WO2022024970A1 - 樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 - Google Patents

樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 Download PDF

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Publication number
WO2022024970A1
WO2022024970A1 PCT/JP2021/027486 JP2021027486W WO2022024970A1 WO 2022024970 A1 WO2022024970 A1 WO 2022024970A1 JP 2021027486 W JP2021027486 W JP 2021027486W WO 2022024970 A1 WO2022024970 A1 WO 2022024970A1
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group
compound
resin composition
resin
mass
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PCT/JP2021/027486
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English (en)
French (fr)
Japanese (ja)
Inventor
陽樹 稲部
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富士フイルム株式会社
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Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Priority to KR1020237000016A priority Critical patent/KR20230019488A/ko
Priority to JP2022540280A priority patent/JP7403662B2/ja
Priority to CN202180045671.8A priority patent/CN115776995B/zh
Publication of WO2022024970A1 publication Critical patent/WO2022024970A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • 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
    • C08K5/05—Alcohols; Metal alcoholates
    • C08K5/053—Polyhydroxylic alcohols
    • 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
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/02—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C09D201/06—Coating compositions based on unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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.
  • the present invention also relates to a film using a resin composition, an optical filter, a solid-state image pickup device, and an image display device.
  • Solid-state image sensors such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor) are used in video cameras, digital still cameras, mobile phones with camera functions, and the like. Further, the solid-state image sensor is provided with an optical filter such as a color filter.
  • the optical filter is manufactured by using, for example, a resin composition (see Patent Document 1).
  • an object of the present invention is to provide a resin composition, a film, an optical filter, a solid-state image pickup device, and an image display device capable of forming a film having excellent adhesion to a support.
  • the present invention provides the following.
  • Q 1 represents an ethylenically unsaturated bond-containing group
  • L 1 represents a divalent linking group.
  • the compound A is a compound represented by the formula (1-1), a compound represented by the formula (1-2), a compound represented by the formula (1-3), or a compound represented by the formula (1-3).
  • the compound B is a compound represented by the formula (2-1), a compound represented by the formula (2-2), a compound represented by the formula (2-3), or a compound represented by the formula (2-3).
  • ⁇ 6> The resin composition according to ⁇ 4> or ⁇ 5>, which contains 0.1 to 120 parts by mass of the compound B with respect to 100 parts by mass of the compound A.
  • the invention according to any one of ⁇ 4> to ⁇ 6>, wherein the total content of the compound A and the compound B in the total solid content of the resin composition is 1 to 300 mass ppm. Resin composition.
  • R 32 represents a hydrogen atom or a methyl group.
  • ⁇ 13> A film obtained by using the resin composition according to any one of ⁇ 1> to ⁇ 12>.
  • ⁇ 14> An optical filter containing the film according to ⁇ 13>.
  • An image display device including the film according to ⁇ 13>.
  • the present invention it is possible to provide a resin composition, a film, an optical filter, a solid-state image pickup device, and an image display device capable of forming a film having excellent adhesion to a support.
  • 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
  • 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 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 is characterized by containing a resin, a compound A having a molecular weight of 300 or less represented by the formula (1), and an organic solvent.
  • the resin composition of the present invention it is possible to form a film having excellent adhesion to a support.
  • the resin composition contains the above-mentioned compound A, the hydroxy group of the compound A and the silanol group (SiOH) present on the surface of the support at the time of film formation and the like are unknown.
  • the compound A undergoes a dehydration condensation reaction to form a chemical bond, and the ethylenically unsaturated bond-containing group of compound A reacts with a component in the membrane such as a resin to form a chemical bond. Therefore, it is presumed that a film having excellent adhesion to the support can be formed.
  • the adhesion of the obtained film to the support can be further improved.
  • the resin composition of the present invention preferably contains 0.3 to 2.0% by mass of water. According to this aspect, the adhesion of the obtained membrane to the support can be further improved. The detailed reason why such an effect is obtained is unknown, but it is presumed as follows. That is, it is presumed that the water contained in the resin composition is not completely volatilized at the stage immediately after being applied with a spin coater or the like, and remains in the film.
  • the water remaining in this film contains the hydroxy group of compound A (in the case of further containing compound B, the hydroxy group of compound A or the epoxy group of compound B) and the silanol group existing on the surface of the support ( It is presumed that it functions as a catalyst when forming a chemical bond by causing a dehydration condensation reaction with SiOH) or the like.
  • the amount of water contained in the resin composition exceeds a predetermined amount, the amount of water remaining in the film immediately after application also increases.
  • the hydroxy group of compound A (or the hydroxy group of compound A or the epoxy group of compound B when compound B is further contained) is present on the surface of the support at the time of prebaking.
  • the upper limit of the water content (moisture content) in the resin composition is preferably 1.5% by mass or less, more preferably 1.3% by mass or less.
  • the lower limit of the water content is preferably 0.4% by mass or more, more preferably 0.5% by mass or more.
  • the water content of the resin composition is a value measured by the Karl Fischer measuring method.
  • 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 color pixel, a cyan color pixel, and a yellow pixel.
  • the colored pixels of the color filter can be formed by using a resin composition containing a chromatic color material.
  • 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 is more preferable, and 100 to 400 is particularly preferable.
  • the near-infrared cut filter can be formed by using a resin composition containing a near-infrared absorbing color material.
  • 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 850 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 be used as a resin composition for forming a transparent film, a light-shielding film, or the like.
  • 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. Further, the resin described in paragraph numbers 0041 to 0060 of JP-A-2017-206689 and the resin described in paragraph numbers 0022-0071 of JP-A-2018-010856 can also be used.
  • the resin composition of the present invention preferably contains a resin containing a group represented by the formula (3) (hereinafter, also referred to as a resin (3)). According to this aspect, it is possible to form a film having excellent adhesion to the support.
  • a resin (3) a resin containing a group represented by the formula (3)
  • Q 31 represents an ethylenically unsaturated bond-containing group
  • L 31 represents a divalent linking group
  • R 31 represents a hydrogen atom or a substituent
  • * represents a linking hand.
  • Examples of the ethylenically unsaturated bond-containing group represented by Q 31 of the formula (3) include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamide group.
  • the (meth) allyl group, the (meth) acryloyl group and the (meth) acryloyloxy group are preferable, and the (meth) acryloyloxy group is more preferable.
  • an alkylene group As the divalent linking group represented by L 31 of the formula (3), an alkylene group, -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two or more of these are used. Examples include combined groups.
  • the alkylene group preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms.
  • the alkylene group may be linear, branched or cyclic, but is preferably linear or cyclic.
  • the alkylene group may have a substituent. Examples of the substituent include a hydroxy group and the like.
  • the divalent linking group represented by L 31 is preferably an alkylene group or a group in which two or more alkylene groups are bonded via a linking group, and more preferably an alkylene group.
  • Examples of the linking group that binds the alkylene groups to each other include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.
  • R 31 of the formula (3) represents a hydrogen atom or a substituent.
  • substituent represented by R 31 include residues of various acid anhydrides such as succinic anhydride, maleic anhydride, phthalic anhydride, and tetrahydrophthalic anhydride. It is preferable that R 31 of the formula (3) is a hydrogen atom. According to this aspect, it is possible to form a film having excellent adhesion to the support.
  • the resin (3) is preferably a resin containing a repeating unit represented by the formula (3-1).
  • Q 31 represents an ethylenically unsaturated bond-containing group
  • L 31 and L 32 each independently represent a divalent linking group
  • R 31 represents a hydrogen atom or a substituent
  • R 32 represents a hydrogen atom or a methyl group.
  • Q 31, L 31 and R 31 of the formula (3-1) are synonymous with Q 31 , L 31 and R 31 of the formula (3), respectively.
  • the divalent linking group represented by L 32 in the formula (3-1) 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, and an aliphatic hydrocarbon group is preferable.
  • the number of carbon atoms of the aliphatic hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably linear 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. Examples of the substituent include a hydroxy group and the like.
  • the divalent linking group represented by L 31 is preferably a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a linking group. Examples of the linking group that binds the hydrocarbon groups to each other include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.
  • 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 (3) may be a resin having an acid group. That is, the resin (3) may further have an acid group.
  • 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 a 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 the polyester structure, More preferably, it is a polymer chain containing at least one structure selected from a polyether 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 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 bonding position of Ac- 2 ) with P10.
  • the trivalent linking group represented by L 12b is a hydrocarbon group; a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Examples thereof include a group in which the above is combined with, 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 bonding position of Ac- 2 ) with P10.
  • the trivalent linking group represented by L 12c is a hydrocarbon group; a hydrocarbon group and at least one 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 ) contains 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 polymer 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 preferably contains a repeating unit containing an ethylenically unsaturated bond-containing group in the side chain. Further, the ratio of the repeating unit containing the ethylenically unsaturated bond - containing group in the side chain in all the repeating units constituting P10 is preferably 5% by mass or more, and more preferably 10% by mass or more. , 20% by mass or more is more preferable. 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.
  • the acidic graft resin examples include resins B-1 to B-7 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.
  • a resin 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 acidic graft resin can also be used as a dispersant.
  • Dispersants are also available as commercial products, and specific examples thereof include DISPERBYK series manufactured by BYK Chemie (for example, DISPERBYK-111, 161 etc.) and Solsparse series manufactured by Japan Lubrizol Co., Ltd. (for example, DISPERBYK-111, 161 etc.). For example, Solsparse 76500) and the like. 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 1 to 45% by mass.
  • the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
  • the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
  • the resin composition of the present invention contains a compound A having a molecular weight of 300 or less (hereinafter, also referred to as compound A) represented by the formula (1).
  • Q 1 represents an ethylenically unsaturated bond-containing group
  • L 1 represents a divalent linking group.
  • Examples of the ethylenically unsaturated bond-containing group represented by Q1 of the formula (1) include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamide group.
  • the (meth) allyl group, the (meth) acryloyl group and the (meth) acryloyloxy group are preferable, and the (meth) acryloyloxy group is more preferable.
  • an alkylene group -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two or more of these are used.
  • Examples include combined groups.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably linear 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. Examples of the substituent include a hydroxy group and the like.
  • Examples of the divalent linking group represented by L 1 include a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a linking group, and a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is preferable. Is more preferable.
  • Examples of the linking group that binds the hydrocarbon groups to each other include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.
  • the compound represented by the formula (1-1) is glycerin monomethacrylate
  • the compound represented by the formula (1-2) is glycerin monoacrylate
  • the compound represented by the formula (1-3) is 4-. It is (2,3-dihydroxypropoxy) butyl methacrylate
  • the compound represented by the formula (1-4) is 4- (2,3-dihydroxypropoxy) butyl acrylate.
  • the compound A is a compound represented by the formula (1-1), a compound represented by the formula (1-2), a compound represented by the formula (1-3), or a compound represented by the formula (1-4). It is preferably a compound represented by the formula (1-1), more preferably a compound represented by the formula (1-4), and a compound represented by the formula (1-1). Is more preferable.
  • the content of compound A in the total solid content of the resin composition is preferably 0.1 to 2000 mass ppm.
  • the upper limit is preferably 1000 mass ppm or less, more preferably 500 mass ppm or less, and particularly preferably 250 mass ppm or less.
  • the lower limit is preferably 10 mass ppm or more, more preferably 25 mass ppm or more, and further preferably 50 mass ppm or more.
  • the resin composition of the present invention preferably contains compound B having a molecular weight of 300 or less (hereinafter, also referred to as compound B) represented by the formula (2).
  • compound B represented by the formula (2).
  • Q 2 represents an ethylenically unsaturated bond-containing group
  • L 2 represents a divalent linking group.
  • Examples of the ethylenically unsaturated bond-containing group represented by Q2 of the formula (2) include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamide group.
  • the (meth) allyl group, the (meth) acryloyl group and the (meth) acryloyloxy group are preferable, and the (meth) acryloyloxy group is more preferable.
  • an alkylene group -O-, -CO-, -COO-, -OCO-, -NH-, -S- and two or more of these are used.
  • Examples include combined groups.
  • the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
  • the aliphatic hydrocarbon group may be linear, branched or cyclic, but is preferably linear 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. Examples of the substituent include a hydroxy group and the like.
  • Examples of the divalent linking group represented by L 2 include a hydrocarbon group or a group in which two or more hydrocarbon groups are bonded via a linking group, and a hydrocarbon group is preferable, and an aliphatic hydrocarbon group is preferable. Is more preferable.
  • Examples of the linking group that binds the hydrocarbon groups to each other include -NH-, -CO-, -O-, -COO-, -OCO-, -S-, -NHCO- and -CONH-.
  • the compound B include compounds having the following structures.
  • the compound represented by the formula (2-1) is glycidyl methacrylate
  • the compound represented by the formula (2-2) is glycidyl acrylate
  • the compound represented by the formula (2-3) is 4-hydroxybutyl. It is a methacrylate glycidyl ether
  • the compound represented by the formula (2-4) is 4-hydroxybutyl acrylate glycidyl ether.
  • the compound B is a compound represented by the formula (2-1), a compound represented by the formula (2-2), a compound represented by the formula (2-3), or a compound represented by the formula (2-4). It is preferably a compound represented by the formula (2-1), more preferably a compound represented by the formula (2-4), and a compound represented by the formula (2-1). Is more preferable.
  • the content of compound B in the total solid content of the resin composition is preferably 0.1 to 300 mass ppm.
  • the upper limit is preferably 100 mass ppm or less, and more preferably 10 mass ppm or less.
  • the lower limit is preferably 0.2 mass ppm or more, and more preferably 0.3 mass ppm or more.
  • the upper limit of the content is preferably 60 parts by mass or less, more preferably 30 parts by mass or less, further preferably 10 parts by mass or less, and particularly preferably 8 parts by mass or less.
  • the lower limit of the content is preferably 0.3 parts by mass or more, and more preferably 0.5 parts by mass or more. According to this aspect, it is possible to form a film having better adhesion. Furthermore, the generation of development residue can be suppressed more effectively.
  • the total content of the compound A and the compound B in the total solid content of the resin composition is preferably 1 to 300 mass ppm.
  • the upper limit is preferably 250 mass ppm or less, more preferably 200 mass ppm or less, further preferably 100 mass ppm or less, and even more preferably 15 mass ppm or less.
  • the lower limit is preferably 2 mass ppm or more, more preferably 3 mass ppm or more, and further preferably 5 mass ppm or more.
  • the resin composition of the present invention can contain a polyfunctional polymerizable monomer having two or more ethylenically unsaturated bond-containing groups (hereinafter, also referred to as a polyfunctional polymerizable monomer).
  • a polyfunctional polymerizable monomer having two or more ethylenically unsaturated bond-containing groups
  • examples of the ethylenically unsaturated bond-containing group of the polyfunctional polymerizable monomer include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and a (meth) acryloylamide group.
  • a (meth) allyl group, a (meth) acryloyl group and a (meth) acryloyloxy group are preferable, and a (meth) acryloyloxy group is more preferable.
  • the polyfunctional polymerizable monomer used in the present invention is preferably a radically polymerizable monomer.
  • the molecular weight of the polyfunctional polymerizable monomer 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 polyfunctional polymerizable monomer 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 is not ethylenically. It is more preferable that the compound contains 3 to 6 saturated bond-containing groups. Further, the polyfunctional polymerizable monomer is preferably a (meth) acrylate compound having 3 to 15 functionalities, and more preferably a (meth) acrylate compound having 3 to 6 functionalities.
  • polyfunctional polymerizable monomer examples include paragraph numbers 0995 to 0108 of JP2009-288705A, paragraph 0227 of JP2013-029760A, and paragraph numbers 0254 to 0257 of JP2008-292970.
  • Japanese Patent Laid-Open Nos. 2013-253224, Paragraph Nos. 0034 to 0038, Japanese Patent Laid-Open No. 2012-208494, Paragraph Nos. 0477, Japanese Patent Laid-Open No. 2017-048637, Japanese Patent No. 6057891, Japanese Patent No. 6031807, Japanese Patent Application Laid-Open No. 2017- Examples include the compounds described in Japanese Patent Publication No. 194662, the contents of which 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.
  • SR454 and SR499 commercially available from Sartmer
  • the polymerizable monomer diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available M-460; manufactured by Toa Synthetic Co., Ltd.), pentaerythritol tetraacrylate (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), NK Ester A-TMMT), 1,6-Hexanediol Diacrylate (manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Toa Synthetic Co., Ltd.) ), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured
  • polyfunctional polymerizable monomer examples include trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide modified tri (meth) acrylate, trimethylolpropane ethylene oxide modified tri (meth) acrylate, and isocyanuric acid ethylene oxide modified tri (meth) acrylate. It is also preferable to use a trifunctional (meth) acrylate compound such as pentaerythritol tri (meth) acrylate. Commercially available trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305.
  • M-303, M-452, M-450 manufactured by Toa Synthetic Co., Ltd.
  • NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT manufactured by Shin Nakamura Chemical Industry Co., Ltd.
  • KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.
  • a polymerizable monomer having an acid group can also be used.
  • the resin composition 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.
  • Examples of commercially available products of the polymerizable monomer having an acid group include Aronix M-305, M-510, M-520, and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
  • the acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g.
  • a polymerizable monomer having a caprolactone structure can also be used.
  • the polymerizable monomer having a caprolactone structure is commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples thereof include DPCA-20, DPCA-30, DPCA-60, and DPCA-120.
  • a polymerizable monomer having an alkyleneoxy group can also be used.
  • a polymerizable monomer having an alkyleneoxy group a polymerizable monomer having an ethyleneoxy group and / or a propyleneoxy group is preferable, a polymerizable monomer 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 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and a trifunctional (meth) having three isobutyleneoxy groups.
  • KAYARAD TPA-330 which is an acrylate, and the like.
  • a polymerizable monomer having a fluorene skeleton can also be used.
  • examples of commercially available products of the polymerizable monomer 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 polyfunctional polymerizable monomer it is also preferable to use a compound that does not substantially contain an environmentally regulatory substance such as toluene.
  • an environmentally regulatory 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.).
  • Examples of the polyfunctional polymerizable monomer include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Patent Application Laid-Open No. 51-037193, Japanese Patent Laid-Open No. 02-032293, and Japanese Patent Application Laid-Open No. 02-016765. Further, urethane compounds having an ethylene oxide-based skeleton described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418 are also suitable.
  • the polyfunctional polymerizable monomers are UA-7200 (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH- Commercially available products such as 600, T-600, AI-600, and LINK-202UA (manufactured by Kyoeisha Chemical Co., Ltd.) can also be used.
  • the polyfunctional polymerizable monomer used in the resin composition of the present invention contains a trifunctional or lower polymerizable monomer C1 containing two or three ethylenically unsaturated bond-containing groups and four ethylenically unsaturated bond-containing groups. It is preferable to contain the above-mentioned tetrafunctional or higher polymerizable monomer C2. According to this aspect, the curing shrinkage of the film is appropriately suppressed and the adhesion to the support is improved, so that the effect of the present invention is more remarkably exhibited.
  • the ratio of the two is preferably 10 to 1000 parts by mass, preferably 30 to 300 parts by mass, based on 100 parts by mass of the polymerizable monomer C1. It is more preferably parts, and even more preferably 50 to 200 parts by mass.
  • the content of the polyfunctional polymerizable monomer in the total solid content of the resin composition is preferably 0.1 to 40% 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 30% by mass or less, more preferably 20% by mass or less.
  • the resin composition of the present invention can contain 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 light 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.
  • oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like.
  • 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.
  • RX2 contains 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 and an aryl.
  • RX3 to RX14 independently represent hydrogen atoms or substituents; However, at least one of RX10 to RX14 is an electron-withdrawing group.
  • 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 functional 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 an organic solvent or the like is improved, the precipitation is less likely to occur with time, and the stability of the resin composition with time is 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 30% 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 20% by mass or less, more preferably 15% by mass or less.
  • only one type of photopolymerization initiator may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
  • the resin composition of the present invention preferably contains a coloring material.
  • the coloring material include a white coloring material, a black coloring material, a chromatic coloring material, and a near-infrared absorbing coloring material.
  • the white color material includes not only pure white color material but also a light gray color material close to white (for example, grayish white, light gray, etc.).
  • the coloring material preferably contains at least one selected from the group consisting of a chromatic color material, a black color material, and a near-infrared absorbing color material, and more preferably contains a chromatic color material. Further, the content of the chromatic color material in the color material is preferably 60% by mass or more, and more preferably 80% by mass or more.
  • a resin composition can be preferably used as a resin composition for forming colored pixels of a color filter.
  • the coloring material may be a pigment or a dye. Pigments and dyes may be used in combination. Further, the pigment may be either an inorganic pigment or an organic pigment. Further, as the pigment, an inorganic pigment or a material in which a part of the organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing the inorganic pigment or the organic-inorganic pigment with an organic chromophore, the hue design can be facilitated.
  • 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 an image 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 content of the pigment in the coloring material is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and preferably 90% by mass or more. Especially preferable.
  • chromatic color material examples include a color material having a maximum absorption wavelength in the wavelength range of 400 to 700 nm. For example, a yellow color material, an orange color material, a red color material, a green color material, a purple color material, a blue color material, and the like can be mentioned. Specific examples of the chromatic color material include those shown below.
  • C. I. Pigment Green 7,10,36,37,58,59,62,63,64 (phthalocyanine type), 65 (phthalocyanine type), 66 (phthalocyanine type) and other green pigments.
  • halogenated zinc phthalocyanine having an average number of halogen atoms in one molecule of 10 to 14, a bromine atom of 8 to 12, and a chlorine atom of 2 to 5 on average. Pigments can also be used. Specific examples include the compounds described in International Publication No. 2015/118720. Further, as a green color material, the compound described in Chinese Patent Application No. 1069090227, the phthalocyanine compound having a phosphoric acid ester described in International Publication No. 2012/102395 as a ligand, and Japanese Patent Application Laid-Open No. 2019-008014. , The phthalocyanine compound described in JP-A-2018-180023, the compound described in JP-A-2019-038958, and the like can also be used.
  • an aluminum phthalocyanine compound having a phosphorus atom can also be used as the blue color material. 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 having the following structure can also be used.
  • 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 color material 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 Patent No. 6248838.
  • Diketopyrrolopyrrole compound described in WO2012 / 102399 Diketopyrrolopyrrole compound described in WO2012 / 117965, naphtholazo compound described in JP2012-229344, patent No. 6516119.
  • the red color material described in Japanese Patent No. 6525101, the red color material described in Japanese Patent No. 6525101, and the like can also be used.
  • 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.
  • diarylmethane compound described in Japanese Patent Publication No. 2020-504758 can also be used as the coloring material.
  • a dye can be used as a chromatic color material.
  • the dye is not particularly limited, and known dyes can be used.
  • pyrazole azo compound, anilino azo compound, triarylmethane compound, anthraquinone compound, anthrapyridone compound, benzylidene compound, oxonol compound, pyrazorotriazole azo compound, pyridone azo compound, cyanine compound, phenothiazine compound, pyrrolopyrazole azomethine compound, xanthene compound examples thereof include phthalocyanine compounds, benzopyran compounds, indigo compounds and pyromethene compounds.
  • 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 chromatic color material may be used in combination of two or more.
  • a green color may be formed in combination with Pigment Yellow 185
  • a green color may be formed in combination with Pigment Yellow 185.
  • black may be formed by a combination of two or more kinds of chromatic color materials.
  • a combination include the following aspects (1) to (7).
  • a near-infrared transmission filter can be used by using such a resin composition. Can be formed.
  • An embodiment containing a red color material, a blue color material, a yellow color material, a purple color material, and a green color material (5) An embodiment containing a red color material, a blue color material, a yellow color material, and a green color material. (6) An embodiment containing a red color material, a blue color material, and a green color material. (7) An embodiment containing a yellow color material and a purple color material.
  • White coloring materials include titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, Examples thereof include hollow resin particles and inorganic pigments (white pigments) such as zinc sulfide.
  • the white pigment is preferably particles having a titanium atom, and more preferably titanium oxide.
  • 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 core particles composed of polymer particles, and core and shell composite particles composed of a shell layer composed of inorganic nanoparticles 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.
  • Black color material The black color material is not particularly limited, and known materials can be used.
  • examples of the inorganic black coloring material include carbon black, titanium black, graphite and the like, 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. For example, it is possible to coat the surface of titanium black with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, it is also possible to treat with a water-repellent substance as shown in Japanese Patent Application Laid-Open No.
  • Titanium black preferably has a small primary particle size and an average primary particle size of each particle. Specifically, it is preferable that the average primary particle size is 10 to 45 nm. Titanium black can also be used as a dispersion. For example, 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. Regarding the above dispersion, the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
  • Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13RN, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilak D (Tilak) D (trade name: manufactured by Mitsubishi Materials Corporation).
  • Examples of the organic black coloring material include a bisbenzofuranone compound, an azomethine compound, a perylene compound, an azo compound and the like, and a bisbenzofuranone compound and a perylene compound are preferable. Examples of the bisbenzofuranone compound are described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No.
  • the near-infrared absorbing color material is preferably a pigment, more preferably an organic pigment. Further, the near-infrared absorbing color material is preferably a compound having a maximum absorption wavelength in the range of more than 700 nm and 1400 nm or less. The maximum absorption wavelength of the near-infrared absorbing color material is preferably 1200 nm or less, more preferably 1000 nm or less, and further preferably 950 nm or less.
  • the near-infrared absorbing color material 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. It is more preferably 0.03 or less, and particularly preferably 0.02 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 color material and the value of the absorbance at each wavelength are values obtained from the absorption spectrum of the film formed by using the photosensitive composition containing the near-infrared absorbing color material.
  • the near-infrared absorbing color material is not particularly limited, but is limited to pyrolopyrrole compound, cyanine compound, squarylium compound, phthalocyanine compound, naphthalocyanine compound, quaterylene compound, merocyanine compound, croconium compound, oxonol compound, iminium compound, dithiol compound, and tria.
  • Examples thereof include a reelmethane compound, a pyrromethene compound, an azomethin compound, an anthraquinone compound, a dibenzofuranone compound, and a dithiolene metal complex.
  • Examples of the pyrrolopyrrole compound include the compounds described in paragraphs 0016 to 0058 of JP2009-263614, the compounds described in paragraphs 0037-0052 of JP2011-066731A, and International Publication No. 2015/166783. Examples thereof include the compounds described in paragraphs 0010 to 0033.
  • Examples of the squarylium compound include the compounds described in paragraphs 0044 to 0049 of JP2011-208101A, the compounds described in paragraphs 0060 to 0061 of Patent No. 6065169, and paragraph numbers 0040 of International Publication No. 2016/181987. , The compound described in JP-A-2015-176046, the compound described in paragraph No. 0072 of International Publication No.
  • JP2012-077153 the oxytitanium phthalocyanine described in JP2006-343631, and paragraphs 0013 to 0029 of JP2013-195480.
  • Examples of the naphthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-07715.
  • dithiolene metal complex include the compounds described in Japanese Patent No. 5733804.
  • Examples of the near-infrared absorbing color material include a squarylium compound described in JP-A-2017-197437, a squarylium compound described in JP-A-2017-025311, a squarylium compound described in International Publication No. 2016/154782, and Patent No. 5884953.
  • Squarylium compound described in Japanese Patent Publication No. 6036689 Squalylium compound described in Japanese Patent No. 581604, Squalylium compound described in International Publication No. 2017/213047, Squarylium compound described in paragraphs 0090 to 0107 of International Publication No.
  • Concatenated squalylium compound compound having a pyrrolbis-type squalylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole-type squalylium compound described in JP-A-2017-082029, JP-A-2017-066120
  • the vanadium phthalocyanine compound described in No. 2020/071486, the phthalocyanine compound described in International Publication No. 2020/071470, and the like can also be used.
  • the content of the coloring material in the total solid content of the resin composition is preferably 20 to 90% by mass.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more.
  • the upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less.
  • the content of the pigment in the total solid content of the resin composition is preferably 20 to 90% by mass.
  • the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, and further preferably 50% by mass or more.
  • the upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less.
  • the content of the dye in the coloring material is preferably 50% by mass or less, more preferably 40% by mass or less, and further preferably 30% by mass or less.
  • the resin composition of the present invention preferably contains a pigment derivative.
  • 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 derivatives 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.
  • the acid group include a sulfo group, a carboxyl group, a phosphoric 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 basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group.
  • 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 contained.
  • 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 Application Laid-Open No.
  • the content of the pigment derivative in the total solid content of the resin composition is preferably 0.3 to 20% by mass.
  • the lower limit is preferably 0.6% by mass or more, and more preferably 0.9% by mass or more.
  • the upper limit is preferably 15% by mass or less, more preferably 12.5% by mass or less, and further preferably 10% by mass or less.
  • the content of the pigment derivative is preferably 1 to 30 parts by mass with respect to 100 parts by mass of the pigment.
  • the lower limit is preferably 2 parts by mass or more, and more preferably 3 parts by mass or more.
  • the upper limit is preferably 25 parts by mass or less, more preferably 20 parts by mass or less, and further preferably 15% by mass or less.
  • only one pigment derivative may be used, or two or more pigment derivatives 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 contains a compound having three or more basic groups in one molecule, an amine value of 2.7 mmol / g or more, and a molecular weight of 100 or more (hereinafter, also referred to as a specific amine compound). You can also.
  • the molecular weight of the specific amine compound 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 the specific amine compound 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 the specific amine compound is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and further preferably 15 mmol / g or more.
  • the number of basic groups contained in the specific amine compound is preferably 4 or more, more preferably 6 or more, and further preferably 10 or more.
  • the basic group of the specific amine compound is preferably an amino group.
  • the specific amine compound is preferably a compound having a primary amino group, more preferably a compound containing a primary amino group and a tertiary amino group, respectively, and a primary amino group and a secondary amino. It is more preferable that the compound contains a group and a tertiary amino group, respectively.
  • the amino group contained in the specific amine compound may be a cyclic amino group.
  • the cyclic amino group may be an aliphatic cyclic amino group such as a piperidino group or an aromatic cyclic amino group such as a pyridyl group.
  • the cyclic amino group is preferably a cyclic amino group having a 5-membered ring or a 6-membered ring structure, more preferably a cyclic amino group having a 6-membered ring structure, and an aliphatic cyclic amino having a 6-membered ring structure. It is more preferably a group.
  • the cyclic amino group preferably has a hindered amine structure, and particularly preferably has a 6-membered ring hindered amine structure.
  • the hindered amine structure it is preferable that the two carbon atoms in the ring structure adjacent to the nitrogen atom of the cyclic amino group have a substituent such as an alkyl group.
  • the cyclic amino group having a hindered amine structure include 1,2,2,6,6-pentamethylpiperidyl group, 2,2,6,6-tetramethylpiperidyl group and 1,2,6,6-trimethylpiperidyl.
  • 2,6-dimethylpiperidyl group 1-methyl-2,6-di (t-butyl) piperidyl group, 2,6-di (t-butyl) piperidyl group, 1,2,2,5,5- Examples thereof include a pentamethylpyrrolidyl group and a 2,2,5,5-tetramethylpyrrolidyl group.
  • 1,2,2,6,6-pentamethylpiperidyl group or 2,2,6,6-tetramethylpiperidyl group is preferable, and 1,2,2,6,6-pentamethylpiperidyl group is preferable. More preferred.
  • the specific amine compound is preferably polyalkyleneimine because it can further improve the storage stability of 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 number of carbon atoms of the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.
  • Specific examples of the alkyleneimine include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and the like, preferably ethyleneimine or propyleneimine, and more preferably ethyleneimine.
  • the polyalkyleneimine is particularly preferably polyethyleneimine. Further, 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 the specific amine compound 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 the specific amine compound is preferably 0.5 to 10 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 8 parts by mass or less, more preferably 7% by mass or less, and further preferably 5 parts by mass or less.
  • the content of the specific amine compound is preferably 0.5 to 50 parts by mass with respect to 100 parts by mass of the graft resin having an acid group.
  • the lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and further preferably 3 parts by mass or more.
  • the upper limit is preferably 45 parts by mass or less, more preferably 40% by mass or less, and further preferably 30 parts by mass or less.
  • 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).
  • examples of the epoxy compound are described in paragraphs 0034 to 0036 of JP2013-011869, paragraph numbers 0147 to 0156 of JP2014-0435556, and paragraph numbers 0083 to 0092 of JP2014-089408.
  • Compounds, compounds described in JP-A-2017-179172 can also be used. These contents are incorporated in the present specification.
  • 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). But it may be.
  • the weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is preferably 10,000 or less, more 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 type.
  • 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 Dicelle Co., Ltd.
  • EPICLON N-695 manufactured by DIC Corporation
  • Marproof G-0150M Marproof G-0150M, G-0105SA, G-0130SP, G. -0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, G-01758 (all manufactured by Nichiyu Co., Ltd., 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, preferably 0.5% by mass or more, and more preferably 1% by mass or more.
  • the upper limit is, for example, preferably 15% by mass or less, and more preferably 10% by mass or less.
  • the compound having a cyclic ether group 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 thereof is within the above range.
  • the resin composition of the present invention contains an organic solvent.
  • the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, hydrocarbon-based solvents and the like.
  • paragraph No. 0223 of International Publication No. 2015/166779 can be referred to, the contents of which are incorporated herein.
  • an ester solvent substituted with a cyclic alkyl group and a ketone solvent substituted with a cyclic alkyl group can also be preferably used.
  • organic solvent examples include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -Heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol acetate, butylcarbi Tall acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-di
  • aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may need to be reduced for environmental reasons (for example, 50 parts by mass (parts) with respect to the total amount of organic solvent. Per millision) or less, 10 mass ppm or less, or 1 mass ppm or less).
  • an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per parts) or less. If necessary, an organic solvent at the mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by, for example, Toyo Synthetic Co., Ltd. (The Chemical Daily, November 13, 2015).
  • Examples of the method for removing impurities such as metals from the organic solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
  • the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene or nylon.
  • the organic solvent may contain isomers (compounds having the same number of atoms but different structures). Further, only one kind of isomer may be contained, or a plurality of kinds may be contained.
  • the content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially free of peroxide.
  • the content of the organic solvent in the resin composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
  • the resin composition of the present invention does not substantially contain 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 corresponding 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.
  • These distillation methods include a raw material stage, a product obtained by reacting the raw materials (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a resin composition stage prepared by mixing these compounds. It is possible at any stage of.
  • 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 curing accelerator when the curing accelerator is contained, the content of the curing accelerator in the total solid content of the resin composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
  • the resin composition of the present invention can contain an ultraviolet absorber.
  • 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. Details thereof are described in paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-066814, and paragraph numbers 0061 to 0080 of JP2016-162946. These compounds are incorporated herein by reference.
  • Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.).
  • Examples of the benzotriazole compound include the MYUA series made of Miyoshi Oil & Fat (The Chemical Daily, February 1, 2016).
  • the ultraviolet absorber the compounds described in paragraphs 0049 to 0059 of Japanese Patent No. 6268967 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 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 Propylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-502), 3-methacryloxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co.,
  • the silane coupling agent 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 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass. preferable.
  • the silane coupling agent 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 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 silicon-based surfactant can be used.
  • the 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 liquid characteristic (particularly, fluidity) is further improved by containing the fluorine-based surfactant in the resin composition in which the surfactant is preferably a fluorine-based surfactant, and the liquid saving property is further improved.
  • the surfactant is preferably a fluorine-based surfactant
  • the liquid saving property is further improved.
  • 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, Megafuck 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.
  • the 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 the description in JP-A-2016-216602 can be referred to, and the content thereof is 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 compounds described in paragraphs 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965, for example, Megafuck RS-101, RS-102, RS-718K manufactured by DIC Corporation. , RS-72-K and the like. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
  • nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and the like.
  • Examples of the silicon-based surfactant include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torre Silicone SH28PA, Torre Silicone SH29PA, Torre Silicone SH30PA, Torre Silicone SH8400 (all of which are Toray Dow Corning Co., Ltd.). ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, manufactured by Momentive Performance Materials), KP-341, KF-6001, KF-6002 (above, (Shinetsu Silicone Co., Ltd.), BYK307, BYK323, BYK330 (all 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.
  • the resin composition of the present invention 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 may be used as a sensitizer, a curing accelerator, a thermosetting accelerator, a plasticizer and other auxiliaries (for example, conductive particles, a filler, an antifoaming agent, a flame retardant), if necessary. , Leveling agent, peeling accelerator, fragrance, surface tension adjusting agent, chain transfer agent, etc.) may be contained. By appropriately containing these components, properties such as film physical characteristics can be adjusted. These components are described in, for example, paragraph No. 0183 or later of JP2012-003225A (paragraph number 0237 of the corresponding US Patent Application Publication No. 2013/0034812), paragraph 2008-250074. The descriptions of Nos.
  • 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.
  • Examples of commercially available products of latent antioxidants include ADEKA ARKULS GPA-5001 (manufactured by ADEKA Corporation).
  • 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 perfluoroalkyl sulfonic acid and its salt and a compound that can substitute for perfluoroalkyl carboxylic acid and its salt, perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic 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 JP-A-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 prepared by mixing the above-mentioned components.
  • all the components may be simultaneously dissolved and / or dispersed in an organic solvent to prepare a resin composition, or if necessary, each component may be appropriately dissolved in two or more solutions or dispersions. However, these may be mixed at the time of use (at the time of application) to prepare a resin composition.
  • the mechanical force used for dispersing the organic pigment includes compression, squeezing, impact, shearing, cavitation and the like.
  • Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like.
  • the process and disperser for dispersing organic pigments are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology and industry centered on suspension (solid / liquid dispersion system)". Practical application The process and disperser described in Section No.
  • the particles may be miniaturized in the salt milling step.
  • 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.
  • 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)
  • 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 film of the present invention is a film obtained from the above-mentioned resin composition of the present invention.
  • the film thickness of the film of the present invention can be appropriately adjusted according to the intended 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 of the present invention can be used for 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 of the present invention can be preferably used as a colored pixel of a color filter. Examples of the colored pixel include a red pixel, a green pixel, a blue pixel, a magenta color pixel, a cyan color pixel, and a yellow pixel.
  • the film of the present invention can be produced through a step of applying the resin composition of the present invention.
  • the film manufacturing method preferably further includes a step of forming a pattern (pixel). Examples of 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) and ArF line (wavelength 193 nm), 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 oxygen concentration performed 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, and for example, the illuminance may be 10,000 W / m 2 when the oxygen concentration is 10% by volume, the illuminance may be 20000 W / m 2 when the oxygen concentration is 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 optical filter of the present invention has the above-mentioned film of the present invention.
  • the type of the 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 optical filter can be used for solid-state image pickup devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), image display devices, and the like.
  • CCD charge-coupled device
  • CMOS complementary metal oxide semiconductor
  • the film thickness of the film of the present invention 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 width of the pixels included in the optical filter is preferably 0.4 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 Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
  • each pixel included in the optical filter has high flatness.
  • the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less.
  • the lower limit is not specified, but it is preferably 0.1 nm or more, for example.
  • the surface roughness of the pixel can be measured using, for example, an AFM (atomic force microscope) Measurement 3100 manufactured by Veeco.
  • the contact angle of water on the pixel can be appropriately set to a preferable value, but is typically in the range of 50 to 110 °.
  • the contact angle can be measured using, for example, a contact angle meter CV-DT ⁇ A type (manufactured by Kyowa Interface Science Co., Ltd.). Further, it is preferable that the volume resistance value of the pixel is high. Specifically, the volume resistance value of the pixel is preferably 109 ⁇ ⁇ cm or more, and more preferably 10 11 ⁇ ⁇ cm or more. The upper limit is not specified, but it is preferably 10 14 ⁇ ⁇ cm or less, for example. The volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by Advantest).
  • a protective layer may be provided on the surface of the film of the present invention.
  • various functions such as oxygen blocking, low reflection, prohydrophobicization, and shielding of light of a specific wavelength (ultraviolet rays, near infrared rays, etc.) can be imparted.
  • the thickness of the protective layer is preferably 0.01 to 10 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • Examples of the method for forming the protective layer include a method of applying a resin composition for forming a protective layer to form the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive.
  • the components constituting the protective layer include (meth) acrylic resin, en-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, and polyimide.
  • Resin polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluorine Examples thereof include resins, polycarbonate resins, polyacrylonitrile resins, cellulose resins, Si, C, W, Al 2 O 3 , Mo, SiO 2 , Si 2 N 4 , and the like, and two or more of these components may be contained.
  • the protective layer in the case of a protective layer for the purpose of blocking oxygen, it is preferable that the protective layer contains a polyol resin, SiO 2 , and Si 2 N 4 . Further, in the case of a protective layer for the purpose of reducing reflection, it is preferable that the protective layer contains a (meth) acrylic resin and a fluororesin.
  • the protective layer may be an additive such as organic / inorganic fine particles, an absorber for light of a specific wavelength (for example, ultraviolet rays, near infrared rays, etc.), a refractive index adjusting agent, an antioxidant, an adhesive, and a surfactant, if necessary. May be contained.
  • organic / inorganic fine particles include polymer fine particles (for example, silicone resin fine particles, polystyrene fine particles, melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, and titanium oxynitride. , Magnesium fluoride, hollow silica, silica, calcium carbonate, barium sulfate and the like.
  • a known absorber can be used as the absorber of light having a specific wavelength.
  • the content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, more preferably 1 to 60% by mass, based on the total mass of the protective layer
  • the protective layer described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.
  • the optical filter may have a base layer.
  • 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.
  • the surface contact angle of the base layer can be adjusted by, for example, adding a surfactant.
  • the optical 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 solid-state image sensor of the present invention has the above-mentioned film of the present invention.
  • the configuration of the solid-state image pickup device of the present invention is not particularly limited as long as it includes the film of the present invention and functions as a solid-state image pickup device, 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 image display device of the present invention has the above-mentioned film of the present invention.
  • the image display device include a liquid crystal display device and an organic electroluminescence display device.
  • the 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".
  • the acid value of the resin was determined by neutralization titration using an aqueous sodium hydroxide solution. Specifically, the obtained resin is dissolved in a solvent and titrated with an aqueous solution of sodium hydroxide using a potential difference measurement method to calculate the number of millimoles of the acid contained in 1 g of the solid content of the resin, and then the number of millimoles is calculated. , The value was determined by multiplying the molecular weight of potassium hydroxide (KOH) by 56.1.
  • C C value (base value containing ethylenically unsaturated bond)>
  • the C C value (base value containing ethylenically unsaturated bond) of the resin was calculated from the raw materials used for the synthesis of the resin.
  • a mixture of 4 parts by mass of Noate (“Perbutyl O” manufactured by Nippon Oil &Fats; hereinafter referred to as “PBO”) and 60 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) was prepared by stirring.
  • PBO Perbutyl O
  • PGMEA propylene glycol monomethyl ether acetate
  • n-DM n-dodecanethiol
  • the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring.
  • the reaction vessel After the temperature of the reaction vessel became stable at 90 ° C., dropping from the monomer dropping tank and the chain transfer agent dropping tank to the reaction tank was started. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, the reaction solution was cooled to room temperature. 1000 parts by mass of water was added to the cooled reaction solution, the precipitated solid (polymer) was collected by filtration, and the collected solid was washed twice with 100 parts by mass of ethanol and once with 500 parts by mass of water. The resin B-1 having the following structure was obtained. The weight average molecular weight (Mw) of the obtained resin B-1 was 18,500, and the acid value was 106 mgKOH / g.
  • Mw weight average molecular weight
  • the purified resin B-1 obtained by the above procedure was dissolved in PGMEA to adjust the resin concentration (solid content concentration) to 30% by mass to produce a resin solution (B-1-c).
  • the resin solution (B-1-c) is one to which neither GLA nor GMA component is added.
  • the contents of GLA and GMA in each resin solution are the results quantified by liquid high performance chromatography (HPLC). Since the lower limit of detection of each component by the HPLC method was 0.1 mass ppm, when it was lower than the lower limit of detection, it was described as " ⁇ 0.1" in the table below. Further, among the components corresponding to compound A contained in each resin solution, the components other than GLA were below the lower limit of detection. Therefore, the content of GLA corresponds to the content of compound A. Further, among the components corresponding to compound B contained in each resin composition, the components other than GMA were below the lower limit of detection. Therefore, the total amount of GMA corresponds to the content of compound B.
  • HPLC liquid high performance chromatography
  • Resin B-2 having the following structure was obtained.
  • the weight average molecular weight (Mw) of the obtained resin B-2 was 18,000, and the acid value was 32 mgKOH / g.
  • the PGMEA solution of GLA and the PGMEA solution of GMA are further added, and the resin concentration (solid content) of the finally obtained resin solution is added.
  • a resin solution (B-2-1) was produced so that the concentration) was 30% and the content of each component was the amount shown in the table below.
  • the components corresponding to compound A contained in the resin solution (B-2-1) the components other than GLA were below the lower limit of detection. Therefore, the content of GLA corresponds to the content of compound A.
  • the components other than GMA were below the lower limit of detection. Therefore, the total amount of GMA corresponds to the content of compound B.
  • the resin B-3 having the following structure was obtained.
  • the weight average molecular weight (Mw) of the obtained resin B-3 was 17,200, and the acid value was 70 mgKOH / g.
  • one of * 1 and * 2 is bonded to * 5 or * 6 to form a polyester main chain, and the other is bonded to * 3 or * 4 to form a polyester main chain. Is forming.
  • * 3 and * 4 one of them is bonded to * 1 or * 2 to form a polyester main chain, and the other is integrated with an OH group to form a carboxylic acid.
  • * 5 and * 6 is bonded to * 1 or * 2 to form a polyester main chain, and the other is integrated with an OH group to form a carboxylic acid.
  • the derivative 1 is a compound represented by the following structural formula.
  • the resin solution B-5-1 is a 30% by mass PGMEA solution of resin B-5 (weight average molecular weight 23000, acid value 50 mgKOH / g) having the following structure.
  • TiB is titanium oxynitride particles (manufactured by Mitsubishi Materials Electronics Co., Ltd.), CB is carbon black particles (manufactured by Cabot, average primary particle diameter 15 nm), and ZrO 2 is zirconium oxide particles (manufactured by Shin Nihon Denko Co., Ltd., average 1).
  • TiO 2 is titanium oxide particles (manufactured by Ishihara Sangyo Co., Ltd., TTO-51 (C), average primary particle diameter 10 to 30 nm, surface alumina / stearic acid treated product).
  • Derivatives 2 to 7 are compounds represented by the following structural formulas.
  • Pigment dispersion (GB-1): 44.5 parts by mass Pigment dispersion (YB-1): 40.5 parts by mass Resin solution (B-1-1): 2.3 parts by mass Polymerizable monomer (M-1) ): 1.2 parts by mass Photopolymerization initiator (I-1): 0.6 parts by mass Ultraviolet absorber (U-1): 0.4 parts by mass Surface active agent (S-1): 4.2 parts by mass Polymerization Initiator (IN-1): 0.005 parts by mass PGMEA: 6.3 parts by mass
  • Polymerizable Monomer (M-1): 7: 3 Mixture of Dipentaerythritol Hexaacrylate (DPHA) and Dipentaerythritol Pentaacrylate (KAYARAD DPHA, manufactured by Nippon Kayaku)
  • Photopolymerization Initiator (I-1): Irgacure OXE-01 (manufactured by BASF)
  • UV absorber (U-1): Triazine-based UV absorber "Tinuvin 477” (manufactured by BASF)
  • Polymerization inhibitor (IN-1): p-methoxyphenol
  • composition layer after exposure was developed using a developing device (Act8 manufactured by Tokyo Electron Limited).
  • a developing device Act8 manufactured by Tokyo Electron Limited
  • TMAH tetramethylammonium hydroxide
  • shower development was performed at 23 ° C. for 60 seconds.
  • rinsing was performed in a spin shower using pure water, then spin-dried, and then heat-treated (post-baked) for 5 minutes using a hot plate at 200 ° C. to obtain a pattern.
  • ⁇ E (E2-E1) between the minimum exposure amount E1 required to form a pattern having a width of 100 ⁇ m and a length of 1000 ⁇ m and the minimum exposure amount E2 required to make all the above-mentioned patterns adhere to each other was obtained and described below. Adhesion was evaluated based on the criteria. The smaller ⁇ E is, the better the adhesion is. The fact that the patterns were in close contact with each other and the size of the patterns were observed using an optical microscope (magnification: 200 times). -Evaluation criteria- 5: ⁇ E is 0 mJ / cm 2 . 4: ⁇ E is more than 0 mJ / cm 2 and 100 mJ / cm 2 or less.
  • ⁇ E exceeds 100 mJ / cm 2 .
  • At an exposure rate of 2: 50 to 1700 mJ / cm 2 at least one pattern of lines having a width of 100 ⁇ m and a length of 1000 ⁇ m could be formed, but not all 25 patterns could be formed.
  • With an exposure amount of 1: 50 to 1700 mJ / cm 2 a pattern having a width of 100 ⁇ m and a length of 1000 ⁇ m could not be formed. (All peeled off)
  • TMAH tetramethylammonium hydroxide
  • Exposure light KrF line (wavelength 248 nm) Maximum instantaneous illuminance: 250,000,000,000 W / m 2 (Average illuminance: 30,000 W / m 2 ) Pulse width: 30 nanoseconds Frequency: 4 kHz
  • S-2 Futergent 710FM (manufactured by NEOS Co., Ltd.)
  • S-3 Futergent 610FM (manufactured by NEOS Co., Ltd.)
  • S-4 Futergent 601AD (manufactured by NEOS Co., Ltd.)
  • S-5 Futergent 601ADH2 (manufactured by NEOS Co., Ltd.)
  • S-6 Futergent 602A (manufactured by NEOS Co., Ltd.)
  • S-7 Futergent 215M (manufactured by NEOS Co., Ltd.)
  • S-8 Futergent 245F (manufactured by NEOS Co., Ltd.)
  • S-10 Megafuck F-557 (manufactured by DIC Corporation)
  • S-11 Megafuck F-563 (manufactured by DIC Corporation)
  • S-12 Megafuck F-5
  • a non-photosensitive resin composition was prepared in which the entire amount of the polymerizable monomer and the photopolymerization initiator was replaced with an epoxy compound (EHPE-3150, manufactured by Daicel Corporation).
  • EHPE-3150 an epoxy compound manufactured by Daicel Corporation.
  • a green pattern green pixel was formed by the same method as described in paragraph Nos. 0460 to 0468 of JP2013-06499, and the adhesion of the pixel pattern was evaluated. However, it was confirmed that good adhesion was obtained.
  • Examples 1 to 48 the i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.) is used instead of the KrF scanner exposure machine, and the pixel (pattern) size is formed in an array of 0.7 ⁇ m square. Pixels were formed in the same manner as above except that light having a wavelength of 365 nm was irradiated at an exposure amount of 500 mJ / cm 2 through a mask having a Bayer pattern to evaluate adhesion and development residue. However, the same results as in Examples 1 to 47 were obtained.
  • Example 1001 The green coloring composition was applied onto the silicon wafer by a spin coating method so that the film thickness after film formation was 1.0 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 2 minutes. Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed with an exposure amount of 1000 mJ / cm 2 via a mask of a 2 ⁇ m square dot pattern. Then, paddle development was performed at 23 ° C. for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH). Then, it was rinsed with a spin shower and then washed with pure water.
  • TMAH tetramethylammonium hydroxide
  • the green coloring composition was patterned to form green pixels by heating at 200 ° C. for 5 minutes using a hot plate.
  • the red coloring composition and the blue coloring composition were patterned by the same process to sequentially form red pixels and blue pixels to form a color filter having green pixels, red pixels and blue pixels.
  • green pixels are formed by a Bayer pattern
  • red pixels and blue pixels are formed by an island 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.
  • a resin composition GR-21
  • the red coloring composition a resin composition (RR-1) was used.
  • the blue coloring composition a resin composition (BR-1) was used.

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CN111727208B (zh) * 2018-02-21 2023-10-17 富士胶片株式会社 固化性组合物、固化物、滤色器、滤色器的制造方法、固体摄像元件及图像显示装置
JP7163741B2 (ja) 2018-11-28 2022-11-01 東洋インキＳｃホールディングス株式会社 感光性着色組成物、カラーフィルタおよび液晶表示装置

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JP2001350009A (ja) * 2000-06-05 2001-12-21 Toppan Printing Co Ltd カラーフィルタ及びその製造方法
JP2004250535A (ja) * 2003-02-19 2004-09-09 Mitsubishi Chemicals Corp 着色樹脂組成物、カラーフィルタ及び液晶表示装置
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