WO2019167681A1 - Composition, film de revêtement, film durci, lentille, dispositif d'imagerie à l'état solide, résine - Google Patents

Composition, film de revêtement, film durci, lentille, dispositif d'imagerie à l'état solide, résine Download PDF

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WO2019167681A1
WO2019167681A1 PCT/JP2019/005653 JP2019005653W WO2019167681A1 WO 2019167681 A1 WO2019167681 A1 WO 2019167681A1 JP 2019005653 W JP2019005653 W JP 2019005653W WO 2019167681 A1 WO2019167681 A1 WO 2019167681A1
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group
general formula
composition
compound
cured film
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PCT/JP2019/005653
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English (en)
Japanese (ja)
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金子　祐士
貴規 田口
大貴 瀧下
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富士フイルム株式会社
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Priority to KR1020207016900A priority Critical patent/KR102335574B1/ko
Priority to JP2020503397A priority patent/JP7008791B2/ja
Publication of WO2019167681A1 publication Critical patent/WO2019167681A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/0622—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
    • C08G73/0638—Polycondensates containing six-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with at least three nitrogen atoms in the ring
    • C08G73/0644—Poly(1,3,5)triazines
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B3/00—Simple or compound lenses
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
    • H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
    • H01L27/144—Devices controlled by radiation
    • H01L27/146—Imager structures

Definitions

  • the present invention relates to a composition, a coating film, a cured film, a lens, a solid-state imaging device, and a resin.
  • Patent Document 1 discloses a triazine ring-containing polymer as a material having high heat resistance, high transparency, high refractive index, high solubility, and low volume shrinkage.
  • the present inventors examined a cured film formed from a composition containing a triazine ring-containing polymer described in Patent Document 1, and repeatedly exposed to a high temperature environment and a low temperature environment (high temperature-low temperature environment). It was clarified that many defects occurred in the cured film.
  • an object of the present invention is to provide a composition capable of providing a cured film in which the occurrence of defects is suppressed even after repeated exposure to a high temperature-low temperature environment. Moreover, this invention makes it a subject to provide the coating film formed with the said composition, the cured film formed by hardening
  • the present inventors have achieved the above-described problems according to a composition comprising a resin containing a triazine ring having a specific structure, a specific metal ion having a predetermined content, and a solvent.
  • a composition comprising a resin containing a triazine ring having a specific structure, a specific metal ion having a predetermined content, and a solvent.
  • a solvent A specific metal ion selected from the group consisting of sodium ion, potassium ion, and calcium ion, A composition having a total content of specific metal ions of 0.01 to 30 ppm by mass relative to the total mass of the composition.
  • the solvent contains toluene, The composition according to (1), wherein the content of toluene is 0.001 to 10 mass ppm with respect to the total mass of the composition.
  • V in the general formula (I-1) is a group represented by the following general formula (II).
  • 10 The composition according to any one of (1) to (9), further comprising a curable compound.
  • (11) The composition according to any one of (1) to (10), further comprising a polymerization initiator.
  • the present invention it is possible to provide a composition capable of providing a cured film in which the generation of defects is suppressed even after repeated exposure to a high temperature-low temperature environment.
  • curing the said coating film, a lens, and a solid-state image sensor can be provided.
  • the novel resin which can be used suitably as a high refractive index material can be provided.
  • a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
  • Actinic light” or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. .
  • light means actinic rays or radiation.
  • exposure in the present specification includes not only exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, X-rays, EUV light, etc., but also an electron beam, an ion beam, etc. The exposure with the particle beam is also included in the exposure.
  • (meth) acrylate represents acrylate and methacrylate
  • (meth) acryl represents acryl and methacryl
  • (meth) acryloyl” represents acryloyl and methacryloyl.
  • the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes.
  • a weight average molecular weight and a number average molecular weight are defined as a polystyrene conversion value in a gel permeation chromatography (GPC) measurement.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are measured using, for example, HLC-8220 (manufactured by Tosoh Corporation) as a measuring device and TSKgel Super AWM-H (Tosoh Corporation) as a column. And 6.0 mm ID (inner diameter) ⁇ 15.0 cm) and a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
  • the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer.
  • the polymerizable group refers to a group that participates in a polymerization reaction.
  • the total solid content refers to the total mass of components excluding the solvent from the entire composition.
  • the substituent includes a group selected from the following substituent group T.
  • substituent T a halogen atom, alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy Group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, amino group (including alkylamino group and anilino group), acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfo group Famoylamino group, alkyl or arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl or arylsulfon
  • a halogen atom for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom
  • Linear or branched alkyl group linear or branched, substituted or unsubstituted alkyl group, preferably an alkyl group having 1 to 30 carbon atoms.
  • a cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms.
  • the cycloalkyl group may be monocyclic or polycyclic. Examples of the monocyclic cycloalkyl group include: , A cyclohexyl group, a cyclopentyl group, etc.
  • the polycyclic cycloalkyl group includes, for example, a bicycloalkyl group (preferably a substituted or unsubstituted bicycloalkyl group having 5 to 30 carbon atoms, Include a bicyclo [1,2,2] heptan-2-yl group and a bicyclo [2,2,2] octan-3-yl group), and a tricycloalkyl group. Is preferably a monocyclic cycloalkyl group or a bicycloalkyl group, more preferably a monocyclic cycloalkyl group).
  • a linear or branched alkenyl group (a linear or branched, substituted or unsubstituted alkenyl group, preferably an alkenyl group having 2 to 30 carbon atoms, for example, a vinyl group, an allyl group, a prenyl group) Group, geranyl group, and oleyl group), Cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms.
  • the cycloalkenyl group may be monocyclic or polycyclic.
  • Examples of the monocyclic cycloalkenyl group include in addition, examples of the polycyclic cycloalkenyl group include a bicycloalkenyl group (preferably a substituted or unsubstituted group having 5 to 30 carbon atoms), and 2-cyclopenten-1-yl group and 2-cyclohexen-1-yl group.
  • Bicycloalkenyl groups such as bicyclo [2,2,1] hept-2-en-1-yl group and bicyclo [2,2,2] oct-2-en-4-yl group) And a tricycloalkenyl group, etc. Among them, a monocyclic cycloalkenyl group is preferable).
  • alkynyl group preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, such as an ethynyl group, a propargyl group, and a trimethylsilylethynyl group
  • Aryl group preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
  • aryl group preferably a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.
  • Heterocyclic group may be a substituted or unsubstituted alicyclic heterocyclic group or an aromatic heterocyclic group.
  • the alicyclic heterocyclic group may be either saturated or unsaturated.
  • the heterocyclic group may be monocyclic or condensed, and the heterocyclic group may be a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom.
  • a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms such as a 2-furyl group, a 2-thienyl group, a 2-pyridyl group, a 4-pyridyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, etc.
  • Cyano group hydroxyl group, nitro group, carboxyl group,
  • Alkoxy groups preferably substituted or unsubstituted alkoxy groups having 1 to 30 carbon atoms, such as methoxy group, ethoxy group, isopropoxy group, tert-butoxy group, n-octyloxy group, and 2-methoxyethoxy group
  • Aryloxy group preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms.
  • phenoxy group 2-methylphenoxy group, 2,4-di-tert-amylphenoxy group, 4-tert-butylphenoxy group) Group, 3-nitrophenoxy group, and 2-tetradecanoylaminophenoxy group
  • a silyloxy group preferably a silyloxy group having 3 to 20 carbon atoms, such as a trimethylsilyloxy group and a tert-butyldimethylsilyloxy group
  • Heterocyclic oxy group preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms.
  • the heterocyclic group in the heterocyclic oxy group is a divalent group obtained by removing one hydrogen atom from the aforementioned heterocyclic group.
  • Examples of the heterocyclic oxy group include a 1-phenyltetrazol-5-oxy group and a 2-tetrahydropyranyloxy group.
  • An acyloxy group (preferably a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms.
  • a formyloxy group Acetyloxy group, pivaloyloxy group, stearoyloxy group, benzoyloxy group, p-methoxyphenylcarbonyloxy group, acryloyloxy group, and methacryloyloxy group
  • Carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms.
  • methoxycarbonyloxy group methoxycarbonyloxy group, ethoxycarbonyloxy group, tert-butoxycarbonyloxy group, n-octylcarbonyloxy group, etc.
  • Aryloxycarbonyloxy group preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms.
  • An amino group (preferably an unsubstituted amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, or a heterocyclic ring having 0 to 30 carbon atoms;
  • An amino group such as an amino group, a methylamino group, a dimethylamino group, an anilino group, an N-methyl-anilino group, a diphenylamino group, and an N-1,3,5-triazin-2-ylamino group)
  • An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms.
  • formylamino group acetyl Amino group, pivaloylamino group, lauroylamino group, benzoylamino group, 3,4,5-tri-n-octyloxyphenylcarbonylamino group, acryloylamino group, and methacryloylamino group
  • Aminocarbonylamino group preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms.
  • carbamoylamino group N, N-dimethylaminocarbonylamino group, N, N-diethylaminocarbonylamino group, and morpholino Carbonylamino group etc.
  • An alkoxycarbonylamino group preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms.
  • Aryloxycarbonylamino group preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms.
  • aryloxycarbonylamino group having 7 to 30 carbon atoms.
  • Sulfamoylamino group preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms.
  • sulfamoylamino group, N, N-dimethylaminosulfonylamino group, and Nn-octylamino A sulfonylamino group For example, sulfamoylamino group, N, N-dimethylaminosulfonylamino group, and Nn-octylamino A sulfonylamino group), An alkyl or arylsulfonylamino group (preferably a substituted or unsubstituted alkylsulfonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonylamino group having 6 to 30 carbon atoms.
  • the heterocyclic group in the heterocyclic thio group is a divalent group obtained by removing one hydrogen atom from the heterocyclic group described above.
  • Examples of the heterocyclic thio group include a 2-benzothiazolylthio group and a 1-phenyltetrazol-5-ylthio group).
  • Sulfamoyl group preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms.
  • a methylsulfinyl group for example, a methylsulfinyl group, an ethylsulfinyl group, a phenylsulfinyl group Group, and p-methylphenylsulfinyl group
  • An alkyl or arylsulfonyl group preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms.
  • an acetyl group for example, an acetyl group, a pivaloyl group, 2- Chloroacetyl group, stearoyl group, benzoyl group, pn-octyloxyphenylcarbonyl group, acryloyl group, and methacryloyl group), Aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms.
  • alkoxycarbonyl group preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a tert-butoxycarbonyl group, and an n-octadecyloxycarbonyl group
  • a carbamoyl group preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms.
  • a carbamoyl group for example, a carbamoyl group, an N-methylcarbamoyl group, an N, N-dimethylcarbamoyl group, an N, N-di-n-octylcarbamoyl group, And N- (methylsulfonyl) carbamoyl group, etc.
  • An aryl or heterocyclic azo group preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, or a substituted or unsubstituted heterocyclic azo group having 3 to 30 carbon atoms (the heterocyclic group in the heterocyclic azo group);
  • divalent heterocyclic groups obtained by removing one hydrogen atom from the above-described heterocyclic group.
  • An imide group preferably a
  • those having a hydrogen atom may have a hydrogen atom portion in the functional group substituted with any of the above groups.
  • functional groups that can be introduced as a substituent include alkylcarbonylaminosulfonyl groups (eg, acetylaminosulfonyl group), arylcarbonylaminosulfonyl groups (eg, benzoylaminosulfonyl group), alkylsulfonylaminocarbonyl groups (eg, , Methylsulfonylaminocarbonyl group and the like), and arylsulfonylaminocarbonyl group (for example, p-methylphenylsulfonylaminocarbonyl group and the like).
  • composition of the present invention comprises a resin containing a repeating unit represented by the following general formula (I-1) or a repeating unit represented by the following general formula (I-2), a solvent, sodium ion, potassium A specific metal ion selected from the group consisting of ions and calcium ions, and the total content of the specific metal ions is 0.01 to 30 ppm by mass relative to the total mass of the composition.
  • compositions include a repeating unit represented by general formula (I-1) described later or a resin containing a repeating unit represented by general formula (I-2) described later (hereinafter referred to as “specific triazine series”).
  • Resin a resin containing a repeating unit represented by general formula (I-2) described later
  • Resin a specific content of specific metal ions are used in combination.
  • a material exhibiting high refractive index, typified by a triazine-based resin is likely to associate and form an aggregate due to its intermolecular interaction.
  • the present inventors have examined a cured film containing the above-mentioned aggregate. When the cured film is repeatedly exposed to a high temperature-low temperature environment, it undergoes microphase separation (phase separation between an agglomerated portion and a non-aggregated portion).
  • the cured film has been found to have increased defects due to this microphase separation.
  • the present inventors have further studied based on the above findings, and according to the composition in which the specific triazine-based resin and the specific metal ion having a predetermined content are blended, the formed cured film is microphase-separated.
  • the above-mentioned cured film suppresses the generation of defects even after repeated exposure to a high temperature-low temperature environment.
  • the specific metal ion easily interacts with nitrogen atoms, etc. in the specific triazine resin, so the association of the specific triazine resin in the process of forming a coating film with the composition.
  • the composition includes a resin (specific triazine resin) containing a repeating unit represented by the general formula (I-1) or a repeating unit represented by the general formula (I-2). (Repeating unit represented by formula (I-1))
  • X 1 , X 2 , and X 3 each independently represent —NR 1 —, —O—, or —S—.
  • X 1 , X 2 , and X 3 the refractive index of the cured film after being repeatedly exposed to a high temperature-low temperature environment is superior, and the spectrum of the cured film even if it is repeatedly exposed to a high temperature-low temperature environment From the viewpoint of small variation, —NR 1 — is preferable.
  • W 1 represents a divalent linking group.
  • the divalent linking group represented by W 1 is not particularly limited. For example, —O—, —CO—, —S—, —SO 2 —, —NR A —, arylene group, alkylene group, heteroarylene And groups consisting of these groups and combinations thereof.
  • the alkylene group may be substituted with a substituent such as a halogen atom (for example, a group exemplified in Substituent Group T).
  • the number of carbon atoms of the arylene group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.
  • Specific examples of the arylene group include 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 1,5-naphthylene group, 2,7-fluorenylene group, 3,6- Examples include a fluorenylene group, a 9,9-fluorenylene group, and an anthracenylene group, and a 1,4-phenylene group is preferable.
  • the arylene group may have a substituent (for example, a group exemplified in the substituent group T).
  • R A represents a hydrogen atom or a substituent, and is preferably a hydrogen atom.
  • the substituent represented by R A has the same meaning as the substituent represented by R 1 .
  • the divalent linking group represented by W 1 is such that the refractive index of the cured film after being repeatedly exposed to a high temperature-low temperature environment is more excellent, and the cured film even if repeatedly exposed to a high temperature-low temperature environment
  • the divalent linking group represented by the following general formula (III) is preferable in that the spectral fluctuation of
  • a 1, A 2, and arylene groups represented by A 3, and R A are as described above.
  • the arylene group represented by A 1 to A 3 is preferably a 1,4-phenylene group.
  • V represents an alkyl group, an aryl group, or a heterocyclic group.
  • the alkyl group represented by V (which may be linear, branched or cyclic) is not particularly limited, and examples thereof include alkyl groups having 1 to 10 carbon atoms, and those having 1 to 6 carbon atoms. An alkyl group is more preferred, and an alkyl group having 1 to 3 carbon atoms is still more preferred.
  • Examples of the aryl group represented by V include an aryl group composed of a 6 to 10 membered ring or a condensed ring thereof.
  • the ring constituting the aryl group are not particularly limited, and examples thereof include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, and a naphthacene ring.
  • the said ring comprises an aryl group by removing one hydrogen atom on a ring.
  • the heterocyclic group represented by V is not particularly limited, and examples thereof include an aliphatic heterocyclic group and an aromatic heterocyclic group.
  • hetero atom which the said aliphatic heterocyclic group contains a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example.
  • the number of carbon atoms in the aliphatic heterocycle is not particularly limited, but is preferably 3-20.
  • Specific examples of the aliphatic heterocyclic ring are not particularly limited, and examples thereof include an oxolane ring, an oxane ring, a piperidine ring, and a piperazine ring.
  • the said aliphatic heterocyclic ring comprises an aliphatic heterocyclic group by removing one hydrogen atom on a ring.
  • hetero atom which the said aromatic heterocyclic group contains a nitrogen atom, an oxygen atom, and a sulfur atom are mentioned, for example.
  • the number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but is preferably 3-20.
  • Specific examples of the aromatic heterocycle include, but are not limited to, a furan ring, a thiophene ring, a pyrrole ring, an oxazole ring, an isoxazole ring, an oxadiazole ring, a thiazole ring, an isothiazole ring, a thiadiazole ring, an imidazole ring, and a pyrazole.
  • the alkyl group, aryl group, and heterocyclic group represented by V may have a substituent (for example, a group exemplified in Substituent Group T).
  • Examples of the halogen atom represented by R 3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
  • the alkylthio group represented by R 3 is not particularly limited, and examples thereof include alkylthio groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 6 carbon atoms are more preferable, and alkylthio groups having 1 to 3 carbon atoms are preferable. Further preferred.
  • the alkylene group in the alkylthio group may be linear, branched, or cyclic.
  • the alkyl group and alkylthio group represented by R 3 may further have a substituent (for example, a group exemplified in the substituent group T).
  • R 4 represents a substituent. Among these, as R 4 , an aryl group, a heterocyclic group, a cyano group, a nitro group, an alkyl group, an alkylthio group, or a halogen atom is preferable.
  • the aryl group and heterocyclic group represented by R 4 have the same meaning as the aryl group and heterocyclic group represented by V.
  • the aryl group represented by R 4 is preferably a phenyl group.
  • the alkyl group, alkylthio group and halogen atom represented by R 4 have the same meanings as the alkyl group, alkylthio group and halogen atom represented by R 3 , and the preferred embodiments are also the same.
  • R 4 is preferably an aryl group, a cyano group, a nitro group, or a halogen atom from the viewpoint that the refractive index of the cured film after being repeatedly exposed to a high temperature-low temperature environment is more excellent
  • the group represented by the general formula (II) is represented by the following general formula (IIA) in that the cured film is more excellent in refractive index after being repeatedly exposed to a high temperature-low temperature environment. Groups are preferred.
  • X 4 , X 5 , and X 6 each independently represent —NR 2 —, —O—, or —S—.
  • W 2 represents a divalent linking group.
  • R 2 represents a hydrogen atom or a substituent.
  • R 2 has the same meaning as R 1 in general formula (I-1), and the preferred embodiment is also the same.
  • W 2 has the same meaning as W 1 in general formula (I-1).
  • the divalent linking group represented by W 2 the refractive index of the cured film after being repeatedly exposed to a high temperature-low temperature environment is excellent, and even if it is repeatedly exposed to a high temperature-low temperature environment,
  • the arylene group represented by A 1 to A 3 is preferably a 1,4-phenylene group.
  • X 4 , X 5 , and X 6 are characterized in that the refractive index of the cured film after being repeatedly exposed to a high temperature-low temperature environment is superior, and the spectrum of the cured film even when repeatedly exposed to a high temperature-low temperature environment From the viewpoint of small variation, —NR 2 — is preferable.
  • Examples of the compound containing the repeating unit represented by the general formula (I-2) include compounds represented by the following (polycondensates and polyaddition products).
  • Y 1 to Y 3 represent a leaving group (for example, a halogen atom) or an isocyanate group.
  • X 7 and X 8 each independently represent —NR 2 —, —O—, or —S—.
  • R 2 represents a hydrogen atom or a substituent.
  • W 3 represents a divalent linking group.
  • the substituent represented by R 2 include the same as R 2 in the above-mentioned general formula (II-2).
  • Examples of the divalent linking group represented by W 3 include the same groups as those described above for W 2 in formula (II-2).
  • Example 2 A polycondensate or polyadduct of a compound represented by the following general formula (VII) and a compound represented by the following general formula (VIII).
  • the repeating unit represented by the general formula (I-1) or the repeating unit represented by the general formula (I-2) is based on all the repeating units in the specific triazine-based resin. 50 to 100 mol% is preferable, 80 to 100 mol% is more preferable, and 90 to 100 mol% is still more preferable.
  • the weight average molecular weight of the specific triazine resin is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and still more preferably 4,000 to 20,000.
  • the degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and even more preferably 1.1 to 2.0. preferable.
  • the specific triazine-based resin may be used alone or in combination of two or more.
  • the content of the specific triazine-based resin (when there are a plurality of types) is generally 80.0% by mass or more based on the total solid content of the composition. 0 mass% or more is preferable and 90.0 mass% or more is more preferable. Although an upper limit in particular is not restrict
  • the composition may contain toluene as a solvent.
  • the total content of toluene is preferably 0.001 to 10 ppm by mass with respect to the total mass of the composition.
  • the total content of toluene in the composition is in the above numerical range, the surface appearance of the coating film formed from the composition is excellent.
  • the total content of toluene in the composition is preferably 0.01 to 100 ppm by mass with respect to the specific triazine resin.
  • the toluene content in the composition can be measured by gas chromatography.
  • the solvents may be used alone or in combination of two or more.
  • Examples of methods for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) or filtration using a filter.
  • the filter pore size of the filter used for filtration is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less.
  • the filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.
  • the solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
  • the content of the curable compound is preferably 1 to 80% by mass with respect to the total solid content of the composition.
  • the lower limit is more preferably 3% by mass or more, and still more preferably 4% by mass or more.
  • the upper limit is more preferably 70% by mass or less, still more preferably 60% by mass or less, and particularly preferably 30% by mass or less.
  • the curable compound may be used alone or in combination of two or more. When the said composition contains 2 or more types of sclerosing
  • polymerizable compound paragraphs 0033 to 0034 of JP2013-253224A can be referred to, and the contents thereof are incorporated in the present specification.
  • the polymerizable compound include ethyleneoxy-modified pentaerythritol tetraacrylate (commercially available NK ester ATM-35E; manufactured by Shin-Nakamura Chemical Co., Ltd.), dipentaerythritol triacrylate (commercially available KAYARAD D-330).
  • diglycerin EO (ethylene oxide) modified (meth) acrylate commercially available product is M-460; manufactured by Toagosei Co., Ltd.
  • pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT
  • pentaerythritol tetraacrylate manufactured by Shin-Nakamura Chemical Co., Ltd., A-TMMT
  • 1 6-hexanediol diacrylate
  • KAYARAD HDDA KAYARAD HDDA
  • oligomer types can also be used. Examples thereof include RP-1040 (manufactured by Nippon Kayaku Co., Ltd.).
  • the polymerizable compound may have an acid group such as a carboxy group, a sulfo group, and a phosphoric acid group.
  • examples of the polymerizable compound having an acid group include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids.
  • a polymerizable compound in which a non-aromatic carboxylic acid anhydride is allowed to react with an unreacted hydroxyl group of the aliphatic polyhydroxy compound to give an acid group is preferred. More preferably, in this ester, the aliphatic polyhydroxy compound is a pentavalent compound. Erythritol and / or dipentaerythritol.
  • the acid value of the polymerizable compound having an acid group is preferably from 0.1 to 40 mgKOH / g.
  • the lower limit is more preferably 5 mgKOH / g or more.
  • the upper limit is more preferably 30 mgKOH / g or less.
  • the compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc. commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and ethylene manufactured by Sartomer.
  • SR-494 which is a tetrafunctional acrylate having four oxy chains
  • TPA-330 which is a trifunctional acrylate having three isobutylene oxy chains.
  • Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, and Urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. . Further, addition-polymerizable compounds having an amino structure and / or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 Can be used.
  • the compound which has an epoxy group can also be used as a sclerosing
  • the compound which has an epoxy group the compound which has 1 or more of epoxy groups in 1 molecule is mentioned, The compound which has 2 or more of epoxy groups in 1 molecule is preferable. It is preferable to have 1 to 100 epoxy groups in one molecule.
  • the upper limit may be 10 or less, and may be 5 or less.
  • the lower limit is preferably 2 or more.
  • the compound having an epoxy group may be either a low molecular compound (for example, a molecular weight of less than 1000) or a high molecular compound (for example, a molecular weight of 1000 or more, and in the case of a polymer, the weight average molecular weight is 1000 or more).
  • the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
  • the upper limit of the weight average molecular weight is more preferably 10,000 or less, still more preferably 5000 or less, and particularly preferably 3000 or less.
  • a commercially available product can also be used as the compound having an epoxy group.
  • examples thereof include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), and the like.
  • compounds having an epoxy group are disclosed in paragraphs 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0086 of JP2014-089408A.
  • the compounds described in 0092 can also be used. These contents are incorporated herein.
  • the composition may contain a polymerization initiator, and preferably contains a photopolymerization initiator.
  • a photoinitiator There is no restriction
  • the photopolymerization initiator is preferably a compound having photosensitivity to light in the ultraviolet region to the visible region.
  • Photopolymerization initiators are trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazoles from the viewpoint of exposure sensitivity.
  • ⁇ -hydroxyketone compounds As the photopolymerization initiator, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and acylphosphine compounds can also be suitably used.
  • ⁇ -aminoketone compounds described in JP-A-10-291969 and acylphosphine compounds described in Japanese Patent No. 4225898 can also be used.
  • Examples of commercially available ⁇ -hydroxyketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (above, manufactured by BASF).
  • oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (above, manufactured by BASF), TR-PBG-304 (manufactured by Changzhou Power Electronics New Materials Co., Ltd.), Adeka Arc Luz NCI-831 (manufactured by ADEKA Corporation), Adeka Arcles NCI-930 (manufactured by ADEKA Corporation), and Adekaoptomer N-1919 (manufactured by ADEKA Corporation, described in JP 2012-14052 A) Photopolymerization initiator 2) and the like.
  • oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
  • the oxime compound is preferably a compound having a maximum absorption in a wavelength region of 350 to 500 nm, and more preferably a compound having a maximum absorption in a wavelength region of 360 to 480 nm.
  • the oxime compound is preferably a compound having high absorbance at 365 nm and 405 nm.
  • the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000 from the viewpoint of sensitivity, and 5,000 to 200,000. More preferably, it is 000.
  • the molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure with an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using an ethyl acetate solvent at a concentration of 0.01 g / L.
  • the photopolymerization initiator preferably contains an oxime compound and an ⁇ -aminoketone compound. By using both in combination, the developability is improved and a pattern having excellent rectangularity can be easily formed.
  • the oxime compound and the ⁇ -aminoketone compound are used in combination, the ⁇ -aminoketone compound is preferably contained in an amount of 50 to 600 parts by mass, more preferably 150 to 400 parts by mass with respect to 100 parts by mass of the oxime compound.
  • the content of the polymerization initiator is preferably from 0.1 to 50% by weight, more preferably from 0.5 to 30% by weight, still more preferably from 1 to 20% by weight, based on the total solid content of the composition. 10% by mass is particularly preferred.
  • the composition may contain only one type of polymerization initiator, or may contain two or more types. When the said composition contains 2 or more types of polymerization initiators, it is preferable that the total content becomes the said range.
  • the composition may contain an antioxidant.
  • the antioxidant include phenol compounds, phosphite compounds, and thioether compounds.
  • a phenol compound having a molecular weight of 500 or more, a phosphite compound having a molecular weight of 500 or more, or a thioether compound having a molecular weight of 500 or more is preferable. You may use these in mixture of 2 or more types.
  • the phenolic compound any phenolic compound known as a phenolic antioxidant can be used, and a polysubstituted phenolic compound is preferred.
  • Multi-substituted phenolic compounds are roughly classified into three types (hindered type, semi-hindered type, and responder type) having different substitution positions and structures.
  • the antioxidant a compound having a phenol group and a phosphite group in the same molecule is preferably used.
  • phosphorus antioxidants are also preferably used as the antioxidant.
  • a commercially available antioxidant can also be used.
  • Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G and ADK STAB AO-80.
  • ADK STAB AO-330 ADK STAB AO-330
  • the antioxidant the description of paragraph numbers 0033 to 0043 of JP2014-032380A can be referred to, and the contents thereof are incorporated in the present specification.
  • the content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition. Only one type of antioxidant may be used, or two or more types may be used. When the said composition contains 2 or more types of antioxidant, it is preferable that the total content becomes said range.
  • the functional group other than the hydrolyzable group is preferably a group that exhibits affinity by forming an interaction or bond with the resin.
  • a vinyl group, a styryl group, a (meth) acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, a phenyl group, and the like, and a (meth) acryloyl group, or Epoxy groups are preferred.
  • silane coupling agent examples include 3-methacryloxypropylmethyldimethoxysilane.
  • examples of the silane coupling agent include compounds described in paragraph Nos. 0018 to 0036 of JP-A-2009-288703, and compounds described in paragraph Nos. 0056 to 0066 of JP-A-2009-242604. Is incorporated herein by reference.
  • a commercial item can also be used for a silane coupling agent.
  • Commercially available silane coupling agents include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM manufactured by Shin-Etsu Silicone Co., Ltd.
  • the content of the silane coupling agent is preferably 0.01 to 15.0 mass%, more preferably 0.05 to 10.0 mass%, based on the total solid content of the composition. Only one type of silane coupling agent may be used, or two or more types may be used. When the said composition contains 2 or more types of silane coupling agents, it is preferable that the total content becomes the said range.
  • the composition may contain a polymerization inhibitor.
  • Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-tert-butylphenol), 2 , 2′-methylenebis (4-methyl-6-tert-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salt, primary cerium salt, etc.). Of these, p-methoxyphenol is preferred.
  • the polymerization inhibitor may function as an antioxidant.
  • the content of the polymerization inhibitor is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 8 parts by mass, and still more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polymerization initiator.
  • the said composition may contain various surfactant from a viewpoint of improving applicability
  • various surfactants such as a fluorosurfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used.
  • paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, the contents of which are incorporated herein.
  • the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and the liquid-saving property can be further improved.
  • the interfacial tension between the coated surface and the coating liquid is reduced, and the wettability to the coated surface is improved.
  • the coating property to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
  • the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
  • a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
  • fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, and F780 (above DIC Corporation), Florard FC430, FC431, and FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC- 101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393, and KH-40 (above, manufactured by Asahi Glass Co., Ltd.) ), And PolyFox PF636, PF656, PF6320, PF6520, and PF7002 (above, manufactured by OMNOVA) Etc. The.
  • a block polymer can also be used as the fluorosurfactant.
  • the fluorosurfactant 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 group or propyleneoxy group) (meta) )
  • a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
  • the following compounds are also exemplified as the fluorosurfactant used in the present invention.
  • the weight average molecular weight of the above compound is preferably, for example, 3,000 to 50,000, and specifically 14,000. % Which shows the ratio of a repeating unit in said compound is the mass%.
  • a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used.
  • Specific examples thereof include compounds described in JP-A 2010-164965, paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. And RS-72-K.
  • the fluorine-based surfactant compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 can also be used.
  • polyoxyethylene lauryl ether polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10 L31, L61, L62, 10R5, 17R2, and 25R2 (BASF), Tetronic 304, 701, 704, 901, 904, and 150R1 (BASF), Solsperse 20000 (Nippon Lubrizol Corporation) NCW-101, NCW-1001, and NCW-1002 (manufactured by Wako Pure Chemical Industries, Ltd.), Pionein D-6112, D-6112-W, and D-6 15 (manufactured by Takemoto Oil & Fat Co.), as well as Olfine E1010, Surfynol 104,400, and 440 (manufactured by Nissin
  • a vinyl ether polymerization type fluorosurfactant can be used as the fluorosurfactant.
  • the vinyl ether polymerization type fluorosurfactant include those described in Examples of JP-A-2016-216602 (eg, fluorosurfactant (1)).
  • the surfactant content is preferably 0.0001 to 5.0% by mass, more preferably 0.0005 to 3.0% by mass, based on the total solid content of the composition. Only one type of surfactant may be used, or two or more types may be used. When the said composition contains 2 or more types of surfactant, it is preferable that the total content becomes said range.
  • the composition may contain an ultraviolet absorber.
  • the ultraviolet absorber include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, and hydroxyphenyltriazine compounds.
  • conjugated diene compounds include UV-503 (manufactured by Daito Chemical Co., Ltd.).
  • the content of the ultraviolet absorber is preferably from 0.1 to 10% by mass, more preferably from 0.1 to 5% by mass, and still more preferably from 0.1 to 3% by mass, based on the total solid content of the composition. Moreover, only one type of ultraviolet absorber may be used, or two or more types may be used. When the said composition contains two or more types of ultraviolet absorbers, it is preferable that the total content becomes the said range.
  • the filler examples include inorganic particles.
  • the inorganic particles colorless, white or transparent inorganic particles having a high refractive index are preferable, and titanium (Ti), zirconium (Zr), aluminum (Al), silicon (Si), zinc (Zn), or magnesium (Mg). And the like, and titanium dioxide (TiO 2 ) particles, zirconium oxide (ZrO 2 ) particles, or silicon dioxide (SiO 2 ) particles are more preferred.
  • the primary particle diameter of the inorganic particles is not particularly limited, preferably 1 to 100 nm, more preferably 1 to 80 nm, and still more preferably 1 to 50 nm.
  • the refractive index of the inorganic particles is not particularly limited, but is preferably 1.75 to 2.70, more preferably 1.90 to 2.70 from the viewpoint of obtaining a high refractive index.
  • the specific surface area is not particularly limited in the inorganic particles is preferably 10 ⁇ 400m 2 / g, more preferably 20 ⁇ 200m 2 / g, more preferably 30 ⁇ 150m 2 / g.
  • an inorganic particle For example, a rice grain shape, a spherical shape, a cube shape, a spindle shape, an indefinite shape, etc. are mentioned.
  • the inorganic particles may be those that have been surface-treated with an organic compound.
  • the organic compound used for the surface treatment include polyols, alkanolamines, stearic acid, silane coupling agents, and titanate coupling agents. Of these, stearic acid or a silane coupling agent is preferable.
  • the surface of the inorganic particles is covered with an oxide such as aluminum, silicon, and zirconia because the weather resistance is further improved.
  • an inorganic particle what is marketed can be used preferably.
  • an inorganic particle may be used individually by 1 type or in combination of 2 or more types.
  • a composition contains a hardening accelerator.
  • Curing accelerators that improve the curing speed include acid anhydrides, bases (such as aliphatic amines, aromatic amines, and modified amines), acids (such as sulfonic acids, phosphoric acids, and carboxylic acids), and polymercaptans. Can be mentioned. Of these, acid anhydrides are preferable, and aliphatic acid anhydrides are more preferable.
  • the above composition can be prepared by mixing the aforementioned components.
  • the respective components may be blended together, or may be blended sequentially after each component is dissolved or dispersed in a solvent.
  • the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time.
  • a composition having a particle property dispersed in a solvent and a resin may be prepared, and the resulting composition may be mixed with other components (for example, a specific triazine resin and a curable compound). Good.
  • the method for preparing the composition includes a process of dispersing the particles.
  • the mechanical force used for dispersing the particles includes compression, squeezing, impact, shearing, and cavitation.
  • Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high speed impeller, a sand grinder, a flow jet mixer, a high pressure wet atomization, and an ultrasonic dispersion.
  • the beads having a small diameter it is preferable to use the beads having a small diameter, and to perform the treatment under the condition of increasing the pulverization efficiency by increasing the filling rate of the beads. Moreover, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment.
  • a filter for the purpose of removing foreign substances and reducing defects.
  • a filter if it is a filter conventionally used for the filtration use etc., it can be used without being restrict
  • a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (eg nylon-6 and nylon-6,6), and a polyolefin resin such as polyethylene and polypropylene (PP) (high density and And / or a filter using a material such as an ultra-high molecular weight polyolefin resin).
  • PTFE polytetrafluoroethylene
  • nylon eg nylon-6 and nylon-6,6
  • PP polypropylene
  • PP polypropylene
  • filters different filters (for example, a first filter and a second filter) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above.
  • the pore diameter here can refer to the nominal value of the filter manufacturer.
  • filters include, for example, various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Nihon Microlith Co., Ltd.), KITZ Micro Filter Co., Ltd., etc. You can choose.
  • the second filter a filter formed of the same material as the first filter can be used. Further, the filtration with the first filter may be performed on the mixed solution obtained by mixing only the resin and the solvent, and after the other components are mixed, the filtration may be performed with the second filter.
  • a high refractive member of a solid-state image sensor (a microlens, a transparent film such as a base layer and an adjacent layer of a color filter, and a color filter) White pixels, etc.), lenses (glass lenses, digital camera lenses, Fresnel lenses, prism lenses, etc.), optical overcoat agents, hard coat agents, antireflection films, optical fibers, optical waveguides, LEDs (Light Emitting Diodes) It is useful as a sealing material for LED, a planarizing material for LED, and a coating material for solar cell.
  • the film of the present invention is a film obtained from the composition of the present invention.
  • the above-mentioned “film” intends both a coating film (uncured film) formed by the composition of the present invention and a cured film formed by curing the coating film.
  • a cured film is obtained by performing a hardening process with respect to the coating film formed with the said composition, when a curable compound is contained in a composition.
  • the refractive index (wavelength 589 nm) of the film is not particularly limited, but is preferably 1.55 or more, more preferably 1.6 to 2.0.
  • a method for producing a patterned cured film includes a step of applying the above composition on a substrate to form a composition layer (coating film) (hereinafter simply referred to as “composition layer forming step”).
  • a step of exposing the composition layer through a mask hereinafter abbreviated as “exposure step” as appropriate
  • exposure step a step of developing the exposed composition layer to form a patterned cured film
  • exposure step a step of developing the exposed composition layer to form a patterned cured film
  • exposure step a step of developing the exposed composition layer to form a patterned cured film
  • exposure step a patterned cured film
  • composition layer forming step the composition is applied on a substrate directly or through another layer to form a composition layer (composition layer forming step), exposed through a predetermined mask pattern, and light.
  • a composition layer forming step By curing only the irradiated composition layer portion (exposure process) and developing with a developer (development process), a patterned cured film composed of pixels can be formed.
  • exposure process Exposure process
  • development process developing with a developer
  • composition layer formation process the said composition is apply
  • the substrate is not particularly limited.
  • non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and the like obtained by attaching a transparent conductive film to these, a solid-state imaging device, etc.
  • a photoelectric conversion element substrate for example, a silicon substrate
  • CCD Charge-Coupled Device
  • CMOS Complementary Metal-Oxide Semiconductor
  • the coating thickness of the composition can be appropriately selected depending on the application, but is, for example, 0.1 to 20 ⁇ m, more preferably 0.1 to 10 ⁇ m, and further preferably 0.5 to 4 ⁇ m.
  • composition coated on the substrate is usually dried at 70 to 110 ° C. for about 2 to 4 minutes. Thereby, a composition layer can be formed.
  • the composition layer (coating film) formed in the composition layer forming process is exposed through a mask, and only the coating film portion irradiated with light is cured.
  • the exposure is preferably performed by irradiation with actinic rays or radiation, and more preferably ultraviolet rays such as g-line, h-line, or i-line.
  • the irradiation intensity is preferably 5 ⁇ 1500mJ / cm 2, more preferably 10 ⁇ 1000mJ / cm 2.
  • An alkali development process (development process) is performed after an exposure process, and the light non-irradiation part in an exposure process is eluted in alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
  • As the developer an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable.
  • the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
  • Examples of the alkaline aqueous solution include an inorganic developer and an organic developer.
  • the inorganic developer sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, or sodium metaoxalate having a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned.
  • the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, choline, pyrrole, piperidine, or 1,8-diazabicyclo- [5.4.
  • An alkaline aqueous solution in which an alkaline compound such as 0.001 to 10% by mass, preferably 0.01 to 1% by mass is dissolved.
  • An appropriate amount of a water-soluble organic solvent such as methanol or ethanol and / or a surfactant can also be added to the alkaline aqueous solution.
  • a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
  • the developing method for example, a paddle developing method or a shower developing method can be used.
  • the film of the present invention (preferably a cured film) can also be used as a lens.
  • the lens can be suitably used for the microlens of the solid-state imaging device described above.
  • the present invention also relates to a novel resin that can be suitably used as a high refractive index material.
  • the resin of the present invention is a resin containing a repeating unit represented by the following general formula (IV-1) or a repeating unit represented by the following general formula (IV-2).
  • the resin containing a repeating unit represented by the following general formula (IV-1) or a repeating unit represented by the following general formula (IV-2) corresponds to one embodiment of the specific triazine-based resin described above.
  • the resin of the present invention will be described in detail.
  • X 1 , X 2, X 3, and W 1 is, X 1 in general formula (I-1), X 2 , X 3, and W 1 in the above formula
  • the preferred embodiment is also the same.
  • the refractive index of the cured film after being repeatedly exposed to a high temperature-low temperature environment is more excellent, and in particular, a group represented by the following general formula (IV-1A) Preferably there is.
  • R 5 is preferably located in the para position.
  • X 4 , X 5 , and X 6 each independently represent —NR 2 —, —O—, or —S—.
  • R 2 represents a hydrogen atom or a substituent.
  • the refractive index of the cured film after being repeatedly exposed to a high temperature-low temperature environment is more excellent, in particular, a group represented by the following general formula (IV-2A) Preferably there is.
  • the repeating unit represented by the general formula (I-1) or the repeating unit represented by the general formula (I-2) is 50 to 100 mol% with respect to all the repeating units in the resin. It is preferably 80 to 100 mol%, more preferably 90 to 100 mol%.
  • the precipitated solid was filtered, and the filtered solid was washed 3 times with 100 g of ion-exchanged water, and then washed once with 100 g of ethanol.
  • the obtained solid was vacuum-dried at 60 ° C. to obtain 7.2 g of Compound (A-1).
  • resins (A-1) to (A-11) are shown below.
  • Table 1 shows the weight average molecular weights (polystyrene equivalent values) of the resins (A-1) to (A-11) measured by GPC (Gel Permeation Chromatography).
  • Photopolymerization initiator The following photopolymerization initiators I-1 to I-12 were used.
  • Me represents a methyl group
  • Ph represents a phenyl group.
  • the contents of sodium ions, potassium ions, and calcium ions in the obtained composition were quantified using an ICP emission spectroscopic analyzer (“Agilent 7800 ICP-MS” manufactured by Agilent Technologies). Further, the content of toluene in the obtained composition was quantified after preparing a calibration curve by gas chromatography according to a known method.
  • the obtained cured film was put into a thermal shock test apparatus (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by Tabai ESPEC)) and subjected to 300 thermal cycles of ⁇ 65 ° C./30 minutes ⁇ 125 ° C./30 minutes.
  • ESPEC THERMAL Shock CHAMBER TSA-70L manufactured by Tabai ESPEC
  • J. et al. A Using a WASEL manufactured by Woollam, the refractive index at a wavelength of 300 to 1500 nm was measured, and the refractive index at a wavelength of 589 nm was taken as the refractive index of each film.
  • the refractive index of the cured film after the thermocycle was evaluated in light of the measured refractive index value according to the following criteria. “A”: Refractive index 1.85 or more “B”: Refractive index 1.70 or more and less than 1.85 “C”: Refractive index less than 1.70
  • the obtained cured film was put into a thermal shock test apparatus (ESPEC THERMAL Shock CHAMBER TSA-70L (manufactured by TABAI ESPEC)), and subjected to 300 thermal cycles of ⁇ 65 ° C./30 minutes ⁇ 125 ° C./30 minutes. Then, the number of defects (pieces / cm 2 ) of the cured film was measured using a defect inspection apparatus (ComPlus manufactured by Applied Materials).
  • ESPEC THERMAL Shock CHAMBER TSA-70L manufactured by TABAI ESPEC
  • the measured number of defects was divided into the following criteria, and the defect suppression of the cured film after the thermocycle was evaluated.
  • C The number of defects is 20 / cm 2 This is the level that is problematic in practice.
  • the observed coating film B was evaluated, and the surface appearance of the coating film was evaluated.
  • A No film surface roughness or foreign matter is observed.
  • B Although the surface roughness of the film or some foreign matter is observed, it is a level that does not cause a problem in practice.
  • C A level where the film surface roughness or foreign matter is partially observed, causing a problem in practical use.
  • Table 2 is shown below.
  • “0” in the “specific metal ion” column means that the content of the specific metal ion in the composition was less than 0.01 mass ppm.
  • “0” in the “toluene” column means that the content of toluene in the composition was less than 0.001 mass ppm.
  • the “remaining amount” in the “solvent other than toluene” column in Table 2 is the total mass ratio of the constituent components other than “solvent other than toluene” in the composition from the total ratio (100%) of the composition. The amount excluding is intended.
  • the cured films obtained were suppressed in the occurrence of defects even after being repeatedly exposed to a high temperature-low temperature environment, and were repeatedly exposed to a high temperature-low temperature environment. It is clear that the spectral fluctuation (change in transmittance) is small even afterwards. Further, in comparison with Examples 1 to 21, when the total content of the specific metal ions in the composition is 0.03 to 10 mass ppm with respect to the total mass of the composition, it is repeated in a high temperature-low temperature environment. It was confirmed that the cured film after exposure was superior in defect suppression.

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Abstract

La présente invention concerne une composition capable de fournir un film durci dans lequel l'apparition des défauts est supprimée même après l'exposition répétée à un environnement de température élevée-température basse. La présente invention concerne également un film de revêtement, un film durci, une lentille, un dispositif d'imagerie à l'état solide, et une nouvelle résine. La composition contient une résine contenant un motif de répétition représenté par la formule générale (I-1) ou un motif de répétition représenté par la formule générale (I-2), un solvant, et un ion métallique spécifique sélectionné dans le groupe constitué d'un ion sodium, ion potassium, et ion calcium, et la teneur totale de l'ion métallique spécifique est de 0,01 à 30 ppm en masse par rapport à la masse totale de la composition.
PCT/JP2019/005653 2018-02-28 2019-02-15 Composition, film de revêtement, film durci, lentille, dispositif d'imagerie à l'état solide, résine WO2019167681A1 (fr)

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JP2020503397A JP7008791B2 (ja) 2018-02-28 2019-02-15 組成物、塗布膜、硬化膜、レンズ、固体撮像素子、樹脂

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US20200142307A1 (en) * 2018-11-07 2020-05-07 Tokyo Ohka Kogyo Co., Ltd. Chemically amplified positive-type photosensitive resin composition, photosensitive dry film, method of manufacturing photosensitive dry film, method of manufacturing patterned resist film, method of manufacturing substrate with template and method of manufacturing plated article
CN114599704A (zh) * 2019-10-25 2022-06-07 日产化学株式会社 含三嗪环的聚合物及含有该聚合物的膜形成用组合物
WO2022225017A1 (fr) * 2021-04-23 2022-10-27 日産化学株式会社 Composition de type sans solvant

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WO2015098788A1 (fr) * 2013-12-24 2015-07-02 日産化学工業株式会社 Composition contenant un polymère de triazine
WO2016114337A1 (fr) * 2015-01-15 2016-07-21 日産化学工業株式会社 Polymère contenant un cycle triazine et composition le contenant
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JP6412316B2 (ja) * 2013-10-01 2018-10-24 出光興産株式会社 トリアジン環含有ポリマーを含む組成物
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JPS5177700A (en) * 1974-12-04 1976-07-06 Bayer Ag Ss toriajinpurehorimaa no seizohoho
JP2004156001A (ja) * 2002-11-07 2004-06-03 Sanei Kagaku Kk フェノール性水酸基を含有するトリアジンジハライド及び芳香族（ポリ）グアナミン、並びにその組成物
JP2007077230A (ja) * 2005-09-13 2007-03-29 Toyobo Co Ltd ポリイミドフィルム
WO2015098788A1 (fr) * 2013-12-24 2015-07-02 日産化学工業株式会社 Composition contenant un polymère de triazine
WO2016114337A1 (fr) * 2015-01-15 2016-07-21 日産化学工業株式会社 Polymère contenant un cycle triazine et composition le contenant
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20200142307A1 (en) * 2018-11-07 2020-05-07 Tokyo Ohka Kogyo Co., Ltd. Chemically amplified positive-type photosensitive resin composition, photosensitive dry film, method of manufacturing photosensitive dry film, method of manufacturing patterned resist film, method of manufacturing substrate with template and method of manufacturing plated article
CN114599704A (zh) * 2019-10-25 2022-06-07 日产化学株式会社 含三嗪环的聚合物及含有该聚合物的膜形成用组合物
EP4050049A4 (fr) * 2019-10-25 2023-11-15 Nissan Chemical Corporation Polymère contenant un cycle triazine et composition filmogène le contenant
WO2022225017A1 (fr) * 2021-04-23 2022-10-27 日産化学株式会社 Composition de type sans solvant

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