WO2023042605A1 - 組成物、膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサ - Google Patents
組成物、膜、光学フィルタ、固体撮像素子、画像表示装置および赤外線センサ Download PDFInfo
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- WO2023042605A1 WO2023042605A1 PCT/JP2022/031413 JP2022031413W WO2023042605A1 WO 2023042605 A1 WO2023042605 A1 WO 2023042605A1 JP 2022031413 W JP2022031413 W JP 2022031413W WO 2023042605 A1 WO2023042605 A1 WO 2023042605A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- 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
- C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
- C08L101/06—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups containing oxygen atoms
- C08L101/08—Carboxyl groups
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- 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
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- 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
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
Definitions
- the present invention relates to a composition containing a near-infrared absorbing pigment.
- the present invention also relates to a film, an optical filter, a solid-state imaging device, an image display device and an infrared sensor using the above composition.
- CCDs charge-coupled devices
- CMOSs complementary metal-oxide semiconductors
- CCDs charge-coupled devices
- CMOSs complementary metal-oxide semiconductors
- These solid-state imaging devices use silicon photodiodes that are sensitive to infrared rays in their light receiving portions. For this reason, a near-infrared cut filter may be provided to correct visibility.
- a near-infrared cut filter is manufactured using a composition containing a near-infrared absorbing dye.
- Pyrrolopyrrole compounds and the like are known as near-infrared absorbing dyes.
- Patent Document 1 proposes a specific boradiazine compound as a near-infrared absorbing dye.
- an object of the present invention is to provide a composition capable of forming a film in which foreign matter defects are suppressed.
- Another object of the present invention is to provide a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor in which foreign matter defects are suppressed.
- the present invention provides the following. ⁇ 1> containing a compound represented by formula (1), a near-infrared absorbing pigment, and a curable compound, A composition in which the content of the compound represented by formula (1) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment;
- R 1 to R 4 each independently represent a substituent, one of R 1 and R 2 is a heteroaryl group, and one of R 3 and R 4 is a heteroaryl group and R5 and R6 each independently represent an alkyl group, an aryl group or a heteroaryl group.
- one of R 1 and R 2 in the above formula (1) is a heteroaryl group and the other is a cyano group;
- the heteroaryl group represented by either one of R 1 and R 2 in the above formula (1) and the heteroaryl group represented by either one of R 3 and R 4 in the above formula (1) are independently The composition according to ⁇ 1> or ⁇ 2>, which is a group represented by formula (A-1) or a group represented by formula (A-2);
- X A1 represents O, S, NR X1 or CR X2 R X3
- R X1 to R X3 each independently represent a hydrogen atom or a substituent
- R A1 and R A2 each independently represent a hydrogen atom or a substituent
- R A1 and R A2 may combine with each other to form a ring
- * represents a bond
- Y A1 to Y A4 each independently represent N or CR Y1
- R Y1 represents a hydrogen atom or a substituent, at least two of Y A1 to Y A4 are CR Y1 ;
- the compound represented by formula (1) is a compound represented by formula (1-1) or formula (1-2) a composition of In formula (1-1), R 11 and R 12 each independently represent a substituent, R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group; X 11 and X 12 each independently represent O, S, NR X11 or CR X12 R X13 , R X11 to R X13 each independently represent a hydrogen atom or a substituent, R 15 to R 18 each independently represent a hydrogen atom or a substituent, R 15 and R 16 may combine with each other to form a ring, R 17 and R 18 may combine with each other to form a ring; In formula (1-2), R 11 and R 12 each independently represent a substituent, R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group; Y 11 to Y 18 each independently represent N or CR
- the near-infrared absorbing pigment is a compound represented by formula (P-1);
- Rp 1 to Rp 4 each independently represent a substituent, one of Rp 1 and Rp 2 is a heteroaryl group, and one of Rp 3 and Rp 4 is a heteroaryl group, Rp 5 and Rp 6 each independently represent an alkyl group, an aryl group or a heteroaryl group;
- B 1 and B 2 each independently represent BRp 11 Rp 12 , Rp 11 and Rp 12 each independently represent a substituent, Rp 11 and Rp 12 may combine with each other to form a ring.
- ⁇ 7> The composition according to any one of ⁇ 1> to ⁇ 6>, wherein the curable compound contains a polymerizable compound.
- ⁇ 8> The composition according to any one of ⁇ 1> to ⁇ 7>, wherein the curable compound contains a resin having an acid group.
- ⁇ 9> A film obtained using the composition according to any one of ⁇ 1> to ⁇ 8>.
- ⁇ 10> An optical filter including the film according to ⁇ 9>.
- ⁇ 11> A solid-state imaging device including the film according to ⁇ 9>.
- ⁇ 12> An image display device comprising the film according to ⁇ 9>.
- ⁇ 13> An infrared sensor including the film according to ⁇ 9>.
- composition capable of forming a film in which foreign matter defects are suppressed, a film in which foreign matter defects are suppressed, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor.
- FIG. 1 is a schematic diagram illustrating one embodiment of an infrared sensor
- ⁇ is used to include the numerical values before and after it as lower and upper limits.
- a description that does not describe substitution or unsubstituted includes a group (atomic group) having no substituent as well as a group (atomic group) having a substituent.
- an "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).
- exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
- Light used for exposure includes actinic rays or radiation such as emission line spectra of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
- EUV light extreme ultraviolet rays
- (meth)acrylate” represents both or either acrylate and methacrylate
- (meth)acryl represents both or either acrylic and methacrylic
- (meth) ) acryloyl refers to acryloyl and/or methacryloyl.
- the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values in gel permeation chromatography (GPC) measurement.
- GPC gel permeation chromatography
- near-infrared light refers to light (electromagnetic waves) with a wavelength of 700 to 2500 nm.
- total solid content refers to the total mass of all components of the composition excluding the solvent.
- a pigment means a compound that is difficult to dissolve in a solvent.
- the term "process” includes not only an independent process, but also when the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. .
- composition of the present invention contains a compound represented by formula (1), a near-infrared absorbing pigment, and a curable compound,
- the content of the compound represented by formula (1) is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.
- the near-infrared absorbing pigment is designed to absorb light in the long wavelength region, and therefore has a high HOMO (Highest Occupied Molecular Orbital) level and a LUMO (Lowest Unoccupied Molecular Orbital) level. tend to be low. Therefore, a nucleophilic agent such as water or an electrophilic agent such as acid tends to react with the near-infrared absorbing pigment to easily produce decomposition products. It is presumed that crystals of this decomposition product precipitate and grow to become foreign matter. Also, the near-infrared absorbing pigment has a structure with a large ⁇ plane.
- the decomposition product of the near-infrared absorbing pigment also has the partial structure of the near-infrared absorbing pigment and has a somewhat large ⁇ plane.
- a compound having a large ⁇ -plane is likely to undergo ⁇ - ⁇ stacking, and is often a highly crystalline compound.
- the composition of the present invention contains 0.01 to 10 parts by mass of the compound represented by formula (1) with respect to 100 parts by mass of the near-infrared absorbing pigment.
- the compound represented by the formula (1) is a compound having a large ⁇ -plane structure, it effectively interacts with the near-infrared absorbing pigment or its decomposition product in the composition to form the near-infrared absorbing pigment or It is presumed that the decomposed product is adsorbed on the surface to suppress aggregation and crystallization. Therefore, although the composition of the present invention is a composition containing a near-infrared absorbing pigment, the compound represented by formula (1) is added in an amount of 0.01 to 0.01 per 100 parts by mass of the near-infrared absorbing pigment. By containing 10 parts by mass, it is possible to form a film in which defects are suppressed even when stored for a long period of time under high temperature conditions.
- composition of the present invention can be used as a composition for optical filters.
- optical filters include near-infrared cut filters and infrared transmission filters.
- the composition of the present invention can be preferably used as a composition for pattern formation in photolithography.
- the composition of the present invention is used as a composition for photolithography, it is preferable to use a resin having an acid group and a polymerizable monomer (monomer type polymerizable compound) as the curable compound, and the acid group and a polymerizable monomer (monomer-type polymerizable compound) having an ethylenically unsaturated bond-containing group.
- the composition further contains a photopolymerization initiator.
- composition of the present invention contains a compound represented by formula (1) (hereinafter also referred to as a specific compound).
- R 1 to R 4 each independently represent a substituent
- one of R 1 and R 2 is a heteroaryl group
- one of R 3 and R 4 is a heteroaryl group
- R5 and R6 each independently represent an alkyl group, an aryl group or a heteroaryl group.
- Substituents represented by R 1 to R 4 include alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups, heteroaryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, hetero aryloxycarbonyl group, acyloxy group, amino group, acylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, heteroaryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, heteroaryl luthio group, alkylsulfonyl group, arylsulfonyl group, heteroarylsulfonyl group, alkylsulfinyl group, arylsulfinyl group, heteroarylsulfinyl group, ureid
- Either one of R 1 and R 2 in formula (1) is a heteroaryl group and the other is an electron-withdrawing group, and either one of R 3 and R 4 is a heteroaryl group and the other is an electron-withdrawing group. is preferably a sexual group.
- a substituent having a positive Hammett's ⁇ p value acts as an electron-withdrawing group.
- a substituent having a Hammett's ⁇ p value of 0.2 or more can be exemplified as an electron-withdrawing group.
- the ⁇ p value is preferably 0.25 or more, more preferably 0.3 or more, and particularly preferably 0.35 or more.
- the upper limit is not particularly limited, it is preferably 0.80 or less.
- the electron-withdrawing group examples include a cyano group (0.66), a carboxyl group (-COOH: 0.45), an alkoxycarbonyl group (e.g., -COOCH 3 : 0.45), an aryloxycarbonyl group ( For example, —COOCH 3 : 0.44), carbamoyl group (for example —CONH 2 : 0.36), alkylcarbonyl group (for example —COCH 3 : 0.50), arylcarbonyl group (for example —COPh: 0 .43), alkylsulfonyl groups (eg —SO 2 CH 3 : 0.72), arylsulfonyl groups (eg —SO 2 Ph: 0.68), and the like.
- a cyano group 0.66
- a carboxyl group -COOH: 0.45
- an alkoxycarbonyl group e.g., -COOCH 3 : 0.45
- the electron-withdrawing group is preferably a cyano group, an alkylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group, more preferably a cyano group. That is, one of R 1 and R 2 and one of R 3 and R 4 in formula (1) are each preferably a cyano group.
- Ph represents a phenyl group.
- Hammett's ⁇ p value can be referred to paragraphs 0024 to 0025 of JP-A-2009-263614, the contents of which are incorporated herein.
- the heteroaryl group represented by either one of R 1 and R 2 in formula (1) and the heteroaryl group represented by either one of R 3 and R 4 in formula (1) are each independently represented by the formula ( A group represented by A-1) or a group represented by formula (A-2) is preferable.
- the heteroaryl group is a group represented by formula (A-1)
- a film with more excellent light resistance can be formed.
- the heteroaryl group is a group represented by formula (A-2)
- a film with more excellent heat resistance can be formed.
- X A1 represents O, S, NR X1 or CR X2 R X3 , and R X1 to R X3 each independently represent a hydrogen atom or a substituent, R A1 and R A2 each independently represent a hydrogen atom or a substituent, R A1 and R A2 may combine with each other to form a ring, * represents a bond;
- Y A1 to Y A4 each independently represent N or CR Y1
- R Y1 represents a hydrogen atom or a substituent, at least two of Y A1 to Y A4 are CR Y1 ;
- the R Y1s in the two adjacent CR Y1 may be bonded to each other to form a ring, * represents a bond.
- X A1 in formula (A-1) represents O, S, NR X1 or CR X2 R X3 , and is preferably O or S because a film with more excellent light resistance can be formed.
- substituents represented by R X1 to R X3 include the groups exemplified for the substituent T described later and the groups represented by the formula (R-100) described later, and a halogen atom, an alkyl group, an alkenyl group or an alkoxy group. is preferably
- the number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 8.
- Alkyl groups and alkoxy groups may be linear, branched, or cyclic, but are preferably linear or branched.
- the alkyl group and alkoxy group may have a substituent or may be unsubstituted. Examples of the substituent include the groups exemplified for the substituent T described below and the groups represented by the formula (R-100) described below.
- the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 2 to 8 carbon atoms.
- the alkenyl group may have a substituent or may be unsubstituted.
- substituent include the groups exemplified for the substituent T described below and the groups represented by the formula (R-100) described below.
- halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
- R A1 and R A2 may combine with each other to form a ring.
- the ring formed may be an aliphatic ring, but is preferably an aromatic ring.
- the group represented by formula (A-1) includes a group represented by formula (A-1-1) and (A-1 -2) and the like.
- X A1 represents O, S, NR X1 or CR X2 R X3 , and R X1 to R X3 each independently represent a hydrogen atom or a substituent, R A11 to R A20 each independently represent a hydrogen atom or a substituent, * represents a bond.
- the substituents represented by R A11 to R A20 include the groups described as the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are also the same.
- Y A1 to Y A4 in formula (A-2) each independently represent N or CR Y1
- R Y1 represents a hydrogen atom or a substituent.
- Examples of the substituent represented by R 1 Y1 include the groups described as the substituent represented by R A1 and R A2 in formula (A-1), and the preferred range is also the same.
- At least two of Y A1 to Y A4 are CR Y1 .
- the R Y1s in the two adjacent CR Y1s may combine with each other to form a ring.
- the ring formed by combining adjacent R Y1s may be an aliphatic ring, but is preferably an aromatic ring.
- the group represented by formula (A-2) includes groups represented by formulas (A-2-1) to (A-2-3). etc.
- Y A1 to Y A4 each independently represent N or CR Y1
- R Y1 represents a hydrogen atom or a substituent
- R A31 to R A42 each independently represent a hydrogen atom or a substituent
- * represents a bond.
- the substituents represented by R A31 to R A42 include the groups described for the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are also the same.
- R 5 and R 6 in formula (1) each independently represent an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, more preferably an aryl group.
- the number of carbon atoms in the alkyl group represented by R 5 and R 6 is preferably 1-30, more preferably 1-20, even more preferably 1-10.
- the alkyl group may be linear, branched or cyclic, but preferably linear or branched.
- the aryl group represented by R 5 and R 6 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.
- the number of carbon atoms constituting the ring of the heteroaryl group represented by R 5 and R 6 is preferably 1-30, more preferably 1-12.
- Types of heteroatoms that constitute the heteroaryl group include, for example, a nitrogen atom, an oxygen atom and a sulfur atom.
- the number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2.
- the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, and still more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers.
- the heteroaryl group represented by R 5 and R 6 is preferably a group represented by the above formula (A-1) or a group represented by the above formula (A-2).
- the alkyl group, aryl group and heteroaryl group represented by R5 and R6 may be unsubstituted or may have a substituent.
- substituents include the groups described below for the substituent T and the groups represented by the formula (R-100).
- L R1 is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, -O-, -S-, -NR L1 -, -CO-, -COO-, - OCO—, —SO 2 —, or an n+1-valent linking group consisting of a combination thereof
- R L1 represents a hydrogen atom, an alkyl group or an aryl group
- X R1 represents an acid group or a basic group
- n represents an integer of 1 or more, and when n is 1, L R1 may be a single bond
- * represents a bond.
- the number of carbon atoms in the aliphatic hydrocarbon group is preferably 1-20, more preferably 2-20, still more preferably 2-10, and particularly preferably 2-5.
- the aliphatic hydrocarbon group may be linear, branched or cyclic.
- the aliphatic hydrocarbon group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
- the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-18, more preferably 6-14, even more preferably 6-10.
- the aromatic hydrocarbon group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
- the heterocyclic group is preferably a monocyclic ring or a condensed ring having 2 to 4 condensed rings.
- the number of heteroatoms constituting the ring of the heterocyclic group is preferably 1-3.
- a heteroatom constituting the ring of the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the number of carbon atoms constituting the ring of the heterocyclic group is preferably 1-30, more preferably 1-18, and more preferably 1-12.
- heterocyclic groups include piperazine ring group, pyrrolidine ring group, pyrrole ring group, piperidine ring group, pyridine ring group, imidazole ring group, pyrazole ring group, oxazole ring group, thiazole ring group, pyrazine ring group, morpholine ring group, thiazine ring group, indole ring group, isoindole ring group, benzimidazole ring group, purine ring group, quinoline ring group, isoquinoline ring group, quinoxaline ring group, cinnoline ring group, carbazole ring group and the following formula (L- 1) to groups represented by (L-7).
- * in the formula represents a bond
- R represents a hydrogen atom or a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
- the aliphatic hydrocarbon group, aromatic hydrocarbon group and heterocyclic group may have a substituent.
- substituents include the groups exemplified for the substituent T described later, preferably a halogen atom, more preferably a fluorine atom.
- the number of carbon atoms in the alkyl group represented by R L1 is preferably 1-20, more preferably 1-15, even more preferably 1-8.
- the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
- the alkyl group represented by R L1 may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
- the number of carbon atoms in the aryl group represented by R L1 is preferably 6-30, more preferably 6-20, even more preferably 6-12.
- the aryl group represented by R L1 may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
- Examples of the acid group represented by X R1 of the formula (R-100) include a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imidic acid group and salts thereof.
- Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like.
- a group represented by —NHCOR XR1 is preferable.
- a group represented by —NHSO 2 R XR2 is preferable.
- the imidic acid group is preferably a group represented by —SO 2 NHSO 2 R XR3 , —CONHSO 2 R XR4 , —CONHCOR XR5 or —SO 2 NHCOR XR6 , and —CONHSO 2 R XR4 or —SO 2 NHSO 2 R.
- XR3 is more preferred.
- R XR1 to R XR6 each independently represent an alkyl group or an aryl group.
- the alkyl groups and aryl groups represented by R XR1 to R XR6 may have substituents.
- the substituent is preferably a halogen atom, more preferably a fluorine atom.
- Basic groups represented by X R1 of formula (R-100) include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
- Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
- the amino group includes groups represented by —NRx R1 Rx R2 and cyclic amino groups.
- Rx R1 and Rx R2 each independently represent a hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group.
- the number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3.
- the alkyl group may be linear, branched or cyclic, preferably linear or branched, more preferably linear.
- the alkyl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later.
- the number of carbon atoms in the aryl group is preferably 6-30, more preferably 6-20, even more preferably 6-12.
- the aryl group may have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Also, Rx R1 and Rx R2 may combine to form a ring. Cyclic amino groups include a pyrrolidine group, a piperidine group, a piperazine group, a morpholine group and the like. These groups may further have a substituent. Examples of the substituent include the groups exemplified for the substituent T described later. Specific examples of substituents include alkyl groups and aryl groups.
- n in formula (R-100) represents an integer of 1 or more, preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.
- R 5 and R 6 in formula (1) at least one of R 5 and R 6 (preferably both R 5 and R 6 ) is a group represented by the above formula (R-100) and an aryl group having as a substituent. According to this aspect, the thermal decomposition temperature of the specific compound is increased, and a film having more excellent heat resistance can be formed.
- R 5 and R 6 in formula (1) is one in which one of R 5 and R 6 is an aryl group and the other is an alkyl group.
- the aryl group and the alkyl group may be unsubstituted or may have a substituent. Examples of substituents include alkyl groups, halogen atoms, alkoxy groups, acyloxy groups, and alkoxycarbonyl groups.
- R 5 and R 6 in formula (1) is an embodiment in which R 5 and R 6 are aryl groups having an alkoxy group having 1 to 16 carbon atoms as a substituent. According to this aspect, a composition with less change in viscosity can be obtained.
- R 5 and R 6 in formula (1) is an embodiment in which R 5 and R 6 are unsubstituted aryl groups. According to this aspect, the thermal decomposition temperature of the specific compound is increased, and a film having more excellent heat resistance can be formed.
- the compound represented by Formula (1) is preferably a compound represented by Formula (1-1) or Formula (1-2). By using such a compound, a film having more excellent light resistance can be formed.
- R 11 and R 12 each independently represent a substituent
- R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group
- X 11 and X 12 each independently represent O, S, NR X11 or CR X12 R X13 , R X11 to R X13 each independently represent a hydrogen atom or a substituent
- R 15 to R 18 each independently represent a hydrogen atom or a substituent
- R 15 and R 16 may combine with each other to form a ring
- R 17 and R 18 may combine with each other to form a ring
- R 11 and R 12 each independently represent a substituent
- R 13 and R 14 each independently represent an alkyl group, an aryl group or a heteroaryl group
- Y 11 to Y 18 each independently represent N or CR Y11
- R Y11 represents a hydrogen atom or a substituent, at least two of Y 11 to Y 14 and at least two of Y 15 to Y 18
- the substituents represented by R 11 and R 12 in formula (1-1) and the substituents represented by R 11 and R 12 in formula (1-2) are represented by R 1 to R 4 in formula (1).
- the groups described as substituents can be mentioned, and electron-withdrawing groups are preferred.
- the substituents represented by R 11 and R 12 in formula (1-1) and the substituents represented by R 11 and R 12 in formula (1-2) are a cyano group, An alkylcarbonyl group, an alkylsulfonyl group or an arylsulfonyl group is preferable, and a cyano group is more preferable.
- R 13 and R 14 in formula (1-1) and R 13 and R 14 in formula (1-2) have the same meanings as R 5 and R 6 in formula (1), and the preferred ranges are also the same. .
- X 11 and X 12 in formula (1-1) each independently represent O, S, NR X11 or CR X12 R X13 , and are O or S is preferred.
- the substituents represented by R X11 to R X13 include the groups described as the substituents represented by R X1 to R X3 in formula (A-1) above, and the preferred ranges are also the same.
- the substituents represented by R 15 to R 18 in formula (1-1) include the groups described as the substituents represented by R A1 and R A2 in formula (A-1), and the preferred ranges are the same.
- R 15 and R 16 may combine to form a ring
- R 17 and R 18 may combine to form a ring.
- the ring formed by combining these groups may be an aliphatic ring, but is preferably an aromatic ring.
- Y 11 to Y 18 in formula (1-2) each independently represent N or CR Y11
- R Y11 represents a hydrogen atom or a substituent
- at least two of Y 11 to Y 14 and Y 15 to Y At least two of 18 are CR Y11
- Examples of the substituent represented by R 1 Y11 include the groups described for the substituent represented by R A1 and R A2 in formula (A-1), and the preferred range is also the same.
- R Y11 in two adjacent CR Y11 may be bonded to each other to form a ring
- the ring formed by combining these groups may be an aliphatic ring, but is preferably an aromatic ring.
- Substituent T includes the following groups.
- Halogen atom e.g., fluorine atom, chlorine atom, bromine atom, iodine atom
- alkyl group preferably alkyl group having 1 to 30 carbon atoms
- alkenyl group preferably alkenyl group having 2 to 30 carbon atoms
- alkynyl group Preferably an alkynyl group having 2 to 30 carbon atoms
- an aryl group preferably an aryl group having 6 to 30 carbon atoms
- a heteroaryl group preferably a heteroaryl group having 1 to 30 carbon atoms
- an amino group preferably amino group having 0 to 30 carbon atoms
- alkoxy group preferably alkoxy group having 1 to 30 carbon atoms
- aryloxy group preferably aryloxy group having 6 to 30 carbon atoms
- heteroaryloxy group preferably carbon 1 to 30 heteroaryloxy groups
- acyl groups preferably acyl groups having 2 to 30 carbon
- the solubility of the specific compound in 100 g of propylene glycol methyl ether acetate at 25°C is preferably 0.1 g or more, more preferably 0.2 g or more, and even more preferably 0.5 g or more.
- Specific examples of the specific compounds include compounds (PP-001 to PP-010) having structures described in Examples described later.
- the content of the specific compound is 0.01 to 10 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.
- the upper limit is preferably 3 parts by mass or less, more preferably 1 part by mass or less, and further preferably 0.8 parts by mass or less for the reason that the effects of the present invention are exhibited more remarkably.
- the lower limit is preferably 0.03 parts by mass or more, more preferably 0.05 parts by mass or more.
- the content of the specific compound is preferably 0.002% by mass or more, more preferably 0.006% by mass or more, and more preferably 0.01% by mass or more in the total solid content of the composition. More preferred.
- the upper limit is preferably 2% by mass or less, more preferably 0.2% by mass or less, and even more preferably 0.1% by mass or less.
- the composition of the present invention may contain only one type of specific compound, or may contain two or more types. When the composition of the present invention contains two or more specific compounds, precipitation of crystals of the specific compound can be suppressed even if the amount of the specific compound added is increased. When the composition of the present invention contains two or more specific compounds, it is preferable not to use a compound having an acid group and a compound having a basic group together from the viewpoint of preventing crystal precipitation due to salt formation. When the composition of the present invention contains two or more specific compounds, the total amount thereof is preferably within the above range.
- the composition of the present invention contains a near-infrared absorbing pigment.
- the near-infrared absorbing pigment is preferably an organic pigment.
- an organic pigment is a pigment composed of an organic compound.
- the near-infrared absorbing pigment is preferably a pigment having a maximum absorption wavelength in the near-infrared region (preferably in the range of 700-1800 nm, more preferably in the range of 700-1300 nm, still more preferably in the range of 700-1000 nm).
- the solubility of the near-infrared absorbing pigment in 100 g of propylene glycol methyl ether acetate at 25°C is preferably less than 1 g, more preferably 0.1 g or less, and even more preferably 0.05 g or less.
- Near-infrared absorbing pigments include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, boradiazine compounds, etc., and more preferably at least one selected from pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds and boradiazine compounds; Pyrrole compounds are more preferred.
- the pyrrolopyrrole compound is preferably a compound represented by formula (P-1).
- Rp 1 to Rp 4 each independently represent a substituent, one of Rp 1 and Rp 2 is a heteroaryl group, and one of Rp 3 and Rp 4 is a heteroaryl group, Rp 5 and Rp 6 each independently represent an alkyl group, an aryl group or a heteroaryl group; B 1 and B 2 each independently represent BRp 11 Rp 12 , Rp 11 and Rp 12 each independently represent a substituent, Rp 11 and Rp 12 may combine with each other to form a ring.
- Examples of the substituents represented by Rp 1 to Rp 4 of formula (P-1) include the groups described as the substituents represented by R 1 to R 4 of formula (1).
- the heteroaryl group represented by either one of Rp 1 and Rp 2 in formula (P-1) and the heteroaryl group represented by either one of Rp 3 and Rp 4 in formula (P-1) are each independently is preferably a group represented by formula (A-1) or a group represented by formula (A-2).
- Either one of Rp 1 and Rp 2 in formula (P-1) is a heteroaryl group, the other is an electron-withdrawing group, and one of Rp 3 and Rp 4 is a heteroaryl group, the other is an electron An attracting group is preferred.
- the electron-withdrawing group is preferably a cyano group, an alkylcarbonyl group, an alkylsulfonyl group and an arylsulfonyl group, more preferably a cyano group.
- Rp 5 and Rp 6 in formula (P-1) each independently represent an alkyl group, an aryl group or a heteroaryl group, preferably an aryl group or a heteroaryl group, more preferably an aryl group. .
- the number of carbon atoms in the alkyl group represented by Rp 5 and Rp 6 is preferably 1-30, more preferably 1-20, even more preferably 1-10.
- the alkyl group may be linear, branched or cyclic, but preferably linear or branched.
- the aryl group represented by Rp 5 and Rp 6 preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 12 carbon atoms.
- the number of carbon atoms constituting the ring of the heteroaryl group represented by Rp 5 and Rp 6 is preferably 1-30, more preferably 1-12.
- Types of heteroatoms that constitute the heteroaryl group include, for example, a nitrogen atom, an oxygen atom and a sulfur atom.
- the number of heteroatoms constituting the heteroaryl group is preferably 1-3, more preferably 1-2.
- the heteroaryl group is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring or a condensed ring with 2 to 8 condensed numbers, and still more preferably a monocyclic ring or a condensed ring with 2 to 4 condensed numbers.
- the heteroaryl group represented by Rp 5 and Rp 6 is preferably a group represented by the above formula (A-1) or a group represented by the above formula (A-2).
- B 1 and B 2 in formula (P-1) each independently represent BRp 11 Rp 12
- Rp 11 and Rp 12 each independently represent a substituent.
- substituents represented by Rp 11 and Rp 12 include halogen atoms, alkyl groups, alkenyl groups, aryl groups, heteroaryl groups, alkoxy groups, aryloxy groups and heteroaryloxy groups. or is preferably a heteroaryl group, more preferably a halogen atom, an alkyl group or an aryl group, and even more preferably an aryl group.
- a halogen atom includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred.
- the number of carbon atoms in the alkyl group and alkoxy group is preferably 1-20, more preferably 1-15, even more preferably 1-8.
- Alkyl groups and alkoxy groups may be linear, branched or cyclic, but are preferably linear or branched.
- the alkyl group and alkoxy group may have a substituent or may be unsubstituted. Substituents include aryl groups, heteroaryl groups, halogen atoms, and the like.
- the alkenyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and still more preferably 2 to 8 carbon atoms.
- the alkenyl group may have a substituent or may be unsubstituted.
- Substituents include alkoxy groups, aryl groups, heteroaryl groups, halogen atoms and the like.
- the aryl group and the aryloxy group preferably have 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
- the aryl group and aryloxy group may have a substituent or may be unsubstituted. Examples of substituents include alkyl groups, alkoxy groups, and halogen atoms.
- a heteroaryl group and a heteroaryloxy group may be monocyclic or condensed.
- the number of heteroatoms constituting the heteroaryl ring of the heteroaryl group and heteroaryloxy group is preferably 1 to 3.
- a heteroatom constituting the heteroaryl ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom.
- the number of carbon atoms constituting the heteroaryl ring is preferably 1-30, more preferably 1-18, even more preferably 1-12.
- the heteroaryl ring is preferably a 5- or 6-membered ring.
- a heteroaryl group and a heteroaryloxy group may have a substituent or may be unsubstituted. Examples of substituents include alkyl groups, alkoxy groups, and halogen atoms.
- Rp 11 and Rp 12 of BRp 11 Rp 12 represented by B 1 and B 2 may combine with each other to form a ring.
- Examples of the ring to be formed include structures shown in (B-1) to (B-5) below.
- Rb represents a substituent
- Rb 1 to Rb 4 each independently represent a hydrogen atom or a substituent
- b1 to b3 each independently represent an integer of 0 to 4
- b4 is 0 to It represents an integer of 6
- * represents a link.
- Substituents represented by Rb and Rb 1 to Rb 4 include the groups exemplified for the substituent T described above, preferably halogen atoms, alkyl groups and alkoxy groups.
- pyrrolopyrrole compound examples include compounds having structures described in Examples described later. Further, as the pyrrolopyrrole compound, compounds described in paragraph numbers 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph numbers 0037-0052 of JP-A-2011-068731, International Publication No. 2015/166873 and the compounds described in paragraph numbers 0010 to 0033 of No. Examples of the squarylium compound include compounds described in paragraph numbers 0044 to 0049 of JP-A-2011-208101, compounds described in paragraph numbers 0060 to 0061 of Japanese Patent No. 6065169, and paragraph number 0040 of WO 2016/181987.
- the squarylium compound include compounds having structures described in Examples described later. Further, as the squarylium compound and the croconium compound, the squarylium compound described in JP-A-2017-197437, the squarylium compound described in JP-A-2017-025311, the squarylium compound described in International Publication No. 2016/154782, the patent Squarylium compounds described in Japanese Patent No. 5884953, squarylium compounds described in Japanese Patent No. 6036689, squarylium compounds described in Japanese Patent No. 5810604, squarylium compounds described in paragraph numbers 0090 to 0107 of International Publication No.
- Examples of boradiazine compounds include compounds having structures described in Examples described later. Further, examples of boradiazine compounds include compounds described in paragraphs 0103 to 0117 of JP-A-2015-040231.
- cyanine compound compounds described in paragraphs 0044 to 0045 of JP-A-2009-108267, compounds described in paragraphs 0026-0030 of JP-A-2002-194040, and JP-A-2015-172004.
- phthalocyanine compound examples include compounds described in paragraph number 0093 of JP-A-2012-077153, oxytitanium phthalocyanine described in JP-A-2006-343631, and paragraph numbers 0013 to 0029 of JP-A-2013-195480. compounds, vanadium phthalocyanine compounds described in Japanese Patent No. 6081771, vanadium phthalocyanine compounds described in International Publication No. 2020/071486, and phthalocyanine compounds described in International Publication No. 2020/071470.
- naphthalocyanine compounds examples include compounds described in paragraph number 0093 of JP-A-2012-077153.
- the solubility S1 of the near-infrared absorbing pigment in 100 g of propylene glycol methyl ether acetate at 25°C is preferably smaller than the solubility S2 of the specific compound described above in 100 g of propylene glycol methyl ether acetate at 25°C.
- the value of solubility S2-solubility S1 is preferably 10 g or less, more preferably 5 g or less, and even more preferably 3 g or less, because the surface adsorption to foreign crystals can be enhanced.
- the content of the near-infrared absorbing pigment is preferably 1 to 50 mass% of the total solid content of the composition.
- the lower limit is preferably 3% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more.
- the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.
- the composition of the invention contains a curable compound.
- curable compounds include polymerizable compounds and resins.
- the resin may be a non-polymerizable resin (a resin having no polymerizable group) or a polymerizable resin (a resin having a polymerizable group).
- Polymerizable groups include ethylenically unsaturated bond-containing groups and cyclic ether groups. Examples of ethylenically unsaturated bond-containing groups include vinyl groups, (meth)allyl groups, and (meth)acryloyl groups.
- the cyclic ether group include an epoxy group and an oxetanyl group, with the epoxy group being preferred.
- the epoxy group may be a cycloaliphatic 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.
- the curable compound it is preferable to use one containing at least a resin.
- the resin preferably contains a resin having an acid group.
- the composition of the present invention when used as a composition for photolithography, it is preferable to use a resin having an acid group and a polymerizable monomer (monomer type polymerizable compound) as the curable compound. It is more preferable to use a resin having an acid group and a polymerizable monomer (monomer-type polymerizable compound) having an ethylenically unsaturated bond-containing group.
- polymerizable compound examples include compounds having an ethylenically unsaturated bond-containing group and compounds having a cyclic ether group.
- a compound having an ethylenically unsaturated bond-containing group can be preferably used as a radically polymerizable compound.
- a compound having a cyclic ether group can also be preferably used as a cationically polymerizable compound.
- resin-type polymerizable compounds include resins containing repeating units having polymerizable groups.
- the molecular weight of the monomer type polymerizable compound is preferably less than 2000, more preferably 1500 or less.
- the lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more.
- the weight average molecular weight (Mw) of the resin-type polymerizable compound is preferably 2,000 to 2,000,000.
- the upper limit of the weight average molecular weight is preferably 1,000,000 or less, more preferably 500,000 or less.
- the lower limit of the weight average molecular weight is preferably 3000 or more, more preferably 5000 or more.
- the compound having an ethylenically unsaturated bond-containing group as a polymerizable monomer is preferably a 3- to 15-functional (meth)acrylate compound, more preferably a 3- to 6-functional (meth)acrylate compound.
- Specific examples include paragraph numbers 0095 to 0108 of JP-A-2009-288705, paragraph 0227 of JP-A-2013-029760, paragraph numbers 0254-0257 of JP-A-2008-292970, and JP-A-2013-253224.
- Examples of compounds having an ethylenically unsaturated bond-containing group include dipentaerythritol tri(meth)acrylate (commercially available as 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 Nippon Kayaku Co., Ltd.
- dipentaerythritol hexa(meth)acrylate ) Acrylate commercially available as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.
- the (meth)acryloyl groups of these compounds are ethylene glycol and / Or a compound having a structure linked via a propylene glycol residue (for example, SR454 and SR499 commercially available from Sartomer).
- diglycerin EO ethylene oxide modified (meth) acrylate
- pentaerythritol tetraacrylate Shin-Nakamura Chemical Industry Co., Ltd., NK Ester A-TMMT
- 1,6-hexanediol diacrylate manufactured by Nippon Kayaku Co., Ltd., KAYARAD HDDA
- RP-1040 manufactured by Nippon Kayaku Co., Ltd.
- DPHA-40H manufactured by Nippon Kayaku Co., Ltd.
- Aronix TO-2349 Toagosei Co., Ltd.
- NK Oligo UA-7200 Shin Nakamura Chemical Co., Ltd.
- 8UH-1006, 8UH-1012 Taisei Fine Chemical Co., Ltd.
- Examples of compounds 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. It is also preferable to use trifunctional (meth)acrylate compounds such as ethylene oxide-modified tri(meth)acrylate and pentaerythritol tri(meth)acrylate. Commercial products of 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.
- a compound having an ethylenically unsaturated bond-containing group a compound having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group can be used.
- Commercially available products of such compounds include Aronix M-305, M-510, M-520 and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.).
- a compound having a caprolactone structure can also be used as the compound having an ethylenically unsaturated bond-containing group.
- the descriptions in paragraphs 0042 to 0045 of JP-A-2013-253224 can be referred to, the contents of which are incorporated herein.
- Compounds having a caprolactone structure include, for example, DPCA-20, DPCA-30, DPCA-60, DPCA-120, etc., which are commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd.
- a compound having an ethylenically unsaturated bond-containing group and an alkyleneoxy group can also be used as the compound having an ethylenically unsaturated bond-containing group.
- 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. More preferably, it is a tri- to hexa-functional (meth)acrylate compound having 4 to 20 ethyleneoxy groups.
- a polymerizable compound having a fluorene skeleton can also be used as the compound having an ethylenically unsaturated bond-containing group.
- Commercially available products include Ogsol EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals 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 such as toluene that does not substantially contain environmentally regulated substances.
- Commercially available products of such compounds include KAYARAD DPHA LT and KAYARAD DPEA-12 LT (manufactured by Nippon Kayaku Co., Ltd.).
- Compounds having a cyclic ether group include compounds having an epoxy group, compounds having an oxetanyl group, and the like, and compounds having an epoxy group are preferred.
- Compounds having an epoxy group include compounds having 1 to 100 epoxy groups in one molecule.
- the upper limit of the number of epoxy groups can be, for example, 10 or less, or 5 or less.
- the lower limit of the number of epoxy groups is preferably two or more.
- a compound having a cyclic ether group may be a low-molecular compound (for example, a molecular weight of less than 1000) or a macromolecule (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight-average molecular weight of 1000 or more).
- the weight average molecular weight of the cyclic ether group is preferably from 200 to 100,000, more preferably from 500 to 50,000.
- the upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.
- the composition of the present invention can use a resin as a curable compound. It is preferable to use a curable compound containing at least a resin.
- the resin is blended, for example, for dispersing a pigment or the like in the composition or for a binder.
- a resin that is mainly used to disperse a pigment or the like in a composition is also called a dispersant.
- such uses of the resin are only examples, and the resin can be used for purposes other than such uses.
- a resin having a polymerizable group also corresponds to a polymerizable compound.
- the weight average molecular weight of the resin is preferably 3,000 to 2,000,000.
- the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
- the lower limit is preferably 4000 or more, more preferably 5000 or more.
- resins include (meth)acrylic resins, epoxy resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, Polyamide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, vinyl acetate resins, polyvinyl alcohol resins, polyvinyl acetal resins, polyurethane resins, polyurea resins, and the like.
- norbornene resin is preferable from the viewpoint of improving heat resistance.
- Commercially available norbornene resins include, for example, 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.
- a resin having a fluorene skeleton can also be preferably used.
- the description of US Patent Application Publication No. 2017/0102610 can be referred to, the content of which is incorporated herein.
- the resin the resin described in paragraphs 0199 to 0233 of JP-A-2020-186373, the alkali-soluble resin described in JP-A-2020-186325, and the Korean Patent Publication No. 10-2020-0078339.
- a resin represented by the formula 1 can also be used.
- a resin having an acid group As the resin.
- acid groups include carboxyl groups, phosphoric acid groups, sulfo groups, and phenolic hydroxy groups. Only one kind of these acid groups may be used, or two or more kinds thereof may be used.
- a resin having an acid group can be used, for example, as an alkali-soluble resin.
- the acid value of the resin having acid groups is preferably 30-500 mgKOH/g.
- the lower limit is preferably 50 mgKOH/g or more, more preferably 70 mgKOH/g or more.
- the upper limit is preferably 400 mgKOH/g or less, more preferably 200 mgKOH/g or less, still more preferably 150 mgKOH/g or less, and most preferably 120 mgKOH/g or less.
- a resin containing a repeating unit derived from a compound represented by the formula (ED1) and/or a compound represented by the formula (ED2) (hereinafter, these compounds may be referred to as an "ether dimer"). It is also preferred to include
- R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the description in JP-A-2010-168539 can be referred to.
- paragraph number 0317 of JP-A-2013-029760 can be referred to, the content of which is incorporated herein.
- the resin it is also preferable to use a resin having a polymerizable group.
- the polymerizable group includes an ethylenically unsaturated bond-containing group and a cyclic ether group, preferably an ethylenically unsaturated bond-containing group.
- 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 0-15.
- the number of carbon atoms in the alkylene group represented by R 21 and R 22 is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly 2 or 3.
- 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 formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylate of paracumylphenol.
- Commercially available products include Aronix M-110 (manufactured by Toagosei Co., Ltd.).
- the composition of the present invention preferably contains a resin as a dispersant.
- Dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is greater than the amount of basic groups.
- the acidic dispersant (acidic resin) 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 possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant (acidic resin) is preferably 10-105 mgKOH/g.
- a basic dispersant represents a resin in which the amount of basic groups is greater than the amount of acid groups.
- a resin containing more than 50 mol % of basic groups is preferable when the total amount of acid groups and basic groups is 100 mol %.
- the basic group possessed by the basic dispersant is preferably an amino group.
- the resin used as the dispersant is also preferably a graft resin.
- graft resin for details of the graft resin, reference can be made to paragraphs 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein.
- the resin used as the dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of its main chain and side chains.
- the polyimine-based dispersant has a main chain having a partial structure having a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and at least one of the main chain and the side chain has a basic nitrogen atom.
- a resin having 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 JP-A-2012-255128 can be referred to, and the contents thereof are incorporated herein.
- the resin used as the dispersant is also preferably a resin having a structure in which a plurality of polymer chains are bonded to the core.
- resins include, for example, dendrimers (including star polymers). Further, specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.
- the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in its side chain.
- the content of repeating units having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol% or more, more preferably 10 to 80 mol%, more preferably 20 to 70, of the total repeating units of the resin. More preferably, it is mol %.
- resins described in JP-A-2018-087939, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077, Polyethyleneimine having a polyester side chain described in International Publication No. 2016/104803, a block copolymer described in International Publication No. 2019/125940, a block polymer having an acrylamide structural unit described in JP-A-2020-066687 , a block polymer having an acrylamide structural unit described in JP-A-2020-066688, a dispersant described in WO 2016/104803, and the like can also be used.
- Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
- Dispersants are also available as commercial products, and specific examples thereof include Disperbyk series manufactured by BYK-Chemie (e.g., Disperbyk-111, 161, 2001, etc.), Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajinomoto Fine-Techno Co., Inc. Ajisper series, and the like.
- the content of the curable compound is preferably 1 to 95% by mass based on the total solid content of the composition.
- the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more.
- the upper limit is preferably 94% by mass or less, more preferably 90% by mass or less, still more preferably 85% by mass or less, and particularly preferably 80% by mass or less.
- the content of the polymerizable compound is preferably 1 to 85% by mass based on the total solid content of the composition.
- the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
- the upper limit is preferably 80% by mass or less, more preferably 70% by mass or less.
- the content of the polymerizable monomer is preferably 1 to 50% by mass based on the total solid content of the composition.
- the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
- the upper limit is preferably 30% by mass or less, more preferably 20% by mass or less.
- the content of the compound having an ethylenically unsaturated bond-containing group is 1 to 70 mass in the total solid content of the composition. % is preferred.
- the lower limit is preferably 2% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more.
- the upper limit is preferably 65% by mass or less, more preferably 60% by mass or less.
- the content of the resin is preferably 1 to 85% by mass based on the total solid content of the composition.
- the lower limit is preferably 2% by mass or more, more preferably 5% by mass or more, still more preferably 7% by mass or more, and particularly preferably 10% by mass or more.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, and particularly preferably 40% by mass or less.
- the content of the resin as a dispersant is preferably 0.1 to 40% by mass based on the total solid content of the composition.
- the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more.
- the content of the resin as a dispersant is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the above specific compound.
- the upper limit is preferably 80 parts by mass or less, more preferably 75 parts by mass or less.
- the lower limit is preferably 2.5 parts by mass or more, more preferably 5 parts by mass or more.
- composition of the present invention may contain only one type of curable compound, or may contain two or more types. When two or more curable compounds are included, the total amount thereof is preferably within the above range.
- composition of the present invention can further contain a dye derivative in addition to the specific compounds described above.
- Dye derivatives are used as dispersing aids.
- Examples of dye derivatives include compounds having a structure in which an acid group or a basic group is bonded to a dye skeleton.
- dye skeletons constituting dye derivatives include squarylium dye skeleton, pyrrolopyrrole dye skeleton, diketopyrrolopyrrole dye skeleton, quinacridone dye skeleton, anthraquinone dye skeleton, dianthraquinone dye skeleton, benzoisoindole dye skeleton, and thiazineindigo dye skeleton.
- a squarylium dye skeleton, a pyrrolopyrrole dye skeleton, a diketopyrrolopyrrole dye skeleton, a phthalocyanine dye skeleton, a quinacridone dye skeleton and a benzimidazolone dye skeleton are preferred, and a squarylium dye skeleton and a pyrrolopyrrole dye skeleton are more preferred.
- the acid group includes a carboxyl group, a sulfo group, a phosphoric acid group, a boronic acid group, a carboxylic acid amide group, a sulfonamide group, an imidic acid group and salts thereof.
- Atoms or atomic groups constituting the salt include alkali metal ions (Li + , Na + , K + etc.), alkaline earth metal ions (Ca 2+ , Mg 2+ etc.), ammonium ions, imidazolium ions, pyridinium ions, phosphonium ion and the like.
- the carboxylic acid amide group a group represented by —NHCOR A1 is preferable.
- a group represented by —NHSO 2 R A2 is preferable.
- the imidic acid group is preferably a group represented by -SO 2 NHSO 2 R A3 , -CONHSO 2 R A4 , -CONHCOR A5 or -SO 2 NHCOR A6 , more preferably -SO 2 NHSO 2 R A3 .
- R A1 to R A6 each independently represent an alkyl group or an aryl group.
- the alkyl groups and aryl groups represented by R A1 to R A6 may have substituents.
- the substituent is preferably a halogen atom, more preferably a fluorine atom.
- Basic groups include amino groups, pyridinyl groups and salts thereof, salts of ammonium groups, and phthalimidomethyl groups.
- Atoms or atomic groups constituting salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
- the dye derivative include the compounds described in Examples described later.
- JP-A-56-118462, JP-A-63-264674, JP-A-01-217077, JP-A-03-009961, JP-A-03-026767, JP-A-03-153780 Publications, JP-A-03-045662, JP-A-04-285669, JP-A-06-145546, JP-A-06-212088, JP-A-06-240158, JP-A-10-030063, JP-A-10-195326, paragraph numbers 0086 to 0098 of International Publication No. 2011/024896, and compounds described in paragraph numbers 0063 to 0094 of International Publication No. 2012/102399, the contents of which are herein incorporated into.
- the content of the dye derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the near-infrared absorbing pigment.
- the lower limit is preferably 3 parts by mass or more, more preferably 5 parts by mass or more.
- the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
- the content of the dye derivative is preferably 1 to 50 parts by mass with respect to 100 parts by mass of the above specific compound.
- the lower limit is preferably 2 parts by mass or more, more preferably 5 parts by mass or more.
- the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less.
- the composition of the present invention may contain only one dye derivative, or may contain two or more dye derivatives. When two or more dye derivatives are included, the total amount thereof is preferably within the above range.
- the composition of the invention preferably contains a solvent.
- the solvent include water and organic solvents, and organic solvents are preferred.
- Organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.
- Ester-based solvents substituted with cyclic alkyl groups and ketone-based solvents substituted with cyclic alkyl groups can also be preferably used.
- organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2 -heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethylcarbitol Acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents may be better reduced for environmental reasons (e.g., 50 mass ppm (parts per million), 10 mass ppm or less, or 1 mass ppm or less).
- an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent with a ppt (parts per trillion) mass level may be used, and such an organic solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Daily, November 13, 2015).
- Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
- the filter pore size of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon.
- the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one isomer may be contained, or a plurality of isomers 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 composition is preferably 10-97% by mass.
- the lower limit is preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, even more preferably 60% by mass or more, and 70% by mass. It is particularly preferable that it is above.
- the upper limit is preferably 96% by mass or less, more preferably 95% by mass or less.
- the composition of the present invention may contain only one type of solvent, or may contain two or more types. When two or more solvents are included, the total amount thereof is preferably within the above range.
- the composition of the invention preferably further contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
- halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
- acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds and the like.
- photopolymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, hexaarylbi imidazole compounds, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl-substituted coumarin compounds, oxime compounds, ⁇ -hydroxyketones compounds, ⁇ -aminoketone compounds, and acylphosphine compounds, more preferably oxime compounds.
- hexaarylbiimidazole compounds include 2,2′,4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1′-biimidazole, etc. is mentioned.
- ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (above company) and the like.
- ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (manufactured by Irgacure 369E, Irgacure 379EG). made), etc.
- acylphosphine compounds include Omnirad 819, Omnirad TPO (manufactured by IGM Resins B.V.), Irgacure 819 and Irgacure TPO (manufactured by BASF).
- Examples of oxime compounds include compounds described in JP-A-2001-233842, compounds described in JP-A-2000-080068, compounds described in JP-A-2006-342166, J. Am. C. S. Compounds described in Perkin II (1979, pp.1653-1660); C. S. Compounds described in Perkin II (1979, pp.156-162), compounds described in Journal of Photopolymer Science and Technology (1995, pp.202-232), compounds described in JP-A-2000-066385, Compounds described in JP-A-2004-534797, compounds described in JP-A-2017-019766, compounds described in Patent No.
- oxime compounds include 3-benzoyloxyiminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxy and imino-1-phenylpropan-1-one.
- An oxime compound having a fluorene ring can also be used as the photopolymerization initiator.
- Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466, compounds described in Japanese Patent No. 6636081, and compounds described in Korean Patent Publication No. 10-2016-0109444. be done.
- an oxime compound having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring can also be used.
- Specific examples of such oxime compounds include compounds described in WO2013/083505.
- An oxime compound having a fluorine atom can also be used as the photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include compounds described in JP-A-2010-262028, compounds 24, 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. and the compound (C-3) of.
- An oxime compound having a nitro group can be used as the photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- Specific examples of the oxime compound having a nitro group include the compounds described in paragraph numbers 0031 to 0047 of JP-A-2013-114249 and paragraph numbers 0008-0012 and 0070-0079 of JP-A-2014-137466; Compounds described in paragraphs 0007 to 0025 of Japanese Patent No. 4223071 and ADEKA Arkles NCI-831 (manufactured by ADEKA Corporation) can be mentioned.
- An oxime compound having a benzofuran skeleton can also be used as the photopolymerization initiator.
- Specific examples include OE-01 to OE-75 described in WO 2015/036910.
- an oxime compound in which a substituent having a hydroxyl group is bonded to the carbazole skeleton can also be used.
- Examples of such a photopolymerization initiator include the compounds described in International Publication No. 2019/088055.
- oxime compounds preferably used in the present invention are shown below, but the present invention is not limited to these.
- the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
- the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or a wavelength of 405 nm is preferably high from the viewpoint of sensitivity, more preferably 1000 to 300000, further preferably 2000 to 300000, even more preferably 5000 to 200000. It is particularly preferred to have
- the molar extinction coefficient of a compound can be measured using known methods. For example, it is preferably measured at a concentration of 0.01 g/L using an ethyl acetate solvent with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
- a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so good sensitivity can be obtained.
- the crystallinity is lowered, the solubility in a solvent or the like is improved, the precipitation becomes difficult over time, and the stability over time of the composition can be improved.
- Specific examples of bifunctional or trifunctional or higher photoradical polymerization initiators include Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
- the content of the photopolymerization initiator is preferably 0.1 to 40% by mass, more preferably 0.5 to 35% by mass, even more preferably 1 to 30% by mass, based on the total solid content of the composition.
- the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more photopolymerization initiators are included, the total amount thereof preferably falls within the above range.
- composition of the present invention contains a compound having a cyclic ether group, it preferably further contains a curing agent.
- curing agents include amine compounds, acid anhydrides, amide compounds, phenol compounds, polyvalent carboxylic acids, and thiol compounds.
- specific examples of curing agents include succinic acid, trimellitic acid, pyromellitic acid, N,N-dimethyl-4-aminopyridine, pentaerythritol tetrakis(3-mercaptopropionate) and the like.
- the curing agent compounds described in paragraphs 0072 to 0078 of JP-A-2016-075720 and compounds described in JP-A-2017-036379 can also be used.
- the content of the curing agent is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 10 parts by mass, and 0.1 to 6.0 parts by mass with respect to 100 parts by mass of the compound having a cyclic ether group. is more preferred.
- the composition of the present invention may contain only one curing agent, or may contain two or more curing agents. When two or more curing agents are included, the total amount thereof is preferably within the above range.
- the composition of the invention may contain chromatic colorants.
- a chromatic colorant means a colorant other than a white colorant and a black colorant.
- the chromatic colorant is preferably a colorant that absorbs in a wavelength range of 400 nm or more and less than 650 nm.
- the chromatic colorants include red colorants, green colorants, blue colorants, yellow colorants, purple colorants and orange colorants.
- a chromatic colorant may be a pigment or a dye.
- a pigment and a dye may be used in combination.
- the pigment may be either an inorganic pigment or an organic pigment.
- an inorganic pigment or a material in which a part of an organic-inorganic pigment is replaced with an organic chromophore can also be used. By replacing inorganic pigments or organic-inorganic pigments with organic chromophores, hue design can be facilitated.
- the average primary particle size of the pigment is preferably 1 to 200 nm.
- the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
- the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
- the average primary particle size of the pigment can be determined from the image photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is obtained, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment.
- the average primary particle size in the present invention is the arithmetic mean value of the primary particle sizes of 400 primary particles of the pigment.
- the primary particles of the pigment refer to independent particles without agglomeration.
- the chromatic colorant preferably contains a pigment.
- the content of the pigment in the chromatic colorant is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and 90% by mass or more. is particularly preferred. Examples of pigments include those shown below.
- a halogenated zinc phthalocyanine pigment having an average number of halogen atoms of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 per molecule.
- Specific examples include compounds described in International Publication No. 2015/118720.
- a phthalocyanine compound a phthalocyanine compound described in JP-A-2018-180023, a compound described in JP-A-2019-038958, a core-shell type dye described in JP-A-2020-076995, and the like can also be used.
- An aluminum phthalocyanine compound having a phosphorus atom can also be used as a blue pigment.
- Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP-A-2012-247591 and paragraph number 0047 of JP-A-2011-157478.
- red pigments diketopyrrolopyrrole compounds in which at least one bromine atom is substituted in the structure described in JP-A-2017-201384, diketopyrrolopyrrole compounds described in paragraphs 0016 to 0022 of Japanese Patent No. 6248838, Diketopyrrolopyrrole compounds described in WO 2012/102399, diketopyrrolopyrrole compounds described in WO 2012/117965, naphthol azo compounds described in JP 2012-229344, Patent No. 6516119 Red pigment described in the publication, red pigment described in Patent No. 6525101, brominated diketopyrrolopyrrole compounds described in paragraph number 0229 of JP 2020-090632, Korean Patent No.
- 10-2019-0140741 Anthraquinone compounds described in publications, anthraquinone compounds described in Korean Patent Publication No. 10-2019-0140744, perylene compounds described in JP-A-2020-079396, and the like can also be used. Also, as a red pigment, a compound having a structure in which an aromatic ring group in which a group having an oxygen atom, a sulfur atom or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton may be used. can.
- the pyrrolopyrrole-based pigment has a crystallite size of 140 ⁇ or less in the plane direction corresponding to the maximum peak in the X-ray diffraction pattern among the eight planes of ( ⁇ 1 ⁇ 1 ⁇ 1) among the crystal lattice planes. It is also preferred to use one. Further, the physical properties of the pyrrolopyrrole pigment are preferably set as described in paragraphs 0028 to 0073 of JP-A-2020-097744.
- Dyes can also be used as chromatic colorants.
- the dye is not particularly limited, and known dyes can be used.
- pyrazole azo dyes anilinoazo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, pyrromethene dyes, and the like.
- a pigment multimer can also be used as a chromatic colorant.
- the dye multimer is preferably a dye dissolved in a solvent and used. Further, the dye multimer may form particles. When the dye multimer is particles, it is usually used in a state of being dispersed in a solvent.
- the particulate dye multimer can be obtained, for example, by emulsion polymerization, and specific examples include the compounds and production methods described in JP-A-2015-214682.
- a dye multimer has two or more dye structures in one molecule, and preferably has three or more dye structures. The upper limit is not particularly limited, but may be 100 or less.
- a plurality of dye structures in one molecule may be the same dye structure or different dye structures.
- the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
- the lower limit is more preferably 3000 or more, and even more preferably 6000 or more.
- the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
- Dye multimers are described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016/031442, etc. Compounds can also be used.
- the chromatic colorant the thiazole compound described in JP-A-2012-158649, the azo compound described in JP-A-2011-184493, the azo compound described in JP-A-2011-145540, published in Korea Triarylmethane dye polymer described in Patent No. 10-2020-0028160, xanthene compound described in JP-A-2020-117638, phthalocyanine compound described in WO2020/174991, JP-A-2020-160279
- An isoindoline compound or a salt thereof described in the publication can be used.
- the content of the chromatic colorant is preferably 1 to 50% by mass based on the total solid content of the composition of the present invention.
- the composition of the present invention may contain only one type of chromatic colorant, or may contain two or more types. When two or more chromatic colorants are included, the total amount thereof is preferably within the above range.
- the composition of the present invention can also contain a coloring material that transmits infrared rays and blocks visible light (hereinafter also referred to as a coloring material that blocks visible light).
- a composition containing a coloring material that blocks visible light is preferably used as a composition for forming an infrared transmission filter.
- the colorant that blocks visible light is preferably a colorant that absorbs light in the wavelength range from violet to red. Further, the coloring material that blocks visible light is preferably a coloring material that blocks light in the wavelength range of 450 to 650 nm. Further, the coloring material that blocks visible light is preferably a coloring material that transmits light with a wavelength of 900 to 1500 nm.
- the colorant that blocks visible light preferably satisfies at least one of the following requirements (A) and (B).
- B Contains an organic black colorant.
- organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred.
- bisbenzofuranone compounds include compounds described in Japanese Patent Application Publication No. 2010-534726, Japanese Patent Application Publication No. 2012-515233, Japanese Patent Application Publication No. 2012-515234, etc.
- perylene compounds include compounds described in paragraphs 0016 to 0020 of JP-A-2017-226821, C.I. I. Pigment Black 31, 32 and the like.
- the azomethine compound include compounds described in JP-A-01-170601, JP-A-02-034664, and the like.
- the combination of chromatic colorants includes, for example, the following aspects (1) to (8).
- the content of the coloring material that blocks visible light is preferably 1 to 50 mass% of the total solid content of the composition.
- the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more.
- the composition of the invention preferably contains a surfactant.
- a surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants and silicone surfactants can be used.
- the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
- Surfactants include those described in paragraphs 0238-0245 of WO2015/166779, the contents of which are incorporated herein.
- JP 2014-041318 Paragraph Nos. 0060 to 0064 (corresponding International Publication No. 2014/017669 Paragraph Nos. 0060 to 0064) surfactants described in, JP 2011- Examples include surfactants described in paragraphs 0117 to 0132 of JP-A-132503 and surfactants described in JP-A-2020-008634, the contents of which are incorporated herein.
- Commercially available fluorosurfactants include Megafac F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143 and F-144.
- fluorine-based surfactant there is also an acrylic compound that has a molecular structure with a functional group containing a fluorine atom, and when heat is applied, the portion of the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes. It can be used preferably.
- fluorine-based surfactants include Megafac DS series manufactured by DIC Corporation (The Chemical Daily (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016)), for example, Megafac and DS-21.
- fluorosurfactant 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 as the fluorosurfactant.
- fluorosurfactants include fluorosurfactants described in JP-A-2016-216602, the contents of which are incorporated herein.
- a block polymer can also be used as the fluorosurfactant.
- a fluorosurfactant 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) (meta)
- 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 fluorine-based surfactants used in the present invention.
- the weight average molecular weight of the above compound is preferably 3000-50000, for example 14000. In the above compounds, % indicating the ratio of repeating units is mol%.
- a fluorine-containing polymer having an ethylenically unsaturated bond-containing group in a side chain can also be used as the fluorine-based surfactant.
- Specific examples include compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP-A-2010-164965, MEGAFACE RS-101, RS-102 and RS-718K manufactured by DIC Corporation, and RS-72-K. Further, compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327 can also be used as the fluorosurfactant.
- a fluorine-containing imide salt compound represented by formula (fi-1) is also preferable to use as a surfactant.
- m represents 1 or 2
- n represents an integer of 1 to 4
- a represents 1 or 2
- X a+ is an a-valent metal ion, primary ammonium ion, Represents secondary ammonium ion, tertiary ammonium ion, quaternary ammonium ion or NH 4 + .
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (e.g., glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF company), Tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF), Solsperse 20000 (manufactured by Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure
- Cationic surfactants include tetraalkylammonium salts, alkylamine salts, benzalkonium salts, alkylpyridium salts, imidazolium salts, and the like. Specific examples include dihydroxyethylstearylamine, 2-heptadecenyl-hydroxyethylimidazoline, lauryldimethylbenzylammonium chloride, cetylpyridinium chloride, stearamidomethylpyridinium chloride and the like.
- Anionic surfactants include dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium lauryl sulfate, sodium alkyldiphenyletherdisulfonate, sodium alkylnaphthalenesulfonate, sodium dialkylsulfosuccinate, sodium stearate, potassium oleate, sodium dioctyl Sulfosuccinate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkyl ether sulfate, sodium polyoxyethylene alkylphenyl ether sulfate, sodium dialkyl sulfosuccinate, sodium stearate, sodium oleate, t-octylphenoxyethoxypolyethoxyethyl sodium sulfate and the like.
- silicone surfactants examples include SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), TSF-4440, and TSF-4300. , TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (Shin-Etsu Chemical Co., Ltd. Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-3760, BYK-UV3510 (manufactured by BYK-Chemie) and the like.
- a compound having the following structure can also be used as the silicone-based surfactant.
- the content of the surfactant is preferably 0.001 to 1% by mass, more preferably 0.001 to 0.5% by mass, and still more preferably 0.001 to 0.2% by mass of the total solid content of the composition.
- the composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more surfactants are included, the total amount thereof is preferably within the above range.
- the composition of the invention may contain a polymerization inhibitor.
- Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4′-thiobis(3-methyl-6-tert-butylphenol), 2,2′-methylenebis(4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), and p-methoxyphenol is preferred.
- the content of the polymerization inhibitor is preferably 0.0001 to 5% by mass based on the total solid content of the composition.
- the composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more polymerization inhibitors are included, the total amount thereof is preferably within the above range.
- the composition of the invention can contain a silane coupling agent.
- a 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 bonded to a silicon atom and capable of forming a siloxane bond by at least one of hydrolysis reaction and condensation reaction.
- Hydrolyzable groups include, for example, halogen atoms, alkoxy groups, acyloxy groups and the like, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
- Examples of functional groups other than hydrolyzable groups include vinyl group, (meth)acryloyl group, mercapto group, epoxy group, oxetanyl group, amino group, ureido group, sulfide group, isocyanate group, and phenyl group. with (meth)acryloyl groups and epoxy groups being preferred.
- the silane coupling agent includes compounds described in paragraph numbers 0018 to 0036 of JP-A-2009-288703 and compounds described in paragraph numbers 0056-0066 of JP-A-2009-242604. incorporated into the specification.
- the content of the silane coupling agent is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass, based on the total solid content of the composition.
- the composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When two or more silane coupling agents are included, the total amount thereof is preferably within the above range.
- the composition of the invention may contain an ultraviolet absorber.
- ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and merocyanine dyes. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP-A-2009-217221, paragraph numbers 0052-0072 of JP-A-2012-208374, paragraph numbers 0317-0317 of JP-A-2013-068814.
- UV absorbers include Tinuvin series and Uvinul series manufactured by BASF. Moreover, as a benzotriazole compound, the MYUA series made from Miyoshi oil and fats (Chemical Daily, February 1, 2016) is mentioned. Further, as the ultraviolet absorber, compounds described in paragraph numbers 0049 to 0059 of Japanese Patent No. 6268967 and paragraph numbers 0059 to 0076 of International Publication No. 2016/181987 can also be used.
- the content of the ultraviolet absorber is preferably 0.01 to 30% by mass, more preferably 0.05 to 25% by mass, based on the total solid content of the composition.
- the composition of the present invention may contain only one type of ultraviolet absorber, or may contain two or more types. When two or more ultraviolet absorbers are included, the total amount thereof is preferably within the above range.
- the compositions of the invention may contain antioxidants.
- Antioxidants include phenol compounds, phosphite ester compounds, thioether compounds and the like. Any phenolic compound known as a phenolic antioxidant can be used as the phenolic compound.
- Preferred phenolic compounds include hindered phenolic compounds.
- a compound having a substituent at a site adjacent to the phenolic hydroxy group (ortho position) is preferred.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred.
- the antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule.
- Phosphorus-based antioxidants can also be suitably used as antioxidants.
- a phosphorus antioxidant tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6 -yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl ) oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, and the like.
- antioxidants include, for example, Adekastab AO-20, Adekastab AO-30, Adekastab AO-40, Adekastab AO-50, Adekastab AO-50F, Adekastab AO-60, Adekastab AO-60G, Adekastab AO-80. , ADEKA STAB AO-330 (manufactured by ADEKA Corporation) and the like.
- antioxidants are compounds described in paragraph numbers 0023 to 0048 of Japanese Patent No. 6268967, compounds described in WO 2017/006600, and compounds described in WO 2017/164024. can also be used.
- the content of the antioxidant is preferably 0.01 to 20% by mass, more preferably 0.3 to 15% by mass, based on the total solid content of the composition.
- the composition of the present invention may contain only one kind of antioxidant, or may contain two or more kinds. When two or more kinds of antioxidants are included, the total amount thereof is preferably within the above range.
- composition of the present invention may optionally contain sensitizers, curing accelerators, fillers, thermosetting accelerators, plasticizers and other auxiliaries (e.g., conductive particles, antifoaming agents, flame retardants, leveling agents, etc.). agents, release accelerators, fragrances, surface tension modifiers, chain transfer agents, etc.). Properties such as film physical properties can be adjusted by appropriately containing these components. These components are, for example, described in JP 2012-003225, paragraph number 0183 and later (corresponding US Patent Application Publication No. 2013/0034812, paragraph number 0237), JP 2008-250074 paragraph The descriptions of numbers 0101 to 0104, 0107 to 0109, etc.
- the composition of the present invention may also contain latent antioxidants, if desired.
- the latent antioxidant is a compound in which the site functioning as an antioxidant is protected by a protective group, and is heated at 100 to 250°C, or heated at 80 to 200°C in the presence of an acid/base catalyst.
- a compound that functions as an antioxidant by removing the protective group by the reaction is exemplified.
- Examples of latent antioxidants include compounds described in International Publication No. 2014/021023, International Publication No. 2017/030005, and JP-A-2017-008219.
- Commercially available latent antioxidants include ADEKA Arkles GPA-5001 (manufactured by ADEKA Co., Ltd.).
- the storage container for the composition of the present invention is not particularly limited, and known storage containers can be used.
- a storage container a multi-layer bottle whose inner wall is composed of 6 types and 6 layers of resin and a bottle with a 7-layer structure of 6 types of resin are used for the purpose of suppressing the contamination of raw materials and compositions with impurities. It is also preferred to use Examples of such a container include the container described in JP-A-2015-123351.
- the inner wall of the container is preferably made of glass or stainless steel for the purpose of preventing metal elution from the inner wall of the container, enhancing the stability of the composition over time, and suppressing deterioration of components.
- compositions of the present invention can be prepared by mixing the aforementioned ingredients.
- the composition may be prepared by dissolving or dispersing all the components in a solvent at the same time, or if necessary, two or more solutions or dispersions in which each component is appropriately blended are prepared in advance. They may be prepared and mixed at the time of use (at the time of application) to prepare a composition.
- the preparation of the composition may include a process of dispersing the pigment.
- mechanical forces used for dispersing pigments include compression, squeezing, impact, shearing, cavitation, and the like.
- Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like.
- pulverizing the pigment in a sand mill (bead mill) it is preferable to use beads with a small diameter or to increase the filling rate of the beads so as to increase the pulverization efficiency.
- the process and dispersing machine for dispersing pigments are described in "Dispersion Technology Complete Works, Information Organization Co., Ltd., July 15, 2005” and "Dispersion technology centered on suspension (solid / liquid dispersion system) and industrial Practical Application General Documents, Published by Management Development Center Publishing Department, October 10, 1978", the process and dispersing machine described in paragraph number 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be suitably used.
- the pigment may be finely divided in the salt milling process. Materials, equipment, processing conditions, etc.
- Beads used for dispersion can be zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, glass, or combinations thereof.
- An inorganic compound having a Mohs hardness of 2 or more can also be used as beads.
- the composition may contain 1 to 10000 ppm of the beads.
- any filter that has been conventionally used for filtration or the like can be used without particular limitation.
- fluorine resin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene, polypropylene (PP) (high density, ultra high molecular weight (including polyolefin resin).
- PTFE polytetrafluoroethylene
- nylon eg nylon-6, nylon-6,6)
- polyolefin resin such as polyethylene
- PP polypropylene
- polypropylene including high density polypropylene
- nylon are preferred.
- the pore size of the filter is preferably 0.01-7.0 ⁇ m, more preferably 0.01-3.0 ⁇ m, and even more preferably 0.05-0.5 ⁇ m. If the pore diameter of the filter is within the above range, fine foreign matter can be removed more reliably.
- the pore size value of the filter reference can be made to the filter manufacturer's nominal value.
- Various filters provided by Nihon Pall Co., Ltd. (DFA4201NIEY, DFA4201NAEY, DFA4201J006P, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (former Japan Microlith Co., Ltd.), Kitz Micro Filter Co., Ltd., etc. can be used as the filter. .
- fibrous filter media include polypropylene fibers, nylon fibers, and glass fibers.
- 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.
- filters When using filters, different filters (eg, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed twice or more. Also, filters with different pore sizes within the range described above may be combined. Further, the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration with the second filter may be performed.
- filters eg, a first filter and a second filter, etc.
- the membrane of the invention is obtained from the composition of the invention described above.
- the film of the present invention can be preferably used as an optical filter.
- Applications of the optical filter are not particularly limited, but examples thereof include a near-infrared cut filter and an infrared transmission filter.
- a near-infrared cut filter for example, a near-infrared cut filter on the light receiving side of the solid-state image sensor (for example, a near-infrared cut filter for a wafer level lens, etc.), a back side of the solid-state image sensor (opposite to the light receiving side)
- Infrared cut filter near-infrared cut filter for ambient light sensor (e.g., illuminance sensor that detects the illuminance and color tone of the environment in which the information terminal device is placed and adjusts the color tone of the display, color correction sensor that adjusts the color tone ) and the like.
- the infrared transmission filter include a filter capable of blocking visible light and selectively transmitting infrared light having a specific wavelength or longer.
- the film of the present invention may have a pattern or may be a film without a pattern (flat film). Moreover, the film of the present invention may be used by laminating it on a support, or may be used by peeling the film of the present invention from the support. Examples of the support include semiconductor substrates such as silicon substrates and transparent substrates.
- a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, or the like may be formed on the semiconductor substrate used as the support. Also, a black matrix that isolates each pixel may be formed on the semiconductor substrate. Further, if necessary, an undercoat layer may be provided on the semiconductor substrate for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the substrate.
- CMOS complementary metal oxide semiconductor
- a transparent conductive film or the like
- an undercoat layer may be provided on the semiconductor substrate for improving adhesion to the upper layer, preventing diffusion of substances, or flattening the surface of the substrate.
- the transparent substrate used as the support is not particularly limited as long as it is composed of a material that can transmit at least visible light.
- Examples thereof include base materials made of materials such as glass and resin.
- resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene, polypropylene, and ethylene vinyl acetate copolymer, acrylic resins such as norbornene resin, polyacrylate, and polymethyl methacrylate, urethane resins, and vinyl chloride resins. , fluororesin, polycarbonate resin, polyvinyl butyral resin, polyvinyl alcohol resin, and the like.
- glass examples include soda-lime glass, borosilicate glass, alkali-free glass, quartz glass, glass containing copper, and the like.
- Glass containing copper includes phosphate glass containing copper, fluorophosphate glass containing copper, and the like.
- a commercially available glass containing copper can also be used.
- Commercially available glass containing copper includes NF-50 (manufactured by AGC Techno Glass Co., Ltd.).
- the thickness of the film of the present invention can be adjusted as appropriate according to the purpose.
- the thickness of the film is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more.
- the film of the present invention When the film of the present invention is used as a near-infrared cut filter, the film of the present invention has a maximum absorption wavelength in the wavelength range of 650 to 1500 nm (preferably 660 to 1200 nm, more preferably 660 to 1000 nm). preferable.
- the average transmittance of light with a wavelength of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, still more preferably 80% or more, and particularly 85% or more. preferable.
- the transmittance in the entire wavelength range of 420 to 550 nm is preferably 50% or more, more preferably 70% or more, and even more preferably 80% or more.
- the film of the present invention preferably has a transmittance of 15% or less at at least one point in the wavelength range of 650 to 1500 nm (preferably 660 to 1200 nm, more preferably 660 to 1000 nm). The following is more preferable, and 5% or less is even more preferable.
- the film of the present invention preferably has an average absorbance of less than 0.030, more preferably less than 0.025 in the wavelength range of 420 to 550 nm when the absorbance at the maximum absorption wavelength is 1.
- the film of the present invention preferably has, for example, any one of the following spectral characteristics (i1) to (i3).
- a film having such spectral characteristics can block light in the wavelength range of 400 to 850 nm and transmit light in the wavelength range of 950 nm or more.
- the maximum transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1100 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
- a film having such spectral characteristics can block light in the wavelength range of 400 to 950 nm and transmit light in the wavelength range of 1050 nm or more.
- the maximum transmittance in the wavelength range of 400 to 1050 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance in the wavelength range of 1200 to 1500 nm is A filter that is 70% or more (preferably 75% or more, more preferably 80% or more).
- a film having such spectral characteristics can block light in the wavelength range of 400 to 1050 nm and transmit light in the wavelength range of 1150 nm or more.
- the film of the present invention can also be used in combination with a color filter containing a chromatic colorant.
- a color filter can be produced using a coloring composition containing a chromatic colorant.
- the color filter is preferably arranged on the optical path of the film of the present invention.
- the film of the present invention may be formed on a support other than the support on which the color filter is formed.
- Other members for example, a microlens, a planarization layer, etc. constituting the solid-state imaging device may be interposed between the film and the color filter.
- the film of the present invention can be used in various devices such as solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors), infrared sensors, and image display devices.
- solid-state imaging devices such as CCDs (charge-coupled devices) and CMOSs (complementary metal oxide semiconductors)
- infrared sensors and image display devices.
- the film of the present invention can be produced through the step of applying the composition of the present invention.
- Examples of the support include those mentioned above.
- a method for applying the composition a known method can be used. For example, drop method (drop cast); slit coating method; spray method; roll coating method; spin coating method (spin coating); methods described in publications); inkjet (e.g., on-demand method, piezo method, thermal method), discharge system printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing method, etc. Examples include various printing methods; transfer methods using molds and the like; nanoimprinting methods and the like.
- the application method for inkjet is not particularly limited.
- the composition layer formed by applying the composition may be dried (pre-baked).
- the pre-baking temperature is preferably 150° C. or lower, more preferably 120° C. or lower, and even more preferably 110° C. or lower.
- the lower limit can be, for example, 50° C. or higher, and can also be 80° C. or higher.
- the prebaking time is preferably 10 seconds to 3000 seconds, more preferably 40 seconds to 2500 seconds, and even more preferably 80 seconds to 220 seconds. Drying can be performed using a hot plate, an oven, or the like.
- the film manufacturing method may further include a step of forming a pattern.
- the pattern forming method include a pattern forming method using a photolithographic method and a pattern forming method using a dry etching method, and the pattern forming method using the photolithographic method is preferable.
- the step of forming a pattern may not be performed. The process of forming the pattern will be described in detail below.
- the pattern formation method by photolithography comprises a step of patternwise exposing the composition layer formed by coating the composition of the present invention (exposure step), and developing and removing the unexposed portion of the composition layer. and a step of forming a pattern (development step). If necessary, a step of baking the developed pattern (post-baking step) may be provided. Each step will be described below.
- the composition layer is exposed in a pattern.
- the composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. Thereby, the exposed portion can be cured.
- Radiation (light) that can be used for exposure includes g-line, i-line, and the like.
- Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
- Light having a wavelength of 300 nm or less includes KrF rays (wavelength: 248 nm), ArF rays (wavelength: 193 nm), etc., and KrF rays (wavelength: 248 nm) are preferable.
- a long-wave light source of 300 nm or more can also be used.
- the light when exposing, the light may be continuously irradiated and exposed, or may be irradiated and exposed in pulses (pulse exposure).
- pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and rest in short-time (for example, millisecond level or less) cycles.
- the irradiation amount is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 .
- the oxygen concentration at the time of exposure can be selected as appropriate, and in addition to exposure in the atmosphere, for example, in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free) or in a high-oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume).
- the exposure illuminance can be set as appropriate, and is usually selected from the range of 1000 W/m 2 to 100000 W/m 2 (eg, 5000 W/m 2 , 15000 W/m 2 or 35000 W/m 2 ). can be done. Oxygen concentration and exposure illuminance may be appropriately combined. For example, illuminance of 10000 W/m 2 at oxygen concentration of 10% by volume and illuminance of 20000 W/m 2 at oxygen concentration of 35% by volume.
- an unexposed portion of the composition layer after exposure is removed by development to form a pattern.
- the development and removal of the composition layer in the unexposed area can be carried out using a developer.
- the unexposed portion of the composition layer in the exposure step is eluted into the developer, leaving only the photocured portion on the support.
- the temperature of the developer is preferably 20 to 30° C., for example.
- the development time is preferably 20 to 180 seconds. Further, in order to improve the residue removability, the step of shaking off the developer every 60 seconds and then supplying new developer may be repeated several times.
- the developer includes an organic solvent, an alkaline developer, etc., and an alkaline developer is preferably used.
- an alkaline developer an alkaline aqueous solution (alkali developer) obtained by diluting an alkaline agent with pure water is preferable.
- alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
- alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate and sodium metasilicate.
- concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
- the developer may further contain a surfactant.
- a nonionic surfactant is preferable as the surfactant.
- the developer may be produced once as a concentrated solution and then diluted to the required concentration when used. Although the dilution ratio is not particularly limited, it can be set, for example, in the range of 1.5 to 100 times.
- wash (rinse) with pure water after development. Rinsing is preferably carried out by supplying a rinse liquid to the composition layer after development while rotating the support on which the composition layer after development is formed. It is also preferable to move the nozzle for discharging the rinsing liquid from the central portion of the support to the peripheral portion of the support.
- the moving speed of the nozzle may be gradually decreased.
- in-plane variations in rinsing can be suppressed.
- a similar effect can be obtained by gradually decreasing the rotation speed of the support while moving the nozzle from the center of the support to the periphery.
- Additional exposure processing and post-baking are post-development curing treatments for complete curing.
- the heating temperature in post-baking is, for example, preferably 100 to 240.degree. C., more preferably 200 to 240.degree.
- Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulating dryer), or a high-frequency heater so that the developed film satisfies the above conditions. .
- the light used for exposure preferably has a wavelength of 400 nm or less.
- the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
- Pattern formation by a dry etching method includes curing the composition layer formed by coating the composition on a support to form a cured product layer, and then forming a photoresist layer patterned on the cured product layer. is formed, and then dry etching is performed on the cured product layer using an etching gas using the patterned photoresist layer as a mask. In forming the photoresist layer, pre-baking is preferably performed.
- description in paragraphs 0010 to 0067 of JP-A-2013-064993 can be referred to, and the contents thereof are incorporated into this specification.
- optical filter of the present invention has the film of the present invention as described above.
- Types of optical filters include near-infrared cut filters and infrared transmission filters.
- the optical filter of the present invention may further have a layer containing copper, a dielectric multilayer film, an ultraviolet absorbing layer, etc., in addition to the film of the present invention described above.
- the ultraviolet absorbing layer include the absorbing layers described in paragraphs 0040 to 0070 and 0119 to 0145 of International Publication No. 2015/099060.
- Dielectric multilayer films include dielectric multilayer films described in paragraphs 0255 to 0259 of JP-A-2014-041318.
- the layer containing copper a glass substrate made of glass containing copper (copper-containing glass substrate) or a layer containing a copper complex (copper complex-containing layer) can be used.
- Copper-containing glass substrates include copper-containing phosphate glass, copper-containing fluorophosphate glass, and the like.
- Commercially available copper-containing glasses include NF-50 (manufactured by AGC Techno Glass Co., Ltd.), BG-60, BG-61 (manufactured by Schott), CD5000 (manufactured by HOYA Corporation), and the like.
- the solid-state imaging device of the present invention includes the film of the present invention described above.
- the configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device. For example, the following configuration can be mentioned.
- a plurality of photodiodes constituting the light receiving area of the solid-state imaging device and transfer electrodes made of polysilicon or the like are provided on the support, and light shielding made of tungsten or the like with only the light receiving portions of the photodiodes being opened on the photodiodes and the transfer electrodes.
- a device protective film made of silicon nitride or the like is formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion, and the film of the present invention is provided on the device protective film. be.
- the color filter may have a structure in which a film forming each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.
- the partition in this case preferably has a lower refractive index than each pixel. Examples of imaging devices having such a structure include devices described in JP-A-2012-227478 and JP-A-2014-179577.
- the image display device of the invention comprises the film of the invention.
- image display devices include liquid crystal display devices and organic electroluminescence (organic EL) display devices.
- organic EL organic electroluminescence
- For the definition and details of the image display device see, for example, “Electronic Display Device (written by Akio Sasaki, Industrial Research Institute, 1990)", “Display Device (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd., 1989). issued)”, etc.
- Liquid crystal display devices are described, for example, in “Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, published by Kogyo Choukai Co., Ltd., 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied.
- the image display device may have a white organic EL element.
- a white organic EL device preferably has a tandem structure. Regarding the tandem structure of organic EL elements, see Japanese Patent Application Laid-Open No. 2003-045676, supervised by Akiyoshi Mikami, "Forefront of Organic EL Technology Development -High Brightness, High Precision, Long Life, Know-how Collection-", Technical Information Association, 326-328, 2008, and others.
- the spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430-485 nm), the green region (530-580 nm) and the yellow region (580-620 nm). In addition to these emission peaks, those having a maximum emission peak in the red region (650 to 700 nm) are more preferred.
- the infrared sensor of the invention comprises the membrane of the invention as described above.
- the configuration of the infrared sensor is not particularly limited as long as it functions as an infrared sensor. An embodiment of the infrared sensor of the present invention will be described below with reference to the drawings.
- reference numeral 110 is a solid-state imaging device.
- a near-infrared cut filter 111 and an infrared transmission filter 114 are arranged on the imaging area of the solid-state imaging device 110 .
- a color filter 112 is arranged on the near-infrared cut filter 111 .
- a microlens 115 is arranged on the incident light h ⁇ side of the color filter 112 and the infrared transmission filter 114 .
- a planarization layer 116 is formed to cover the microlens 115 .
- the near-infrared cut filter 111 can be formed using the composition of the present invention.
- the color filter 112 is a color filter formed with pixels that transmit and absorb light of a specific wavelength in the visible region, and is not particularly limited, and conventionally known color filters for forming pixels can be used. For example, a color filter having red (R), green (G), and blue (B) pixels is used. For example, paragraph numbers 0214 to 0263 of JP-A-2014-043556 can be referred to, and the contents thereof are incorporated herein.
- the characteristics of the infrared transmission filter 114 are selected according to the emission wavelength of the infrared LED used. Infrared transmission filter 114 can be formed using the composition of the present invention.
- a near-infrared cut filter different from the near-infrared cut filter 111 may be further arranged on the flattening layer 116 .
- Other near-infrared cut filters include those having copper-containing layers and/or dielectric multilayer films. These details are given above.
- a dual bandpass filter may be used as another near-infrared cut filter.
- the weight-average molecular weight of the resin is determined by using HPC-8220GPC (manufactured by Tosoh Corporation) as a measuring device, TSKguardcolumn SuperHZ-L as a guard column, and TSKgel SuperHZM-M, TSKgel SuperHZ4000, TSKgel SuperHZ3000, and TSKgel SuperHZ2000 as columns.
- the column temperature is set to 40 ° C., 10 ⁇ L of a tetrahydrofuran solution with a sample concentration of 0.1% by mass is injected into the column, tetrahydrofuran is flowed at a flow rate of 0.35 mL per minute as an elution solvent, and an RI (differential refractive index) detector. A sample peak was detected at , and measured using a calibration curve prepared using standard polystyrene.
- the viscosity of the pigment dispersion liquid was obtained by adjusting the temperature of the pigment dispersion liquid to 25° C. and measuring it using an E-type viscometer at a rotation speed of 1000 rpm.
- the average particle diameter D50 value of the pigment is obtained by measuring the particle size distribution of the pigment in the pigment dispersion on a volume basis using MICROTRACUPA 150 manufactured by Nikkiso Co., Ltd., and the particle diameter at which the cumulative volume in the particle size distribution becomes 50%. Measured and sought.
- Pigment Compounds having the following structures (near-infrared absorbing pigments, pyrrolopyrrole compounds, and the solubility of Pig-001 to Pig-005 in 100 g of propylene glycol methyl ether acetate at 25° C. are all 0.05 g or less.
- Pig-101 compound having the following structure (near-infrared absorbing pigment, squarylium compound, solubility in 100 g of propylene glycol methyl ether acetate at 25°C is 0.05 g or less)
- Pig-102 compound having the following structure (near-infrared absorbing pigment, boradiazine compound, solubility in 100 g of propylene glycol methyl ether acetate at 25°C is 0.1 g or less)
- PY150 C.I. I. Pigment Yellow150 (yellow pigment)
- PR254 C.I. I. Pigment Red254 (red pigment)
- Dis-001 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight 25000, dispersion degree 2.0)
- Dis-002 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 32,000, dispersity: 2.5)
- Dis-003 Resin having the following structure (the numerical value attached to the main chain is the molar ratio, and the numerical value attached to the side chain is the number of repeating units. Weight average molecular weight: 15,000, dispersity: 2.8)
- composition Materials other than the solvent shown in the table below are mixed in the ratio shown in the table below, and the solvent shown in the table below is added to adjust the solid content concentration to 20% by mass, then stirred and nylon with a pore size of 0.45 ⁇ m. filter (manufactured by Nippon Pall Co., Ltd.) to prepare a composition.
- Numerical values in the columns of compounding amounts in the table are values in parts by mass in terms of solid content. Also, the value of parts by mass of the specific compound with respect to 100 parts by mass of the near-infrared absorbing pigment is shown in the column of "content of specific compound".
- B003 Resin having the following structure (the numerical values attached to the main chain are the molar ratios of the repeating units, the weight average molecular weight is 15,000, the degree of dispersion is 2.1)
- C-1 Irgacure OXE01 (manufactured by BASF, oxime ester initiator)
- C-2 Irgacure OXE02 (manufactured by BASF, oxime ester initiator)
- M-1 Aronix M-305 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate. The content of pentaerythritol triacrylate is 55% by mass to 63% by mass.)
- M-2 KAYARAD RP-1040 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide-modified pentaerythritol tetraacrylate)
- M-3 Aronix M-510 (manufactured by Toagosei Co., Ltd., polybasic acid-modified acrylic oligomer)
- F-1 Megafac RS-72-K (manufactured by DIC Corporation, fluorine-based surfactant)
- F-2 A compound having the following structure (weight average molecular weight: 14,000, % indicating the ratio of repeating units is mol %)
- F-3 KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., carbinol-modified polydimethylsiloxane at both ends, hydroxyl value 62 mgKOH/g)
- U-1 Uvinul 3050 (manufactured by BASF, UV absorber)
- U-2 Tinuvin477 (manufactured by BASF, hydroxyphenyltriazine-based UV absorber)
- U-3 Tinuvin326 (manufactured by BASF, UV absorber)
- i-line stepper exposure apparatus FPA-3000i5+ manufactured by Canon Inc.
- exposure was performed at an exposure amount of 1000 mJ/cm 2 through a mask having a Bayer pattern of 1 ⁇ m.
- TMAH tetramethylammonium hydroxide
- puddle development was performed at 23° C. for 60 seconds.
- the substrate was rinsed with a spin shower, washed with pure water, and then heated at 200° C. for 5 minutes on a hot plate to form a pattern (pixels).
- the glass substrate on which the pixels are formed is observed with a microscope at a magnification of 10,000 times, and the number of foreign crystals having a size of 1 ⁇ m or more present in the pixels formed on the glass substrate is counted. Defects were evaluated.
- E The number of foreign crystals is 1000 more than one
- Viscosity change rate ((composition after storage at 50°C for 3 months - viscosity of composition immediately after production)/viscosity of composition immediately after production) x 100
- the glass substrate on which the film was formed was irradiated with a xenon lamp at 100,000 lux for 20 hours (equivalent to 2,000,000 lux ⁇ h), and the transmittance of the film after irradiation with the xenon lamp was measured.
- the change in average transmittance ( ⁇ T) in the wavelength range of 600 to 800 nm before and after irradiation with the xenon lamp was measured. Based on the largest change in transmittance ( ⁇ T) in the entire measurement wavelength range, the light resistance was evaluated according to the following criteria. The smaller the value of ⁇ T, the better the light resistance.
- the compositions of the examples were able to form films in which foreign matter defects were suppressed.
- the composition of the example when the same pixel as described above was formed on a glass substrate using the composition immediately after production and microscopic observation was performed, no foreign matter was observed.
- the composition of Example 22 had a higher liquid permeation rate in filter filtration during preparation of the composition than the compositions of other Examples, but was superior in liquid permeation.
- 110 solid-state imaging device
- 111 near-infrared cut filter
- 112 color filter
- 114 infrared transmission filter
- 115 microlens
- 116 flattening layer
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Physics & Mathematics (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Optical Filters (AREA)
- Solid State Image Pick-Up Elements (AREA)
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| WO (1) | WO2023042605A1 (https=) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011068731A (ja) * | 2009-09-24 | 2011-04-07 | Fujifilm Corp | 近赤外吸収性色素を含有する硬化性組成物、インク用組成物および近赤外線吸収フィルタの製造方法 |
| WO2017038252A1 (ja) * | 2015-09-04 | 2017-03-09 | 富士フイルム株式会社 | 材料、組成物、硬化性組成物、硬化膜、光学フィルタ、固体撮像素子、赤外線センサ、カメラモジュールおよび材料の製造方法 |
| WO2017146092A1 (ja) * | 2016-02-26 | 2017-08-31 | 富士フイルム株式会社 | 組成物、硬化性組成物、硬化膜、近赤外線カットフィルタ、赤外線透過フィルタ、固体撮像素子、赤外線センサおよびカメラモジュール |
| WO2018061781A1 (ja) * | 2016-09-27 | 2018-04-05 | 富士フイルム株式会社 | ドライエッチング用組成物、キット、パターン形成方法および光学フィルタの製造方法 |
| JP2018119077A (ja) * | 2017-01-26 | 2018-08-02 | 富士フイルム株式会社 | 硬化性組成物、膜、光学フィルタ、積層体、固体撮像素子、画像表示装置および赤外線センサ |
| WO2018142804A1 (ja) * | 2017-02-01 | 2018-08-09 | 富士フイルム株式会社 | 樹脂組成物、樹脂膜、樹脂膜の製造方法、光学フィルタ、固体撮像素子、画像表示装置、および、赤外線センサ |
-
2022
- 2022-08-19 JP JP2023548374A patent/JPWO2023042605A1/ja not_active Abandoned
- 2022-08-19 WO PCT/JP2022/031413 patent/WO2023042605A1/ja not_active Ceased
- 2022-08-29 TW TW111132391A patent/TW202311405A/zh unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011068731A (ja) * | 2009-09-24 | 2011-04-07 | Fujifilm Corp | 近赤外吸収性色素を含有する硬化性組成物、インク用組成物および近赤外線吸収フィルタの製造方法 |
| WO2017038252A1 (ja) * | 2015-09-04 | 2017-03-09 | 富士フイルム株式会社 | 材料、組成物、硬化性組成物、硬化膜、光学フィルタ、固体撮像素子、赤外線センサ、カメラモジュールおよび材料の製造方法 |
| WO2017146092A1 (ja) * | 2016-02-26 | 2017-08-31 | 富士フイルム株式会社 | 組成物、硬化性組成物、硬化膜、近赤外線カットフィルタ、赤外線透過フィルタ、固体撮像素子、赤外線センサおよびカメラモジュール |
| WO2018061781A1 (ja) * | 2016-09-27 | 2018-04-05 | 富士フイルム株式会社 | ドライエッチング用組成物、キット、パターン形成方法および光学フィルタの製造方法 |
| JP2018119077A (ja) * | 2017-01-26 | 2018-08-02 | 富士フイルム株式会社 | 硬化性組成物、膜、光学フィルタ、積層体、固体撮像素子、画像表示装置および赤外線センサ |
| WO2018142804A1 (ja) * | 2017-02-01 | 2018-08-09 | 富士フイルム株式会社 | 樹脂組成物、樹脂膜、樹脂膜の製造方法、光学フィルタ、固体撮像素子、画像表示装置、および、赤外線センサ |
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| TW202311405A (zh) | 2023-03-16 |
| JPWO2023042605A1 (https=) | 2023-03-23 |
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