WO2022085485A1 - 樹脂組成物、樹脂組成物の製造方法、膜の製造方法、光学フィルタの製造方法、固体撮像素子の製造方法および画像表示装置の製造方法 - Google Patents

樹脂組成物、樹脂組成物の製造方法、膜の製造方法、光学フィルタの製造方法、固体撮像素子の製造方法および画像表示装置の製造方法 Download PDF

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WO2022085485A1
WO2022085485A1 PCT/JP2021/037301 JP2021037301W WO2022085485A1 WO 2022085485 A1 WO2022085485 A1 WO 2022085485A1 JP 2021037301 W JP2021037301 W JP 2021037301W WO 2022085485 A1 WO2022085485 A1 WO 2022085485A1
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Prior art keywords
pigment
group
resin composition
mass
compound
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PCT/JP2021/037301
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English (en)
French (fr)
Japanese (ja)
Inventor
和也 尾田
翔一 中村
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富士フイルム株式会社
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Priority to JP2022556903A priority Critical patent/JPWO2022085485A1/ja
Publication of WO2022085485A1 publication Critical patent/WO2022085485A1/ja

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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
    • 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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/06—Ethers; Acetals; Ketals; Ortho-esters
    • 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

Definitions

  • the present invention relates to a resin composition containing a pigment.
  • the present invention also relates to a method for manufacturing a resin composition, a film, an optical filter, a solid-state image sensor, and an image display device.
  • Optical filters such as color filters are manufactured using resin compositions containing pigments.
  • Patent Document 1 describes a colorant (A) such as an organic pigment or an inorganic pigment, a binder polymer (B), a photopolymerizable compound (C), a photopolymerization initiator (D), and a propylene glycol monomethyl. It is described that a color filter is produced using a resin composition containing a solvent (E) containing ether acetate and 4-hydroxy-4-methyl-2-pentanone.
  • a film When forming a film using a resin composition, a film may be formed using a resin composition stored at a low temperature for a long period of time.
  • the pigment in the resin composition aggregates during storage of the resin composition even if the average particle size of the pigment is small in the resin composition immediately after production.
  • the average particle size of the pigment tends to be large.
  • the viscosity of the resin composition increases and the coatability tends to decrease. Therefore, as the storage period of the resin composition becomes longer, the thickness unevenness of the obtained film tends to increase.
  • the average particle size of the pigment increases during storage of the resin composition, a film formed by using the resin composition immediately after production and a film formed by using the resin composition after long-term storage are used. There may also be differences in performance such as the spectral characteristics of the film.
  • an object of the present invention is to provide a resin composition in which fluctuations in the average particle size of the pigment are suppressed even after long-term storage at a low temperature.
  • the present invention also provides a method for manufacturing a resin composition, a film, an optical filter, a solid-state image sensor, and an image display device.
  • the present invention provides the following.
  • ⁇ 1> Containing a pigment, a resin, and a solvent The solvent is a resin composition containing an ether solvent represented by the formula (1);
  • R 1 represents a hydrocarbon group
  • R 2 to R 6 independently represent a hydrogen atom or a hydrocarbon group, respectively.
  • the ether solvent represented by the above formula (1) is at least one selected from anisole, phenetol, 4-methylanisole, 3-methylanisole and 2-methylanisole, according to ⁇ 1>. Resin composition.
  • ⁇ 3> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the solvent contains 1 to 100% by mass of an ether solvent represented by the above formula (1).
  • ⁇ 4> The resin composition according to ⁇ 1> or ⁇ 2>, wherein the solvent contains 1 to 50% by mass of an ether solvent represented by the above formula (1).
  • ⁇ 5> The resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the resin composition contains 0.5% by mass or more of an ether solvent represented by the above formula (1).
  • the solvent is any one of ⁇ 1> to ⁇ 5>, which comprises an ether solvent represented by the above formula (1) and a solvent other than the ether solvent represented by the above formula (1).
  • ⁇ 12> A method for producing a film, which comprises a step of applying the resin composition according to any one of ⁇ 1> to ⁇ 10> to a support.
  • ⁇ 13> A method for manufacturing an optical filter, which comprises the method for manufacturing a film according to ⁇ 12>.
  • ⁇ 14> A method for manufacturing a solid-state image sensor, which comprises the method for manufacturing a film according to ⁇ 12>.
  • ⁇ 15> A method for manufacturing an image display device including the method for manufacturing a film according to ⁇ 12>.
  • the present invention it is possible to provide a resin composition in which fluctuations in the average particle size of the pigment are suppressed even after long-term storage at a low temperature. Further, it is possible to provide a method for manufacturing a resin composition, a film, an optical filter, a solid-state image pickup device, and an image display device.
  • the contents of the present invention will be described in detail.
  • "to” is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.
  • the notation not describing substitution and non-substitution also includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
  • the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
  • the term "exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
  • Examples of the light used for exposure include the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, active rays such as electron beams, or radiation.
  • EUV light extreme ultraviolet rays
  • (meth) acrylate” represents both acrylate and methacrylate, or either
  • “(meth) acrylic” represents both acrylic and methacrylic, or either.
  • Acryloyl "represents both acryloyl and / or methacryloyl.
  • Me in the structural formula represents a methyl group
  • Et represents an ethyl group
  • Bu represents a butyl group
  • Pr represents a propyl group
  • Ph represents a phenyl group.
  • the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values measured by a GPC (gel permeation chromatography) method.
  • the near infrared ray means light having a wavelength of 700 to 2500 nm.
  • the total solid content means the total mass of all the components of the composition excluding the solvent.
  • the pigment means a coloring material that is difficult to dissolve in a solvent.
  • the solubility of the pigment in 100 g of water at 23 ° C. and 100 g of propylene glycol monomethyl ether acetate at 23 ° C. is preferably 0.1 g or less, and more preferably 0.01 g or less.
  • the dye means a coloring material that is easily dissolved in a solvent.
  • the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
  • the resin composition of the present invention contains a pigment, a resin, and a solvent, and the solvent is characterized by containing an ether solvent represented by the formula (1).
  • R 1 represents a hydrocarbon group
  • R 2 to R 6 independently represent a hydrogen atom or a hydrocarbon group, respectively.
  • the ether solvent contained in the resin composition of the present invention has a high affinity with pigments and can weaken the cohesiveness between pigments. Therefore, the resin composition of the present invention can suppress fluctuations in the average particle size of the pigment even after being stored at a low temperature (for example, 5 ° C.) for a long period of time. It is presumed that the ether solvent represented by the formula (1) can interact with the conjugated system of the organic pigment to further enhance the affinity with the organic pigment. Therefore, when an organic pigment is used as the pigment, the fluctuation of the average particle size can be suppressed more effectively.
  • the resin composition of the present invention it is possible to form a film having excellent film thickness uniformity. It is presumed that the reason why such an effect is obtained is that the thixotropic property of the resin composition can be reduced by suppressing the aggregation of the pigment.
  • the resin composition of the present invention is preferably used as a resin composition for an optical filter.
  • the optical filter include a color filter, a near-infrared transmission filter, a near-infrared cut filter, and the like, and a color filter is preferable.
  • the resin composition of the present invention is preferably used for a solid-state image sensor. More specifically, it is preferably used as a resin composition for an optical filter used in a solid-state image sensor, and more preferably used as a resin composition for forming colored pixels of a color filter used in a solid-state image sensor.
  • Examples of the color filter include a filter having colored pixels that transmit light of a specific wavelength.
  • Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta pixel, a cyan pixel, a yellow pixel, and the like, and a green pixel or a cyan pixel is preferable, and a green pixel is more preferable.
  • the colored pixels of the color filter can be formed by using a resin composition containing a chromatic pigment.
  • the maximum absorption wavelength of the near-infrared cut filter is preferably in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. ..
  • the transmittance of the near-infrared cut filter in the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, still 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. , 70 to 450, more preferably 100 to 400, and particularly preferably 100 to 400.
  • the near-infrared cut filter can be formed by using a resin composition containing a near-infrared absorbing pigment.
  • the near-infrared ray transmission filter is a filter that transmits at least a part of near-infrared rays.
  • the near-infrared transmission filter may be a filter (transparent film) that transmits both visible light and near-infrared light, and is a filter that shields at least a part of visible light and transmits at least a part of near-infrared light. May be good.
  • the maximum value of the transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the transmittance in the wavelength range of 1100 to 1300 nm.
  • a filter satisfying the spectral characteristics having a minimum value of 70% or more is preferably mentioned.
  • the near-infrared transmission filter is preferably a filter that satisfies any of the following spectral characteristics (1) to (5).
  • a filter of 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 900 to 1500 nm is.
  • a filter of 70% or more (preferably 75% or more, more preferably 80% or more).
  • the maximum value of the transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1000 to 1500 nm is.
  • a filter of 70% or more preferably 75% or more, more preferably 80% or more).
  • the maximum value of the transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1100 to 1500 nm is.
  • a filter of 70% or more preferably 75% or more, more preferably 80% or more.
  • the maximum value of the transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of the transmittance in the wavelength range of 1200 to 1500 nm is.
  • a filter of 70% or more preferably 75% or more, more preferably 80% or more).
  • the resin composition of the present invention can also be used as a light-shielding film or 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, still more preferably 15% by mass or less.
  • the resin composition of the present invention contains a pigment.
  • the pigment include a white pigment, a black pigment, a chromatic pigment, and a near-infrared absorbing pigment.
  • the white pigment includes not only pure white but also light gray (for example, grayish white, light gray, etc.) pigment close to white.
  • a chromatic pigment is used as the pigment.
  • the chromatic pigment may be only one kind or may contain two or more kinds.
  • a near-infrared absorbing pigment is used as the pigment.
  • the near-infrared absorbing pigment may be only one kind, or may contain two or more kinds.
  • two or more kinds of chromatic pigments are used in combination as pigments, or black pigments are used.
  • the average primary particle size 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, still more preferably 100 nm or less.
  • the primary particle size of the pigment can be obtained from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.
  • the average primary particle size in the present invention is an arithmetic average value of the primary particle size for the primary particles of 400 pigments.
  • the primary particles of the pigment refer to independent particles without aggregation.
  • the pigment used in the present invention is preferably an organic pigment because the effect of the present invention is more prominent, and is preferably a phthalocyanine pigment, a diketopyrrolopyrrole pigment, an anthraquinone pigment, an isoindrin pigment, an azo pigment, and an azomethine. It is more preferably at least one selected from pigments, quinophthalone pigments, dioxazine pigments and pteridine pigments, and even more preferably phthalocyanine pigments.
  • the phthalocyanine pigment is a green pigment, Color Index (CI). Pigment Green7, 36, 58, 59, 62, 63, etc., which is a blue pigment, C.I. I.
  • Pigment Blue 15: 3, 15: 4, 15: 6, 16 and the like are preferable.
  • the diketopyrrolopyrrole pigment is a red pigment, C.I. I. Pigment Red 254, 264, 272, 291 and the like are preferable.
  • As the anthraquinone pigment C.I. I. Pigment Red 177 and the like are preferable.
  • the isoindoline pigment is C.I. I. Pigment Yellow 139, 185 and the like are preferable.
  • As the azo pigment C.I. I. Pigment Yellow 150, a red pigment, C.I. I. Pigment Red 269 and the like are preferable.
  • an azobarbituric acid nickel complex pigment having the following structure can also be used.
  • the quinophthalone pigment is a yellow pigment, C.I. I. Pigment Yellow 138, 231 and 233 are preferable.
  • the dioxazine pigment is a purple pigment, C.I. I. Pigment Violet23 and the like are preferable.
  • the pteridine pigment is a yellow pigment, C.I. I. Pigment Yellow 215 and the like are preferable.
  • the azomethine pigment is a yellow pigment, C.I. I. Pigment Yellow 129 and the like are preferable.
  • the chromatic pigment is not particularly limited, and a known chromatic pigment can be used.
  • the chromatic pigment include pigments having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, yellow pigments, orange pigments, red pigments, green pigments, purple pigments, blue pigments and the like can be mentioned.
  • the chromatic pigment is preferably an organic pigment. Specific examples of these include those shown below.
  • a green pigment a halogen having an average number of halogen atoms in one molecule of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5.
  • Halogenated zinc phthalocyanine pigments can also be used. Specific examples include the phthalocyanine pigment described in International Publication No. 2015/118720.
  • a green pigment a compound described in Chinese Patent Application No. 106900927, a phthalocyanine compound having a phosphate ester described in International Publication No. 2012/102395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014.
  • Phthalocyanine compounds phthalocyanine compounds described in JP-A-2018-180023, compounds described in JP-A-2019-038958, core-shell pigments described in JP-A-2020-076955, and the like can also be used.
  • an aluminum phthalocyanine pigment having a phosphorus atom can also be used. Specific examples thereof include the compounds described in paragraph numbers 0022 to 0030 of JP2012-247591A and paragraph numbers 0047 of JP2011-157478A.
  • a nickel azobarbiturate complex pigment having the above-mentioned structure can also be used.
  • the yellow pigment the compounds described in JP-A-2017-201003, the compounds described in JP-A-2017-197719, and paragraph numbers 0011 to 0062 and 0137-0276 of JP-A-2017-171912 are described.
  • X 1 to X 16 independently represent a hydrogen atom or a halogen atom, and Z 1 represents an alkylene group having 1 to 3 carbon atoms.
  • Specific examples of the compound represented by the formula (QP1) include the compound described in paragraph No. 0016 of Japanese Patent No. 6443711.
  • Y1 to Y3 independently represent halogen atoms.
  • n and m represent integers of 0 to 6, and p represents an integer of 0 to 5.
  • (N + m) is 1 or more.
  • Specific examples of the compound represented by the formula (QP2) include the compounds described in paragraphs 0047 to 0048 of Japanese Patent No. 6432077.
  • red pigment a diketopyrrolopyrrole compound in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, and a diketopyrrolopyrrole compound described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838.
  • red pigment a compound having a structure in which an aromatic ring group having an oxygen atom, a sulfur atom or a nitrogen atom bonded to the aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used. can.
  • a halogenated zinc phthalocyanine pigment having a Raman spectrum described in Japanese Patent No. 6474002 is also preferable to use a dioxazine pigment having a controlled contact angle described in International Publication No. 2019/107166 as the pigment from the viewpoint of viscosity adjustment.
  • the descriptions of Japanese Patent No. 6561862, Japanese Patent No. 6413872, Japanese Patent No. 6281345, and Japanese Patent Application Laid-Open No. 2020-026503 can be referred to. Incorporated herein.
  • the pyrolopyrrolop pigment shall have a crystallite size of 140 ⁇ or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes ( ⁇ 1 ⁇ 1 ⁇ 1) of the crystal lattice planes. Is also preferable. Further, it is also preferable to set the physical characteristics of the pyrrolopyrrole pigment as described in paragraphs 0028 to 0073 of JP-A-2020-097744.
  • Two or more kinds of chromatic pigments may be used in combination.
  • the resin composition of the present invention when used for forming green pixels of a color filter, it is preferable to use a green pigment and a yellow pigment in combination.
  • the resin composition of the present invention when used for forming red pixels of a color filter, it is preferable to use a red pigment and a yellow pigment in combination.
  • the resin composition of the present invention when used for forming blue pixels of a color filter, it is preferable to use a blue pigment and a purple pigment in combination.
  • the pigment used in the coloring composition of the present invention preferably contains a green pigment, and more preferably contains a green pigment and a yellow pigment, respectively.
  • the green pigment is preferably a phthalocyanine pigment (also referred to as a phthalocyanine green pigment).
  • the phthalocyanine green pigment tends to have high cohesiveness and low dispersibility of the pigment, but according to the resin composition of the present invention, excellent dispersibility can be obtained even when the phthalocyanine green pigment is used.
  • the effect of the present invention is remarkably exhibited when the phthalocyanine green pigment is used.
  • the phthalocyanine green pigment is preferably a phthalocyanine pigment having a central metal (also referred to as a metal phthalocyanine pigment). Examples of the metal phthalocyanine pigment include copper phthalocyanine pigments, zinc phthalocyanine pigments and aluminum phthalocyanine pigments, and copper phthalocyanine pigments and zinc phthalocyanine pigments are preferable.
  • black may be formed by a combination of two or more kinds of chromatic color pigments.
  • a combination include the following aspects (1) to (7).
  • the resin composition of the present invention is used for forming a near-infrared transmission filter. It can be preferably used as a resin composition.
  • An embodiment containing a red pigment, a blue pigment, a yellow pigment, a purple pigment, and a green pigment An embodiment containing a red pigment, a blue pigment, a yellow pigment, and a green pigment. (6) An embodiment containing a red pigment, a blue pigment, and a green pigment. (7) An embodiment containing a yellow pigment and a purple pigment.
  • White pigments 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, hollow. Examples include resin particles and zinc sulfide.
  • the white pigment is preferably particles having a titanium atom, and more preferably titanium oxide. Further, the white pigment is preferably particles having a refractive index of 2.10 or more with respect to light having a wavelength of 589 nm. The above-mentioned refractive index is preferably 2.10 to 3.00, and more preferably 2.50 to 2.75.
  • titanium oxide described in "Titanium Oxide Physical Properties and Applied Technology, by Manabu Kiyono, pp. 13-45, published on June 25, 1991, published by Gihodo Publishing" can also be used.
  • the white pigment is not limited to a single inorganic substance, but particles compounded with other materials may be used. For example, particles having pores or other materials inside, particles in which a large number of inorganic particles are attached to core particles, core particles composed of polymer particles and shell layers composed of inorganic nanoparticles are used, and core and shell composite particles are used. Is preferable.
  • the core and shell composite particles composed of the core particles composed of the polymer particles and the shell layer composed of the inorganic nanoparticles for example, the description in paragraphs 0012 to 0042 of JP2015-047520 can be referred to. This content is incorporated herein.
  • Hollow inorganic particles can also be used as the white pigment.
  • Hollow inorganic particles are inorganic particles having a structure having cavities inside, and refer to inorganic particles having cavities surrounded by an outer shell.
  • Examples of the hollow inorganic particles include the hollow inorganic particles described in JP-A-2011-075786, International Publication No. 2013/06621, JP-A-2015-164881, and the like, and the contents thereof are incorporated in the present specification. Is done.
  • the black pigment is not particularly limited, and known ones can be used.
  • carbon black, titanium black, graphite and the like can be mentioned, with carbon black and titanium black being preferable, and titanium black being more preferable.
  • Titanium black is black particles containing a titanium atom, and low-order titanium oxide or titanium oxynitride is preferable. Titanium black can modify the surface as needed for the purpose of improving dispersibility and suppressing cohesion.
  • Titanium black can also be used as a dispersion.
  • a dispersion containing titanium black particles and silica particles and having a content ratio of Si atoms and Ti atoms in the dispersion adjusted to be in the range of 0.20 to 0.50 can be mentioned.
  • the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
  • titanium black products examples include titanium black 10S, 12S, 13R, 13M, 13M-C, 13RN, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilac D (Tilack) D (trade name: manufactured by Mitsubishi Materials Corporation). Product name: Ako Kasei Co., Ltd.) and the like.
  • the near-infrared absorbing pigment is preferably an organic pigment. Further, the near-infrared absorbing pigment preferably has a maximum absorption wavelength in a range of more than 700 nm and 1400 nm or less. The maximum absorption wavelength of the near-infrared absorbing pigment is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less. Further, the near-infrared absorbing pigment preferably has A 550 / A max , which is the ratio of the absorbance A 550 at a wavelength of 550 nm and the absorbance A max at the maximum absorption wavelength, to be 0.1 or less, preferably 0.05 or less.
  • the lower limit is not particularly limited, but may be, for example, 0.0001 or more, or 0.0005 or more.
  • the maximum absorption wavelength of the near-infrared absorbing pigment and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the resin composition containing the near-infrared absorbing pigment.
  • the near-infrared absorbing pigment is not particularly limited, but is a pyrolopyrrole compound, a lilene compound, an oxonol compound, a squarylium compound, a cyanine compound, a croconium compound, a phthalocyanine compound, a naphthalocyanine compound, a pyrylium compound, an azurenium compound, an indigo compound and a pyrromethene compound.
  • a pyrolopyrrole compound is at least one selected from a pyrolopyrrole compound, a squarylium compound, a cyanine compound, a phthalocyanine compound and a naphthalocyanine compound, and more preferably a pyrolopyrrole compound or a squarylium compound, which is a pyrolopyrrole compound.
  • a pyrolopyrrole compound a squarylium compound, a cyanine compound, a phthalocyanine compound and a naphthalocyanine compound
  • a pyrolopyrrole compound or a squarylium compound which is a pyrolopyrrole compound.
  • Specific examples of the near-infrared absorbing pigment include the compounds described in Examples described later.
  • the content of the pigment in the total solid content of the resin composition is preferably 30 to 80% by mass.
  • the lower limit is preferably 35% by mass or more, and more preferably 40% by mass or more.
  • the upper limit is preferably 75% by mass or less, and more preferably 70% by mass or less.
  • the content of the organic pigment in the pigment is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and further preferably 70 to 100% by mass.
  • the content of the chromatic pigment in the pigment is preferably 50 to 100% by mass, more preferably 60 to 100% by mass, and even more preferably 70 to 100% by mass.
  • the resin composition of the present invention may contain a dye.
  • the dye is not particularly limited, and known dyes can be used. Examples of the dye include chromatic dyes, black dyes, and near-infrared absorbing dyes. As the dye, a known dye can be used. Further, the methine dye described in JP-A-2019-073695, the methine dye described in JP-A-2019-073696, the methine dye described in JP-A-2019-073697, and JP-A-2019-073698 are described. The methine dye of No. 2020, the azo dye described in JP-A-2020-09394, and the like can also be used. Further, as the dye, a dye multimer can also be used.
  • 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 have the same dye structure or may have different dye structures.
  • the weight average molecular weight (Mw) of the dye multimer is preferably 2000 to 50,000.
  • the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
  • the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
  • the compounds described in 031442 and the like can also be used.
  • the content of the dye in the total solid content of the resin composition is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
  • the content of the dye in the resin composition is preferably 100 parts by mass or less, more preferably 80 parts by mass or less, and further preferably 60 parts by mass or less with respect to 100 parts by mass of the pigment. preferable.
  • the resin composition of the present invention contains substantially no dye. According to this aspect, the ratio of the pigment in the resin composition can be increased, and the effect of the present invention is more remarkable.
  • the case where the dye is substantially not contained means that the content of the dye in the total solid content of the resin composition is 0.1% by mass or less, and is 0.01% by mass. The following is preferable, and it is more preferable that the dye is not contained.
  • the resin composition of the present invention contains a resin.
  • the resin is blended, for example, for the purpose of dispersing a pigment or the like in a resin composition or for a binder.
  • the resin mainly used for dispersing the pigment is also referred to as a dispersant.
  • such use of the resin is an example, and it can be used for purposes other than such use.
  • the weight average molecular weight (Mw) of the resin is preferably 3000 to 2000000.
  • 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 examples include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, and polyamideimide resin. , Polyimine resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin and the like. One of these resins may be used alone, or two or more thereof may be mixed and used.
  • the resin composition of the present invention preferably contains a resin having an acid group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, a phenolic hydroxy group and the like, and a carboxyl group is preferable.
  • the resin having an acid group can be used, for example, as an alkali-soluble resin.
  • the resin having an acid group preferably contains a repeating unit having an acid group in the side chain, and more preferably contains 5 to 70 mol% of the repeating unit having an acid group in the side chain in all the repeating units of the resin.
  • the upper limit of the content of the repeating unit having an acid group in the side chain is preferably 50 mol% or less, more preferably 30 mol% or less.
  • the lower limit of the content of the repeating unit having an acid group in the side chain is preferably 10 mol% or more, more preferably 20 mol% or more.
  • the resin having an acid group is a monomer 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 include repeating units derived from the components.
  • R 1 and R 2 each independently represent a hydrocarbon group having 1 to 25 carbon atoms which may have a hydrogen atom or a substituent.
  • R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
  • the resin used in the present invention preferably contains a repeating unit derived from the compound represented by the following formula (X).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkylene group having 2 to 10 carbon atoms
  • R 3 represents a hydrogen atom or a benzene ring having 1 to 20 carbon atoms.
  • n represents an integer from 1 to 15.
  • the acid value of the resin having an acid group is preferably 5 to 200 mgKOH / g.
  • the upper limit is preferably 150 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less.
  • the lower limit is preferably 10 mgKOH / g or more, more preferably 15 mgKOH / g or more, and even more preferably 20 mgKOH / g or more.
  • the weight average molecular weight (Mw) of the resin having an acid group is preferably 3000 to 35000.
  • the upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.
  • a resin having a basic group can also be used.
  • the resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, and has both a repeating unit having a basic group in the 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 the side chain and a repeating unit not containing a basic group is further 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, and more preferably 20 mgKOH / g or more.
  • the upper limit is preferably 200 mgKOH / g or less, and more preferably 100 mgKOH / g or less.
  • Examples of the resin having a basic group are described in the block copolymers (B) described in paragraphs 0063 to 0112 of JP2014-219665A and paragraphs 0046 to 0076 of JP-A-2018-156021.
  • the block copolymer A1 can be mentioned.
  • the resin composition of the present invention preferably contains a graft resin having an acid group (hereinafter, also referred to as an acidic graft resin).
  • the acidic graft resin can be preferably used as a dispersant.
  • the graft resin means a resin containing a repeating unit having a graft chain.
  • the graft chain means a polymer chain that branches and extends from the main chain of the repeating unit.
  • the graft chain is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure, and is preferably a polyester structure or a poly structure. More preferably, it is a polymer chain containing at least one structure selected from an ether 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.
  • substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, a hydroxy group, an amino group and the like.
  • a group having a steric repulsion effect is preferable, and an alkyl group or an alkoxy group having 5 to 24 carbon atoms is preferable, from the viewpoint of improving the dispersibility of pigments and the like.
  • the alkyl group and the alkoxy group may be linear, branched, or cyclic, and linear or branched is preferable.
  • the weight average molecular weight of the graft chain is preferably 500 to 10000.
  • the upper limit is preferably 5000 or less, and more preferably 3000 or less.
  • the lower limit is preferably 800 or more, and more preferably 1000 or more.
  • the weight average molecular weight of the graft chain is a value calculated from the weight average molecular weight of the raw material monomer used for the polymerization of the repeating unit having the graft chain.
  • repeating units with graft chains can be formed by polymerizing macromonomers.
  • the macromonomer means a polymer compound having a polymerizable group introduced at the end of the polymer.
  • the value of the weight average molecular weight of the raw material monomer the polystyrene-equivalent value measured by the GPC (gel permeation chromatography) method is used.
  • Examples of the acid group contained in the acidic graft resin include a carboxyl group, a sulfo group, and a phosphoric acid group, and a carboxyl group is preferable.
  • the acid value of the acidic graft resin is preferably 20 to 150 mgKOH / g.
  • the upper limit is preferably 120 mgKOH / g or less, more preferably 100 mgKOH / g or less, and even more preferably 80 mgKOH / g or less.
  • the lower limit is preferably 25 mgKOH / g or more, more preferably 30 mgKOH / g or more, and even more preferably 35 mgKOH / g or more.
  • the weight average molecular weight of the acidic graft resin is preferably 3000 to 35000.
  • the upper limit is preferably 25,000 or less, more preferably 20,000 or less, and even more preferably 15,000 or less.
  • the lower limit is preferably 4000 or more, more preferably 6000 or more, and further preferably 7000 or more.
  • the acidic graft resin examples include a resin containing a repeating unit having a graft chain and a repeating unit having an acid group, and a resin having a repeating unit represented by the following formula (Ac-2).
  • the acidic graft resin may further contain other repeating units such as repeating units having a polymerizable group.
  • the polymerizable group examples include an ethylenically unsaturated bond-containing group and a cyclic ether group.
  • the ethylenically unsaturated bond-containing group examples include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
  • the cyclic ether group examples include an epoxy group and an oxetanyl group.
  • the acidic graft resin is a resin containing a repeating unit having a graft chain and a repeating unit having an acid group
  • the acidic graft resin contains 1 mol of the repeating unit having a graft chain in all the repeating units of the acidic graft resin.
  • % Or more is preferable, 2 mol% or more is more preferable, and 3 mol% or more is further preferable.
  • the upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can.
  • the acidic graft resin preferably contains 1 mol% or more of the repeating units having an acid group in all the repeating units of the acidic graft resin, more preferably 2 mol% or more, and 3 mol% or more. Is more preferable.
  • the upper limit can be 90 mol%, 80 mol% or less, 70 mol% or less, 60 mol% or less, 50 mol% or less. can.
  • Ar 10 represents a group containing an aromatic carboxyl 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 carboxyl group represented by Ar 10 in the formula (Ac-2) 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 acid anhydride and the aromatic tetracarboxylic acid anhydride include compounds having the following structures.
  • Q 1 is represented by a single bond, -O-, -CO-, -COOCH 2 CH 2 OCO-, -SO 2- , -C (CF 3 ) 2- , and the following formula (Q-1). Represents a group to be used or a group represented by the following formula (Q-2).
  • the group containing an aromatic carboxyl group represented by Ar 10 may have a polymerizable group.
  • the polymerizable 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 carboxyl group represented by Ar 10 include a group represented by the formula (Ar-11), a group represented by the formula (Ar-12), and a group represented by the formula (Ar-13). Examples include the base.
  • 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-). It represents a group represented by 1) or a group represented by the above formula (Q-2).
  • * 1 represents the bonding position with L 11 .
  • L 11 is preferably —COO ⁇ .
  • the trivalent linking group represented by L 12 in the formula (Ac-2) includes a hydrocarbon group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two of these.
  • a group that combines species or more can be mentioned.
  • the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
  • the number of carbon atoms of 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 number of carbon atoms of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10.
  • the hydrocarbon group may have a substituent.
  • substituent include a hydroxy group and the like.
  • the trivalent linking group represented by L 12 is preferably a group represented by the formula (L12-1), and more preferably a group represented by the formula (L12-2).
  • L 12b represents a trivalent linking group
  • X 1 represents S
  • * 1 represents the bonding position with L 11 in the formula (Ac-2)
  • * 2 represents the bonding position with L 11 in the formula (Ac-2). It represents the binding position of Ac- 2 ) with P10.
  • the trivalent linking group represented by L 12b includes a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined, and a hydrocarbon group or a group in which a hydrocarbon group and —O— are combined is preferable.
  • L 12c represents a trivalent linking group
  • X 1 represents S
  • * 1 represents the bonding position with L 11 of the formula (Ac-2)
  • * 2 represents the binding position of the formula (L12-2). It represents the binding position of Ac- 2 ) with P10.
  • the trivalent linking group represented by L 12c includes a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined, and a hydrocarbon group is preferable.
  • the polymer chain represented by P10 of the formula (Ac- 2 ) is a polymer containing at least one structure selected from a polyester structure, a polyether structure, a poly (meth) acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure and a polyamide structure.
  • the chain is mentioned and is preferably a polymer chain containing at least one structure selected from a polyester structure, a polyether structure and a poly (meth) acrylic structure.
  • the weight average molecular weight of the polymer chain represented by P 10 is preferably 500 to 10000.
  • the upper limit is preferably 5000 or less, and more preferably 3000 or less.
  • the lower limit is preferably 800 or more, and more preferably 1000 or more.
  • the polymer chain represented by P 10 may contain a polymerizable group.
  • the polymerizable group include an ethylenically unsaturated bond-containing group and a cyclic ether group.
  • the ratio of the repeating unit containing the polymerizable group in all the repeating units constituting P 10 is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 20% by mass or more. More preferred.
  • the upper limit can be 100% by mass, preferably 90% by mass or less, and more preferably 60% by mass or less.
  • the polymer chain represented by P 10 contains a repeating unit containing an acid group.
  • the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
  • the ratio of the repeating unit containing an acid group in all the repeating units constituting P 10 is preferably 1 to 30% by mass, more preferably 2 to 20% by mass, and 3 to 10% by mass. Is even more preferable.
  • a polyimine resin containing a nitrogen atom in at least one of the main chain and the side chain can also be used.
  • the polyimine resin has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain. Is preferable.
  • the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
  • the acidic graft resin examples include resins B-1 to B-5 described in Examples described later. Further, as the acidic graft resin, the resin described in paragraphs 0025 to 0094 of JP2012-255128 and the polyimine resin described in paragraphs 0102 to 0166 of JP2012-255128 may be used. can.
  • the resin composition of the present invention preferably contains a resin as a dispersant.
  • the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
  • the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
  • the acid dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, and is substantially acid. A resin consisting only of a group is more preferable.
  • the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
  • the acid value of the acidic dispersant (acidic resin) is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and even more preferably 60 to 105 mgKOH / g.
  • the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger 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 the amount of acid groups and the amount of basic groups is 100 mol%.
  • the basic group of the basic dispersant is preferably an amino group.
  • the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to the core portion.
  • resins include dendrimers (including star-shaped polymers).
  • specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
  • a resin such as the above-mentioned block copolymer or acidic graft resin can also be used.
  • the resin described in JP-A-2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraph numbers 0219 to 0221 of Patent No. 6432077, and the like Polyethylenimine having a polyester side chain described in WO2016 / 104803, a block copolymer described in WO2019 / 125940, and a block polymer having an acrylamide structural unit described in JP-A-2020-06667.
  • Block polymers having an acrylamide structural unit described in JP-A-2020-066688 can also be used.
  • Dispersants are also available as commercial products, and specific examples thereof include BYK series and DISPERBYK series manufactured by Big Chemie, SOLSERSE series manufactured by Japan Lubrizol Co., Ltd., and Efka series manufactured by BASF. Can be mentioned. Further, the pigment dispersants described in paragraphs 0041 to 0130 of JP2014-130338A can also be used, and the contents thereof are incorporated in the present specification.
  • the resin described as the dispersant can also be used for purposes other than the dispersant. For example, it can also be used as a binder.
  • the content of the resin in the total solid content of the resin composition is preferably 5 to 40% by mass.
  • the lower limit is preferably 10% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the content of the resin having an acid group in the total solid content of the resin composition is preferably 5 to 40% by mass.
  • the lower limit is preferably 10% by mass or more.
  • the upper limit is preferably 30% by mass or less, more preferably 25% by mass or less.
  • the content of the resin as a dispersant is preferably 10 to 60 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
  • the upper limit is preferably 50 parts by mass or less, more preferably 40 parts by mass or less.
  • the resin composition of the present invention contains a solvent.
  • the solvent is preferably a liquid at 20 ° C.
  • the solvent contained in the resin composition of the present invention includes an ether solvent represented by the formula (1) (hereinafter, also referred to as solvent SA). Only one type of solvent SA may be used, or two or more types may be used in combination.
  • solvent SA ether solvent represented by the formula (1)
  • R 1 represents a hydrocarbon group
  • R 2 to R 6 independently represent a hydrogen atom or a hydrocarbon group, respectively.
  • Examples of the hydrocarbon group represented by R 1 to R 6 of the formula (1) include an alkyl group, an alkenyl group and an alkynyl group, and an alkyl group is preferable, and a methyl group is more preferable.
  • the number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1.
  • the alkyl group is preferably a linear or branched alkyl group, preferably a linear alkyl group.
  • the alkenyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms.
  • the alkenyl group is preferably a linear or branched alkenyl group, preferably a linear alkenyl group.
  • the alkynyl group preferably has 2 to 5 carbon atoms, more preferably 2 or 3 carbon atoms.
  • the alkynyl group is preferably a linear or branched alkynyl group, preferably a linear alkynyl group.
  • R2 to R6 of the formula ( 1 ) one or more are preferably hydrogen atoms, two or more are more preferably hydrogen atoms, and three or more are more preferably hydrogen atoms. ..
  • R2 to R6 of the formula (1) are preferably any of the following embodiments (R - 1) to (R-3), and in the embodiment (R-1) or (R-2). It is more preferable that there is, and it is further preferable that it is the aspect of (R-1).
  • R - 1) Aspect in which all of R2 to R6 are hydrogen atoms
  • R - 2 Aspect in which any one of R2 to R6 is an alkyl group and the rest are hydrogen atoms (R-1).
  • -3) A mode in which any two of R2 to R6 are alkyl groups and the rest are hydrogen atoms.
  • the molecular weight of the solvent SA is preferably 108 to 200, more preferably 108 to 180, and even more preferably 108 to 160.
  • the boiling point of the solvent SA is preferably 100 to 220 ° C, more preferably 120 to 180 ° C, and even more preferably 140 to 180 ° C.
  • the solubility parameter (SP value) of the solvent SA at 25 ° C. is preferably 15 to 24 (MPa) 0.5 , more preferably 17 to 22 (MPa) 0.5 , and 19 to 20 (MPa). ) 0.5 is more preferable.
  • the viscosity of the solvent SA at 25 ° C. is preferably 0.5 to 2.0 mPa ⁇ s, more preferably 0.6 to 1.7 mPa ⁇ s, and 0.7 to 1.4 mPa ⁇ s. Is more preferable.
  • the solvent SA include anisole, phenetol, 4-methylanisole, 3-methylanisole, 2-methylanisole, 4-ethylanisole, 3-ethylanisole, 2-ethylanisole, isopropoxybenzene, propoxybenzene, 2 , 4-Dimethylanisole, 2,5-dimethylanisole, 2,6-dimethylanisole, 3,5-dimethylanisole, butylphenyl ether, 4-ethylphenetol, 4-tert-butylanisole, etc. It is preferably at least one selected from anisole, phenetol, 4-methylanisole, 3-methylanisole and 2-methylanisole because it is possible to obtain a resin composition having excellent film thickness uniformity at the time. , Anisole is more preferred.
  • the solvent contained in the resin composition preferably contains 1 to 100% by mass of the solvent SA, more preferably 1 to 99% by mass, and even more preferably 1 to 50% by mass.
  • the lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more.
  • the upper limit is preferably 40% by mass or less, and more preferably 30% by mass or less.
  • the solvent contained in the resin composition may be only the solvent SA, but the solvent solubility of the polymerizable compound, the resin, the photopolymerization initiator, etc. used in the resin composition can be improved, or the resin composition can be produced.
  • a solvent other than the ether solvent represented by the formula (1) hereinafter, also referred to as solvent SB.
  • the solvent SB include an ether solvent, an ester solvent, and a ketone solvent. Only one type of solvent SB may be used, or two or more types may be used in combination.
  • ether-based solvent used as the solvent SB examples include propylene glycol monomethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether. It is preferably propylene glycol monomethyl ether.
  • ester-based solvent used as the solvent SB examples include propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethyl acetate, and acetate-n-.
  • Methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, Methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, acetoacetic acid Methyl, ethyl acetoacetate, methyl 2-oxobutate, ethyl 2-oxobutate, cyclohexyl acetate, 1-methyl-2-methoxyethyl propionate and the like can be mentioned, such as propylene glycol monomethyl ether acetate,
  • Ketone-based solvents used as the solvent SB include 2-pentanone, 3-pentanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 3-octanone, 4-octanone, 2-nonanone, 3-.
  • Examples thereof include nonanonone, 4-nonanonone, 5-nonanonone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cyclopentanone, diacetone alcohol, methylethylketone, methylisoamylketone, methylisobutylketone, and the like.
  • Cyclopentanone, 2-octanone, diacetone alcohol is preferred.
  • the solvent SB preferably contains at least one selected from an ester solvent and a ketone solvent, more preferably contains an ester solvent, and further preferably contains propylene glycol monomethyl ether acetate.
  • the content of the solvent SB is preferably 100 to 9900 parts by mass with respect to 100 parts by mass of the solvent SA.
  • the lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more.
  • the upper limit is preferably 3500 parts by mass or less, and more preferably 2000 parts by mass or less.
  • the content of the solvent SB 1 is preferably 100 to 9900 parts by mass with respect to 100 parts by mass of the solvent SA.
  • the lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more.
  • the upper limit is preferably 3500 parts by mass or less, and more preferably 2000 parts by mass or less.
  • the content of propylene glycol monomethyl ether acetate is preferably 100 to 9900 parts by mass with respect to 100 parts by mass of the solvent SA.
  • the lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more.
  • the upper limit is preferably 3500 parts by mass or less, and more preferably 2000 parts by mass or less.
  • the total content of the solvent SA and the propylene glycol monomethyl ether acetate in the solvent contained in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, and 70% by mass. The above is more preferable.
  • the upper limit may be 100% by mass or less, 90% by mass or less, or 80% by mass or less.
  • the content of the solvent SB 2 is preferably 10 to 900 parts by mass with respect to 100 parts by mass of the solvent SA.
  • the lower limit is preferably 25 parts by mass or more, and more preferably 40 parts by mass or more.
  • the upper limit is preferably 400 parts by mass or less, more preferably 250 parts by mass or less.
  • the solvent contained in the resin composition has a solvent SA content of 1 to 50% by mass. It is preferable that the content of the solvent SB 1 is 20 to 95% by mass and the content of the solvent SB 2 is 1 to 40% by mass. In this case, the content of the solvent SA is preferably 3 to 45% by mass, more preferably 5 to 40% by mass.
  • the content of the solvent SB 1 is preferably 25 to 90% by mass, more preferably 30 to 85% by mass.
  • the content of the solvent SB 2 is preferably 3 to 35% by mass, more preferably 5 to 30% by mass.
  • the total content of the solvent SA, the solvent SB 1 and the solvent SB 2 in the solvent contained in the resin composition is preferably 50% by mass or more, more preferably 60% by mass or more, 70. It is more preferably mass% or more.
  • the upper limit may be 100% by mass or less, 90% by mass or less, or 80% by mass or less.
  • the content of the solvent in the resin composition is preferably 50 to 95% by mass.
  • the upper limit is preferably 92.5% by mass or less, and more preferably 90% by mass or less.
  • the lower limit is preferably 50% by mass or more, more preferably 60% by mass or more, further preferably 70% by mass or more, and further preferably 80% by mass or more.
  • the content of the solvent SA in the resin composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more.
  • the content of the solvent SA in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, and further preferably 80% by mass or less.
  • the resin composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations.
  • substantially free of the environmentally regulated substance means that the content of the environmentally regulated substance in the resin composition is 50 mass ppm or less, and preferably 30 mass ppm or less. It is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
  • the environmentally regulated substance include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene.
  • REACH Registration Evolution Analysis and Restriction of Chemicals
  • PRTR Policy Release and Transfer Register
  • VOC Volatile and Transfer Registor
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • VOC Volatile Organic Compounds
  • a method for reducing the environmentally regulated substance there is a method of heating or depressurizing the inside of the system to raise the boiling point of the environmentally regulated substance or higher and distilling off the environmentally regulated substance from the system to reduce the amount. Further, when distilling off a small amount of an environmentally regulated substance, it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the solvent in order to improve efficiency.
  • a polymerization inhibitor or the like is added and the mixture is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding and cross-linking between molecules during distillation under reduced pressure. May be.
  • distillation methods are the stage of the raw material, the stage of the product obtained by reacting the raw material (for example, the resin solution after polymerization or the polyfunctional monomer solution), or the stage of the resin composition prepared by mixing these compounds. It is possible at any stage such as.
  • the resin composition of the present invention may also contain polyalkyleneimine.
  • Polyalkyleneimine is used, for example, as a dispersion aid.
  • the dispersion aid is a material for enhancing the dispersibility of the pigment in the resin composition.
  • the polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and has a branched structure containing a primary amino group, a secondary amino group and a tertiary amino group, respectively.
  • the carbon number of the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.
  • the molecular weight of polyalkyleneimine is preferably 200 or more, more preferably 250 or more.
  • the upper limit is preferably 100,000 or less, more preferably 50,000 or less, further preferably 10,000 or less, and particularly preferably 2000 or less.
  • the molecular weight of polyalkyleneimine is the value calculated from the structural formula.
  • the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used. If the measurement cannot be performed by the boiling point elevation method or is difficult to measure, the value of the number average molecular weight measured by the viscosity method is used.
  • the value of the number average molecular weight in the polystyrene conversion value measured by the GPC (gel permeation chromatography) method is used.
  • the amine value of polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.
  • alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and the like, preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine. preferable.
  • the polyalkyleneimine is particularly preferably polyethyleneimine.
  • polyethyleneimine preferably contains a primary amino group in an amount of 10 mol% or more, more preferably 20 mol% or more, based on the total of the primary amino group, the secondary amino group and the tertiary amino group. , 30 mol% or more is more preferable.
  • Examples of commercially available polyethyleneimine products include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
  • the content of alkyleneimine in the total solid content of the resin composition is preferably 0.1 to 5% by mass.
  • the lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
  • the upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and further preferably 3% by mass or less.
  • the content of alkyleneimine is preferably 0.5 to 20 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 2 parts by mass or more.
  • the upper limit is preferably 10 parts by mass or less, and more preferably 8 parts by mass or less.
  • As the alkyleneimine only one kind may be used, or two or more kinds may be used. When two or more kinds are used, it is preferable that the total amount thereof is in the above range.
  • the resin composition of the present invention can contain a pigment derivative.
  • Pigment derivatives are used, for example, as dispersion aids.
  • examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.
  • the pigment skeletons constituting the pigment derivative include quinoline pigment skeleton, benzoimidazolone pigment skeleton, benzoisoindole pigment skeleton, benzothiazole pigment skeleton, iminium pigment skeleton, squarylium pigment skeleton, croconium pigment skeleton, oxonol pigment skeleton, and pyrolopyrrole pigment.
  • Examples of the acid group include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imic acid group and salts thereof.
  • alkali metal ions Li + , Na + , K + , etc.
  • alkaline earth metal ions Ca 2+ , Mg 2+ , etc.
  • ammonium ions imidazolium ions, pyridinium ions, etc.
  • Examples include phosphonium ion.
  • the carboxylic acid amide group a group represented by -NHCOR X1 is preferable.
  • sulfonamide group a group represented by -NHSO 2 RX2 is preferable.
  • imidic acid group a group represented by -SO 2 NHSO 2 R X3 , -CONHSO 2 R X4 , -CONHCOR X5 or -SO 2 NHCOR X6 is preferable, and -SO 2 NHSO 2 R X3 is more preferable.
  • RX1 to RX6 independently represent an alkyl group or an aryl group, respectively.
  • the alkyl group and aryl group represented by RX1 to RX6 may have a substituent.
  • the substituent is preferably a halogen atom, more preferably a fluorine atom.
  • Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group.
  • Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
  • a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative) can be used.
  • the maximum molar extinction coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L ⁇ mol -1 ⁇ cm -1 or less, and 1000 L ⁇ mol -1 ⁇ cm -1 or less. Is more preferable, and 100 L ⁇ mol -1 ⁇ cm -1 or less is further preferable.
  • 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 derivative examples include the compounds described in Examples described later, JP-A-56-118462, JP-A-63-246674, JP-A-01-217077, and JP-A-03-009961.
  • Japanese Patent Laid-Open No. 03-026767 Japanese Patent Application Laid-Open No. 03-153780
  • Japanese Patent Application Laid-Open No. 03-045662 Japanese Patent Application Laid-Open No. 04-285669
  • Japanese Patent Application Laid-Open No. 06-145546 Japanese Patent Application Laid-Open No. 06-212088, Kaihei 06-240158
  • Japanese Patent Laid-Open No. 10-030063 Japanese Patent Laid-Open No. 10-195326
  • Paragraph Nos Japanese Patent Laid-Open Nos.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 1 to 20 parts by mass, still more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the pigment.
  • the pigment derivative only one kind may be used, or two or more kinds may be used in combination. When two or more types are used in combination, the total amount thereof is preferably in the above range.
  • the resin composition of the present invention preferably contains a polymerizable compound.
  • a polymerizable compound a known compound that can be crosslinked by radicals, acids or heat can be used.
  • the polymerizable compound is preferably, for example, a compound having an ethylenically unsaturated bond-containing group.
  • the ethylenically unsaturated bond-containing group include a vinyl group, a (meth) allyl group, and a (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, a prepolymer or an oligomer, but a monomer is preferable.
  • the molecular weight of the polymerizable compound is preferably 100 to 3000.
  • the upper limit is more preferably 2000 or less, and even more preferably 1500 or less.
  • the lower limit is more preferably 150 or more, and even more preferably 250 or more.
  • the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and more preferably an ethylenically unsaturated bond. It is more preferable that the compound contains 3 to 6 containing groups. Further, the polymerizable compound is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
  • polymerizable compound examples include paragraph numbers 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-029760, paragraphs 0254 to 0257 of JP2008-292970, and JP-A.
  • the compounds described in paragraph numbers 0034 to 0038 of Japanese Patent Application Laid-Open No. 2013-253224, paragraph numbers 0477 of Japanese Patent Application Laid-Open No. 2012-208494, Japanese Patent Application Laid-Open No. 2017-048637, Japanese Patent No. 6057891 and Japanese Patent Application Laid-Open No. 6031807 are These contents are incorporated herein by reference.
  • dipentaerythritol tri (meth) acrylate commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.
  • dipentaerythritol tetra (meth) acrylate commercially available KAYARAD D-320.
  • diglycerin EO ethylene oxide modified (meth) acrylate
  • pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Industry Co., Ltd., NK ester A
  • 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 Toa Synthetic Co., Ltd.
  • NK Oligo UA-7200 manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • DPHA-40H manufactured by Nippon Kayaku Co., Ltd.
  • the polymerizable compounds include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy-modified tri (meth) acrylate, trimethylolpropane ethyleneoxy-modified tri (meth) acrylate, and isocyanuric acid ethyleneoxy-modified tri (meth).
  • Trifunctional (meth) acrylate compounds such as acrylate and pentaerythritol tri (meth) acrylate can also be used.
  • 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.
  • a compound having an acid group can also be used as the polymerizable compound.
  • the polymerizable compound having an acid group By using a polymerizable compound having an acid group, the polymerizable compound in the unexposed portion can be easily removed during development, and the generation of development residue can be suppressed.
  • the acid group include a carboxyl group, a sulfo group, a phosphoric acid group and the like, and a carboxyl group is preferable.
  • the polymerizable compound having an acid group include succinic acid-modified dipentaerythritol penta (meth) acrylate.
  • Examples of commercially available products of the polymerizable compound having an acid group include Aronix M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • the preferable acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
  • the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the solubility in a developing solution is good, and when the acid value is 40 mgKOH / g or less, it is advantageous in production and handling.
  • a compound having a caprolactone structure can also be used.
  • examples of commercially available products of the polymerizable compound having a caprolactone structure include KAYARAD DPCA-20, DPCA-30, DPCA-60, DPCA-120 (all manufactured by Nippon Kayaku Co., Ltd.) and the like.
  • a polymerizable compound having an alkyleneoxy group can also be used.
  • a polymerizable compound having an alkyleneoxy group a polymerizable compound having an ethyleneoxy group and / or a propyleneoxy group is preferable, a polymerizable compound having an ethyleneoxy group is more preferable, and 3 to 3 having 4 to 20 ethyleneoxy groups.
  • a hexafunctional (meth) acrylate compound is more preferred.
  • SR-494 manufactured by Sartmer
  • methacrylate having four ethyleneoxy groups
  • trifunctional manufactured by Sartmer
  • examples thereof include KAYARAD TPA-330 (manufactured by Nippon Kayaku Co., Ltd.), which is a meta) acrylate.
  • a polymerizable compound having a fluorene skeleton can also be used.
  • the polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound.
  • Examples of the polymerizable compound having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr).
  • R f1 and R f2 each independently represent a substituent
  • m and n each independently represent an integer of 0 to 5.
  • m R f1s may be the same or different from each other, and two R f1s out of m R f1s are bonded to each other to form a ring. May be good.
  • n R f2s may be the same or different from each other, and two R f2s out of the n R f2s are bonded to each other to form a ring. May be good.
  • R f1 and R f2 include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR f11 , -COR f12 , -COOR f13 , -OCOR f14 , and -NR f15 .
  • R f16 , -NHCOR f17 , -CONR f18 R f19 , -NHCONR f20 R f21 , -NHCOOR f22 , -SR f23 , -SO 2 R f24 , -SO 2 OR f25 , -NHSO 2 R f26 or -SO 2 NR f27 R f28 can be mentioned.
  • R f11 to R f28 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
  • polymerizable compound having a fluorene skeleton examples include compounds having the following structures.
  • examples of commercially available products of the polymerizable compound having a fluorene skeleton include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., a (meth) acrylate monomer having a fluorene skeleton).
  • the polymerizable compound it is also preferable to use a compound that does not substantially contain an environmentally restrictive substance such as toluene.
  • an environmentally restrictive substance such as toluene.
  • commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
  • the content of the polymerizable compound in the total solid content of the resin composition is preferably 0.1 to 50% by mass.
  • the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, still more preferably 25% by mass or less.
  • the polymerizable compound may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total of them is within the above range.
  • the resin composition of the present invention preferably contains a photopolymerization initiator.
  • the photopolymerization initiator is not particularly limited and may be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet region to the visible region is preferable.
  • the photopolymerization initiator is preferably a photoradical polymerization initiator.
  • photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazoles, oxime compounds, organic peroxides, and thio compounds. , Ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
  • the photopolymerization initiator is a trihalomethyltriazine compound, a benzyldimethylketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, or a triarylimidazole.
  • It is preferably a dimer, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound and a 3-aryl substituted coumarin compound, preferably an oxime compound and an ⁇ -hydroxyketone compound.
  • ⁇ -Aminoketone compound, and a compound selected from an acylphosphine compound are more preferable, and an oxime compound is further preferable.
  • the photopolymerization initiator the compound described in paragraphs 0065 to 0111 of JP-A-2014-130173 and JP-A-6301489, MATERIAL STAGE 37-60p, vol. 19, No. Peroxide-based photopolymerization initiator described in 3, 2019, photopolymerization initiator described in International Publication No. 2018/221177, photopolymerization initiator described in International Publication No. 2018/110179, JP-A-2019-043864.
  • Examples thereof include the above-mentioned aminoacetophenone-based initiators having an oxazolidine group, the oxime-based photopolymerization initiators described in JP-A-2013-190459, and the contents thereof are incorporated in the present specification.
  • ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, Irgacure29. (Manufactured by the company) and the like.
  • Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369, Irger Made) and so on.
  • acylphosphine compounds examples include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
  • Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No.
  • oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like.
  • ADEKA Corporation Photopolymerization Initiator 2
  • Japanese Patent Application Laid-Open No. 2012-014052 Japanese Patent Application Laid-Open No. 2012-014052.
  • the oxime compound it is also preferable to use a compound having no coloring property or a compound having high transparency and difficult to discolor. Examples of commercially available products include ADEKA ARCLUS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).
  • an oxime compound having a fluorene ring can also be used.
  • Specific examples of the oxime compound having a fluorene ring include the compound described in JP-A-2014-137466 and the compound described in Japanese Patent No. 06636081.
  • an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
  • Specific examples of such an oxime compound include the compounds described in International Publication No. 2013/083505.
  • an oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
  • Specific examples of the oxime compound having a fluorine atom are described in the compounds described in JP-A-2010-262028, compounds 24, 36-40 described in JP-A-2014-500852, and JP-A-2013-164471.
  • Compound (C-3) and the like can be mentioned.
  • an oxime compound having a nitro group can be used as the photopolymerization initiator.
  • the oxime compound having a nitro group is also preferably a dimer.
  • Specific examples of the oxime compound having a nitro group include the compounds described in paragraphs 0031 to 0047 of JP2013-114249A and paragraphs 0008-0012 and 0070-0079 of JP-A-2014-137466. Examples thereof include the compound described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071, ADEKA ARCULDS 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.
  • an oxime compound in which a substituent having a hydroxy group is bonded to the carbazole skeleton can also be used.
  • Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
  • an oxime compound having an aromatic ring group Ar OX1 having an electron-attracting group introduced into the aromatic ring (hereinafter, also referred to as oxime compound OX) can also be used.
  • the electron-attracting group of 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.
  • the benzoyl group may have a substituent.
  • the substituent include a halogen atom, a cyano group, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkenyl group, an alkylsulfanyl group and an arylsulfanyl group.
  • an acyl group or an amino group 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, and more preferably an alkoxy group or an alkyl group. It is more preferably a sulfanyl group or an amino group.
  • the oxime compound OX is preferably at least one selected from the compound represented by the formula (OX1) and the compound represented by the formula (OX2), and more preferably the compound represented by the formula (OX2). preferable.
  • RX1 is an alkyl group, an alkenyl group, an alkoxy group, an aryl group, an aryloxy group, a heterocyclic group, a heterocyclic oxy group, an alkylsulfanyl group, an arylsulfanyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group.
  • Examples of the electron-attracting group 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, preferably an acyl group and a nitro group, and lightfast resistance.
  • An acyl group is more preferable, and a benzoyl group is further preferable, because it is easy to form a film having excellent properties.
  • RX12 is an electron-withdrawing group and RX10 , RX11 , RX13 , and RX14 are hydrogen atoms.
  • oxime compound OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.
  • the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, and more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
  • the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high, more preferably 1000 to 300,000, still more preferably 2000 to 300,000, and more preferably 5000 to 200,000. It is particularly preferable to have.
  • the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
  • a bifunctional or trifunctional or higher photoradical polymerization initiator may be used as the photopolymerization initiator.
  • two or more radicals are generated from one molecule of the photoradical polymerization initiator, so that good sensitivity can be obtained.
  • the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time can be improved.
  • Specific examples of the bifunctional or trifunctional or higher functional photo-radical polymerization initiators include 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 10% by mass or less, more preferably 8% by mass or less, still more preferably 6% by mass or less.
  • the photopolymerization initiator may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total of them is within the above range.
  • the resin composition of the present invention can contain a compound having a cyclic ether group.
  • the cyclic ether group include an epoxy group and an oxetanyl group.
  • the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter, also referred to as an epoxy compound).
  • the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferable.
  • the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
  • the upper limit of the epoxy group contained in the epoxy compound may be, for example, 10 or less, or 5 or less.
  • the lower limit of the epoxy group contained in the epoxy compound is preferably two or more.
  • the epoxy compound may be a low molecular weight compound (for example, a molecular weight of less than 2000, further, a molecular weight of less than 1000), or a polymer compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). It may be any of.
  • the weight average molecular weight of the compound having an epoxy 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 5000 or less, and even more preferably 3000 or less.
  • an epoxy resin can be preferably used as the epoxy compound.
  • the epoxy resin include an epoxy resin which is a glycidyl etherified product of a phenol compound, an epoxy resin which is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester.
  • Examples thereof include a copolymer with another polymerizable unsaturated compound.
  • the epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and even more preferably 310 to 1000 g / eq.
  • EHPE3150 manufactured by Daicel Corporation
  • EPICLON N-695 manufactured by DIC Corporation
  • Marproof G-0150M G-0105SA, G-0130SP, G. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by NOF CORPORATION, epoxy group-containing polymer) and the like can be mentioned.
  • the content of the compound having a cyclic ether group 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, further preferably 1% by mass or more.
  • the upper limit is, for example, more preferably 15% by mass or less, further preferably 10% by mass or less.
  • the compound having a cyclic ether group only one kind may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention may contain a curing accelerator.
  • the curing accelerator include thiol compounds, methylol compounds, amine compounds, phosphonium salt compounds, amidin salt compounds, amide compounds, base generators, isocyanate compounds, alkoxysilane compounds, onium salt compounds and the like.
  • Specific examples of the curing accelerator include the compound described in paragraph Nos. 0094 to 0097 of International Publication No. 2018/056189, the compound described in paragraph numbers 0246 to 0253 of JP-A-2015-034963, and JP-A-2013-041165. Compounds described in Japanese Patent Laid-Open 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 a surfactant.
  • a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
  • the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
  • the surfactant described in paragraph Nos. 0238 to 0245 of International Publication No. 2015/166779 is mentioned, and the content thereof is incorporated in the present specification.
  • the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity in the thickness of the coating film and liquid saving, and has good solubility in the resin composition.
  • fluorine-based surfactant examples include the surfactants described in paragraphs 0060 to 0064 of Japanese Patent Laid-Open No. 2014-041318 (paragraphs 0060 to 0064 of the corresponding International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-.
  • the surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification.
  • fluorine-based surfactants include, for example, Megafax F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560.
  • the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
  • a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
  • fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
  • a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
  • the fluorine-based surfactant a block polymer can also be used.
  • the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (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-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
  • the weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000.
  • % indicating the ratio of the repeating unit is mol%.
  • a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K, manufactured by DIC Corporation. RS-72-K and the like can be mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • a fluorine-containing imide salt compound represented by the formula (fi-1) is also preferable to use as a surfactant.
  • m represents 1 or 2
  • n represents an integer of 1 to 4
  • ⁇ represents 1 or 2
  • X ⁇ + represents an ⁇ -valent metal ion, a primary ammonium ion, and a first.
  • Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ethers, polyoxyethylene stearyl ethers, etc.
  • silicone-based surfactant examples include DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400, SH 8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Addive, SF84 and above.
  • TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 all manufactured by Momentive Performance Materials Co., Ltd.
  • KP-341, KF- 6000, KF-6001, KF-6002, KF-6003 all manufactured by Shin-Etsu Chemical Co., Ltd.
  • BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK -UV3510 (above, manufactured by Big Chemie) and the like.
  • 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. Only one type of surfactant 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 thereof is 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 hydrolyzable group refers to a substituent that is directly linked to a silicon atom and can form a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
  • the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group and the like, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
  • Examples of the functional group other than the hydrolyzable group include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group and an isocyanate group.
  • a phenyl group and the like preferably an amino group, a (meth) acryloyl group and an epoxy group.
  • silane coupling agent examples 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 KBE-903), 3-methacryloxy There are propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co
  • silane coupling agent examples include the compounds described in paragraphs 0018 to 0036 of JP2009-288703 and the compounds described in paragraphs 0056 to 0066 of JP2009-242604A. , These contents are incorporated herein.
  • the content of the silane coupling agent in the total solid content of the resin composition is preferably 0.1 to 5% by mass.
  • the upper limit is more preferably 3% by mass or less, further preferably 2% by mass or less.
  • the lower limit is more preferably 0.5% by mass or more, further preferably 1% by mass or more. Only one kind of silane coupling agent may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention can contain an ultraviolet absorber.
  • an ultraviolet absorber a conjugated diene compound, an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, an indole compound, a triazine compound and the like can be used. Examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, and paragraph numbers 0317 to 0334 of JP2013-066814.
  • the compounds described in paragraphs 0061 to 0080 of JP 2016-162946 are mentioned, the contents of which are incorporated herein by reference.
  • Examples of commercially available ultraviolet absorbers include UV-503 manufactured by Daito Kagaku Co., Ltd., Tinuvin series manufactured by BASF, and Uvinul series manufactured by BASF.
  • Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016).
  • the ultraviolet absorber is a compound described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967, a compound described in paragraph numbers 0059 to 0076 of International Publication No. 2016/181987, and International Publication No. 2020/137819.
  • the thioaryl group-substituted benzotriazole type ultraviolet absorber described in 1 can also be used.
  • 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 kind of ultraviolet absorber may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention can contain an antioxidant.
  • the antioxidant include phenol compounds, phosphite ester compounds, thioether compounds and the like.
  • the phenol compound any phenol compound known as a phenolic antioxidant can be used.
  • Preferred phenolic compounds include hindered phenolic compounds.
  • a compound having a substituent at a site (ortho position) adjacent to the phenolic hydroxy group is preferable.
  • a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferable.
  • the antioxidant a compound having a phenol group and a phosphite ester group in the same molecule is also preferable.
  • a phosphorus-based antioxidant can also be preferably used.
  • the compound 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 kind of antioxidant may be used, or two or more kinds may be used. When two or more types are used, the total amount is preferably in the above range.
  • the resin composition of the present invention can contain a polymerization inhibitor.
  • the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis (3-methyl-6-tert-butylphenol), and the like.
  • examples thereof include 2,2'-methylenebis (4-methyl-6-t-butylphenol) and N-nitrosophenylhydroxyamine salts (ammonium salt, first cerium salt, etc.). Of these, p-methoxyphenol is preferable.
  • the content of the polymerization inhibitor in the total solid content of the resin composition is preferably 0.0001 to 5% by mass.
  • the polymerization inhibitor may be only one kind or two or more kinds. In the case of two or more types, it is preferable that the total amount is within the above range.
  • the resin composition is, if necessary, a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a filler, a defoaming agent). , Flame retardant, leveling agent, peeling accelerator, fragrance, surface tension modifier, chain transfer agent, etc.) may be contained.
  • auxiliary agents for example, conductive particles, a filler, a defoaming agent.
  • the resin composition of the present invention may contain a latent antioxidant, if necessary.
  • the latent antioxidant is a compound in which the site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst. This includes compounds in which the protecting group is desorbed and functions as an antioxidant. Examples of the latent antioxidant include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
  • the resin composition of the present invention may contain an aromatic group-containing phosphonium salt described in JP-A-2020-079833.
  • the resin composition of the present invention may contain a light resistance improving agent.
  • the light resistance improving agent include the compounds described in paragraphs 0036 to 0037 of JP-A-2017-198787, the compounds described in paragraphs 0029 to 0034 of JP-A-2017-146350, and JP-A-2017-129774.
  • the resin composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less, which is not bonded or coordinated with a pigment or the like. , It is particularly preferable that it is not substantially contained. According to this aspect, stabilization of pigment dispersibility (suppression of aggregation), improvement of spectral characteristics due to improvement of dispersibility, stabilization of curable components, suppression of conductivity fluctuation due to elution of metal atoms / metal ions, Effects such as improvement of display characteristics can be expected.
  • the types of free metals include Na, K, Ca, Sc, Ti, Mn, Cu, Zn, Fe, Cr, Co, Mg, Al, Sn, Zr, Ga, Ge, Ag, Au, Pt, and the like.
  • the resin composition of the present invention preferably has a content of free halogen not bonded or coordinated with a pigment or the like of 100 ppm or less, more preferably 50 ppm or less, and more preferably 10 ppm or less. It is more preferable, and it is particularly preferable that it is not substantially contained.
  • the halogen include F, Cl, Br, I and their anions.
  • the method for reducing free metals and halogens in the resin composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.
  • the resin composition of the present invention does not substantially contain a terephthalic acid ester.
  • substantially free means that the content of the terephthalic acid ester is 1000 mass ppb or less in the total amount of the resin composition, and more preferably 100 mass ppb or less. Zero is particularly preferred.
  • perfluoroalkyl sulfonic acid and its salt and perfluoroalkyl carboxylic acid and its salt may be restricted.
  • the perfluoroalkyl sulfonic acid particularly the perfluoroalkyl sulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group
  • a salt thereof and a per.
  • the content of the fluoroalkylcarboxylic acid (particularly the perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salt is 0.01 ppb to 1,000 ppb with respect to the total solid content of the resin composition. It is preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb.
  • the resin composition of the present invention may be substantially free of perfluoroalkyl sulfonic acid and salts thereof, as well as perfluoroalkyl carboxylic acid and salts thereof.
  • a compound that can substitute for perfluoroalkylsulfonic acid and its salt and a compound that can substitute for perfluoroalkylcarboxylic acid and its salt, perfluoroalkylsulfonic acid and its salt, and perfluoroalkylcarboxylic acid can be used.
  • a resin composition that is substantially free of salts thereof may be selected.
  • compounds that can substitute for the regulated compound include compounds excluded from the regulation due to the difference in the number of carbon atoms of the perfluoroalkyl group.
  • the above-mentioned contents do not prevent the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt.
  • the resin composition of the present invention may contain a perfluoroalkyl sulfonic acid and a salt thereof, and a perfluoroalkyl carboxylic acid and a salt thereof within the maximum allowable range.
  • the storage container for the resin composition is not particularly limited, and a known storage container can be used.
  • a storage container for the purpose of suppressing impurities from being mixed into raw materials and resin compositions, a multi-layer bottle having a container inner wall composed of 6 types and 6 layers of resin and a bottle having 6 types of resin having a 7-layer structure. It is also preferable to use. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
  • the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, improving the storage stability of the resin composition, and suppressing the deterioration of the components.
  • the resin composition of the present invention can be produced by mixing the above-mentioned materials.
  • all the components may be simultaneously dissolved and / or dispersed in a solvent to produce the resin composition, or each material may be appropriately used as two or more solutions or dispersions as required. Then, these may be mixed at the time of use (at the time of application) to produce a resin composition.
  • the method for producing a resin composition of the present invention includes a step (dispersion step) of dispersing a pigment in the presence of a resin and a solvent containing an ether solvent (solvent SA) represented by the above formula (1).
  • solvent SA an ether solvent represented by the above formula (1).
  • the dispersibility of the pigment in the resin composition can be further improved, and the average particle size of the pigment in the resin composition can be further reduced.
  • the detailed reason why such an effect is obtained is unknown, but it is presumed to be due to the following. It is presumed that the solvent SA has a high affinity with the pigment and can weaken the cohesiveness between the pigments.
  • the reaggregation of the pigment at the time of dispersion can be effectively suppressed, and the average particle size of the pigment in the resin composition can be made smaller. can do.
  • the solvent SA can interact with the conjugated system of the organic pigment to further enhance the affinity with the organic pigment. Therefore, when an organic pigment is used as the pigment, the reaggregation of the pigment at the time of dispersion can be suppressed more effectively, and the average particle size of the pigment in the resin composition can be further reduced.
  • the solvent used in the dispersion step is other than solvent SA from the viewpoints of solubility of the resin used at the time of dispersion, solvent solubility of polymerizable compounds, resins, photopolymerization initiators, etc., and control of the drying speed at the time of film formation of the resin composition. It is preferable to contain the solvent (solvent SB) of the above.
  • the solvent SB include the above-mentioned solvents, preferably those containing at least one selected from an ester solvent and a ketone solvent, more preferably those containing an ester solvent, and containing propylene glycol monomethyl ether acetate. It is more preferable that it is a solvent.
  • the solvent used in the dispersion step preferably contains 1% by mass or more of the solvent SA, more preferably 3% by mass or more, and further preferably 5% by mass or more.
  • the upper limit may be 100% by mass or less, 50% by mass or less, or 30% by mass or less.
  • the content of the solvent SB is preferably 1 to 99% by mass, more preferably 30 to 90% by mass, and 50 to 70% by mass. It is more preferable to have.
  • the content of the solvent SB is preferably 10 to 3000 parts by mass with respect to 100 parts by mass of the solvent SA.
  • the lower limit is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more.
  • the upper limit is preferably 2000 parts by mass or less, and more preferably 1000 parts by mass or less.
  • the solvent used in the dispersion step preferably contains 1 to 99% by mass of propylene glycol monomethyl ether acetate, more preferably 30 to 90% by mass, and even more preferably 50 to 70% by mass.
  • the content of propylene glycol monomethyl ether acetate is preferably 10 to 3000 parts by mass with respect to 100 parts by mass of the solvent SA.
  • the lower limit is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more.
  • the upper limit is preferably 2000 parts by mass or less, and more preferably 1000 parts by mass or less.
  • Mechanical forces used to disperse pigments include compression, squeezing, impact, shearing, cavitation, etc. Specific means 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. Further, in the pulverization of the pigment in the sand mill (bead mill), it is preferable to use beads having a small diameter and to perform the treatment under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads.
  • the process and disperser for dispersing pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005” and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial". Practical application The process and disperser described in Paragraph No. 0022 of JP-A-2015-157893, "Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978" can be preferably used. Further, in the process of dispersing the pigment, the particles may be miniaturized in the salt milling step. For the materials, equipment, processing conditions, etc. used in the salt milling step, for example, the descriptions in JP-A-2015-194521 and JP-A-2012-046629 can be referred to.
  • a resin composition material (particularly, a dispersion liquid, a polymerizable compound, a photopolymerization initiator, etc.) that has been refrigerated at a temperature of 5 to 10 ° C.
  • the refrigerated material is stored in an environment with a temperature of 17 to 27 ° C and a relative humidity of 40 to 80% for 12 hours or more, and the temperature of the material is returned to 17 to 27 ° C. It is preferable to mix it with other materials.
  • a resin, a polymerizable compound, a photopolymerization initiator, or the like is further added to the dispersion liquid produced through the above dispersion step, the order of addition of each material is not particularly limited, but the dissolution rate and handleability are improved.
  • a photopolymerization initiator, a polymerization inhibitor, and other additives are further mixed to produce a monomer liquid, and then the monomer liquid is added to the dispersion liquid. It is also preferable.
  • the resin composition in an environment of a temperature of 17 to 27 ° C. and a relative humidity of 40 to 80% from the viewpoint of preventing excessive water from being mixed into the resin composition.
  • the method for producing the resin composition includes a step of filtering the resin composition with a filter for the purpose of removing foreign substances and reducing defects.
  • a filter any filter that has been conventionally used for filtration or the like can be used without particular limitation.
  • fluororesins such as polytetrafluoroethylene (PTFE) and polyvinylidene fluoride (PVDF), polyamide resins such as nylon (eg, nylon-6, nylon-6,6), and polyolefin resins such as polyethylene and polypropylene (PP).
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylidene fluoride
  • nylon eg, nylon-6, nylon-6,6)
  • polyolefin resins such as polyethylene and polypropylene (PP).
  • filters using materials such as (including high-density, ultra-high molecular weight polyethylene resin).
  • polypropylene (including high-density polypropylene) and nylon are preferable.
  • the pore diameter of the filter is preferably 0.01 to 7.0 ⁇ m, more preferably 0.01 to 3.0 ⁇ m, and even more preferably 0.05 to 0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
  • the nominal value of the filter manufacturer can be referred to.
  • various filters provided by Nippon Pole Co., Ltd. DFA4201NXEY, DFA4201NAEY, DFA4201J006P, etc.
  • Advantech Toyo Co., Ltd. Japan Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc.
  • KITZ Microfilter Co., Ltd. etc.
  • a fiber-like filter medium As the filter.
  • the fiber-like filter medium include polypropylene fiber, nylon fiber, glass fiber and the like.
  • examples of commercially available products include SBP type series (SBP008, etc.), TPR type series (TPR002, TPR005, etc.) and SHPX type series (SHPX003, etc.) manufactured by Roki Techno Co., Ltd.
  • filters for example, a first filter and a second filter
  • the filtration with each filter may be performed only once or twice or more.
  • filters having different pore diameters may be combined within the above-mentioned range.
  • the filtration with the first filter may be performed only on the dispersion liquid, and after mixing the other components, the filtration may be performed with the second filter.
  • the produced resin composition (particularly when it contains a green pigment) in a light-shielded container from the viewpoint of imparting stability. Further, it is preferable that the gas occupying the void inside the container has an oxygen concentration of 23% or more from the viewpoint of imparting stability.
  • the method for producing a film of the present invention includes a step of applying the resin composition of the present invention to a support.
  • the film thickness of the manufactured film can be appropriately adjusted according to 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, still more preferably 0.3 ⁇ m or more.
  • the film produced by the film manufacturing method of the present invention can be used as a color filter, a near-infrared transmission filter, a near-infrared cut filter, a black matrix, a light-shielding film, and the like.
  • the film manufacturing method of the present invention preferably further includes a step of forming a pattern (pixel).
  • the pattern (pixel) forming method include a photolithography method and a dry etching method, and the photolithography method is preferable.
  • the 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 in a pattern, and a step of exposing the resin composition layer in a pattern. 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-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided.
  • the resin composition layer of the present invention is used to form the resin composition layer on the support.
  • the support is not particularly limited and may be appropriately selected depending on the intended use. Examples thereof include a glass substrate and a silicon substrate, and a silicon substrate is preferable. Further, a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the silicon substrate. Further, a black matrix that separates each pixel may be formed on the silicon substrate. Further, the silicon substrate may be provided with a base layer for improving the adhesion with the upper layer, preventing the diffusion of substances, or flattening the surface of the substrate.
  • the surface contact angle of the base layer is preferably 20 to 70 ° when measured with diiodomethane. Further, it is preferably 30 to 80 ° when measured with water. When the surface contact angle of the base layer is within the above range, the coating property of the resin composition is good.
  • the surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
  • a known method can be used as a method for applying the resin composition.
  • a drop method drop cast
  • a slit coat method a spray method
  • a roll coat method a rotary coating method
  • spin coating a cast coating method
  • a slit and spin method a pre-wet method (for example, JP-A-2009-145395).
  • Methods described in the publication Inkjet (for example, on-demand method, piezo method, thermal method), ejection system printing such as nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc.
  • Various printing methods; transfer method using a mold or the like; nanoinprint method and the like can be mentioned.
  • the method of application in inkjet is not particularly limited, and is, for example, the method shown in "Expandable / usable inkjet-infinite possibilities seen in patents-, published in February 2005, Sumi Betechno Research" (especially from page 115). Page 133), JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, JP-A-2006-169325, and the like. Can be mentioned. Further, regarding the method of applying the resin composition, the description of International Publication No. 2017/030174 and International Publication No. 2017/018419 can be referred to, and these contents are incorporated in the present specification.
  • the resin composition layer formed on the support may be dried (prebaked).
  • prebaking may not be performed.
  • the prebake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower, still 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, still more preferably 80 to 220 seconds. Pre-baking can be performed on a hot plate, an 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 through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. As a result, the exposed portion can be cured.
  • Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can also be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm) and the like, and KrF line (wavelength 248 nm) is preferable. Further, a long wave light source having a diameter of 300 nm or more can also be used.
  • pulse exposure is an exposure method of a method in which light irradiation and pause are repeated in a cycle of a short time (for example, a 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 at the time of exposure can be appropriately selected, and in addition to the operation in the atmosphere, for example, in a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially). It may be exposed in an oxygen-free environment (for example, 22% by volume, 30% by volume, or 50% by volume) in a high oxygen atmosphere having an oxygen concentration of more than 21% by volume.
  • the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15,000 W / m 2 , or 35,000 W / m 2 ). Can be done.
  • the oxygen concentration and the exposure illuminance may be appropriately combined with each other.
  • the illuminance may be 10,000 W / m 2 at an oxygen concentration of 10% by volume, an illuminance of 20,000 W / m 2 at an oxygen concentration of 35% by volume, and the like.
  • the unexposed portion of the resin composition layer is developed and removed to form a pattern (pixel).
  • the unexposed portion of the resin composition layer can be developed and removed using a developing solution.
  • the resin composition layer in the unexposed portion in the exposure step is eluted in the developer, and only the photocured portion remains.
  • the temperature of the developer is preferably, for example, 20 to 30 ° C.
  • the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the steps of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
  • Examples of the developing solution include organic solvents and alkaline developing solutions, and alkaline developing solutions are preferably used.
  • the alkaline developer an alkaline aqueous solution (alkaline developer) obtained by diluting an alkaline agent with pure water is preferable.
  • the alkaline agent include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
  • Ethyltrimethylammonium hydroxide Ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene, etc.
  • examples thereof include organic alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate and sodium metasilicate.
  • the alkaline agent a compound having a large molecular weight is preferable in terms of environment and safety.
  • the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
  • the developer may further contain a surfactant. From the viewpoint of convenience of transfer and storage, the developer may be once produced as a concentrated solution and diluted to a concentration required for use.
  • the dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferable to wash (rinse) with pure water after development. Further, it is preferable that the rinsing is performed by supplying the rinsing liquid to the developed resin composition layer while rotating the support on which the developed resin composition layer is formed.
  • the nozzle for discharging the rinse liquid from the central portion of the support it is also preferable to move the nozzle for discharging the rinse liquid from the central portion of the support to the peripheral edge of the support.
  • the nozzle may be moved while gradually reducing the moving speed. By rinsing in this way, in-plane variation of the rinse can be suppressed. Further, the same effect can be obtained by gradually reducing the rotation speed of the support while moving the nozzle from the central portion of the support to the peripheral portion.
  • Additional exposure processing and post-baking are post-development curing treatments to complete the curing.
  • the heating temperature in the post-bake is, for example, preferably 100 to 240 ° C, more preferably 200 to 240 ° C.
  • Post-baking can be performed on the developed film in a continuous or batch manner using a heating means such as a hot plate, a convection oven (hot air circulation type dryer), or a high frequency heater so as to meet the above conditions. ..
  • the light used for the exposure is preferably light having 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.
  • the pattern formation by the dry etching method includes a step 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.
  • the method for manufacturing an optical filter of the present invention includes the above-mentioned method for manufacturing a film of the present invention. That is, the method for manufacturing an optical filter of the present invention includes the step of applying the above-mentioned resin composition of the present invention to a support.
  • the type of optical filter include a color filter, a near-infrared cut filter, a near-infrared transmission filter, and the like, and a color filter is preferable.
  • the color filter preferably has the film of the present invention as its pixel, more preferably has the film of the present invention as a colored pixel, and further preferably has the film of the present invention as a green pixel.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the purpose.
  • the film thickness is preferably 2 ⁇ m or less, more preferably 1 ⁇ m or less, still more preferably 0.5 ⁇ m or less.
  • the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, still more preferably 0.3 ⁇ m or more.
  • the width of the pixels included in the optical filter is preferably 0.1 to 10.0 ⁇ m.
  • the lower limit is preferably 0.4 ⁇ m or more, more preferably 0.5 ⁇ m or more, and further preferably 0.6 ⁇ m or more.
  • the upper limit is preferably 5.0 ⁇ m or less, more preferably 2.0 ⁇ m or less, further preferably 1.0 ⁇ m or less, and even more preferably 0.8 ⁇ m or less.
  • the method for manufacturing a solid-state image sensor of the present invention includes the above-mentioned method for manufacturing a film of the present invention. That is, the method for manufacturing a solid-state image sensor of the present invention includes the step of applying the above-mentioned resin composition of the present invention to a support.
  • the configuration of the solid-state image sensor is not particularly limited as long as it functions as a solid-state image sensor, and examples thereof include the following configurations.
  • a solid-state image pickup device CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.
  • a transfer electrode made of polysilicon or the like.
  • the color filter may have a structure in which each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
  • the partition wall preferably has a low refractive index for each pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478, JP-A-2014-179757, and International Publication No. 2018/043654.
  • an ultraviolet absorbing layer may be provided in the structure of the solid-state image sensor to improve the light resistance.
  • the image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones and the like), but also for in-vehicle cameras and surveillance cameras.
  • the method for manufacturing an image display device of the present invention includes the above-mentioned method for manufacturing a film of the present invention. That is, the method for manufacturing an image display device of the present invention includes the step of applying the above-mentioned resin composition of the present invention to a support.
  • the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • liquid crystal display device is described in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)".
  • the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the above-mentioned "next-generation liquid crystal display technology".
  • Dispersion prescription 1 A mixed solution of 13.3 parts by mass of the pigment, 0.7 parts by mass of the dispersion aid, 4.9 parts by mass of the resin, and 81.1 parts by mass of the solvent was mixed with a bead mill (zirconia beads 0.1 mm diameter). ) was mixed and dispersed for 3 hours to prepare a dispersion. Then, a dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under the conditions of a pressure of 2000 kg / cm 3 and a flow rate of 500 g / min. This dispersion treatment was repeated up to a total of 10 times to obtain a dispersion liquid. The materials shown in the table below were used for the pigment, dispersion aid, resin and solvent.
  • Dispersion prescription 2 A mixed solution of 13.3 parts by mass of the pigment, 0.7 parts by mass of the dispersion aid, 3.5 parts by mass of the resin, and 82.5 parts by mass of the solvent was mixed with a bead mill (zirconia beads 0.1 mm diameter). ) was mixed and dispersed for 3 hours to prepare a dispersion. Then, a dispersion treatment was performed using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism under the conditions of a pressure of 2000 kg / cm 3 and a flow rate of 500 g / min. This dispersion treatment was repeated up to a total of 10 times to obtain a dispersion liquid. The materials shown in the table below were used for the pigment, dispersion aid, resin solution, and solvent.
  • P-1 C.I. I. Pigment Green7 (green pigment)
  • P-2 C.I. I. Pigment Green36 (green pigment)
  • P-3 C.I. I. Pigment Green58 (green pigment)
  • P-4 C.I. I. Pigment Green59 (green pigment)
  • P-5 C.I. I. Pigment Green63 (green pigment)
  • P-6 C.I. I. Pigment Yellow 129 (yellow pigment)
  • P-7 C.I. I. Pigment Yellow 138 (yellow pigment)
  • P-8 C.I. I. Pigment Yellow 139 (yellow pigment)
  • P-9 C.I. I. Pigment Yellow 150 (yellow pigment)
  • P-10 C.I. I.
  • Pigment Yellow 185 (yellow pigment) P-11: C.I. I. Pigment Yellow 215 (yellow pigment) P-12: C.I. I. Pigment Yellow 231 (yellow pigment) P-13: C.I. I. Pigment Yellow233 (yellow pigment) P-14: C.I. I. Pigment Red177 (red pigment) P-15: C.I. I. Pigment Red 254 (red pigment) P-16: C.I. I. Pigment Red 264 (red pigment) P-17: C.I. I. Pigment Red272 (red pigment) P-18: C.I. I. Pigment Red 291 (red pigment) P-19: C.I. I. Pigment Blue 15: 4 (blue pigment) P-20: C.I. I.
  • (resin) B-1 Resin B-1 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 (3-ethyloxetane-3-yl) methyl methacrylate, and 45.4 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) were charged into the reaction vessel to create an atmosphere. The gas was replaced with nitrogen gas. The inside of the reaction vessel is heated to 70 ° C., 6 parts by mass of 3-mercapto-1,2-propanediol is added, and 0.12 parts by mass of AIBN (azobisisobutyronitrile) is further added, and the reaction is carried out for 12 hours. I let you.
  • PMEA propylene glycol monomethyl ether acetate
  • Resin B-2 Resin B-2 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 in a reaction vessel, and the atmosphere gas was replaced with nitrogen gas. The reaction was carried out at 120 ° C. for 5 hours (first step). By measuring the acid value, it was confirmed that 95% or more of the acid anhydride was half-esterified.
  • the compound obtained in the first step is 160 parts by mass in terms of solid content, 200 parts by mass of 2-hydroxypropyl methacrylate, 200 parts by mass of ethyl acrylate, 150 parts by mass of t-butyl acrylate, and 200 parts by mass of 2-methoxyethyl acrylate.
  • 200 parts by mass of methyl acrylate, 50 parts by mass of methacrylic acid, and 663 parts by mass of PGMEA are charged in a reaction vessel, and the inside of the reaction vessel is heated to 80 ° C. to 2,2'-azobis (2,4-dimethylvaleronitrile) 1 .2 parts by mass was added and reacted for 12 hours (second step).
  • the resin having an acid value of 68 mgKOH / g, an ethylenically unsaturated bond base value of 0.62 mmol / g, and a weight average molecular weight of 13000 has the following structure. Obtained B-2.
  • B-6 A material obtained by drying BYK-LPN21116 (quaternary ammonium salt type acrylic block copolymer manufactured by Big Chemie) and adjusting the non-volatile content (solid content concentration) to 100% by mass.
  • Resin B-9 Resin B-9 synthesized by the following method A flask equipped with a cooling tube and a stirrer was charged with 100 parts by mass of PGMEA and replaced with nitrogen. Heated to 80 ° C. and at the same temperature, 100 parts by mass of PGMEA, 15 parts by mass of methacrylic acid, 15 parts by mass of styrene, 5 parts by mass of benzyl methacrylate, 15 parts by mass of 2-hydroxyethyl methacrylate, 23 parts by mass of 2-ethylhexyl methacrylate, N.
  • Resin B-10 Resin B-10 synthesized by the following method A flask equipped with a cooling tube and a stirrer was charged with 100 parts by mass of PGMEA and replaced with nitrogen. Heated to 80 ° C. and at the same temperature, 100 parts by mass of PGMEA, 7 parts by mass of methacrylic acid, 15 parts by mass of styrene, 10 parts by mass of benzyl methacrylate, 20 parts by mass of 2-hydroxyethyl methacrylate, 28 parts by mass of 2-ethylhexyl methacrylate, N.
  • each material was mixed at a ratio according to the following formulations 1 to 4 to produce each resin composition.
  • Some of the dispersions, polymerizable compounds, and photopolymerization initiators listed in the table below were refrigerated at 5 to 10 ° C. Refrigerated dispersions, polymerizable compounds and photopolymerization initiators were taken out of the refrigerator 12 hours or more before the production of the resin composition and controlled to a temperature of 17 to 27 ° C. and a relative humidity of 40 to 80%. It was temporarily stored indoors and used after returning the temperature of these materials to the indoor temperature.
  • each resin composition was produced by the following procedure.
  • a polymerizable compound, a resin, and a solvent were added to a mixing tank equipped with stirring blades installed in a room controlled at a temperature of 17 to 27 ° C. and a relative humidity of 40 to 80%, and stirring was started. Then, a photopolymerization initiator, a polymerization inhibitor, and an additive were added, and the mixture was stirred until the total stirring time was 30 minutes or more. A monomer solution was produced by such a procedure. Next, the dispersion liquid was added to a mixing tank equipped with stirring blades installed in a room controlled by the temperature and humidity, then the above-mentioned monomer liquid was added, and then a surfactant was added and the mixture was stirred for 10 minutes or more.
  • a resin composition was produced by such a procedure. Finally, the obtained resin composition is filtered through a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m, filled in a storage container, and then filled in the voids of the storage container with a gas having an oxygen concentration of 30% by volume. Was stored in a filled state.
  • a nylon filter manufactured by Nippon Pole Co., Ltd.
  • the details other than the dispersion liquid are as follows.
  • the above-mentioned dispersion was used as the dispersion.
  • M-1 Compound with the following structure
  • M-2 Compound with the following structure
  • M-3 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.)
  • M-4 Compound with the following structure
  • W-1 FZ-2122 (Silicone-based surfactant manufactured by Dow Corning Toray Specialty Materials Co., Ltd.)
  • W-2 BYK-330 (Silicone-based surfactant manufactured by Big Chemie)
  • W-3 KF-6001 (Silicone-based surfactant manufactured by Shin-Etsu Chemical Co., Ltd.)
  • W-4 PolyFox PF6320 (OMNOVA, fluorine-based surfactant)
  • W-5 Megafuck F-554 (manufactured by DIC Corporation, fluorine-based surfactant)
  • Average particle size of pigment ⁇ 70 nm 4 70 nm ⁇ average particle size of pigment ⁇ 100 nm 3: 100 nm ⁇ average particle size of pigment ⁇ 150 nm 2: 150 nm ⁇ average particle size of pigment ⁇ 200 nm 1: Average particle size of pigment> 200 nm
  • the film thickness uniformity was evaluated according to the following criteria using the larger value of
  • the resin composition of the example had good dispersibility and film thickness uniformity.
  • the green resin composition was applied onto the support with the underlayer film by a spin coating method so that the film thickness after film formation was 0.4 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes.
  • i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
  • exposure was performed with an exposure amount of 1000 mJ / cm 2 through a mask having a Bayer pattern on each side of 1.4 ⁇ m square.
  • paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).
  • TMAH tetramethylammonium hydroxide
  • the green resin composition was patterned to form green pixels by heating at 200 ° C. for 5 minutes using a hot plate.
  • the red resin composition and the blue resin composition are patterned in the same process via a mask having a dot pattern of 1.4 ⁇ m square on each side to sequentially form red pixels and blue pixels to form green pixels, red pixels and the like.
  • a color filter having blue pixels was formed.
  • green pixels are formed by a Bayer pattern
  • red pixels and blue pixels are formed by a dot pattern in an adjacent region thereof.
  • the obtained color filter was incorporated into a solid-state image sensor according to a known method. This solid-state image sensor had suitable image recognition ability.
  • the green resin composition the resin composition of Example 141 was used.
  • the red resin composition the resin composition of Example 75 was used.
  • the blue resin composition the resin composition of Example 82 was used.
  • composition for forming a lower layer film The composition for forming an underlayer film was produced by mixing the following materials in the ratio shown below and filtering with a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m. I used a thing.
  • -Surfactant A 0.2% by mass PGMEA solution of a compound having the following structure (weight average molecular weight 14000, the numerical value of% indicating the ratio of repeating units is mol%. Fluorosurfactant)

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PCT/JP2021/037301 2020-10-21 2021-10-08 樹脂組成物、樹脂組成物の製造方法、膜の製造方法、光学フィルタの製造方法、固体撮像素子の製造方法および画像表示装置の製造方法 WO2022085485A1 (ja)

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WO2024043110A1 (ja) 2022-08-22 2024-02-29 富士フイルム株式会社 感光性組成物、膜および光センサ
WO2024053471A1 (ja) 2022-09-09 2024-03-14 富士フイルム株式会社 光硬化性組成物、膜、光センサおよび光センサの製造方法
WO2025041642A1 (ja) * 2023-08-23 2025-02-27 富士フイルム株式会社 組成物、膜、光学フィルタ、固体撮像素子および画像表示装置

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JP2018045011A (ja) * 2016-09-13 2018-03-22 富士フイルム株式会社 赤外線吸収剤、組成物、膜、光学フィルタ、積層体、固体撮像素子、画像表示装置および赤外線センサ
JP2018048217A (ja) * 2016-09-20 2018-03-29 富士フイルム株式会社 顔料分散液の製造方法および硬化性組成物の製造方法

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JP2018045011A (ja) * 2016-09-13 2018-03-22 富士フイルム株式会社 赤外線吸収剤、組成物、膜、光学フィルタ、積層体、固体撮像素子、画像表示装置および赤外線センサ
JP2018048217A (ja) * 2016-09-20 2018-03-29 富士フイルム株式会社 顔料分散液の製造方法および硬化性組成物の製造方法

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WO2024043110A1 (ja) 2022-08-22 2024-02-29 富士フイルム株式会社 感光性組成物、膜および光センサ
WO2024053471A1 (ja) 2022-09-09 2024-03-14 富士フイルム株式会社 光硬化性組成物、膜、光センサおよび光センサの製造方法
WO2025041642A1 (ja) * 2023-08-23 2025-02-27 富士フイルム株式会社 組成物、膜、光学フィルタ、固体撮像素子および画像表示装置

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