Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
  • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B32—LAYERED PRODUCTS
  • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
  • B32B27/00—Layered products comprising a layer of synthetic resin
  • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy 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
  • 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
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B57/00—Other synthetic dyes of known constitution
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
  • C09B67/006—Preparation of organic pigments
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
  • G02B5/22—Absorbing filters
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
  • H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
  • H10F39/10—Integrated devices
  • H10F39/12—Image sensors

Definitions

• the present invention relates to a curable composition used for manufacturing an optical filter or the like.
• the present invention also relates to a film, an optical filter, a solid-state image sensor, and an image display device.
• CCD charge-coupled device
• CMOS complementary metal oxide semiconductor
• an ultraviolet cut filter is also provided separately in addition to the infrared cut filter.
• Patent Document 1 has a transparent resin body having a one-layer or multilayer structure made of a transparent resin and a light reflecting layer made of a dielectric multilayer film, and the transparent resin body has a maximum absorption wavelength of 370 to 425 nm.
• An invention relating to an optical filter including a near-ultraviolet absorbing dye (U) having a wavelength of 600 to 800 nm and a near-infrared absorbing dye (A) having a maximum absorption wavelength at a wavelength of 600 to 800 nm is described.
• the present invention provides: ⁇ 1> A curable composition containing an infrared absorbing dye, an ultraviolet absorbing agent, and a curable compound, which contains 100 to 5000 parts by mass of the ultraviolet absorbing agent with respect to 100 parts by mass of the infrared absorbing dye. , The curable composition, wherein the content of the ultraviolet absorber in the total solid content of the curable composition is 15 to 50% by mass. ⁇ 2> The curable composition according to ⁇ 1>, wherein the curable compound contains a compound having an epoxy group. ⁇ 3> The curable composition according to ⁇ 2>, wherein the compound having an epoxy group has a weight average molecular weight of 5000 to 100,000.
• ⁇ 4> The curable composition according to ⁇ 2> or ⁇ 3>, wherein the epoxy group-containing compound has an epoxy group value of 1 mmol / g or more.
• ⁇ 5> The curable composition according to any one of ⁇ 1> to ⁇ 4>, wherein the ultraviolet absorber is a compound having a maximum absorption wavelength in the wavelength range of 340 to 420 nm.
• ⁇ 6> The above-mentioned one of ⁇ 1> to ⁇ 5>, wherein the maximum value of the molar extinction coefficient in the wavelength range of 340 to 420 nm of the ultraviolet absorber is 5000 L ⁇ mol -1 ⁇ cm -1 or more. Curable composition.
• ⁇ 7> The curable composition according to any one of ⁇ 1> to ⁇ 6>, wherein the infrared absorbing dye is a compound having a maximum absorption wavelength in the wavelength range of 650 to 1000 nm.
• the maximum value of the molar extinction coefficient in the wavelength range of 650 to 1000 nm of the infrared absorbing dye is 50,000 L ⁇ mol -1 ⁇ cm -1 or more. Curable composition.
• ⁇ 9> The curable composition according to any one of ⁇ 1> to ⁇ 8>, wherein the infrared absorbing dye is at least one selected from a pyrrolopyrrole compound, a cyanine compound, a phthalocyanine compound, and a squarylium compound.
• the curable composition according to any one of ⁇ 1> to ⁇ 9> which contains 50 to 500 parts by mass of the curable compound with respect to 100 parts by mass of the ultraviolet absorber.
• the transmittance for light having a wavelength of 390 nm in the thickness direction of the film is 20% or less, and the transmittance for light having a wavelength of 650 to 1000 nm.
• ⁇ 13> A film obtained by curing the curable composition according to any one of ⁇ 1> to ⁇ 12>.
• ⁇ 14> A laminate having the film according to ⁇ 13> and a film containing an infrared absorber.
• ⁇ 16> A solid-state image sensor including the film according to ⁇ 13>.
• ⁇ 17> An image display device including the film according to ⁇ 13>.
• a curable composition capable of forming a film having excellent ultraviolet shielding properties and infrared shielding properties. Further, it is possible to provide a film, an optical filter, a solid-state image pickup device, and an image display device having excellent infrared ray shielding property and ultraviolet ray shielding property.
• 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 emission line spectra of mercury lamps, far ultraviolet rays typified by excimer lasers, 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.
• weight average molecular weight and number average molecular weight are defined as polystyrene-equivalent values in gel permeation chromatography (GPC) measurements.
• GPC gel permeation chromatography
• Me in the chemical formula represents a methyl group
• Et represents an ethyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• infrared rays refer to light (electromagnetic waves) having a wavelength of 700 to 2500 nm.
• the total solid content means the total mass of all the components of the composition excluding the solvent.
• the pigment means a coloring material that is difficult to dissolve in a solvent.
• the 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 curable composition of the present invention is a curable composition containing an infrared absorbing dye, an ultraviolet absorber, and a curable compound, and the ultraviolet absorber is 100 to 100 parts by mass with respect to 100 parts by mass of the infrared absorbing dye. It contains 5000 parts by mass and is characterized in that the content of the ultraviolet absorber in the total solid content of the curable composition is 15 to 50% by mass.
• the curable composition of the present invention it is possible to form a film having excellent ultraviolet shielding properties and infrared shielding properties.
• the transmittance for light having a wavelength of 390 nm in the thickness direction of the film is 20% or less, and the minimum value of the transmittance for light having a wavelength of 650 to 1000 nm. Is preferably 25% or less.
• the transmittance of the film with respect to light having a wavelength of 390 nm is preferably 20% or less, more preferably 10% or less, and even more preferably 3% or less.
• the minimum value of the transmittance of the film for light having a wavelength of 650 to 1000 nm is preferably 25% or less, and more preferably 10% or less.
• the minimum value of the transmittance of the film for light having a wavelength of 450 to 550 nm is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more.
• the average transmittance of the film for light having a wavelength of 450 to 550 nm is preferably 80% or more, more preferably 85% or more, and further preferably 90% or more.
• the film exhibiting the above spectral characteristics is preferably a film having a film thickness of 8 ⁇ m formed by applying a curable composition onto a support such as a glass substrate and drying at 200 ° C. for 5 minutes.
• the curable composition of the present invention can be used as a composition for an optical filter.
• the optical filter include a filter that shields infrared rays and ultraviolet rays and transmits visible light.
• the solid content concentration of the curable composition of the present invention is preferably 10 to 50% by mass, more preferably 15 to 45% by mass, and even more preferably 20 to 40% by mass.
• the curable composition of the present invention contains an infrared absorbing dye.
• the infrared absorbing dye is preferably an organic compound.
• the infrared absorbing dye is preferably a compound having a maximum absorption wavelength in the wavelength range of 650 to 1000 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 650 to 900 nm, and a wavelength of 650 to 800 nm. It is more preferable that the compound has a maximum absorption wavelength in the range of.
• the maximum value of the molar extinction coefficient in the wavelength range of 650 to 1000 nm of the infrared absorbing dye is preferably 50,000 L ⁇ mol -1 ⁇ cm -1 or more, and more preferably 100,000 L ⁇ mol -1 ⁇ cm -1 or more. , 150,000 L ⁇ mol -1 ⁇ cm -1 or more is more preferable.
• the infrared absorbing dye may be a pigment (hereinafter, also referred to as an infrared absorbing pigment) or a dye (hereinafter, also referred to as an infrared absorbing dye).
• the infrared absorbing dye is preferably a compound having a ⁇ -conjugated plane containing an aromatic ring of a monocyclic ring or a condensed ring.
• the number of atoms other than hydrogen constituting the ⁇ -conjugated plane of the above-mentioned compound is preferably 6 or more, and more preferably 14 or more.
• the upper limit is preferably, for example, 50 or less.
• the total number of atoms other than hydrogen constituting each ⁇ -conjugated plane is preferably 14 or more, and more preferably 20 or more.
• the upper limit is preferably 80 or less, for example.
• the number of atoms other than hydrogen constituting one ⁇ -conjugated plane is preferably 6 or more, and more preferably 14 or more.
• the upper limit is preferably, for example, 50 or less.
• the ⁇ -conjugated plane of the above-mentioned compound preferably contains two or more aromatic rings of a monocyclic or condensed ring, more preferably three or more of the above-mentioned aromatic rings, and more preferably three or more of the above-mentioned aromatic rings. It is more preferable to contain 4 or more of the above-mentioned aromatic rings, and it is particularly preferable to contain 5 or more of the above-mentioned aromatic rings.
• the upper limit is preferably 100 or less, more preferably 50 or less, and even more preferably 30 or less.
• aromatic ring examples include a benzene ring, a naphthalene ring, a pentalene ring, an inden ring, an azulene ring, a heptalene ring, an indacene ring, a perylene ring, a pentacene ring, a quaterylene ring, an acenaphthene ring, a phenanthren ring, anthracene ring, and a naphthacene ring.
• Examples of the infrared absorbing dye include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds and azomethine.
• Examples thereof include compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes and the like, and pyrrolopyrrole compounds, cyanine compounds or squarylium compounds and phthalocyanine compounds are preferable because they can achieve both heat resistance and infrared shielding properties at a high level. , Pyrrolopyrrole compounds are more preferred.
• 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 paragraph No. 0124 of JP-A-2017-066963, the compound described in International Publication No. 2017/135359, the compound described in JP-A-2017-114956, the compound described in Japanese Patent Application Laid-Open No. 6197940 examples thereof include the compounds described in International Publication No. 2016/120166.
• Examples of the cyanine compound include the compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, the compounds described in paragraph numbers 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004. , The compound described in JP-A-2015-172102, the compound described in JP-A-2008-084246, the compound described in paragraph No. 0090 of International Publication No. 2016/190162, JP-A-2017-031394. Examples thereof include the compounds described in.
• Examples of the croconium compound include the compounds described in JP-A-2017-082029.
• Examples of the iminium compound include the compound described in JP-A-2008-528706, the compound described in JP-A-2012-02239, the compound described in JP-A-2007-09260, and International Publication No. 2018/043564. Examples thereof include the compounds described in paragraphs 0048 to 0063 of.
• Examples of the phthalocyanine compound include the compound described in paragraph No. 0093 of JP2012-077153, the oxytitanium phthalocyanine described in JP2006-343631, and paragraphs 0013 to 0029 of JP2013-195480. , The vanadium phthalocyanine compound described in Japanese Patent No. 6081771, and the compound described in International Publication No. 2020/071470.
• naphthalocyanine compound examples include the compound described in paragraph No. 0093 of JP2012-07715A.
• dithiolene metal complex examples include the compounds described in Japanese Patent No. 5733804.
• Examples of the infrared absorbing dye 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. 2017/213047, The pyrrole ring-containing compound described in paragraphs 0019 to 0075 of Japanese Patent Application Laid-Open No.
• Concatenated squalylium compound compound having a pyrrolbis-type squalylium skeleton or croconium skeleton described in JP-A-2017-141215, dihydrocarbazole-type squarylium compound described in JP-A-2017-082029, JP-A-2017-066120
• the asymmetric compound described in paragraphs 0027 to 0114 of Japanese Patent Application Laid-Open No. 2017-067963, the pyrrol ring-containing compound (carbazole type) described in Japanese Patent Application Laid-Open No. 2017-067963, the phthalocyanine compound described in Japanese Patent No. 6251530, and the like are used. You can also do it.
• the infrared absorbing dye a commercially available product can also be used as the infrared absorbing dye. Examples of commercially available infrared absorbing dyes include FDR-003 and FDR-004 (all manufactured by Yamada Chemical Co., Ltd.
• a compound having an acid group or a basic group can also be used.
• the acid group include a carboxyl group, a sulfo group, a carboxylic acid amide group, a sulfonamide group, an imic acid group and salts thereof.
• the atoms or atomic groups constituting the salt 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 ions.
• RX1 to RX6 independently represent an alkyl group or an aryl group, respectively.
• the alkyl group and aryl group represented by RX1 to RX6 may have a substituent.
• the substituent is preferably a halogen atom, more preferably a fluorine atom.
• Examples of the basic group include an amino group, a pyridinyl group and a salt thereof, a salt of an ammonium group, and a phthalimidemethyl group.
• Examples of the atom or atomic group constituting the salt include hydroxide ion, halogen ion, carboxylic acid ion, sulfonic acid ion, and phenoxide ion.
• infrared absorbing dye examples include the compounds described in Examples described later.
• the content of the infrared absorbing dye in the total solid content of the curable composition is preferably 1 to 25% by mass.
• the upper limit is preferably 23% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
• the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and further preferably 4% by mass or more.
• the infrared absorbing dye may be used alone or in combination of two or more. When two or more types are used together, the total of them is in the above range.
• the curable composition of the present invention contains an ultraviolet absorber.
• the ultraviolet absorber in the present specification is an organic compound having an ultraviolet absorbing function.
• the ultraviolet absorber is preferably a compound having an action of absorbing ultraviolet rays, converting them into heat energy and the like, and diverging them.
• the ultraviolet absorber is preferably a compound that is stable against ultraviolet rays. That is, the ultraviolet absorber is preferably a compound in which the molecule is not easily broken by a reaction such as decomposition, oxidation, or reduction by irradiation with ultraviolet rays.
• the ultraviolet absorber is preferably a compound having a maximum absorption wavelength in the wavelength range of 340 to 420 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 345 to 400 nm, and a wavelength of 350 to 390 nm. It is more preferable that the compound has a maximum absorption wavelength in the range of. Further, the maximum value of the molar extinction coefficient in the wavelength range of 340 to 420 nm of the ultraviolet absorber is preferably 5000 L ⁇ mol -1 ⁇ cm -1 or more, and preferably 10000 L ⁇ mol -1 ⁇ cm -1 or more. It is more preferably 13000 L ⁇ mol -1 ⁇ cm -1 or more. The upper limit is preferably, for example, 100,000 L ⁇ mol -1 ⁇ cm -1 or less.
• the ultraviolet absorber examples include conjugated diene compounds, methyldibenzoyl compounds, triazine compounds, benzotriazole compounds, benzophenone compounds, salicylate compounds, coumarin compounds, acrylonitrile compounds, benzodithiazole compounds, silicic acid compounds, and ⁇ - ⁇ unsaturated ketones. , Carbostylyl compound, merocyanine compound and the like, and triazine compounds, benzotriazole compounds and benzophenone compounds are preferable because they can achieve both heat resistance and ultraviolet shielding property at a high level. Further, the ultraviolet absorber is preferably a compound different from the photopolymerization initiator such as a photoradical polymerization initiator that efficiently generates active species such as radicals by irradiation with ultraviolet rays.
• the ultraviolet absorber is preferably a compound having at least one functional group selected from a hydroxy group, a carboxyl group and an amino group, and more preferably a compound having a hydroxy group.
• an ultraviolet absorber having such a functional group when a compound having an epoxy group is used as the curable compound described later, the functional group of the ultraviolet absorber and the epoxy group of the compound having an epoxy group are used.
• the apparent molecular weight is improved, and the ultraviolet absorber is incorporated into the membrane to suppress the sublimation and decomposition of the ultraviolet absorber when the membrane is heated. can. Therefore, by using the compound having an epoxy group and the ultraviolet absorber having the above-mentioned functional group in combination, a film having more excellent heat resistance can be formed.
• the conjugated diene compound is preferably a compound represented by the following formula (UV-1).
• R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 are They may be the same or different from each other. However, at least one of R 1 and R 2 is an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms. R 1 and R 2 may form a cyclic amino group together with the nitrogen atom to which R 1 and R 2 are bonded.
• cyclic amino group examples include a piperidino group, a morpholino group, a pyrrolidine group, a hexahydroazepino group, a piperazino group and the like.
• R 1 and R 2 are each independently preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 5 carbon atoms.
• R 3 and R 4 each independently represent an electron-withdrawing group.
• Each of R 3 and R 4 shall be an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group or a sulfamoyl group, respectively.
• an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group or a sulfamoyl group is more preferable.
• R 3 and R 4 may be bonded to each other to form a cyclic electron-withdrawing group. Cyclic electron-withdrawing groups formed by bonding R 3 and R 4 to each other include, for example, a 6-membered ring containing two carbonyl groups.
• At least one of R 1 , R 2 , R 3 and R 4 of the formula (UV-1) may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.
• UV-1 The description of the substituent of the ultraviolet absorber represented by the formula (UV-1) can be referred to in paragraphs 0024 to 0033 of JP2009-265642A, and the contents thereof are incorporated in the present specification.
• Specific examples of the ultraviolet absorber represented by the formula (UV-1) include compounds having the following structures, compounds described in paragraphs 0034 to 0036 of JP2009-265642A, and the like.
• UV-503 manufactured by Daito Chemical Co., Ltd.
• UV-1 can be mentioned as a commercially available product of the ultraviolet absorber represented by the formula (UV-1).
• the methyldibenzoyl compound is preferably a compound represented by the following formula (UV-2).
• R 101 and R 102 each independently represent a substituent, and m1 and m2 each independently represent 0-4.
• the substituents represented by R 101 and R 102 include a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroarryloxy group, an alkylthio group, an arylthio group and a heteroally.
• Lucio group -NR U1 R U2 , -COR U3 , -COOR U4 , -OCOR U5 , -NHCOR U6 , -CONR U7 R U8 , -NHCONR U9 R U10 , -NHCOOR U11 , -SO 2 R U12 , -SO 2 OR U13 , -NHSO 2 RU14 and -SO 2 NR U15 RU16 can be mentioned.
• Each of RU1 to RU16 independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.
• the substituents represented by R 101 and R 102 are independently alkyl groups or alkoxy groups, respectively.
• the number of carbon atoms of the alkyl group is preferably 1 to 20, more preferably 1 to 10.
• Examples of the alkyl group include linear, branched and cyclic, and linear or branched is preferable, and branching is more preferable.
• the number of carbon atoms of the alkoxy group is preferably 1 to 20, more preferably 1 to 10.
• the alkoxy group is preferably linear or branched, more preferably branched.
• UV-2 a combination in which one of R 101 and R 102 is an alkyl group and the other is an alkoxy group is preferable.
• M1 and m2 independently represent 0 to 4, respectively.
• M1 and m2 are each independently preferably 0 to 2, more preferably 0 to 1, and particularly preferably 1.
• UV-2 Specific examples of the compound represented by the formula (UV-2) include avobenzone.
• the triazine compound is preferably a compound represented by the following formula (UV-3-1), (UV-3-2) or (UV-3-3).
• R d1 is independently a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 3 to 8 carbon atoms or an aryl group having 6 to 18 carbon atoms, an alkylaryl group having 7 to 18 carbon atoms or carbon. Represents an arylalkyl group of number 7-18.
• the alkyl group, alkenyl group, aryl group, alkylaryl group and arylalkyl group may have a substituent. Examples of the substituent include the groups described in the above-mentioned substituent Ti.
• R d2 to R d9 are independently hydrogen atom, halogen atom, hydroxy group, alkyl group having 1 to 15 carbon atoms, alkenyl group having 3 to 8 carbon atoms or aryl group having 6 to 18 carbon atoms, and carbon.
• the alkyl group, alkenyl group, aryl group, alkylaryl group and arylalkyl group may have a substituent. Examples of the substituent include the groups described in the above-mentioned substituent Ti.
• triazine compound examples include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine, 2- [4-[(2-Hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3 , 5-Triazine, 2- (2,4-dihydroxyphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-Triazine and other mono (hydroxyphenyl) triazine compounds; 2,4 -Bis (2-hydroxy-4-propyloxyphenyl) -6- (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-3-methyl-4-propyl) Oxyphenyl) -6
• the benzotriazole compound is preferably a compound represented by the following formula (UV-4).
• R e1 to R e3 are independently hydrogen atom, halogen atom, hydroxy group, alkyl group having 1 to 9 carbon atoms, alkoxy group having 1 to 9 carbon atoms, alkylaryl group having 7 to 18 carbon atoms or carbon. Represents an arylalkyl group of number 7-18.
• Alkyl groups, alkylaryl groups and arylalkyl groups may have substituents. Examples of the substituent include the group described in the above-mentioned substituent Ti, and an alkoxycarbonyl group having 1 to 9 carbon atoms is preferable.
• benzotriazole compound examples include 2- (2'-hydroxy-3', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole and 2- (2'-hydroxy-3'-tert-. Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy) -3'-Isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2' -Hydroxy-3', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- [2'-hydroxy-5'-(
• Examples of commercially available products include TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 326, TINUVIN 328, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 171 and TINUVIN 1130 (all manufactured by BASF).
• the benzotriazole compound the MYUA series made by Miyoshi Oil & Fat may be used.
• benzophenone compound examples include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, and 2-hydroxy-. Examples thereof include 4-methoxybenzophenone, 2,4-dihydroxybenzophenone and 2-hydroxy-4-octoxybenzophenone. Examples of commercially available benzophenone compounds include UvinulA, Uvinul049, and Uvinul3050 (all manufactured by BASF).
• salicylate compound examples include phenyl salicylate, p-octylphenyl salicylate, and pt-butylphenyl salicylate.
• Examples of the coumarin compound include coumarin-4, 4-hydroxycoumarin, 7-hydroxycoumarin and the like.
• Examples of the acrylonitrile compound include ethyl 2-cyano-3,3-diphenylacrylate and 2-ethylhexyl 2-cyano-3,3-diphenylacrylate.
• the ultraviolet absorbers include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraph numbers 0052 to 0072 of JP2012-208374A, paragraph numbers 0317 to 0334 of JP2013-066814, and the like.
• the compounds described in paragraphs 0061 to 0080 of JP 2016-162946, paragraphs 0049 to 0059 of Japanese Patent No. 6268967, and paragraphs 0059 to 0076 of International Publication No. 2016/181987 can also be used.
• the curable composition of the present invention contains 100 to 5000 parts by mass of an ultraviolet absorber with respect to 100 parts by mass of an infrared absorbing dye.
• the upper limit is preferably 4000 parts by mass or less, and more preferably 3000 parts by mass or less.
• the lower limit is preferably 200 parts by mass or more, and more preferably 1000 parts by mass or more.
• the total content of the infrared absorbing dye and the ultraviolet absorbing agent in the total solid content of the curable composition is preferably 15 to 50% by mass.
• the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
• the lower limit is preferably 20% by mass or more, and more preferably 25% by mass or more.
• the content of the ultraviolet absorber in the total solid content of the curable composition is 15 to 50% by mass.
• the upper limit is preferably 45% by mass or less, and more preferably 40% by mass or less.
• the lower limit is preferably 18% by mass or more, and more preferably 20% by mass or more.
• the ultraviolet absorber may be used alone or in combination of two or more. When two or more types are used together, the total of them is in the above range.
• the curable composition contains a curable compound.
• the curable compound include compounds having a curable group.
• Specific examples of the curable compound include a compound having an ethylenically unsaturated bond-containing group, a compound having an epoxy group, and the like, and the epoxy group is used because it can form a film having excellent heat resistance and solvent resistance. It is preferably a compound having.
• the epoxy group contained in the compound having an epoxy group may be an alicyclic epoxy group.
• the alicyclic epoxy group means a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed.
• Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a vinylphenyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acryloylamide group, and the like (meth). Allyl groups, (meth) acryloyl groups and (meth) acryloyloxy groups are preferred, and (meth) acryloyloxy groups are more preferred.
• the curable compound may be a monomer or a resin.
• the molecular weight is preferably less than 2000, more preferably 1500 or less.
• the lower limit of the molecular weight is preferably 100 or more, and more preferably 200 or more.
• the weight average molecular weight (Mw) is preferably 2000 to 2000000.
• the upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less, and further preferably 100,000 or less.
• the lower limit of the weight average molecular weight is preferably 3000 or more, and more preferably 5000 or more.
• the compound having an epoxy group used as the curable compound may be a monomer, but is preferably a resin (resin having an epoxy group) because it can form a film having excellent heat resistance.
• the weight average molecular weight of the compound having an epoxy group is preferably 2000 to 100,000, more preferably 2000 to 100,000, still more preferably 5000 to 100,000.
• the epoxy group value of the compound having an epoxy group is preferably 1 mmol / g or more, more preferably 2 mmol / g or more, and further preferably 3 mmol / g or more.
• the upper limit can be 15 mmol / g or less.
• the epoxy base value of the compound having an epoxy group is a numerical value representing the molar amount of the epoxy group per 1 g of the solid content of the compound having an epoxy group.
• a resin containing a repeating unit having an epoxy group (resin having an epoxy group) is preferably used.
• the repeating unit having an epoxy group include a repeating unit represented by the following formula (Ep-1).
• X ep1 represents a trivalent linking group
• Lep1 represents a single bond or a divalent linking group
• Z ep1 represents an epoxy group
• Examples of the trivalent linking group represented by X ep1 of the formula (Ep-1) include a poly (meth) acrylic linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, and a polyurea-based linking group.
• Examples thereof include polyamide-based linking groups, polyether-based linking groups, polystyrene-based linking groups, bisphenol-based linking groups, novolak-based linking groups, poly (meth) acrylic-based linking groups, polyether-based linking groups, polyester-based linking groups, Bisphenol-based linking groups and novolak-based linking groups are preferable, and poly (meth) acrylic-based linking groups are more preferable.
• Examples of the divalent linking group represented by Lep1 of the formula (Ep-1) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), and-. NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S- and groups consisting of a combination of two or more of these can be mentioned.
• the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
• the content of the repeating unit having an epoxy group in all the repeating units of the resin having an epoxy group is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, and 50 to 100% by mass. Is more preferable.
• the resin having an epoxy group may further contain a repeating unit other than the repeating unit having an epoxy group.
• Examples of the compound having an epoxy group include the compounds described in paragraphs 0034 to 0036 of JP2013-011869, the compounds described in paragraphs 0147 to 0156 of JP2014-043556, and JP-A-2014.
• the compounds described in paragraphs 805 to 0092 of Japanese Patent Application Laid-Open No. 089408 and the compounds described in JP-A-2017-179172 can also be used.
• a resin having an ethylenically unsaturated bond-containing group can be preferably used as the compound having an ethylenically unsaturated bond-containing group.
• the resin having an ethylenically unsaturated bond-containing group include a resin containing a repeating unit having an ethylenically unsaturated bond-containing group.
• the repeating unit having an ethylenically unsaturated bond-containing group include a repeating unit represented by the following formula (E-1).
• X e1 represents a trivalent linking group
• Le 1 represents a single bond or a divalent linking group
• Z e1 represents an ethylenically unsaturated bond-containing group.
• Examples of the trivalent linking group represented by X e1 of the formula (E-1) include a poly (meth) acrylic linking group, a polyalkyleneimine-based linking group, a polyester-based linking group, a polyurethane-based linking group, and a polyurea-based linking group.
• Examples thereof include a polyamide-based linking group, a polyether-based linking group, a polystyrene-based linking group, and the like, a poly (meth) acrylic-based linking group, a polyether-based linking group, and a polyester-based linking group are preferable, and a poly (meth) acrylic-based linking group is preferable. Is more preferable.
• Examples of the divalent linking group represented by Le 1 of the formula (E-1) include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), and-. NH-, -SO-, -SO 2- , -CO-, -O-, -COO-, -OCO-, -S- and groups composed of a combination of two or more of these can be mentioned.
• the alkylene group may be linear, branched, or cyclic, and is preferably linear or branched. Further, the alkylene group may have a substituent or may be unsubstituted. Examples of the substituent include a hydroxy group and an alkoxy group.
• Examples of the ethylenically unsaturated bond-containing group represented by Z e1 of the formula (E-1) include a vinyl group, a vinylphenyl group, a (meth) allyl group, a (meth) acryloyl group, a (meth) acryloyloxy group, and (meth). Examples thereof include an acryloyl amide group.
• a monomer type compound can also be used as the compound having an ethylenically unsaturated bond-containing group.
• a compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound. Specific examples thereof include paragraph numbers 0995 to 0108 of JP2009-288705, paragraphs 0227 of JP2013-029760, paragraphs 0254 to 0257 of JP2008-292970, and paragraphs 0254 to 0257 of JP2013-253224.
• Examples of the compound having an ethylenically unsaturated bond-containing group include dipentaerythritol tri (meth) acrylate (commercially available KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.) and dipentaerythritol tetra (meth) acrylate (commercially available).
• KAYARAD D-320 manufactured by Nippon Kayaku Co., Ltd.
• dipentaerythritol penta (meth) acrylate commercially available KAYARAD D-310; manufactured by Nihonkayaku Co., Ltd.
• dipentaerythritol hexa (meth) ) Acrylate (as a commercial product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
• the (meth) acryloyl group of these compounds is ethylene glycol and / Or a compound having a structure bonded via a propylene glycol residue (for example, SR454, SR499 commercially available from Sartmer), diglycerin EO (ethylene oxide) modified (meth) acrylate (commercially available as M-).
• Examples of the compound having an ethylenically unsaturated bond-containing group include trimethylolpropane tri (meth) acrylate, trimethylolpropane propylene oxide-modified tri (meth) acrylate, trimethylolpropane ethylene oxide-modified tri (meth) acrylate, and isocyanuric acid ethylene oxide. It is also preferable to use a trifunctional (meth) acrylate compound such as a modified tri (meth) acrylate or pentaerythritol tri (meth) acrylate.
• trifunctional (meth) acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305. , M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) And so on.
• a compound having an ethylenically unsaturated bond-containing group a compound having an acid group such as a carboxyl group, a sulfo group and a phosphoric acid group can also be used.
• Examples of commercially available products of such compounds include Aronix M-305, M-510, M-520, Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) and the like.
• a compound having a caprolactone structure can also be used.
• the description in paragraphs 0042 to 0045 of JP2013-253224A can be referred to, and the content thereof is incorporated in the present specification.
• Examples of the compound having a caprolactone structure include DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series.
• a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used.
• Such a compound is preferably a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group and / or a propyleneoxy group, and is a compound having an ethylenically unsaturated bond-containing group and an ethyleneoxy group. It is more preferable to have a 3 to 6 functional (meth) acrylate compound having 4 to 20 ethyleneoxy groups.
• SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartmer, and trifunctional (meth) acrylate having three isobutyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. KAYARAD TPA-330 and the like.
• a polymerizable compound having a fluorene skeleton can also be used.
• examples of commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemical Co., Ltd., (meth) acrylate monomer having a fluorene skeleton).
• the compound having an ethylenically unsaturated bond-containing group 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.).
• the content of the curable compound in the total solid content of the curable composition is preferably 20 to 75% by mass.
• the upper limit is preferably 70% by mass or less, and more preferably 65% by mass or less.
• 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. Further, it is preferable to contain 50 to 500 parts by mass of the curable compound with respect to 100 parts by mass of the ultraviolet absorber.
• the upper limit is preferably 450 parts by mass or less, more preferably 400 parts by mass or less, and further preferably 300 parts by mass or less.
• the lower limit is preferably 75 parts by mass or more, more preferably 100 parts by mass or more, and further preferably 150 parts by mass or more.
• the content of the compound having an epoxy group in the total solid content of the curable composition is preferably 20 to 75% by mass.
• the upper limit is preferably 70% by mass or less, and more preferably 65% by mass or less.
• 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. Further, it is preferable that the compound having an epoxy group is contained in an amount of 50 to 500 parts by mass with respect to 100 parts by mass of the ultraviolet absorber.
• the upper limit is preferably 450 parts by mass or less, more preferably 400 parts by mass or less, and further preferably 300 parts by mass or less.
• the lower limit is preferably 75 parts by mass or more, more preferably 100 parts by mass or more, and further preferably 150 parts by mass or more.
• the curable compound may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total of them is within the above range.
• the curable composition may further contain a resin in addition to the curable compound described above.
• the resin is blended, for example, for the purpose of dispersing a pigment or the like in a resin composition or for the purpose of a binder.
• a resin mainly used for dispersing a pigment or the like in a resin composition is also referred to as a dispersant.
• such an application of the resin is an example, and the resin can be used for purposes other than such an application.
• the resin having a curable group is a curable compound.
• the weight average molecular weight (Mw) of the resin is preferably 2000 to 2000000.
• the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 100,000 or less.
• the lower limit is preferably 3000 or more, and 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 polyamide resin.
• examples thereof include polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyurethane resin, polyurea resin and the like.
• One of these resins may be used alone, or two or more thereof may be mixed and used.
• a norbornene resin is preferable from the viewpoint of improving heat resistance.
• Examples of commercially available norbornene resins include the ARTON series manufactured by JSR Corporation (for example, ARTON F4520). Further, as the resin, the resin described in the examples of International Publication No. 2016/088644 can also be used.
• a resin having an acid group can also be used.
• the acid group include a carboxyl group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group. These acid groups may be only one kind or two or more kinds.
• the resin having an acid group can also be used as a dispersant.
• the acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g.
• the lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more.
• the upper limit is preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, further preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.
• the resin contains a repeating unit derived from a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimer”). It is also preferable to use a resin.
• 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 description in JP-A-2010-168539 can be referred to.
• paragraph number 0317 of JP2013-209760A can be referred to, and this content is incorporated in the present specification.
• R 1 represents a hydrogen atom or a methyl group
• R 21 and R 22 each independently represent an alkylene group
• n represents an integer of 0 to 15.
• the alkylene group represented by R 21 and R 22 preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, further preferably 1 to 3 carbon atoms, and particularly preferably 2 or 3 carbon atoms.
• n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and even more preferably an integer of 0 to 3.
• Examples of the compound represented by the formula (X) include ethylene oxide of paracumylphenol or propylene oxide-modified (meth) acrylate.
• Examples of commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
• a resin as a dispersant can also be used.
• 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 basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
• the acid dispersant a resin having an acid group content of 70 mol% or more is preferable when the total amount of the acid group and the basic group is 100 mol%.
• 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 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 basic dispersant (basic resin) a resin in which the amount of basic groups is 60 mol% or more is preferable when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%.
• the basic group contained in the basic dispersant is preferably an amino group.
• the amine value of the basic dispersant (basic resin) is preferably 5 to 100 mgKOH / g.
• the upper limit is preferably 80 mgKOH / g or less, more preferably 60 mgKOH / g or less, and even more preferably 45 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 resin used as the dispersant is a graft resin.
• the description in paragraphs 0025 to 0094 of JP2012-255128A can be referred to, and the contents thereof are incorporated in the present specification.
• the resin used as the dispersant is a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain.
• the polyimine-based dispersant has a main chain having a partial structure having a functional group of pKa14 or less, a side chain having 40 to 10,000 atoms, and a basic nitrogen atom in at least one of the main chain and the side chain.
• the resin to have is preferable.
• the basic nitrogen atom is not particularly limited as long as it is a nitrogen atom exhibiting basicity.
• the description in paragraphs 0102 to 0166 of JP2012-255128A can be referred to, and the contents thereof are incorporated in the present specification.
• the resin used as the dispersant is a resin having a structure in which a plurality of polymer chains are bonded to the core portion.
• resins include dendrimers (including star-shaped polymers).
• specific examples of the dendrimer include the polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962.
• the resin described in Japanese Patent Application Laid-Open No. 2018-087939 can also be used.
• Dispersants are also available as commercial products, and specific examples thereof include DISPERBYK series manufactured by Big Chemie Japan, SOLSPERSE series manufactured by Japan Lubrizol, Efka series manufactured by BASF, and Ajinomoto Fine-Techno (Ajinomoto Fine Techno). Examples include the Ajispar series manufactured by Co., Ltd. Further, the product described in paragraph number 0129 of JP2012-137564A and the product described in paragraph number 0235 of JP2017-194662 can also be used as a dispersant.
• the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077 can also be used.
• the content of the resin in the total solid content of the curable composition is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and 10% by mass. The following is even more preferable.
• the lower limit is preferably 1% by mass or more, more preferably 2% by mass or more, and further preferably 5% by mass or more.
• the total content of the curable compound and the resin in the total solid content of the curable composition is preferably 20 to 75% by mass.
• the upper limit is preferably 70% by mass or less, and more preferably 65% by mass or less.
• the lower limit is preferably 30% by mass or more, more preferably 30% by mass or more, and further preferably 40% by mass or more.
• the resin may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable that the total of them is within the above range.
• the curable composition of the present invention can contain a polymerization initiator.
• the polymerization initiator include a photopolymerization initiator, a thermal polymerization initiator and the like, and a thermal polymerization initiator is preferable.
• the polymerization initiator include radical polymerization initiators and cationic polymerization initiators. It is preferable to select and use it according to the type of curable compound. When a compound having an epoxy group is used as the curable compound, it is preferable to use a cationic polymerization initiator as the polymerization initiator.
• Examples of the cationic polymerization initiator include a thermal acid generator and a photoacid generator.
• the thermal acid generator means a compound that generates an acid by thermal decomposition.
• the photoacid generator means a compound that generates an acid by light irradiation.
• Examples of the thermoacid generator include halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, carboxylic acid ester compounds, phosphoric acid ester compounds, sulfonimide compounds, and sulfonebenzotriazole compounds.
• Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
• onium salt compounds trichloromethyl-s-triazines
• sulfonium salts iodonium salts
• quaternary ammonium salts quaternary ammonium salts
• diazomethane compounds imide sulfonate compounds
• oxime sulfonate compounds examples of the photoacid generator.
• radical polymerization initiator examples include 2,2'-azobisisobutyronitrile (AIBN), 3-carboxypropionitrile, azobismalononitrile, and dimethyl- (2,2') -azobis (2-methyl).
• Azo compounds such as propionate); organic peroxides such as tert-butylperoxybenzoate, benzoyl peroxide, lauroyl peroxide, potassium persulfate; pinacol compounds; trihalomethyltriazine compounds; benzyldimethylketal compounds; ⁇ -hydroxy
• examples thereof include ketone compounds; ⁇ -aminoketone compounds; acylphosphin compounds; phosphinoxide compounds; metallocene compounds; oxime compounds; onium compounds; benzothiazole compounds; coumarin compounds.
• the polymerization 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. 3, 2019 Peroxide-based Photopolymerization Initiator, International Publication No. 2018/221177, Photopolymerization Initiator, International Publication No. 2018/110179, Photopolymerization Initiator, JP-A-2019-043864. Examples thereof include the photopolymerization initiator described in JP-A-2019-044030, the photopolymerization initiator described in JP-A-2019-167313, and the contents thereof are described in the present invention. Incorporated in the specification.
• ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (above, IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure27, Irgacure29. (Manufactured by the company) and the like.
• Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (above, IGM Resins BV), Irgacure 907, Irgacure 369, Irgacure 369, Irger Made) and so on.
• acylphosphine compounds examples include Omnirad 819, Omnirad TPO (above, manufactured by IGM Resins BV), Irgacure 819, and Irgacure TPO (above, manufactured by BASF).
• Examples of the oxime compound include the compound described in JP-A-2001-233842, the compound described in JP-A-2000-080068, the compound described in JP-A-2006-342166, and J. Am. C. S. The compound according to Perkin II (1979, pp. 1653-1660), J. Mol. C. S. The compound described in Perkin II (1979, pp. 156-162), the compound described in Journal of Photopolisr Science and Technology (1995, pp. 202-232), the compound described in JP-A-2000-066385, the compound described in JP-A-2000-066385. Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-109766, compounds described in Japanese Patent No.
• oxime compound examples include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminovtan-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, and the like.
• Examples thereof include a photopolymerization initiator 2) manufactured by ADEKA and described in Japanese Patent Application Laid-Open No. 2012-014052), ADEKA ARCULDS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA Corporation).
• the content of the polymerization initiator in the total solid content of the curable composition is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.
• the lower limit can be 1% by mass or more.
• the curable composition may contain only one type of polymerization initiator, or may contain two or more types of polymerization initiators. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
• the curable composition of the present invention preferably contains a solvent.
• the solvent include water and organic solvents, and organic solvents are preferable.
• 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 tension) 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 solvent in the curable composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass. Only one type of solvent 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 curable composition of the present invention preferably contains a surfactant.
• a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
• the surfactant 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.
• 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 International Publication No. 2014/017669) and the like, Japanese Patent Application Laid-Open No. 2011-.
• the surfactants described in paragraphs 0117 to 0132 of Japanese Patent Application Laid-Open No. 132503 and the surfactants described in JP-A-2020-008634 are mentioned, and the contents thereof are incorporated in the present specification.
• fluorine-based surfactants include, for example, Megafax F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144. , F-437, F-475, F-477, F-479, F-482, F-554, F-555-A, F-556, F-557, F-558, F-559, F-560.
• the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cut off and the fluorine atom volatilizes when heat is applied.
• a fluorine-based surfactant include the Megafuck DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafuck. DS-21 can be mentioned.
• fluorine-based surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
• a fluorine-based surfactant include the fluorine-based surfactants described in JP-A-2016-216602, the contents of which are incorporated in the present specification.
• the fluorine-based surfactant a block polymer can also be used.
• the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy groups and propyleneoxy groups) (meth).
• a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
• the fluorine-containing surfactants described in paragraphs 0016 to 0037 of JP-A-2010-032698 and the following compounds are also exemplified as the fluorine-based surfactants used in the present invention.
• the weight average molecular weight of the above compounds is preferably 3000 to 50,000, for example 14000.
• % indicating the ratio of the repeating unit is mol%.
• a fluorine-based surfactant a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in the side chain can also be used. Specific examples thereof include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP2010-164965, Megafuck RS-101, RS-102, RS-718K, manufactured by DIC Corporation. RS-72-K and the like can be mentioned. Further, as the fluorine-based surfactant, the compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used.
• a fluorine-containing imide salt compound represented by the formula (fi-1) is also preferable to use as a surfactant.
• m represents 1 or 2
• n represents an integer of 1 to 4
• ⁇ represents 1 or 2
• X ⁇ + represents an ⁇ -valent metal ion, a primary ammonium ion, and a first.
• nonionic 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.
• cationic surfactant examples include tetraalkylammonium salt, alkylamine salt, benzalkonium salt, alkylpyridium salt, imidazolium salt and the like. Specific examples thereof include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stealamidomethylpyridium chloride and the like.
• anionic surfactants include dodecylbenzene sulfonic acid, sodium dodecylbenzene sulfonate, sodium lauryl sulfate, sodium alkyldiphenyl ether disulfonate, sodium alkylnaphthalene sulfonate, sodium dialkyl sulfosuccinate, sodium stearate, potassium oleate, and sodium dioctyl.
• Examples thereof include sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkylsulfosuccinate, sodium stearate, sodium oleate, and sodium salt of t-octylphenoxyethoxypolyethoxyethyl sulfate.
• silicone-based surfactant examples 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, 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, Shin-Etsu Chemical Industry Co., Ltd.
• BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 all manufactured by Big Chemie
• FZ-2122 Dow Toray Co., Ltd.
• a compound having the following structure can also be used as the silicone-based surfactant.
• the content of the surfactant in the total solid content of the curable composition is preferably 0.001 to 5% by mass, more preferably 0.005 to 3% by mass. Only one type of surfactant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
• the curable 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 salt (ammonium salt, first cerium salt, etc.), and p-methoxyphenol is preferable.
• the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the curable composition.
• the curable composition may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more kinds are contained, it is preferable that the total amount thereof is within the above range.
• the curable 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 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 and a phenyl group. And the like, the (meth) acryloyl group and the epoxy group are preferable.
• Examples of 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 JP2009-242604. Incorporated in the specification.
• the content of the silane coupling agent in the total solid content of the curable composition is preferably 0.01 to 15% by mass, more preferably 0.05 to 10% by mass. Only one kind of silane coupling agent may be used, or two or more kinds may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
• the curable 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.
• a phosphorus-based antioxidant Tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepine-6] -Il] Oxy] Ethyl] amine, Tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl] ) Oxy] ethyl] amine, ethylbis phosphite (2,4-di-tert-butyl-6-methylphenyl) and the like.
• antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, and Adekastab AO-80. , ADEKA STAB AO-330 (above, manufactured by ADEKA Corporation) and the like. Further, as the antioxidant, the compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compound described in International Publication No. 2017/006600, and the compound described in International Publication No. 2017/1604024 are used. It can also be used.
• the content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
• the curable composition of the present invention is, if necessary, a sensitizer, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer and other auxiliary agents (for example, conductive particles, a defoaming agent, a flame retardant). , 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 curable 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 storage container for the curable composition of the present invention is not particularly limited, and a known storage container can be used.
• a storage container a multi-layer bottle composed of 6 types and 6 layers of resin and 6 types of resin have a 7-layer structure for the purpose of suppressing impurities from being mixed into raw materials and curable compositions. It is also preferable to use a bottle. Examples of such a container include the container described in Japanese Patent Application Laid-Open No. 2015-123351.
• the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the storage stability of the curable composition, and suppressing deterioration of the components.
• the curable composition of the present invention can be prepared by mixing the above-mentioned components. In the production of the curable composition, all the components may be dissolved or dispersed in a solvent at the same time to produce the curable composition, or if necessary, two or more solutions in which each component is appropriately blended or The dispersion may be prepared in advance and mixed at the time of use (at the time of application).
• the mechanical force used for dispersing the particles 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 particles are "Dispersion Technology Complete Works, Published by Information Organization Co., Ltd., July 15, 2005" and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial". Practical application The process and disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open 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.
• a fluororesin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6, nylon-6,6), and a polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultrahigh molecular weight).
• PP polypropylene
• a filter using a material such as (including a polyolefin resin) can be mentioned.
• 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. DFA4201NIEY, 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 obtained by curing the curable composition of the present invention described above.
• the film of the present invention may have a pattern or may be a film having no pattern (flat film).
• the film of the present invention may be laminated on a support and used, or may be peeled off from the support and used.
• the support include a semiconductor base material such as silicon and a transparent base material.
• the transparent base material used as the support is not particularly limited as long as it is made of a material capable of transmitting at least visible light.
• a base material made of a material such as glass or resin can be mentioned.
• the resin include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene and ethylene vinyl acetate copolymers, norbornene resins, polyacrylates and acrylic resins such as polymethylmethacrylate, urethane resins and vinyl chloride resins. , Fluorine resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin and the like.
• the glass examples include soda lime glass, borosilicate glass, non-alkali glass, quartz glass, and glass containing copper.
• the copper-containing glass examples include copper-containing phosphate glass and copper-containing fluoride glass.
• the copper content in the copper-containing glass is preferably 0.1 to 20% by mass, more preferably 0.3 to 17% by mass, and more preferably 0.5 to 15% by mass. Is more preferable.
• the copper-containing glass preferably has a maximum absorption wavelength in the wavelength range of 700 to 1100 nm.
• the lower limit is preferably 800 nm or more, and more preferably 900 nm or more.
• the upper limit is preferably 1050 nm or less, and more preferably 1000 nm or less.
• the glass containing copper a commercially available product can also be used.
• examples of commercially available copper-containing glass include NF-50 (manufactured by AGC Technoglass Co., Ltd.) and the like.
• 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, further preferably 8 ⁇ m or less, and particularly 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, further preferably 0.3 ⁇ m or more, and particularly preferably 0.5 ⁇ m or more.
• the film of the present invention preferably has a maximum absorption wavelength in the wavelength range of 340 to 420 nm, more preferably has a maximum absorption wavelength in the wavelength range of 345 to 400 nm, and has a maximum absorption wavelength in the wavelength range of 350 to 390 nm. It is more preferred that the wavelength is present. Further, the film of the present invention preferably has a maximum absorption wavelength in the wavelength range of 650 to 1000 nm, more preferably has a maximum absorption wavelength in the wavelength range of 650 to 900 nm, and preferably has a maximum absorption wavelength in the wavelength range of 650 to 800 nm. It is more preferable that a maximum absorption wavelength is present.
• the transmittance of the film of the present invention with respect to light having a wavelength of 390 nm is preferably 20% or less, more preferably 10% or less, still more preferably 5% or less.
• the minimum value of the transmittance of the film of the present invention with respect to light having a wavelength of 650 to 1000 nm is preferably 25% or less, more preferably 10% or less, still more preferably 3% or less.
• the minimum value of the transmittance of the film of the present invention with respect to light having a wavelength of 450 to 550 nm is preferably 75% or more, more preferably 80% or more, still more preferably 85% or more.
• the average transmittance of the film of the present invention with respect to light having a wavelength of 450 to 550 nm is preferably 80% or more, more preferably 85% or more, still more preferably 90% or more.
• the film of the present invention can also be used in combination with a film containing an infrared absorber (hereinafter, also referred to as film IR).
• a film containing an infrared absorber hereinafter, also referred to as film IR.
• the infrared absorber contained in the film IR include the infrared absorbing dyes mentioned above as those that can be contained in the curable composition of the present invention.
• the film IR is preferably used by laminating with the film of the present invention.
• the film IR is arranged on the optical path of the film of the present invention. That is, it is preferable that the film of the present invention and the film IR are laminated and used as a laminated body. In the laminated body, the stacking order of the film of the present invention and the film IR is not particularly limited.
• the film of the present invention may be arranged on the incident light side, or the film IR may be arranged.
• the film of the present invention can also be used in combination with a color filter containing a chromatic colorant.
• the color filter can be produced by using a coloring composition containing a chromatic colorant.
• the color filter is arranged on the optical path of the film of the present invention.
• the film of the present invention and a color filter can be laminated and used as a laminated body.
• the film of the present invention and the color filter may or may not be adjacent to each other in the thickness direction.
• the film of the present invention may be formed on a support different from the support on which the color filter is formed, and the film of the present invention may be formed.
• Other members for example, a microlens, a flattening layer, etc. constituting the solid-state image sensor may be interposed between the film and the color filter.
• the film of the present invention can be produced through a step of forming a curable composition layer by applying the above-mentioned curable composition of the present invention and a step of curing the curable composition layer.
• the support include the above-mentioned supports.
• a method for applying the curable composition to the support a known method can be used. For example, 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).
• 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, etc.
• Various printing methods; transfer method using a mold or the like; nano-imprint 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).
• the curable composition applied to the support may be dried (prebaked).
• 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 seconds to 3000 seconds, more preferably 40 to 2500 seconds, and even more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven, or the like.
• the heating temperature is preferably 100 to 240 ° C, more preferably 180 to 230 ° C.
• the heating time is preferably 2 to 10 minutes, more preferably 4 to 8 minutes.
• the heat treatment can be performed on a hot plate, an oven, or the like.
• the film manufacturing method of the present invention may further include a step of forming a pattern.
• the pattern forming method include a pattern forming method using a photolithography method and a pattern forming method using a dry etching method.
• a pattern is formed by a photolithography method, it is preferable to perform a curing treatment of the curable composition layer after forming the pattern.
• the pattern is formed by the dry etching method, it is preferable to form the pattern after performing the curing treatment of the curable composition layer.
• the film of the present invention is used as a flat film, it is not necessary to perform the step of forming a pattern.
• the optical filter of the present invention includes the film of the present invention.
• the optical filter of the present invention preferably has the film of the present invention on a support.
• the support include the above-mentioned supports, and a transparent base material is preferable, a glass base material is more preferable, and a glass base material containing copper is further preferable. According to this aspect, a wide range of infrared rays can be shielded.
• the optical filter of the present invention may further have an inorganic film in addition to the film of the present invention.
• the inorganic film include a dielectric multilayer film.
• the dielectric multilayer film is a film that shields infrared rays by utilizing the effect of light interference. Specifically, it is a film formed by alternately laminating two or more dielectric layers (high-refractive index material layer and low-refractive index material layer) having different refractive indexes. As the material constituting the high refractive index material layer, it is preferable to use a material having a refractive index of 1.7 or more (preferably 1.7 to 2.5).
• titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide or indium oxide are the main components, and titanium oxide, tin oxide and / or cerium oxide are contained in a small amount. Things can be mentioned.
• the material constituting the low refractive index material layer it is preferable to use a material having a refractive index of 1.6 or less (preferably 1.2 to 1.6).
• silica, alumina, lanthanum fluoride, magnesium fluoride and sodium hexafluoride are mentioned.
• each of the high refractive index material layer and the low refractive index material layer is preferably 0.1 ⁇ to 0.5 ⁇ of the wavelength ⁇ (nm) of the infrared ray to be blocked.
• the total number of layers of the high-refractive index material layer and the low-refractive index material layer in the dielectric multilayer film is preferably 2 to 100, more preferably 2 to 60, and even more preferably 2 to 40.
• the description in paragraphs 0255 to 0259 of JP-A-2014-041318 can be referred to, and the contents thereof are incorporated in the present specification.
• the inorganic film may be formed on the surface of the film of the present invention, may be formed between the support and the film of the present invention, and may be formed on the side of the support on which the film of the present invention is formed. May be formed on the opposite surface. Further, the inorganic film may be formed on both sides of the support.
• the optical filter of the present invention can be used for solid-state image pickup devices such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor), and various devices such as infrared sensors and image display devices.
• CCD charge-coupled device
• CMOS complementary metal oxide semiconductor
• the solid-state image sensor of the present invention includes the film of the present invention described above.
• the configuration of the solid-state image sensor is not particularly limited as long as it has the film of the present invention and functions as a solid-state image sensor. For example, the following configuration can be mentioned.
• the support has a transfer electrode formed of a plurality of photodiodes constituting the light receiving area of the solid-state image sensor and polyvinyl, etc., and the photodiode and the transfer electrode are made of tungsten or the like in which only the light receiving portion of the photodiode is opened.
• It has a light-shielding film to be formed, has a device protective film formed of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part on the light-shielding film, and has a color filter on the device protective film.
• the configuration has the membrane of the present invention above or below the color filter.
• a light collecting means (for example, a microlens or the like; the same applies hereinafter) may be provided on or below the color filter on the device protective film.
• the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern.
• the partition wall preferably has a lower refractive index than each pixel. Examples of the image pickup apparatus having such a structure include the apparatus described in JP-A-2012-227478 and JP-A-2014-179757.
• the image display device of the present invention includes the film of the present invention.
• Examples of the image display device include a liquid crystal display device and an organic electroluminescence (organic EL) display device.
• organic EL organic electroluminescence
• the image display device for example, “Electronic Display Device (Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", “Display Device (Junaki Ibuki, Sangyo Tosho Co., Ltd., 1989)” Issuance) ”and so on.
• 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 image display device may have a white organic EL element.
• the white organic EL element preferably has a tandem structure.
• Japanese Patent Application Laid-Open No. 2003-045676 supervised by Akiyoshi Mikami, "Frontiers of Organic EL Technology Development-High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, It is described on pages 326 to 328, 2008 and the like.
• the spectrum of white light emitted by the organic EL element preferably has a strong maximum emission peak in the blue region (430 to 485 nm), the green region (530 to 580 nm), and the yellow region (580 to 620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 to 700 nm) are more preferable.
• ⁇ Preparation of curable composition The raw materials described below were mixed and filtered using a nylon filter (manufactured by Nippon Pole Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a curable composition.
• the dispersion liquid prepared as follows was used.
• the types of near-infrared absorbing dyes, dispersants, and solvents described in the dispersion column of the table below are mixed by parts by mass described in the dispersion column of the table below, and zirconia beads having a diameter of 0.3 mm are further added.
• a dispersion treatment was carried out for 5 hours using a paint shaker, and the beads were separated by filtration to produce a dispersion liquid.
• A-1 Compound with the following structure A-2: Compound with the following structure A-3: Compound with the following structure A-4: Compound with the following structure A-5: Compound with the following structure A-6: Compounds with the following structure A-7: Compound with the following structure A-8: Compounds with the following structure A-9: Compound with the following structure A-10: Compound with the following structure A-111: Compounds with the following structure A-12: Compounds with the following structure A-13: Compound with the following structure A-14: Compound with the following structure A-15: Compound with the following structure A-16: Compound with the following structure A-17: FDR-003 (manufactured by Yamada Chemical Co., Ltd.) A-18: FDR-004 (manufactured by Yamada Chemical Co., Ltd.)
• U-1 Uvinul3050 (manufactured by BASF, a compound having the following structure)
• U-2 Uvinul3049 (manufactured by BASF, a compound having the following structure)
• U-3 Tinuvin477 (made by BASF, hydroxyphenyltriazine-based UV absorber)
• U-4 Tinuvin326 (manufactured by BASF, a compound having the following structure)
• (Dispersant) C-1 Resin having the following structure (the numerical value added to the main chain is the molar ratio, and the numerical value added to the side chain is the number of repeating units. Weight average molecular weight 21000, acid value 36.0 mgKOH / g, amine value 47.0 mgKOH / g)
• C-2 Dispersant (J-1) according to paragraph No. 0211 of JP-A-2011-137125.
• C-4 DISPERBYK-167
• C-5 DISPERBYK-2026
• D-1 Resin having the following structure (the numerical value added to the main chain is the molar ratio.
• D-2 Resin having the following structure (the numerical value added to the main chain is the molar ratio.
• D-3 Resin having the following structure (the numerical value added to the main chain is the molar ratio.
• D-4 Resin having the following structure (the numerical value added to the main chain is the molar ratio.
• E-1 Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 40,000) (Binder resin)
• E-2 Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 11000)
• E-3 Binder 1 according to paragraph No. 0229 of JP2012-173635A.
• E-4 Resin having the following structure (the numerical value added to the main chain is the molar ratio. Weight average molecular weight 30,000)
• F-1 KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., both-terminal carbinol-modified polydimethylsiloxane, hydroxyl value 62 mgKOH / g)
• F-2 KF-6000 (manufactured by Shin-Etsu Chemical Co., Ltd., both-terminal carbinol-modified polydimethylsiloxane, hydroxyl value 120 mgKOH / g)
• the content of the ultraviolet absorber in 100 parts by mass of the infrared absorbing dye of each curable composition and the content of the ultraviolet absorber in the total solid content of the curable composition are shown in the table below.
• Residual color ratio [%] (400 nm optical density of film after heat resistance test / 400 nm optical density before heat resistance test) x 100 [%]
• Transmittance at wavelength 390 nm is less than 5% 4: Transmittance at wavelength 390 nm is 5% or more and less than 10% 3: Transmittance at wavelength 390 nm is 10% or more and less than 20% 2: At wavelength 390 nm Transmittance is 20% or more and less than 30% 1: Transmittance at a wavelength of 390 nm is 30% or more.
• the minimum transmittance at a wavelength of 650 nm to 1000 nm is less than 1% 4: The minimum transmittance at a wavelength of 650 nm to 1000 nm is 1% or more and less than 3% 3: The minimum transmittance at a wavelength of 650 nm to 1000 nm The value is 3% or more and less than 5% 2: The minimum value of the transmittance at a wavelength of 650 nm to 1000 nm is 5% or more and less than 10% 1: The minimum value of the transmittance at a wavelength of 650 nm to 1000 nm is 10% or more.
• the residual color ratio of 400 nm before and after the heat resistance test is 80% or more 4: The residual color ratio of 400 nm before and after the heat resistance test is 70% or more and less than 80% 3: The residual color ratio of 400 nm before and after the heat resistance test is 50 % Or more and less than 70% 2: 400 nm residual color ratio before and after the heat resistance test is 30% or more and less than 50% 1: 400 nm residual color ratio before and after the heat resistance test is less than 30%
• the examples were superior in ultraviolet shielding property and infrared shielding property as compared with the comparative example.
• the curable composition for the first layer shown in the table below was spin-coated on a glass substrate so that the film thickness after post-baking was 8 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a heat treatment (post-baking) was performed at 200 ° C. for 300 seconds using a hot plate to form a first-layer film. The curable composition for the second layer was spin-coated on the obtained first-layer film on a glass substrate so that the film thickness after post-baking was 8 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a heat treatment (post-baking) was performed at 200 ° C.
• the curable composition for the first layer shown in the table below was spin-coated on a glass substrate so that the film thickness after post-baking was 2 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a heat treatment (post-baking) was performed at 200 ° C. for 300 seconds using a hot plate to form a first-layer film.
• the curable composition for the second layer was spin-coated on the obtained first-layer film on a glass substrate so that the film thickness after post-baking was 8 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a heat treatment (post-baking) was performed at 200 ° C.
• the obtained laminate was heat-treated (heat resistance test) at 260 ° C. for 300 seconds using a hot plate.
• the spectroscopy of the laminate after the heat treatment was measured using an ultraviolet-visible near-infrared spectrophotometer, the residual color ratio at 400 nm was measured, and the heat resistance was evaluated according to the same evaluation criteria as in Test Example 1.
• the curable composition for the first layer shown in the table below was spin-coated on a glass substrate so that the film thickness after post-baking was 5 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a heat treatment (post-baking) was performed at 200 ° C. for 300 seconds using a hot plate to form a first-layer film.
• the curable composition for the second layer was spin-coated on the obtained first-layer film on a glass substrate so that the film thickness after post-baking was 1 ⁇ m. Then, using a hot plate, it was heated at 100 ° C. for 120 seconds. Next, a heat treatment (post-baking) was performed at 200 ° C.
• the obtained laminate was heat-treated (heat resistance test) at 260 ° C. for 300 seconds using a hot plate.
• the spectroscopy of the laminate after the heat treatment was measured using an ultraviolet-visible near-infrared spectrophotometer, the residual color ratio at 400 nm was measured, and the heat resistance was evaluated according to the same evaluation criteria as in Test Example 1.

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