 0169 of International Publication No. 2022/085485 can be used.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorine-based surfactant has a repeating unit derived from a (meth)acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy group, propyleneoxy group) (meth).
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A No. 2010-032698 and the following compounds are also exemplified as the fluorine-containing surfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example 14,000. In the above compounds, % indicating the proportion of repeating units is mol%.
  • fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in its side chain can also be used. Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A No. 2010-164965, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation, Examples include RS-72-K. Further, as the fluorine-based surfactant, compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 and fluorine-containing copolymers described in JP-A No. 2022-000494 can also be used.
  • a fluorine-containing imide salt compound represented by formula (fi-1) is also preferable to use as a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • a represents 1 or 2
  • X a+ represents an a-valent metal ion, a primary ammonium ion
  • a Re represents a secondary ammonium ion, a tertiary ammonium ion, a quaternary ammonium ion, or NH 4 + .
  • nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Japan Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Fujifilm Wa
  • silicone surfactants examples include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), and TSF- 4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK Chemie), and the like.
  • a compound having the following structure can also be used as the silicone surfactant.
  • the content of the surfactant in the total solid content of the resin composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% to 3.0% by mass.
  • the number of surfactants may be one, or two or more. In the case of two or more types, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention can contain an antioxidant.
  • antioxidants include phenol compounds, phosphite compounds, thioether compounds, and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenol compounds include hindered phenol compounds.
  • a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
  • the above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms.
  • the antioxidant a compound having a phenol group and a phosphorous acid ester group in the same molecule is also preferable.
  • phosphorus-based antioxidants can also be suitably used.
  • a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepine-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl )oxy]ethyl]amine, ethylbis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
  • antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Co., Ltd.).
  • antioxidants include compounds described in paragraph numbers 0023 to 0048 of Patent No. 6268967, compounds described in International Publication No. 2017/006600, compounds described in International Publication No. 2017/164024, Compounds described in Korean Patent Publication No. 10-2019-0059371 can also be used.
  • the content of the antioxidant in the total solid content of the resin composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount falls within the above range.
  • the resin composition of the present invention may contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents (for example, conductive particles, antifoaming agents, flame retardants, (leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.) may also be included.
  • sensitizers for example, curing accelerators, fillers, thermosetting accelerators, plasticizers, and other auxiliary agents
  • auxiliary agents for example, conductive particles, antifoaming agents, flame retardants, (leveling agents, peeling accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.
  • the resin composition of the present invention may contain a latent antioxidant, if necessary.
  • a latent antioxidant is a compound whose moiety that functions as an antioxidant is protected with a protecting group, and is heated at 100 to 250°C or heated at 80 to 200°C in the presence of an acid/base catalyst. Examples include compounds that function as antioxidants by removing protective groups. Examples of the latent antioxidant include compounds described in WO 2014/021023, WO 2017/030005, and JP 2017-008219. Commercially available latent antioxidants include Adeka Arcles GPA-5001 (manufactured by ADEKA Co., Ltd.).
  • the resin composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film.
  • metal oxides include TiO 2 , ZrO 2 , Al 2 O 3 , and SiO 2 .
  • the primary particle diameter of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, even more preferably 5 to 50 nm.
  • the metal oxide may have a core-shell structure. Further, in this case, the core portion may be hollow.
  • the resin composition of the present invention may also contain a light resistance improver.
  • the light resistance improver include compounds described in paragraph number 0183 of International Publication No. 2022/085485.
  • the resin composition of the present invention does not substantially contain terephthalic acid ester.
  • substantially not containing means that the content of terephthalic acid ester is 1000 mass ppb or less in the total amount of the resin composition, more preferably 100 mass ppb or less, Particularly preferred is zero.
  • the resin composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. Further, the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Examples of methods for reducing free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification using ion-exchange resins.
  • perfluoroalkyl sulfonic acids and their salts may be regulated.
  • perfluoroalkylsulfonic acids particularly perfluoroalkylsulfonic acids whose perfluoroalkyl group has 6 to 8 carbon atoms
  • salts thereof and perfluoroalkylsulfonic acids
  • the content of fluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid whose perfluoroalkyl group has 6 to 8 carbon atoms) and its salt is 0.01 ppb to 1,000 ppb based on the total solid content of the resin composition.
  • the resin composition of the present invention may be substantially free of perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid and its salt.
  • a compound that can be substituted for perfluoroalkylsulfonic acid and its salt and a compound that can be substituted for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid
  • Compounds that can be substituted for regulated compounds include, for example, compounds that are excluded from regulated targets due to differences in the number of carbon atoms in perfluoroalkyl groups.
  • the resin composition of the present invention may contain perfluoroalkyl sulfonic acids and salts thereof, and perfluoroalkyl carboxylic acids and salts thereof, within the maximum allowable range.
  • the water content of the resin composition of the present invention is usually 3% by mass or less, preferably from 0.01 to 1.5% by mass, and more preferably from 0.1 to 1.0% by mass.
  • the water content can be measured by the Karl Fischer method.
  • the resin composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface condition (flatness, etc.), adjusting the film thickness, etc.
  • the value of viscosity can be appropriately selected as required, but for example, at 25° C., 0.3 mPa ⁇ s to 50 mPa ⁇ s is preferable, and 0.5 mPa ⁇ s to 20 mPa ⁇ s is more preferable.
  • the viscosity can be measured using, for example, a cone plate type viscometer with the temperature adjusted to 25°C.
  • the container for storing the resin composition is not particularly limited, and any known container can be used.
  • any known container can be used.
  • the inner wall of the container is preferably made of glass, stainless steel, etc. for the purpose of preventing metal elution from the inner wall of the container, increasing the storage stability of the resin composition, and suppressing component deterioration.
  • the resin composition of the present invention can be prepared by mixing the above-mentioned components.
  • the resin composition may be prepared by simultaneously dissolving and/or dispersing all components in a solvent, or, if necessary, each component may be prepared as two or more solutions or dispersions as appropriate.
  • the resin composition may be prepared by mixing these at the time of use (at the time of application).
  • a process of dispersing the pigment when preparing the resin composition.
  • mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like.
  • the particles may be made finer in a salt milling step.
  • Bead materials used for dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass.
  • an inorganic compound having a Mohs hardness of 2 or more can also be used for the beads.
  • the resin composition may contain 1 to 10,000 ppm of the beads.
  • the resin composition In preparing the resin composition, it is preferable to filter the resin composition with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter for the purpose of removing foreign substances and reducing defects.
  • Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraph numbers 0196 to 0199 of International Publication No. 2022/085485.
  • the membrane of the present invention is a membrane obtained from the resin composition of the present invention described above.
  • the film of the present invention can be used for optical filters such as color filters, near-infrared transmission filters, and near-infrared cut filters.
  • the film thickness of the film of the present invention can be adjusted as appropriate depending on the purpose.
  • the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and even more preferably 0.3 ⁇ m or more.
  • the film of the present invention When the film of the present invention is used as a color filter, the film of the present invention preferably has a green, red, blue, cyan, magenta, or yellow hue, and more preferably a red hue. Further, the film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc., and red pixels are more preferable.
  • the film of the present invention can be manufactured through a step of applying the resin composition of the present invention.
  • the film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of methods for forming patterns (pixels) include photolithography and dry etching, with photolithography being preferred. By forming a pattern using the resin composition of the present invention by photolithography, the generation of development residues can be further suppressed.
  • Pattern formation by the photolithography method includes a step of forming a resin composition layer on a support using the resin composition of the present invention, a step of exposing the resin composition layer to light in a pattern, and a step of exposing the resin composition layer to light. It is preferable to include a step of developing and removing the exposed portion to form a pattern (pixel). If necessary, a step of baking the resin composition layer (pre-bake step) and a step of baking the developed pattern (pixel) (post-bake step) may be provided.
  • a resin composition layer is formed on a support using the resin composition of the present invention.
  • the support is not particularly limited and can be appropriately selected depending on the application.
  • a glass substrate, a silicon substrate, etc. may be mentioned, and a silicon substrate is preferable.
  • a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the silicon substrate.
  • CMOS complementary metal oxide semiconductor
  • a black matrix that isolates each pixel may be formed on the silicon substrate.
  • the silicon substrate may be provided with a base layer for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface.
  • the surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. Further, it is preferable that the angle is 30 to 80° when measured with water.
  • a known method can be used.
  • the coating method described in paragraph number 0207 of International Publication No. 2022/085485 can be used.
  • the resin composition layer formed on the support may be dried (prebaked). If the film is manufactured by a low-temperature process, prebaking may not be performed.
  • the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower.
  • the lower limit can be, for example, 50°C or higher, or 80°C or higher.
  • the prebake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, even more preferably 80 to 220 seconds. Prebaking can be performed on a hot plate, oven, or the like.
  • the resin composition layer is exposed in a pattern (exposure step).
  • the resin composition layer can be exposed in a pattern by exposing the resin composition layer to light through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portion to be cured.
  • Radiation (light) that can be used during exposure includes g-line, i-line, etc. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm). Furthermore, a long-wave light source of 300 nm or more can also be used. As a light source, an electrodeless ultraviolet lamp system, a hybrid ultraviolet and infrared curing can be used.
  • pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).
  • the irradiation amount is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 .
  • the oxygen concentration during exposure can be appropriately selected, and in addition to being carried out in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially
  • the exposure may be performed in an oxygen-free atmosphere (without oxygen), or in a high oxygen atmosphere where the oxygen concentration exceeds 21 volume % (for example, 22 volume %, 30 volume %, or 50 volume %).
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000W/m 2 to 100000W/m 2 (for example, 5000W/m 2 , 15000W/m 2 , or 35000W/m 2 ). Can be done.
  • the oxygen concentration and the exposure illuminance may be appropriately combined.
  • the illuminance may be 10,000 W/m 2 when the oxygen concentration is 10% by volume, and 20,000 W/m 2 when the oxygen concentration is 35% by volume.
  • the unexposed areas of the resin composition layer are developed and removed to form a pattern (pixel).
  • the unexposed areas of the resin composition layer can be removed by development using a developer.
  • the unexposed portions of the resin composition layer in the exposure step are eluted into the developer, leaving only the photocured portions.
  • the temperature of the developer is preferably, for example, 20 to 30°C.
  • the development time is preferably 20 to 180 seconds. Furthermore, in order to improve the ability to remove residues, the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used.
  • the developer and cleaning method after development the developer and cleaning method described in paragraph number 0214 of International Publication No. 2022/085485 can be used.
  • Additional exposure processing and post-bake are post-development curing processing to complete curing.
  • the heating temperature in post-baking is, for example, preferably 100 to 240°C, more preferably 200 to 240°C.
  • Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions.
  • the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
  • Pattern formation by the dry etching method includes the steps of forming a resin composition layer on a support using the resin composition of the present invention, and curing the entire resin composition layer to form a cured product layer; A step of forming a photoresist layer on this cured material layer, a step of exposing the photoresist layer in a pattern and then developing it to form a resist pattern, and etching the cured material layer using this resist pattern as a mask. It is preferable to include a step of dry etching using gas. In forming the photoresist layer, it is preferable to further perform a prebaking process.
  • the optical filter of the present invention has the film of the present invention described above.
  • Types of optical filters include color filters, near-infrared cut filters, near-infrared transmission filters, etc., and color filters are preferred.
  • the color filter preferably has the film of the invention as its pixels, more preferably the film of the invention as colored pixels, and still more preferably the film of the invention as red pixels.
  • the optical filter may be provided with a protective layer on the surface of the film of the present invention.
  • a protective layer By providing a protective layer, various functions such as oxygen blocking, low reflection, hydrophilic and hydrophobic properties, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
  • the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • Examples of the method for forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of pasting a molded resin with an adhesive.
  • Components constituting the protective layer include (meth)acrylic resin, ene thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide.
  • Resin polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples include resin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 and the like, and two or more of these components may be contained.
  • the protective layer preferably contains a polyol resin, SiO 2 and Si 2 N 4 .
  • the protective layer preferably contains a (meth)acrylic resin and a fluororesin.
  • a protective layer by applying a resin composition known methods such as a spin coating method, a casting method, a screen printing method, an inkjet method, etc. can be used as a method for applying the resin composition.
  • organic solvent contained in the resin composition known organic solvents (eg, propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used.
  • chemical vapor deposition methods thermal chemical vapor deposition, plasma enhanced chemical vapor deposition, photochemical vapor deposition
  • photochemical vapor deposition can be used as the chemical vapor deposition method.
  • the protective layer may contain organic/inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet rays, near-infrared rays, etc.), refractive index adjusters, antioxidants, adhesives, surfactants, and other additives, as necessary. It may contain.
  • organic/inorganic fine particles include polymer fine particles (e.g., silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride. , magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate, and the like.
  • the absorber for light of a specific wavelength a known absorber can be used.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by weight, more preferably 1 to 60% by weight, based on the total weight of the protective layer.
  • the protective layer the protective layers described in paragraph numbers 0073 to 0092 of JP-A No. 2017-151176 can also be used.
  • the optical filter may have a structure in which each pixel is embedded in a space partitioned into a lattice shape by partition walls, for example.
  • the solid-state imaging device of the present invention has the film of the present invention described above.
  • the structure of the solid-state image sensor is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image sensor, but examples include the following structure.
  • the substrate has a plurality of photodiodes that constitute the light receiving area of a solid-state image sensor (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and a transfer electrode made of polysilicon or the like.
  • a device protective film made of silicon nitride or the like is formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a configuration in which a color filter is provided on the device protective film.
  • the color filter may have a structure in which each colored pixel is embedded in a space partitioned into, for example, a lattice shape by partition walls.
  • the partition wall preferably has a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No.
  • an ultraviolet absorbing layer may be provided within the structure of the solid-state image sensor to improve light resistance.
  • An imaging device equipped with the solid-state imaging device of the present invention can be used not only as a digital camera or an electronic device having an imaging function (such as a mobile phone), but also as a vehicle-mounted camera or a surveillance camera.
  • the image display device of the present invention has the film of the present invention described above.
  • Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • Examples of an image display device and details of each image display device see, for example, “Electronic Display Devices (written by Akio Sasaki, Kogyo Chosenkai Co., Ltd., published in 1990)” and “Display Devices (written by Junaki Ibuki, published by Sangyo Tosho)”. Co., Ltd., issued in 1989).
  • liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994)".
  • Next Generation Liquid Crystal Display Technology edited by Tatsuo Uchida, published by Kogyo Chosenkai Co., Ltd., 1994.
  • the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology.”
  • the average particle diameter of the pigment was measured by a dynamic light scattering method using a particle diameter measuring device (nanoSAQLA, manufactured by Otsuka Electronics Co., Ltd.).
  • the viscosity of the pigment dispersion was measured using a viscometer (RE-85L, manufactured by Toki Sangyo Co., Ltd.) while adjusting the temperature of the pigment dispersion to 25°C.
  • PR122 C. I. Pigment Red 122 (quinacridone pigment, red pigment)
  • PR224 C. I. Pigment Red 224 (perylene pigment, red pigment)
  • PR254 C. I. Pigment Red 254 (diketopyrrolopyrrole pigment, red pigment)
  • PR272 C. I. Pigment Red 272 (diketopyrrolopyrrole pigment, red pigment)
  • PY138 C. I. Pigment Yellow 138 (quinophthalone pigment, yellow pigment)
  • PY139 C. I. Pigment Yellow 139 (isoindoline pigment, yellow pigment)
  • PY150 C. I.
  • Pigment Yellow 150 (azo pigment, yellow pigment) PY185:C. I. Pigment Yellow 185 (isoindoline pigment, yellow pigment)
  • PG36 C. I. Pigment Green 36 (phthalocyanine pigment, green pigment)
  • PB15:6 C.
  • I. Pigment Blue 15:6 phthalocyanine pigment, blue pigment
  • PV23 C.
  • I. Pigment Violet 23 (dioxazine pigment, purple pigment)
  • PBk32 C.
  • I. Pigment Black 32 perylene pigment, organic black pigment
  • IR coloring material 1 Compound with the following structure (pyrrolopyrrole pigment, near-infrared absorbing pigment)
  • the molecular weights and maximum molar absorption coefficients ( ⁇ max ) in the wavelength range of 400 to 700 nm of the dispersion aids M-1 to M-53 are as follows.
  • MC-1 Compound with the following structure (molecular weight: 255, ⁇ max : 10 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less)
  • MC-2 Compound with the following structure (molecular weight: 785, ⁇ max : more than 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 )
  • Derivative A Compound with the following structure (molecular weight: 768, ⁇ max : more than 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 )
  • Derivative B Compound with the following structure (molecular weight: 403, ⁇ max : more than 3000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 )
  • (resin) P-1 Resin with the following structure. The numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight: 7000.
  • P-2 Resin synthesized by the following method 50 parts by mass of methyl methacrylate, 50 parts by mass of n-butyl methacrylate, and 45.4 parts by mass of PGMEA (propylene glycol monomethyl ether acetate) were charged into a reaction vessel, and the atmosphere was replaced with nitrogen gas. Replaced. The inside of the reaction vessel was heated to 70°C, 6 parts by mass of 3-mercapto-1,2-propanediol was added, and further 0.12 parts by mass of AIBN (azobisisobutyronitrile) was added, followed by reaction for 12 hours. I let it happen. It was confirmed by solid content measurement that 95% had reacted.
  • AIBN azobisisobutyronitrile
  • P-3 Resin synthesized by the following method 50 parts by mass of methyl methacrylate, 30 parts by mass of n-butyl methacrylate, 20 parts by mass of t-butyl methacrylate, and 45.4 parts by mass of PGMEA were charged into a reaction vessel, and the atmosphere was replaced with nitrogen gas. Replaced. The inside of the reaction vessel was heated to 70°C, 6 parts by mass of 3-mercapto-1,2-propanediol was added, and further 0.12 parts by mass of AIBN (azobisisobutyronitrile) was added, followed by reaction for 12 hours. I let it happen. It was confirmed by solid content measurement that 95% had reacted.
  • AIBN azobisisobutyronitrile
  • Resin synthesized by the following method Resin P-3 was synthesized in the same manner except that 20 parts by mass of t-butyl methacrylate was changed to "Karens MOI-BM" manufactured by Showa Denko, and the acid value was 43 mgKOH/ Resin P-5 having a weight average molecular weight of 9,000 was obtained.
  • P-6 Resin synthesized by the following method 6.0 parts by mass of 3-mercapto-1,2-propanediol, 9.5 parts by mass of pyromellitic anhydride, 62 parts by mass of PGMEA, 1,8-diazabicyclo-[5 .4.0]-7-undecene was charged into a reaction vessel, and the atmospheric gas was replaced with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours.
  • the temperature in the system was cooled to 70°C, and 65 parts by mass of methyl methacrylate, 5.0 parts by mass of ethyl acrylate, and t - Add 53.5 parts by mass of a PGMEA solution in which 15 parts by mass of butyl acrylate, 5.0 parts by mass of methacrylic acid, 10 parts by mass of hydroxyethyl methacrylate, and 0.1 part by mass of 2,2'-azobisisobutyronitrile are dissolved. The mixture was reacted for 10 hours. After confirming that 95% of the polymerization had progressed by solid content measurement, the reaction was terminated to obtain resin P-6 having an acid value of 70.5 mgKOH/g and a weight average molecular weight of 10,000.
  • P-7 Resin synthesized by the following method 108 parts by mass of 1-thioglycerol, 174 parts by mass of pyromellitic anhydride, 650 parts by mass of methoxypropyl acetate, and 0.2 parts by mass of monobutyltin oxide as a catalyst were charged into a reaction vessel. After replacing the atmospheric gas with nitrogen gas, the reaction was carried out at 120° C. for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride was half-esterified.
  • P-8 Resin with the following structure.
  • the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units.
  • P-9 Resin with the following structure.
  • the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 18,000.
  • P-10 Resin with the following structure.
  • the numerical value appended to the main chain is the molar ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 22,000.
  • P-12 Resin with the following structure.
  • the numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units.
  • Weight average molecular weight 18000 P-13 Resin with the following structure.
  • the numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units.
  • Weight average molecular weight 18000 P-14 Resin with the following structure.
  • Weight average molecular weight 18000 P-15 Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units.
  • Weight average molecular weight 20000 P-16 Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units.
  • Weight average molecular weight 23000 P-17 Resin with the following structure. The numerical value appended to the main chain is the mass ratio, and the numerical value appended to the side chain is the number of repeating units. Weight average molecular weight 25000
  • Pigment dispersion Pigment dispersion of the type listed in the table below
  • Polymerizable compound 1 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
  • Photoinitiator 1 Irgacure OXE02 (manufactured by BASF, oxime compound)
  • Surfactant 1 KF6000 (manufactured by Shin-Etsu Chemical Co., Ltd., polydimethylsiloxane modified with carbinol at both ends, hydroxyl value 120 mgKOH/g, silicone surfactant)
  • Polymerization inhibitor 1 p-methoxyphenol
  • Solvent 1 Propylene glycol monomethyl ether acetate
  • Solvent 2 cyclopentanone
  • Solvent 3 Propylene glycol monomethyl ether
  • a base layer forming composition (CT-4000, manufactured by Fujifilm Electronics Materials Co., Ltd.) was coated on a glass substrate using a spin coater to a thickness of 0.1 ⁇ m after post-baking, and coated on a hot plate. was heated at 220° C. for 300 seconds to form a base layer, thereby obtaining a glass substrate (support) with a base layer.
  • the resin compositions of Examples 1 to 175 and Comparative Examples 1 and 2 were applied on the glass substrate with the base layer by spin coating, and then heated at 100°C for 2 minutes using a hot plate to form a film. A film with a thickness of 0.5 ⁇ m was formed.
  • Foreign matter contained in this film is detected using a foreign matter evaluation device (Complas III, manufactured by Applied Materials), and foreign matter (coarse particles) with a maximum width of 1.0 ⁇ m or more are visually checked from all detected foreign matter.
  • the particles were classified, and the number of classified coarse particles having a maximum width of 1.0 ⁇ m or more (number of coarse particles per 1 cm 2 ) was counted.
  • B The number of coarse particles per 1 cm 2 of the membrane is 10 or more and less than 30.
  • C The number of coarse particles per 1 cm 2 of the membrane is 30.
  • D The number of coarse particles is 100 or more per 1cm2 of the membrane.
  • a base layer forming composition (CT-4000, manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied to a glass wafer using a spin coater to a thickness of 0.1 ⁇ m after post-baking, and then using a hot plate.
  • a base layer was formed by heating at 220° C. for 300 seconds to obtain a glass wafer (support) with a base layer.
  • the resin composition described in the first type column of the table below was applied by spin coating so that the film thickness after post-baking was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100° C. for 2 minutes.
  • the film was exposed to light with a wavelength of 365 nm at an exposure dose of 1000 mJ/cm 2 through a mask with a 2 ⁇ m square dot pattern.
  • the glass wafer on which the exposed coating film has been formed is placed on the horizontal rotary table of a spin shower developing machine (Model DW-30, manufactured by Chemitronics Co., Ltd.), After puddle development was performed at 23°C for 60 seconds using a 60% diluted solution (manufactured by Materials Co., Ltd.), the glass wafer was fixed on a horizontal rotating table using a vacuum chuck method, and the glass wafer was rotated at a rotation speed of 50 rpm using a rotating device. While rotating, pure water was supplied in a shower form from a jet nozzle above the center of rotation for rinsing treatment, followed by spray drying. Furthermore, heat treatment (post-bake) was performed for 480 seconds using a 200° C.
  • a spin shower developing machine Model DW-30, manufactured by Chemitronics Co., Ltd.
  • the obtained multilayer filter is developed, rinsed, and dried in the same manner as the formation of the first layer of pixels, and the second type of resin composition layer formed on the first type of pixel is removed by development. did.
  • the transmittance of the first type of pixel before forming the second type of resin composition layer and the first type of pixel after developing and removing the second type of resin composition layer was measured using MCPD-3000 (manufactured by Otsuka Electronics Co., Ltd.). ) to determine the maximum value of transmittance variation ( ⁇ T%max), and the spectral variation was evaluated based on the following criteria.
  • Amount of variation in transmittance
  • the smaller ⁇ T%max means that the spectral fluctuation of the first type of pixel is less likely to occur.
  • a base layer forming composition (CT-4000, manufactured by Fujifilm Electronics Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness became 0.1 ⁇ m after post-baking.
  • the base layer was formed by coating the base layer and heating it for 300 seconds at 220° C. using a hot plate to obtain a silicon wafer (support) with the base layer.
  • each resin composition was applied by spin coating so that the film thickness after post-baking was 0.62 ⁇ m. Then, using a hot plate, it was heated at 100° C. for 2 minutes.
  • the silicon wafer on which the exposed coating film has been formed is placed on the horizontal rotary table of a spin shower developer (Model DW-30, manufactured by Chemitronics Co., Ltd.), After puddle development was performed at 23°C for 60 seconds using a 60% diluted solution (manufactured by Materials Co., Ltd.), the silicon wafer was fixed on a horizontal rotating table using a vacuum chuck method, and the silicon wafer was rotated at a rotation speed of 50 rpm using a rotating device. While rotating, pure water was supplied in a shower form from a jet nozzle above the center of rotation for rinsing treatment, followed by spray drying. Further, a heat treatment (post-bake) was performed for 300 seconds using a 200° C.
  • a spin shower developer Model DW-30, manufactured by Chemitronics Co., Ltd.
  • the resin compositions of Examples had excellent storage stability. Furthermore, the evaluation of spectral fluctuation and developability was also excellent.
  • Films obtained from the resin compositions described in Examples can be suitably used for optical filters, solid-state imaging devices, and image display devices.
  • Example 6 similar effects were obtained even when polymerizable compound 1 was changed to compound M-2 or M-3 having the structure shown below.
  • Example 6 similar effects were obtained even when the photopolymerization initiator 1 was changed to compounds I-2 to I-5 having the structures shown below.
  • the surfactant 1 was a compound having the structure shown below (a fluorine-based surfactant with a weight average molecular weight of 14,000, and the numerical value of % indicating the proportion of repeating units is mol%) or PolyFox PF6320 (OMNOVA Co., Ltd.). Similar effects were obtained even when the fluorine-based surfactant was used.
  • Example 6 similar effects were obtained even when the polymerization inhibitor 1 was changed to compound H-2 or H-3 having the structure shown below.

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Abstract

L'invention concerne une composition de résine qui contient : un matériau coloré contenant un pigment ; une résine ; et un composé représenté par la formule (1), ledit composé ayant une valeur maximale du coefficient d'extinction molaire dans la plage de longueurs d'onde de 400 à 700 nm ne dépassant pas 3 000 L·mol-1·cm-1 et ayant un poids moléculaire inférieur ou égal à 475. Dans la formule (1), A1 représente un groupe qui contient un groupe acide ou un groupe basique ; X1 représente un groupe urée, un groupe thiourée, un groupe uréthane, un groupe thiouréthane ou un groupe amide ; L1 représente un groupe n-valent ; et n représente un nombre entier de 1 à 4. L'invention concerne également un film, un filtre optique, un élément d'imagerie à semi-conducteurs et un dispositif d'affichage d'image qui utilisent chacun la composition de résine.
PCT/JP2023/020455 2022-06-13 2023-06-01 Composition de résine, film, filtre optique, élément d'imagerie à semi-conducteurs et dispositif d'affichage d'image WO2023243414A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117736127A (zh) * 2024-02-20 2024-03-22 广饶六合化工有限公司 一种耐温耐剪切压裂液增粘剂的制备工艺

Citations (4)

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Publication number Priority date Publication date Assignee Title
JP2003238842A (ja) * 2002-02-15 2003-08-27 Fuji Photo Film Co Ltd 顔料分散組成物
JP2016133604A (ja) * 2015-01-19 2016-07-25 東洋インキＳｃホールディングス株式会社 カラーフィルタ用着色組成物及びカラーフィルタ
WO2017164161A1 (fr) * 2016-03-25 2017-09-28 富士フイルム株式会社 Composition photosensible, filtre coloré, procédé de formation de motif, capteur d'image à semi-conducteurs et dispositif d'affichage d'image
WO2021002237A1 (fr) * 2019-07-03 2021-01-07 富士フイルム株式会社 Composition colorante, film, filtre de couleur et dispositif d'imagerie à semi-conducteurs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003238842A (ja) * 2002-02-15 2003-08-27 Fuji Photo Film Co Ltd 顔料分散組成物
JP2016133604A (ja) * 2015-01-19 2016-07-25 東洋インキＳｃホールディングス株式会社 カラーフィルタ用着色組成物及びカラーフィルタ
WO2017164161A1 (fr) * 2016-03-25 2017-09-28 富士フイルム株式会社 Composition photosensible, filtre coloré, procédé de formation de motif, capteur d'image à semi-conducteurs et dispositif d'affichage d'image
WO2021002237A1 (fr) * 2019-07-03 2021-01-07 富士フイルム株式会社 Composition colorante, film, filtre de couleur et dispositif d'imagerie à semi-conducteurs

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117736127A (zh) * 2024-02-20 2024-03-22 广饶六合化工有限公司 一种耐温耐剪切压裂液增粘剂的制备工艺
CN117736127B (zh) * 2024-02-20 2024-04-26 广饶六合化工有限公司 一种耐温耐剪切压裂液增粘剂的制备工艺

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