WO2024090311A1 - Composition d'absorption de lumière, procédé de production de composition d'absorption de lumière, film d'absorption de lumière, filtre optique et procédé de fabrication de filtre optique - Google Patents

Composition d'absorption de lumière, procédé de production de composition d'absorption de lumière, film d'absorption de lumière, filtre optique et procédé de fabrication de filtre optique Download PDF

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Publication number
WO2024090311A1
WO2024090311A1 PCT/JP2023/037742 JP2023037742W WO2024090311A1 WO 2024090311 A1 WO2024090311 A1 WO 2024090311A1 JP 2023037742 W JP2023037742 W JP 2023037742W WO 2024090311 A1 WO2024090311 A1 WO 2024090311A1
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group
light
light absorbing
optical filter
mass
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PCT/JP2023/037742
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Japanese (ja)
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雄一郎 久保
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日本板硝子株式会社
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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
    • C09B13/00—Oxyketone dyes
    • C09B13/06—Oxyketone dyes of the acetophenone series
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • 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 light-absorbing composition, a light-absorbing film, and an optical filter.
  • solid-state imaging elements such as CCD (Charge Coupled Device) or CMOS (Complementary Metal Oxide Semiconductor)
  • various optical filters are placed in front of the solid-state imaging element to obtain images with good color reproducibility.
  • solid-state imaging elements have a spectral sensitivity in a wider wavelength range than the human visual sensitivity corresponding to the visible light region.
  • an optical filter that blocks some infrared or ultraviolet light is placed in front of the solid-state imaging element in order to bring the spectral sensitivity of the solid-state imaging element in the imaging device closer to the human visual sensitivity.
  • optical filters have generally used a dielectric multilayer film to block infrared or ultraviolet rays.
  • optical filters with a film containing a light absorbing agent have been attracting attention.
  • the transmittance characteristics of optical filters with a film containing a light absorbing agent are not easily affected by the angle of incidence, so good images with little change in color can be obtained even when light is incident on the optical filter at an angle in an imaging device.
  • light absorbing optical filters that do not use a light reflecting film can suppress the occurrence of ghosts and flares caused by multiple reflections by the light reflecting film, making it easier to obtain good images in backlit conditions or when photographing night scenes.
  • optical filters with a film containing a light absorbing agent are also advantageous in terms of making imaging devices smaller and thinner.
  • Patent Document 1 describes an optical filter having a light absorbing layer containing a light absorber formed from phosphonic acid having a phenyl group or a halogenated phenyl group (phenyl-based phosphonic acid) and copper ions.
  • Patent Document 2 describes an optical filter having a UV-IR absorbing layer capable of absorbing infrared and ultraviolet rays.
  • the UV-IR absorbing layer contains a UV-IR absorbent formed of phosphonic acid and copper ions.
  • the UV-IR absorbing composition contains, for example, a phenyl-based phosphonic acid and a phosphonic acid having an alkyl group or a halogenated alkyl group (alkyl-based phosphonic acid).
  • Patent document 3 also describes an ophthalmic device that includes a vertical violet cutoff filter.
  • the vertical violet cutoff filter sharply absorbs light with wavelengths in the range of approximately 400 nm to 450 nm.
  • Patent Documents 1 and 2 need to be reconsidered from the perspective of the blocking properties of light in the short wavelength region of 410 nm or less.
  • the violet light vertical cutoff filter described in Patent Document 3 is thought to have a low transmittance of visible light with a wavelength of 450 nm or more.
  • the technologies described in Patent Documents 1 to 3 need to be reconsidered in terms of cleaning of the optical filter or durability during the manufacturing process of the optical filter.
  • the present invention provides a light-absorbing composition, a light-absorbing film, and an optical filter that are advantageous in terms of reproducing human visual sensitivity, particularly in terms of light absorption characteristics in the short wavelength region, and that are also advantageous in terms of durability during cleaning or manufacturing processes of the optical filter.
  • the present invention relates to an ultraviolet absorbing compound having a hydroxy group and a carbonyl group in the molecule; Metal components, Polyvinyl butyral, Contains an isocyanate, At least a portion of the metal component is bonded to an organic oxy group.
  • a light absorbing composition is provided.
  • the present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: an organic solvent, a UV-absorbing compound having a hydroxyl group and a carbonyl group in the molecule, The method includes adding and mixing a compound containing a metal component, polyvinyl butyral, and an isocyanate. A method for producing the light absorbing composition is provided.
  • the present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: an ultraviolet absorbing compound having a hydroxy group and a carbonyl group in the molecule; Metal components, A resin having a urethane bond, At least a portion of the metal component is bonded to an organic oxy group. A light absorbing film is provided.
  • the present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: An optical filter including the above light absorbing film is provided.
  • the present invention also provides a method for producing a method for manufacturing a semiconductor device comprising the steps of: A method for producing an optical filter including the light absorbing film, comprising the steps of:
  • the manufacturing method provides a method for manufacturing an optical filter, the method including the steps of: (i) forming a first insulating film; (i) forming the light absorbing film on an imaging element or an optical component; (ii) forming the light absorbing film on a substrate and peeling the light absorbing film from the substrate;
  • the above light absorbing composition is advantageous from the viewpoint of reproducing human visual sensitivity, particularly the absorption characteristics of light in the short wavelength region, and is also advantageous from the viewpoint of durability during cleaning or manufacturing of the optical filter.
  • the above light absorbing film and the above optical filter are advantageous from the viewpoint of reproducing human visual sensitivity, particularly the absorption characteristics of light in the short wavelength region.
  • the above light absorbing film and the above optical filter are also advantageous from the viewpoint of durability, as they are less likely to be scratched when the surface is cleaned or wiped.
  • FIG. 1 is a cross-sectional view showing an example of a light absorbing film according to the present invention.
  • FIG. 2A is a cross-sectional view showing an example of an optical filter according to the present invention.
  • FIG. 2B is a cross-sectional view showing an example of an optical filter according to the present invention.
  • FIG. 3 shows the transmission spectrum of the optical filter according to the first embodiment.
  • FIG. 4 shows the transmission spectrum of the optical filter according to the fifth embodiment.
  • FIG. 5 shows the transmission spectrum of the optical filter according to the seventh embodiment.
  • FIG. 6 shows the transmission spectrum of the optical filter according to the ninth embodiment.
  • FIG. 7 shows the transmission spectrum of the optical filter according to the eleventh embodiment.
  • FIG. 8 shows the reflection spectrum of the optical filter according to the first embodiment.
  • FIG. 3 shows the transmission spectrum of the optical filter according to the first embodiment.
  • FIG. 4 shows the transmission spectrum of the optical filter according to the fifth embodiment.
  • FIG. 5 shows the transmission spectrum of the optical filter according to the seventh embodiment.
  • FIG. 9 shows the reflection spectrum of the optical filter according to the fifth embodiment.
  • FIG. 10 shows the reflection spectrum of the optical filter according to the seventh embodiment.
  • FIG. 11 shows the reflection spectrum of the optical filter according to the ninth embodiment.
  • FIG. 12 shows the reflection spectrum of the optical filter according to the eleventh embodiment.
  • FIG. 13 shows the transmission spectrum of a transparent glass substrate.
  • an optical filter for an imaging device using a solid-state imaging element can effectively absorb light in the short wavelength region of 410 nm or less, the value of the optical filter can be further increased in terms of reproducing human visual sensitivity.
  • the wavelength at which the spectral transmittance is 50% in the wavelength range of 350 nm to 450 nm is less than 400 nm.
  • the wavelength at which the spectral transmittance is 50% in the wavelength range of 350 nm to 450 nm is in the range of approximately 390 nm to 415 nm.
  • the optical filters described in Patent Documents 1 and 2 are advantageous in terms of effectively absorbing light in the short wavelength region of 410 nm or less.
  • the purple light vertical cutoff filter described in Patent Document 3 may be able to effectively absorb light in the short wavelength region of 410 nm or less, but the transmittance of the filter for visible light of wavelengths of 450 nm or more is considered to be low.
  • the inventors therefore conducted extensive research to develop a light-absorbing composition that is advantageous from the standpoint of reproducing human visual sensitivity, particularly in terms of effectively absorbing light in the short-wavelength region of wavelengths of 410 nm or less.
  • a light-absorbing composition containing a specific ultraviolet absorbing compound and a metal component is advantageous from the standpoint of effectively absorbing light in the short-wavelength region.
  • the present inventors have further studied whether advantageous properties can be imparted to the light absorbing composition containing the above ultraviolet absorbing compound and metal component in terms of durability during the cleaning or manufacturing process of the optical filter.
  • the optical filter may be cleaned by wiping it with a wipe or cloth such as a wiping cloth impregnated with an organic solvent such as alcohol or acetone, or with a microfiber.
  • the portion containing the light absorbing composition or the solidified product of the light absorbing composition may come into contact with another member or the like.
  • the light absorbing composition containing the above ultraviolet absorbing compound and metal component it is important for the light absorbing composition containing the above ultraviolet absorbing compound and metal component to have advantageous properties in terms of durability or solvent resistance regarding the mechanical strength of the surface during the cleaning or manufacturing process of the optical filter in order to increase the added value of the light absorbing composition, light absorbing film, or optical filter.
  • the light absorbing composition it is important for the light absorbing composition to have advantageous properties in terms of scratch resistance and solvent resistance during the cleaning or manufacturing process of the optical filter.
  • the inventor has newly identified an additive component that can provide advantageous characteristics in terms of durability during cleaning or manufacturing of optical filters in the light absorbing composition containing the above ultraviolet absorbing compound and metal component without impairing effective absorption of light in the short wavelength region of 410 nm or less, and has completed the present invention.
  • the light-absorbing composition according to the present invention contains an ultraviolet absorbing compound having a hydroxyl group and a carbonyl group in the molecule, a metal component, polyvinyl butyral (PVB), and an isocyanate.
  • at least a part of the metal component is bonded to an organic oxy group.
  • at least a part of the metal component is bonded to an oxygen atom in the organic oxy group.
  • Favourable conditions for ultraviolet absorbing compounds include appropriate light absorption and transmission ranges, photochemical stability, low enough photosensitisation to have no effect within the range of use, and thermochemical stability. From this perspective, it is considered that the mechanism of light absorption of ultraviolet absorbing compounds is the use of a hydrogen transfer reaction of a hydroxyl group in a molecule due to photoexcitation (intramolecular hydrogen abstraction reaction). Examples of ultraviolet absorbing compounds that exhibit this mechanism include compounds such as hydroxybenzophenone, salicylic acid, hydroxyphenylbenzotriazole, hydroxyphenyltriazine, and substituted acrylonitrile.
  • a phenomenon occurs in which a part of the light absorption band at wavelengths of 300 to 500 nm shifts to the long wavelength side in a light absorbing film or an optical filter having a light absorbing film obtained by curing a light absorbing composition containing an ultraviolet absorbing compound having a hydroxy group and a carbonyl group in the molecule and a metal component.
  • a light absorbing film has advantageous properties for effectively and appropriately absorbing light having a wavelength of 410 nm or less.
  • the light absorption band shifts to the longer wavelength side for example, the phenomenon of the maximum absorption wavelength shifting to the longer wavelength side within the wavelength range of 300 nm to 500 nm of the transmission spectrum, or the phenomenon of the wavelength at which the transmittance is 50% (UV cutoff wavelength) shifting to the longer wavelength side may become apparent.
  • the light-absorbing composition of the present invention the light-absorbing film which is the cured product thereof, and the optical filter equipped with the light-absorbing film, the absorption characteristics inherent to the ultraviolet absorbing compound are adjusted so that light in the short wavelength region can be effectively absorbed.
  • the spectral transmittance of such a light-absorbing film or optical filter is likely to be more appropriate when used together with a solid-state imaging device or the like.
  • the light-absorbing composition contains PVB and isocyanate. This makes the light-absorbing composition more likely to have advantageous properties in terms of durability during the cleaning or manufacturing process of the optical filter.
  • the light-absorbing composition containing PVB and isocyanate is advantageous in terms of improving scratch resistance and solvent resistance during the cleaning or manufacturing process of the optical filter.
  • the light-absorbing composition contains PVB and isocyanate, this does not prevent the absorption properties inherent to the ultraviolet absorbing compound from being adjusted so that light in the short wavelength region can be effectively absorbed by the above-mentioned mechanism of action.
  • PVB for example, tends to have high transparency and can have high compatibility with organic solvents and the like.
  • PVB has high weather resistance and high light resistance, and since the light absorbing composition contains PVB, the light absorbing film and optical filter obtained from the light absorbing composition also tend to exhibit high weather resistance and light resistance.
  • PVB can exhibit advantageous properties as a binder for functional components such as the above-mentioned ultraviolet absorbing compound.
  • the light absorbing composition may have advantageous properties for producing composite optical elements or optical components that combine multiple members or parts.
  • PVB is represented, for example, by the following structural formula:
  • k is the mole fraction [%] of structural units having vinyl butyral groups
  • m is the mole fraction [%] of structural units derived from vinyl alcohol and having hydroxyl groups
  • n is the mole fraction [%] of structural units derived from vinyl acetate.
  • PVB is obtained by reacting polyvinyl alcohol (PVA) with butyraldehyde. Since it is not possible to esterify all of the vinyl groups in PVA, some of the PVB contains groups that contain hydroxyl groups.
  • the number average molecular weight of PVB contained in the light absorbing composition is not limited to a specific value.
  • the number average molecular weight is, for example, 12.0 ⁇ 10 4 or less. This makes it easy to form a film of the light absorbing composition, and the haze of the light absorbing film and optical filter obtained from the light absorbing composition is likely to be low.
  • the number average molecular weight of PVB is, for example, 1.0 ⁇ 10 4 or more. This makes it difficult for the light absorbing composition to shrink during curing, and the haze of the light absorbing film and optical filter obtained from the light absorbing composition is likely to be low.
  • the number average molecular weight of PVB may be 1.2 ⁇ 10 4 or more, or 1.5 ⁇ 10 4 or more.
  • the number average molecular weight of PVB may be 11.5 ⁇ 10 4 or less, or 11.0 ⁇ 10 4 or less.
  • the number average molecular weight of PVB can be measured, for example, according to Japanese Industrial Standards (JIS) K7252-1:2016.
  • the butyralization degree of PVB is not limited to a specific value.
  • the butyralization degree is, for example, 60 mol% or more. This makes it easy to adjust the hydrophobicity and toughness of the surface of the light-absorbing film or optical filter obtained from the light-absorbing composition to the desired level.
  • the butyralization degree is preferably 65 mol% or more.
  • the butyralization degree is, for example, 90 mol% or less. This makes it easy for the desired amount of hydroxyl groups to be present in the PVB.
  • the butyralization degree is preferably 80 mol% or less.
  • the butyralization degree of PVB is, for example, a value expressed as a percentage of the molar fraction calculated by dividing the amount of ethylene groups to which butyral groups are bonded by the total amount of ethylene groups in the main chain.
  • This butyralization degree can be calculated, for example, by measuring the degree of acetylation and the hydroxyl group content according to a method conforming to JIS K 6728 (Testing method for polyvinyl butyral), calculating the molar fraction from the measurement results, and then subtracting the degree of acetylation and the hydroxyl group content from 100 mol%.
  • the content of hydroxyl groups in PVB is not limited to a specific value.
  • the content is, for example, 10 mol% or more.
  • a sufficient amount of hydroxyl groups is likely to be present in PVB to be subjected to a reaction with isocyanate during curing of the light absorbing composition.
  • the content of hydroxyl groups in PVB is preferably 20 mol% or more.
  • the content of hydroxyl groups in PVB is, for example, 50 mol% or less.
  • the PVB is likely to contain a desired amount of butyral groups from the viewpoint of toughness.
  • the content of hydroxyl groups in PVB is preferably 40 mol% or less.
  • the content of hydroxyl groups can be calculated, for example, according to a method in accordance with JIS K6728 (Test method for polyvinyl butyral).
  • PVB examples include S-LEC KS-1, S-LEC KS-10, S-LEC BX-L, S-LEC BX-1, S-LEC BL-S, and S-LEC BL-1 manufactured by Sekisui Chemical Co., Ltd. S-LEC is a registered trademark.
  • Other examples of PVB are Mobital B20H, Mobital B30T, Mobital B30H, and Mobital B45H manufactured by Kuraray Co., Ltd. Mobital is a registered trademark.
  • one or more types of PVB are selected from these PVBs or are mixed and used.
  • the isocyanate contained in the light absorbing composition has, for example, two or more isocyanate groups in the molecule, and each isocyanate group is bonded to a carbon atom.
  • the presence or absence of a urethane bond can be understood by obtaining an infrared spectrum of a sample by a method such as Fourier transform infrared spectroscopy (FT-IR) and analyzing the presence or absence or intensity of peaks characteristic of a urethane bond in the infrared spectrum.
  • FT-IR Fourier transform infrared spectroscopy
  • the isocyanate contained in the light absorbing composition is not limited to a specific isocyanate.
  • the isocyanate is a compound having an isocyanate group in the molecule.
  • Examples of the isocyanate are tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), phenylene diisocyanate, dinaphthalene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate.
  • Other examples of the isocyanate are trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, and trimethylhexamethylene diisocyanate.
  • the isocyanate may be an alicyclic polyisocyanate.
  • the alicyclic polyisocyanate are isophorone diisocyanate, dicyclohexylmethane diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, and bis(isocyanatomethyl)norbornane.
  • the isocyanate may be an araliphatic polyisocyanate.
  • araliphatic polyisocyanates are xylylene diisocyanate, tetramethyl xylylene diisocyanate, and ⁇ , ⁇ '-diisocyanate-1,4-diethylbenzene.
  • the metal component is bonded to the organic oxy group, and the compound includes a metal component bonded to the organic oxy group.
  • the compound containing a metal component bonded to the organic oxy group is generally a compound represented by (R k -O) n -M.
  • M represents a metal component such as a metal atom or a metal ion.
  • the (R k -O) n - group represents n organic oxy groups (or collectively referred to as organic oxy groups, the same applies hereinafter), R k represents an organic group containing at least a carbon atom (C) and a hydrogen atom (H), etc., and n represents the number of groups bonded or coordinated to the metal component M, and one or more organic oxy groups may be bonded or coordinated to the metal component M.
  • the organic oxy group (R k -O)- may contain two or more O (oxygen), and the organic oxy group may be bonded or coordinated to the metal component M via these two or more O (oxygen).
  • the organic group R k may be the same or different for each organic oxy group (R k -O)- to be bonded or coordinated, and a plurality of organic oxy groups may be bonded without the metal component M being interposed therebetween.
  • the organic oxy group is not particularly limited as long as it satisfies such conditions, and may be, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propyloxy group, a phenoxy group, or an alkylphenoxy group, or a vinyl group.
  • the organic oxy group may be an organic group R k that contains a partial structure (group) such as an acyl group, an acetyl group, a ketone group, a vinyl group, a propionyl group, an acrylyl group, an acetoxy group, an acryloyl group, an ethyl acetate group, an ethyl acetoacetate group, an acetylacetone group, or other ester or ether.
  • the organic oxy group may contain one or more groups selected from these.
  • the metal component M may include at least one selected from the group consisting of metal components such as metal atoms and ions of, for example, Li, Na, Mg, Ca, Sr, Ba, Ge, Sn, Pb, Al, Ga, In, Tl, Zn, Cd, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Mn, Cr, Mo, W, V, Nb, Ta, Ti, and Zr.
  • metal components such as metal atoms and ions of, for example, Li, Na, Mg, Ca, Sr, Ba, Ge, Sn, Pb, Al, Ga, In, Tl, Zn, Cd, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Mn, Cr, Mo, W, V, Nb, Ta, Ti, and Zr.
  • the arrangement of the hydroxyl group and the carbonyl group in the ultraviolet absorbing compound is not limited to a specific arrangement.
  • the hydroxyl group and the carbonyl group are preferably arranged with one to three atoms between them. This is thought to facilitate the transfer of hydrogen between the hydroxyl group and the carbonyl group in the ultraviolet absorbing compound. This effectively facilitates the shift of the light absorption band in the wavelength range of 300 to 500 nm to the longer wavelength side.
  • the light absorbing film obtained by curing the light absorbing composition more reliably and effectively absorbs light with a wavelength of 410 nm or less.
  • the ultraviolet absorbing compound is not limited to a specific compound as long as it has a hydroxyl group and a carbonyl group in its molecule.
  • the ultraviolet absorbing compound is preferably a compound that does not easily aggregate even when mixed with a metal component.
  • the ultraviolet absorbing compound preferably contains a benzophenone compound represented by the following formula (A1).
  • the light absorbing film or optical filter produced using the light absorbing composition is more likely to effectively absorb light in the short wavelength region of 410 nm or less.
  • R 11 , R 12 , R 21 , and R 22 is a hydroxy group.
  • R 11 , R 12 , R 21 , or R 22 is a functional group other than a hydroxy group, a plurality of R 11 , a plurality of R 12 , a plurality of R 21 , or a plurality of R 22 may be present, and at least one of R 11 , R 12 , R 21 , and R 22 may not be present.
  • R 11 , R 12 , R 21 , or R 22 is a functional group other than a hydroxy group
  • the functional group is, for example, a carboxyl group, an aldehyde group, a halogen atom, an alkyl group having 1 to 12 carbon atoms, an alkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with halogen atoms.
  • the ultraviolet absorbing compound contains a benzophenone compound represented by the following formula (A2).
  • the light absorbing film or optical filter produced using the light absorbing composition is more likely to effectively absorb light in the short wavelength region of 410 nm or less.
  • R 31 is a hydrogen atom, a hydroxyl group, a carboxyl group, an aldehyde group, a halogen atom, a group having a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms.
  • R 41 and R 42 may be a hydroxyl group, a carboxyl group, an aldehyde group, a group having a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms, and R 41 and R 42 may not be present.
  • a plurality of R 41 may be present, and a plurality of R 42 may be present.
  • the group having a halogen atom may be a halogenated alkyl group in which at least one hydrogen atom in the alkyl group is substituted with a halogen atom.
  • the group having a halogen atom may be a halogenated aryl group in which at least one hydrogen atom in the aryl group is substituted with a halogen atom.
  • the group having a halogen atom may be a halogenated alkoxy group in which at least one hydrogen atom in the alkoxy group is substituted with a halogen atom.
  • the benzophenone compound represented by formula (A1) or formula (A2) is not limited to a specific compound.
  • the benzophenone compound is, for example, at least one selected from the group consisting of 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-chlorobenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-dodecyloxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-n-octoxybenzophenone, 2-hydroxy-5-chlorobenzophenone, and 2,4-dibenzoylresorcinol.
  • the ultraviolet absorbing compound may contain a salicylic acid compound represented by the following formula (B).
  • the light absorbing film or optical filter produced using the light absorbing composition is more likely to effectively absorb light in the short wavelength region around 410 nm.
  • R 51 may be a hydroxy group, a carboxy group, a group containing a halogen atom, an alkyl group having 1 to 12 carbon atoms, an aryl group having 6 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. In formula (B), a plurality of R 51 may be present, or R 51 may not be present.
  • R 52 is a hydrogen atom, an aryl group, or a halogenated aryl group in which one or more hydrogen atoms are substituted with halogen atoms.
  • the group having a halogen atom may be a halogenated alkyl group in which at least one hydrogen atom in the alkyl group is substituted with a halogen atom.
  • the group having a halogen atom may be a halogenated aryl group in which at least one hydrogen atom in the aryl group is substituted with a halogen atom.
  • the group having a halogen atom may be a halogenated alkoxy group in which at least one hydrogen atom in the alkoxy group is substituted with a halogen atom.
  • the salicylic acid compound represented by formula (B) is not limited to a specific compound.
  • the salicylic acid compound represented by formula (B) includes, for example, at least one selected from the group consisting of phenyl salicylate, 4-butylphenyl salicylate, and octylphenyl salicylate.
  • the metal component is not limited to a specific metal component.
  • the metal component is typically a component that does not aggregate in the light absorbing composition and the light absorbing film produced using the light absorbing composition, and is thermally and chemically stable.
  • the metal component is typically a component that can interact with the ultraviolet absorbing compound.
  • the metal component includes at least one selected from the group consisting of, for example, Li, Na, Mg, Ca, Sr, Ba, Ge, Sn, Pb, Al, Ga, In, Tl, Zn, Cd, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Mn, Cr, Mo, W, V, Nb, Ta, Ti, and Zr.
  • the metal component is likely to interact with the above-mentioned ultraviolet absorbing compound.
  • the content C M of the metal component in the light-absorbing composition is not limited to a specific value.
  • the content C M is, for example, 0.005% to 2% by mass. This makes it easier for a light-absorbing film or optical filter produced using the light-absorbing composition to more reliably absorb light in the short wavelength region of 410 nm or less.
  • the content C M is preferably 0.01% to 1%, more preferably 0.01% to 0.5%, and even more preferably 0.01% to 0.3%.
  • the content C UV of the ultraviolet absorbing compound in the light absorbing composition is not limited to a specific value.
  • the content C UV is, for example, 0.1% to 20% by mass. This makes it easier for a light absorbing film or optical filter produced using the light absorbing composition to more reliably absorb light in the short wavelength region of 410 nm or less.
  • the content C UV is preferably 0.1% to 15%, more preferably 0.2 to 10%, even more preferably 0.5% to 10%, and particularly preferably 1% to 10%.
  • the ratio R UV/M of the content of the ultraviolet absorbing compound to the content of the metal component is not limited to a specific value.
  • the ratio R UV/M is, for example, 5 to 300 on a mass basis. This makes it easier for a light-absorbing film or optical filter produced using the light-absorbing composition to more reliably absorb light in the short wavelength region of 410 nm or less effectively.
  • the ratio R UV/M is preferably 10 to 300, more preferably 20 to 300, and even more preferably 30 to 280.
  • the ratio R I/P of the mass of isocyanate to the mass of PVB is not limited to a specific value.
  • the ratio R I/P is, for example, 0.05 to 3.0. This makes it easier for the surface hardness of the cured product of the light absorbing composition to be increased by the crosslinking reaction between PVB and isocyanate.
  • the ratio R I/P is preferably 0.05 to 3.0, more preferably 0.1 to 0.3, and even more preferably 0.2 to 3.0.
  • the ratio R I/UV of the mass of the isocyanate to the mass of the ultraviolet absorbing compound is not limited to a specific value.
  • the ratio R I/UV is, for example, 0.1 to 3.0. This makes it easier to increase the hardness of the surface of the cured product of the light-absorbing composition, and makes it easier to achieve advantageous mechanical properties and solvent resistance from the viewpoint of durability during cleaning or manufacturing of optical filters.
  • the ratio R I/UV is preferably 0.2 to 3.0, more preferably 0.25 to 3.0.
  • the method for producing the light-absorbing composition is not limited to a specific method.
  • the light-absorbing composition can be produced by a method including adding an ultraviolet-absorbing compound having a hydroxyl group and a carbonyl group in the molecule, a compound containing a metal component, polyvinyl butyral, and an isocyanate to an organic solvent and mixing them.
  • the light absorbing composition can be used to provide, for example, the light absorbing film 10 shown in FIG. 1.
  • the light absorbing film 10 can be obtained, for example, by curing the light absorbing composition.
  • the light absorbing film 10 contains an ultraviolet absorbing compound having a hydroxyl group and a carbonyl group in the molecule, a metal component, and a resin having a urethane bond.
  • at least a part of the metal component is bonded to an organic oxy group.
  • At least a part of the metal component is bonded to an oxygen atom in the organic oxy group.
  • the light absorbing film 10 contains a resin having a urethane bond, the light absorbing film 10 is easy to have advantageous characteristics in terms of improving durability or solvent resistance in cleaning optical filters.
  • the metal component is bonded to the organic oxy group, and the compound includes a metal component bonded to the organic oxy group.
  • the compound containing the metal component bonded to the organic oxy group is generally a compound represented by (R k -O) n -M.
  • M represents a metal component such as a metal atom or a metal ion.
  • the (R k -O) n - group represents n organic oxy groups (or collectively referred to as organic oxy groups, the same applies hereinafter), R k represents an organic group containing at least a carbon atom (C) and a hydrogen atom (H), etc., n represents the number of atoms bonded or coordinated to the metal component M, and one or more organic oxy groups may be bonded or coordinated to the metal component M.
  • the organic oxy group (R k -O)- may contain two or more O (oxygen), and the organic oxy group may be bonded or coordinated to the metal component M via these two or more O (oxygen).
  • the organic group R k may be the same or different for each organic oxy group (R k -O)- to be bonded or coordinated, and a plurality of organic oxy groups may be bonded without the metal component M being interposed therebetween.
  • the organic oxy group is not particularly limited as long as it satisfies such conditions, and may be, for example, an alkoxy group such as a methoxy group, an ethoxy group, a propyloxy group, a phenoxy group, or an alkylphenoxy group, or a vinyl group.
  • the organic oxy group may be an organic group R k that contains a partial structure (group) such as an acyl group, an acetyl group, a ketone group, a vinyl group, a propionyl group, an acrylyl group, an acetoxy group, an acryloyl group, an ethyl acetate group, an ethyl acetoacetate group, an acetylacetone group, or other ester or ether.
  • the organic oxy group may contain one or more groups selected from these.
  • the metal component M may include at least one selected from the group consisting of metal components such as metal atoms and ions of, for example, Li, Na, Mg, Ca, Sr, Ba, Ge, Sn, Pb, Al, Ga, In, Tl, Zn, Cd, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Mn, Cr, Mo, W, V, Nb, Ta, Ti, and Zr.
  • metal components such as metal atoms and ions of, for example, Li, Na, Mg, Ca, Sr, Ba, Ge, Sn, Pb, Al, Ga, In, Tl, Zn, Cd, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Mn, Cr, Mo, W, V, Nb, Ta, Ti, and Zr.
  • the hydroxyl group and the carbonyl group are preferably spaced apart by 1 to 3 atoms. This makes it easier to improve the light absorbing film 10's ability to absorb light in the wavelength range of 410 nm or less.
  • the ultraviolet absorbing compound in the light absorbing film 10 includes, for example, a benzophenone-based compound represented by the above formula (A1). This makes it easier to improve the ability of the light absorbing film 10 to absorb light in the wavelength range of 410 nm or less.
  • the ultraviolet absorbing compound in the light absorbing film 10 preferably contains a benzophenone-based compound represented by the above formula (A2). This makes it particularly easy to improve the ability of the light absorbing film 10 to absorb light in the wavelength range of 410 nm or less.
  • the ultraviolet absorbing compound in the light absorbing film 10 may contain, for example, a salicylic acid compound represented by the above formula (B). In this case, it is easy to improve the ability of the light absorbing film 10 to absorb light in the wavelength range of 410 nm or less.
  • the metal component in the light absorbing film 10 includes at least one selected from the group consisting of, for example, Li, Na, Mg, Ca, Sr, Ba, Ge, Sn, Pb, Al, Ga, In, Tl, Zn, Cd, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Fe, Mn, Cr, Mo, W, V, Nb, Ta, Ti, and Zr.
  • the ratio r UV/M of the content of the ultraviolet absorbing compound to the content of the metal component is not limited to a specific value.
  • the ratio r UV/M is, for example, 5 to 300 on a mass basis. This makes it easier for the light absorbing film or optical filter produced using the light absorbing composition to more reliably absorb light in the short wavelength region of 410 nm or less effectively.
  • the ratio r UV/M is preferably 10 to 300, more preferably 20 to 300, and even more preferably 30 to 280.
  • the transmittance T400 of the light absorbing film 10 is, for example, 5% or less. This is advantageous from the viewpoint of reproducing the visual sensitivity of the human eye.
  • the transmittance T400 is the transmittance at a wavelength of 400 nm in the transmission spectrum at an incident angle of 0°.
  • the transmittance T400 is preferably 4.5% or less, and more preferably 4% or less.
  • the content of the ultraviolet absorbing compound in the light absorbing film 10 is not limited to a specific value.
  • the content is, for example, 0.1% to 90%, preferably 0.5% to 80%, and more preferably 2% to 70%, by mass.
  • the content of the metal component in the light absorbing film 10 is not limited to a specific value.
  • the content is, for example, 0.005% to 5% by mass, preferably 0.01% to 4%, and more preferably 0.03% to 3%.
  • the ratio r I/P of the mass of isocyanate to the mass of PVB is not limited to a specific value.
  • the ratio r I/P is, for example, 0.05 to 3.0, preferably 0.05 to 2.5, more preferably 0.05 to 2.0, and further preferably 1.0 to 2.0.
  • the ratio r I/UV of the mass of the isocyanate to the mass of the ultraviolet absorbing compound is not limited to a specific value.
  • the ratio r I/UV is, for example, 0.1 to 3.0, preferably 0.2 to 2.8, and more preferably 0.2 to 2.5.
  • the thickness of the light absorbing film 10 is not limited to a specific value.
  • the thickness of the light absorbing film 10 is, for example, 0.5 ⁇ m to 500 ⁇ m, may be 1 ⁇ m to 100 ⁇ m, or may be 1 ⁇ m to 50 ⁇ m.
  • the method of curing the light absorbing composition is not limited to a specific method.
  • the conditions for curing the light absorbing composition are adjusted so that a crosslinking reaction occurs between the PVB contained in the light absorbing composition and the isocyanate.
  • the light absorbing film 10 contains a resin having a urethane bond.
  • the light absorbing composition may be cured by heating at a predetermined temperature.
  • the predetermined temperature is, for example, 80°C or higher, preferably 100°C or higher, more preferably 120°C or higher, and even more preferably 140 to 180°C. This makes it easier for the light absorbing film 10 to have advantageous characteristics in terms of durability in cleaning the optical filter while preventing deterioration of the ultraviolet absorbing compound.
  • optical filters 1a and 1b equipped with a light absorbing film 10 can be provided.
  • the optical filters 1a and 1b tend to effectively absorb light in the short wavelength region of 410 nm or less.
  • the transmittance T 410 at a wavelength of 410 nm is, for example, 20% or less, preferably 15% or less, and more preferably 10% or less.
  • the maximum transmittance T M 300-380 in the wavelength range of 300 to 380 nm is, for example, 3% or less. This makes it easy for the optical filter to effectively absorb light in the wavelength range shorter than 400 nm.
  • the maximum transmittance T M 300-380 is preferably 2% or less, and more preferably 1% or less.
  • the wavelength at which the transmittance in the wavelength range of 300 to 520 nm is 50% is defined as the ultraviolet cutoff wavelength ⁇ UV .
  • the condition 405 nm ⁇ UV ⁇ 500 nm is satisfied. This makes it easier for the light absorbing film 10 to effectively absorb light in the short wavelength region around the wavelength of 410 nm, and makes it easier for light in a wavelength region that is difficult for humans to recognize to be cut in an imaging device used in combination with an imaging element.
  • the optical filters 1a and 1b preferably satisfy the condition 405 nm ⁇ UV ⁇ 490 nm, and more preferably satisfy the condition 405 nm ⁇ UV ⁇ 480 nm.
  • the minimum transmittance T m 480-600 in the wavelength range of 480 to 600 nm is, for example, 85% or more. This allows the optical filters 1a and 1b to appropriately transmit visible light, and in an imaging device used in combination with an imaging element, it is possible to increase the light flux reaching the imaging element from the subject.
  • the minimum value of the transmittance T m 480-600 is preferably 86% or more, and more preferably 87% or more.
  • the transmission spectrum obtained by irradiating light having a wavelength in the range of 300 nm to 1200 nm on the optical filters 1a and 1b at an incident angle of 0° may satisfy the following requirements (ia), (ii-a), (iii-a), (iv-a), (va), and (vi-a).
  • the maximum transmittance T M 300-380 in the wavelength range of 300 nm to 380 nm is 3% or less.
  • the transmittance T 400 at a wavelength of 400 nm is 5% or less.
  • the transmittance T 410 at a wavelength of 410 nm is 10% or less.
  • the wavelength ⁇ UV [nm] at which the transmittance is 50% is within the range of 405 nm to 490 nm.
  • the minimum transmittance T m 480-600 in the wavelength range of 480 to 600 nm is 85% or more.
  • the ratio T 0 UV+ /T 0 UV- of the transmittance T 0 UV+ at a wavelength of ( ⁇ UV +10) nm to the transmittance T 0 UV- at a wavelength of ( ⁇ UV -10) nm is 1.8 or more.
  • the optical filters 1a and 1b can exhibit high ultraviolet absorption properties.
  • the optical filters 1a and 1b can exhibit higher ultraviolet absorbing properties.
  • the optical filters 1a and 1b can be applied to optical filter applications that require higher ultraviolet absorbing performance.
  • the transmittance T400 is preferably 4% or less.
  • the optical filters 1a and 1b can exhibit high ultraviolet absorption properties, and the spectrum to which the image sensor is sensitive can easily partially match the spectrum corresponding to the human visual sensitivity.
  • the wavelength ⁇ UV is preferably 420 nm to 490 nm, more preferably 420 nm to 450 nm.
  • purple fringing is easily suppressed in the obtained image.
  • Purple fringing is a color bleeding that appears approximately purple, especially on the contours of the subject.
  • the transmittance of light belonging to the human visible light range can be increased, making it easier to obtain a bright image.
  • the transmittance of light in the human visible light range tends to be high, making it easier to obtain bright images.
  • the transmittance of the wavelength range corresponding to the maximum sensitivity on the human luminosity curve tends to be high, making it easier for humans to perceive brightness when viewing an image.
  • the ratio T 0 UV+ /T 0 UV- is preferably 1.9 or more, more preferably 2.0 or more, even more preferably 2.2 or more, and particularly preferably 2.4 or more.
  • the reflection spectrum obtained by making light in the wavelength range of 300 nm to 1200 nm incident on the optical filters 1a and 1b at an incident angle of 5° may satisfy the following requirements (ib) and (ii-b).
  • the reflection spectrum obtained by making light in the wavelength range of 300 nm to 1200 nm incident on the optical filters 1a and 1b at an incident angle of 40° may satisfy the following requirements (iii-b) and (iv-b).
  • the reflection spectrum obtained by making light in the wavelength range of 300 nm to 1200 nm incident on the optical filters 1a and 1b at an incident angle of 60° may satisfy the following requirements (vb) and (vi-b).
  • the maximum reflectance R 5 300-450 in the wavelength range of 300 nm to 450 nm is 20% or less.
  • the maximum reflectance R 5 300-600 in the wavelength range of 300 nm to 600 nm is 25% or less.
  • the maximum reflectance R 40 300-450 in the wavelength range of 300 nm to 450 nm is 20% or less.
  • the maximum reflectance R 40 300-600 in the wavelength range of 300 nm to 600 nm is 25% or less.
  • the maximum reflectance R 60 300-450 in the wavelength range of 300 nm to 450 nm is 30% or less.
  • the maximum reflectance R 60 300-600 in the wavelength range of 300 nm to 600 nm is 35% or less.
  • the maximum value R5 300-450 is preferably 15% or less.
  • the maximum value R40 300-450 is preferably 15% or less.
  • the maximum value R60 300-450 is preferably 20% or less.
  • the maximum value R5 300-600 is preferably 20% or less.
  • the maximum value R40 300-600 is preferably 20% or less.
  • the maximum value R60 300-600 is preferably 25% or less.
  • the optical filters 1a and 1b may satisfy the following requirements (ic), (ii-c), (iii-c), (iv-c), and (vc).
  • the ⁇ 30 UV [nm] in (ic) is a wavelength at which the transmittance is 50% in the range of 350 nm to 500 nm in the transmission spectrum when light in the range of 300 nm to 1200 nm is incident on the optical filter at an incident angle of 30°.
  • the ⁇ 40 UV [nm] in (ii-c) is a wavelength at which the transmittance is 50% in the range of 350 nm to 500 nm in the transmission spectrum when light in the range of 300 nm to 1200 nm is incident on the optical filter at an incident angle of 40°.
  • the ⁇ 50 UV [nm] in (iii-c) is a wavelength at which the transmittance is 50% in the range of 350 nm to 500 nm in the transmission spectrum when light in the range of 300 nm to 1200 nm is incident on the optical filter at an incident angle of 50°.
  • the ⁇ 60 UV [nm] of (iv-c) is a wavelength at which the transmittance is 50% in the range of 350 nm to 500 nm in the transmission spectrum when light in the range of 300 nm to 1200 nm is incident on the optical filter at an incident angle of 60°.
  • the ⁇ 70 UV [nm] of (vc) is a wavelength at which the transmittance is 50% in the range of 350 nm to 500 nm in the transmission spectrum when light in the range of 300 nm to 1200 nm is incident on the optical filter at an incident angle of 70°.
  • UV cut filters have the advantage that the angle dependency of the transmission spectrum is small.
  • UV cut filters that cut UV rays with a reflective film made of a dielectric multilayer film tend to have a UV cutoff wavelength that shifts to the short wavelength side for light incident at an angle. For this reason, the UV light that you want to cut may be detected by the sensor depending on the angle of incidence.
  • optical filters 1a and 1b satisfy the above requirements (i-c) to (v-c), and there is little change in the UV cutoff wavelength for oblique incidence, and the UV cutoff wavelength is unlikely to shift to the short wavelength side. Therefore, optical filters 1a and 1b, in addition to the function of suppressing ghosts and flares, make it easy to achieve good color reproducibility that is less likely to cause color unevenness within the surface, making it easy to obtain high-quality images.
  • preferably satisfies
  • preferably satisfies
  • is preferably
  • the optical filter 1a is, for example, composed of a single light absorbing film 10.
  • the optical filter 1a can be used, for example, separately from the imaging element or optical component.
  • the optical filter 1a may be bonded to the imaging element and the optical component.
  • the optical filter 1a may be constructed by applying the above-mentioned light absorbing composition to the imaging element or optical component and curing the light absorbing composition. In this way, the optical filter 1a may be manufactured by forming the light absorbing film 10 on the imaging element or optical component.
  • the optical filter 1a can be produced, for example, by peeling off the light absorbing film 10 formed on the substrate from the substrate.
  • the material of the substrate may be glass, resin, or metal.
  • the surface of the substrate may be subjected to a surface treatment such as coating with a fluorine-containing compound. In this way, the optical filter 1a may be manufactured by forming the light absorbing film 10 on the substrate and peeling off the light absorbing film 10 from the substrate.
  • the optical filter 1b includes a light absorbing film 10 and a transparent dielectric substrate 20.
  • the light absorbing film 10 is provided parallel to one of the main surfaces of the transparent dielectric substrate 20.
  • the light absorbing film 10 may be in contact with one of the main surfaces of the transparent dielectric substrate 20, for example.
  • the light absorbing film 10 can be formed, for example, by applying the above-mentioned light absorbing composition to one of the main surfaces of the transparent dielectric substrate 20 and curing the light absorbing composition.
  • the type of the transparent dielectric substrate 20 is not limited to a specific type.
  • the transparent dielectric substrate 20 may have an absorption ability in the infrared region.
  • the transparent dielectric substrate 20 may have an average spectral transmittance of 90% or more at wavelengths of, for example, 350 nm to 900 nm.
  • the material of the transparent dielectric substrate 20 is not limited to a specific material, but may be, for example, a specific glass or resin.
  • the transparent dielectric substrate 20 may be, for example, transparent glass made of silicate glass such as soda-lime glass and borosilicate glass, or phosphate glass and fluorophosphate glass containing coloring components such as Cu and Co.
  • Phosphate glass and fluorophosphate glass containing coloring components are, for example, infrared absorbing glass, and are themselves light absorbing.
  • the light absorbing film 10 is used together with the transparent dielectric substrate 20 of infrared absorbing glass, the light absorption and transmission spectrum of both can be adjusted to produce an optical filter having desired optical characteristics, and the degree of freedom in designing the optical filter is high.
  • the resin is, for example, a cyclic olefin resin such as a norbornene resin, a polyarylate resin, an acrylic resin, a modified acrylic resin, a polyimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polycarbonate resin, or a silicone resin.
  • a cyclic olefin resin such as a norbornene resin, a polyarylate resin, an acrylic resin, a modified acrylic resin, a polyimide resin, a polyetherimide resin, a polysulfone resin, a polyethersulfone resin, a polycarbonate resin, or a silicone resin.
  • Each of the optical filters 1a and 1b may be modified to further include other functional films such as an infrared absorbing film, an infrared reflecting film, and an anti-reflection film.
  • Such functional films may be provided on the light absorbing film 10 or the transparent dielectric substrate 20.
  • the optical filter may include an anti-reflection film to increase the transmittance in a predetermined wavelength range (for example, the visible light range).
  • the anti-reflection film may be configured as a layer of a low refractive index material such as MgF2 and SiO2 , or may be configured as a laminate of such a layer of a low refractive index material and a layer of a high refractive index material such as TiO2 , or may be configured as a dielectric multilayer film.
  • a low refractive index material such as MgF2 and SiO2
  • Such an anti-reflection film may be formed by a method involving a physical reaction such as vacuum deposition and sputtering, or by a method involving a chemical reaction such as CVD and sol-gel.
  • the optical filter may be configured, for example, with the light absorbing film 10 disposed between two sheets of glass.
  • the light absorbing film 10 acts as a so-called intermediate film. This improves the rigidity and mechanical strength of the optical filter.
  • the main surface of the optical filter becomes hard, which is advantageous from the standpoint of preventing scratches, etc. This advantage is particularly important when a relatively flexible resin is used as the binder or matrix in the light absorbing film 10.
  • an optical filter 1c can be provided that includes a light absorbing film 10 and an anti-reflection film 30.
  • an optical filter having an anti-reflection film when light is incident on the optical filter at a predetermined angle of incidence, the light reflected from the optical filter is reduced and approaches zero. This is extremely advantageous in an imaging device equipped with an optical filter having an anti-reflection film, from the viewpoint of preventing ghosts, flares, and noise that occur due to multiple scattering of reflected light within the imaging device or camera module, for example.
  • the material of the anti-reflective film is not limited to a specific material.
  • the method of forming the anti-reflective film is not limited to a specific method.
  • the method of forming the anti-reflective film may be a gas phase method or a liquid phase method.
  • the method of forming the anti-reflective film may be a vapor deposition method.
  • the method of forming the anti-reflective film may be a sol-gel method using a reactive material containing silicon, which is a liquid phase method that is excellent for forming anti-reflective films.
  • the anti-reflective film may be a single layer film made of the same type of material, or a multilayer film made of two or more different materials.
  • the material constituting each layer of the film and multilayer film is not limited to a specific material.
  • the material is, for example, an inorganic compound such as SiO 2 , TiO 2 , Ta 2 O 3 , MgF 2 , Al 2 O 3 , CaF 2 , ZrO 2 , CeO 2 , and ZnS.
  • the film or layer may be formed by a so-called sol-gel method using an alkoxysilane compound as a starting material.
  • the alkoxysilane compound is hydrolyzed and then condensed in the presence of water and a catalyst to obtain a dense and hard film containing SiO 2.
  • the sol-gel method has the advantage that a film or layer containing SiO 2 can be formed without requiring high temperatures.
  • the starting material is not limited to a specific material, and the functional group of the starting material is not limited to a specific functional group.
  • the starting material preferably includes "trifunctional silanes containing alkyl groups" such as MTES (methyltriethoxysilane) and TEOS (tetraethoxysilane), and "tetrafunctional silanes". Tetrafunctional silanes are essential for forming a film or layer with a strong and dense skeleton. On the other hand, it is difficult to control the reactivity with tetrafunctional silanes alone, and it is difficult to adjust the polarity of the film or layer. In addition, cracks are likely to occur in the film or layer.
  • the starting material contains trifunctional silane in addition to tetrafunctional silane, the flexibility of the silica skeleton is improved, the polarity of the film or layer is easily adjusted, and cracks in the film or layer are easily suppressed. It is desirable to be able to easily adjust the polarity of the film or layer from the viewpoint of adjusting the refractive index of the anti-reflective coating.
  • the organic functional groups in the trifunctional silanes are not originally limited to specific functional groups.
  • trifunctional silanes that have a methyl group as an organic functional group are desirable in order to form homogeneous liquids and coatings when combined with tetrafunctional silanes.
  • the ratio of the amount of "trifunctional silane containing an alkyl group” to the amount of "tetrafunctional silane” is not limited to a specific value.
  • the relationship of the amount of "trifunctional silane containing an alkyl group” to the amount of "tetrafunctional silane” 5:1 to 1:3 is satisfied on a mass basis. This makes it easier to suppress cracks in the anti-reflective film, and makes it easier for the tetrafunctional silane to form a strong skeleton.
  • the starting material may contain components other than those involved in the sol-gel method.
  • the starting material may contain fine particles and fillers for adjusting the refractive index.
  • the fine particles and fillers may be hollow or may be high refractive index materials.
  • the starting material may contain components that decompose at low temperatures. This makes it easier to adjust the refractive index of the anti-reflective film.
  • the temperature at which the coating film is baked in the sol-gel method is not limited to a specific temperature. The temperature is, for example, in the range of 60°C to 250°C, preferably in the range of 70°C to 230°C, and more preferably in the range of 80°C to 200°C.
  • the material of the single-layer film has a low refractive index.
  • n 0 is the refractive index of the substrate on which the anti-reflective film is formed.
  • the anti-reflective film contains hollow particles formed of metal oxides such as SiO 2 and TiO 2 or organic materials such as PMMA, the inside of the hollow particles is occupied by air with a refractive index of about 1, so that the effective refractive index of the particles can be lowered and the refractive index of the anti-reflective film is likely to be low.
  • the dielectric constant and refractive index of a mixture consisting of multiple phases can be obtained by an effective medium approximation method using the Bruggemann formula.
  • the anti-reflective film may contain solid particles formed of the above materials.
  • mechanical strength such as scratch resistance is required for the anti-reflective film, it is advantageous for the anti-reflective film to contain such solid particles.
  • a film may be formed by a sol-gel method in a state containing such hollow particles or solid particles.
  • the affinity between the SiO2 in the film formed by the sol-gel method and the hollow or solid particles is good, and aggregation of the hollow or solid particles is suppressed, which is expected to suppress bleed-out, etc.
  • the anti-reflection film may have a multilayer structure including a layer containing SiO 2 formed by a sol-gel method and a layer formed by, for example, a vacuum deposition method, a sol-gel method, or other methods.
  • a multilayer structure including a layer containing SiO 2 formed by a sol-gel method and a layer formed by, for example, a vacuum deposition method, a sol-gel method, or other methods.
  • the layer to be combined may be, for example, a layer containing hollow particles and containing SiO 2 formed by a sol-gel method, a layer made of a material having a relatively high refractive index such as TiO 2 and Ta 2 O 3 , or a layer made of other materials such as MgF 2 .
  • ⁇ Thickness measurement> The distance from the surface of each optical filter was measured using a laser displacement meter (Keyence Corporation, product name: LK-H008), and the thickness of the light absorbing film was measured by subtracting the thickness of the transparent glass substrate.
  • Kuraray Kuraclean Wiper LF-8G was soaked with ethanol, propylene glycol monomethyl ether (PGME), or propylene glycol monomethyl ether acetate (PGMEA) to obtain an alcohol-soaked wiper.
  • the alcohol-soaked wiper was pressed against the light-absorbing film obtained in each Example and Comparative Example at a pressure of 40 to 60 g/cm 2 and reciprocated 10 times over a length of about 3 cm to rub the surface of the light-absorbing film.
  • UV absorbing compound ⁇ Ultraviolet absorbing compound> The following ultraviolet absorbing compounds were used in the production of the optical filters according to the examples and comparative examples.
  • the structural formulas of the ultraviolet absorbing compounds (1-1) and (1-2) are represented by the following formulas (C) and (D), respectively.
  • Example 1 5.0 g of the ultraviolet absorber (1-1) shown in Table 1, 80.0 g of cyclohexanone as a solvent, and 8.0 g of polyvinyl butyral (PVB) S-LEC KS-10 (molecular weight 1.7 ⁇ 10 4 , degree of acetalization 74 mol %, hydroxyl group content 25 mol %) manufactured by Sekisui Chemical Co., Ltd. were mixed and stirred for 30 minutes. Next, 0.308 g of the material (2-1) containing a metal component shown in Table 2 was added to the obtained mixture and stirred for 30 minutes.
  • PVB polyvinyl butyral
  • Example 1 4.0 g of tolylene diisocyanate (TDI) was further added to the obtained mixture and stirred for 30 seconds to obtain a light absorbing composition according to Example 1.
  • the content of each component, the mass ratio of the predetermined components, and the substance amount ratio of the predetermined components in the light absorbing composition according to Example 1 are shown in Tables 3 and 4. Note that the content of the metal component in the material (2-1) containing a metal component was determined to be 6.5 mass %, as shown in Table 2, and the mass ratio or substance amount ratio of the components of the light-absorbing composition according to Example 1 was calculated based on this premise.
  • the light absorbing composition according to Example 1 was spin-coated at 500 rotations per minute (rpm) on one main surface of a transparent glass substrate (manufactured by SCHOTT, product name: D263T eco) made of borosilicate glass having dimensions of 76 mm x 76 mm x 0.21 mm to form a coating film.
  • the resulting coating film was thoroughly dried at room temperature, and then placed in an oven and heat-treated at 140°C for 1 hour and at 160°C for 2 hours to cause a crosslinking reaction between PVB and TDI, thereby obtaining a light absorbing film according to Example 1.
  • an optical filter provided with a light absorbing film according to Example 1 was produced.
  • Figure 3 shows the transmission spectrum of the optical filter according to Example 1.
  • Figure 8 shows the reflection spectrum of the optical filter according to Example 1. Values related to the film thickness and optical properties of the light absorbing film of the optical filter according to Example 1 are shown in Tables 5, 6, and 7. The results of the scratch resistance test of the light absorbing film according to Example 1 are shown in Table 8. Figure 13 shows the transmission spectrum of the transparent glass substrate at an incident angle of 0 degrees.
  • Examples 2 to 4 The light-absorbing compositions according to Examples 2 to 4 were prepared in the same manner as in Example 1, except that the amount of isocyanate added and/or the type of PVB were changed as shown in Table 3.
  • the light-absorbing films and optical filters according to Examples 2 to 4 were produced in the same manner as in Example 1, except that the light-absorbing compositions according to Examples 2 to 4 were used instead of the light-absorbing composition according to Example 1.
  • the PVB used in Example 4 was S-LEC KS-1 (molecular weight 2.7 ⁇ 10 4 , acetalization degree 74 mol %, hydroxyl group content 25 mol %) manufactured by Sekisui Chemical Co., Ltd.
  • Tables 5, 6, and 7 show values related to the optical properties that can be seen from the transmission spectrum and reflection spectrum of the optical filters according to Examples 2 to 4. From these results, it can be understood that good optical properties can be obtained even if the ratio of the mass of isocyanate to the mass of PVB in the light-absorbing composition varies in the range of 0.18 to 1.50.
  • the results of the scratch resistance test of the light-absorbing films according to Examples 2 to 4 are shown in Table 8.
  • Examples 5 and 6 Light absorbing compositions according to Examples 5 and 6 were prepared in the same manner as in Example 1, except that the type of PVB and the type and amount of isocyanate added were changed as shown in Table 3. Light absorbing films and optical filters according to Examples 5 and 6 were produced in the same manner as in Example 1, except that the light absorbing compositions according to Examples 5 and 6 were used instead of the light absorbing composition according to Example 1.
  • the PVB used in Example 5 was S-LEC BX-L (molecular weight 1.8 ⁇ 10 4 , acetalization degree 67 mol %, hydroxyl group content 32 mol %) manufactured by Sekisui Chemical Co., Ltd.
  • the PVB used in Example 6 was S-LEC BX-1 (molecular weight 10 ⁇ 10 4 , acetalization degree 72 mol %, hydroxyl group content 27 mol %) manufactured by Sekisui Chemical Co., Ltd.
  • the isocyanate used in Example 5 was diphenylmethane diisocyanate (MDI), and the isocyanate used in Example 6 was hexamethylene diisocyanate (HDI).
  • FIG. 4 shows the transmission spectrum of the optical filter according to Example 5.
  • FIG. 9 shows the reflection spectrum of the optical filter according to Example 5.
  • Tables 5, 6, and 7 show the optical property values of the optical filters according to Examples 5 and 6. According to Examples 5 and 6, it is understood that good optical properties can be obtained even if MDI or HDI is used instead of TDI.
  • Table 8 shows the results of the scratch resistance test of the light absorbing films according to Examples 5 and 6.
  • Example 7 to 14 Light absorbing compositions according to Examples 7 to 14 were prepared in the same manner as in Example 1, except that the type or amount of the ultraviolet absorbing compound, the material containing a metal component, the PVB, or the isocyanate was changed as shown in Table 3. Light absorbing films and optical filters according to Examples 7 to 14 were produced in the same manner as in Example 1, except that the light absorbing compositions according to Examples 7 to 14 were used instead of the light absorbing composition according to Example 1.
  • the PVB used in Example 7 was S-LEC BX-1 manufactured by Sekisui Chemical Co., Ltd.
  • the PVB used in Example 8 was S-LEC KS-1 manufactured by Sekisui Chemical Co., Ltd.
  • the PVB used in Example 12 was S-LEC BL-S manufactured by Sekisui Chemical Co., Ltd. (molecular weight 2.3 ⁇ 10 4 , acetalization degree 72 mol%, hydroxyl group content 23 mol%).
  • the PVB used in Example 13 was S-LEC BL-1 (molecular weight 1.9 ⁇ 10 4 , acetalization degree 63 mol %, hydroxyl group content 36 mol %) manufactured by Sekisui Chemical Co., Ltd.
  • S-LEC KS-10 manufactured by Sekisui Chemical Co., Ltd. was used as the PVB.
  • Figures 5, 6, and 7 show the transmission spectra of the optical filters according to Examples 7, 9, and 11, respectively.
  • Figures 10, 11, and 12 show the reflection spectra of the optical filters according to Examples 7, 9, and 11, respectively. Furthermore, values related to the optical properties of the optical filters according to Examples 7 to 14 are shown in Tables 5, 6, and 7. The results of the scratch resistance test of the light absorbing films according to Examples 7 to 14 are shown in Table 8.
  • a light-absorbing composition according to Comparative Example 1 was prepared in the same manner as in Example 1, except that no isocyanate was added.
  • a light-absorbing film and an optical filter according to Comparative Example 1 were produced in the same manner as in Example 1, except that the light-absorbing composition according to Comparative Example 1 was used instead of the light-absorbing composition according to Example 1.
  • Values relating to the optical properties of the optical filter according to Comparative Example 1 are shown in Tables 5, 6, and 7.
  • the results of the scratch resistance test of the light-absorbing film according to Comparative Example 1 are shown in Table 8.
  • the optical filters according to each of the Examples and Comparative Example 1 had good optical characteristics from the viewpoint of reproducing the visual sensitivity of humans.
  • a comparison between the Examples and Comparative Examples suggested that the light-absorbing composition containing both PVB and isocyanate is likely to provide good solvent resistance and scratch resistance.
  • good solvent resistance and scratch resistance are likely to be obtained when the ratio of the mass of isocyanate to the mass of PVB in the light-absorbing composition is 0.15 or more.
  • the ratio of the mass of isocyanate to the mass of PVB is preferably 0.15 or more, and more preferably 0.18 or more.
  • the upper limit of the ratio of the mass of isocyanate to the mass of PVB is not limited to a specific value, but from the viewpoint of suppressing the hardening of the light-absorbing composition immediately after application of the light-absorbing composition due to an increase in isocyanate, and facilitating the formation of a light-absorbing film with a flat and uniform thickness, it is considered that the ratio is preferably 1.50 or less. From the viewpoint of good optical properties, solvent resistance, and scratch resistance, it was suggested that the ratio of the mass of the isocyanate to the mass of the UV-absorbing compound is preferably 0.3 or more, and more preferably in the range of 0.3 to 2.4.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optical Filters (AREA)

Abstract

Une composition absorbant la lumière selon la présente invention contient : un composé absorbant les rayons ultraviolets ayant un groupe hydroxy et un groupe carbonyle dans une molécule ; des composants métalliques ; du polyvinylbutyral ; et de l'isocyanate. Au moins certains des composants métalliques sont liés à des groupes oxy organiques.
PCT/JP2023/037742 2022-10-27 2023-10-18 Composition d'absorption de lumière, procédé de production de composition d'absorption de lumière, film d'absorption de lumière, filtre optique et procédé de fabrication de filtre optique WO2024090311A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019219496A (ja) * 2018-06-19 2019-12-26 キヤノン株式会社 電子写真感光体の検査方法および製造方法
WO2020262658A1 (fr) * 2019-06-28 2020-12-30 ホヤ レンズ タイランド リミテッド Composition durcissable, son procédé de production, verre de lunettes, lunettes et procédé de production de verre de lunettes
JP2021067932A (ja) * 2019-10-18 2021-04-30 キヤノン株式会社 プロセスカートリッジ及び電子写真装置
WO2022239590A1 (fr) * 2021-05-14 2022-11-17 日本板硝子株式会社 Composition d'absorption de lumière, film d'absorption de lumière, procédé de fabrication de film d'absorption de lumière et filtre optique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019219496A (ja) * 2018-06-19 2019-12-26 キヤノン株式会社 電子写真感光体の検査方法および製造方法
WO2020262658A1 (fr) * 2019-06-28 2020-12-30 ホヤ レンズ タイランド リミテッド Composition durcissable, son procédé de production, verre de lunettes, lunettes et procédé de production de verre de lunettes
JP2021067932A (ja) * 2019-10-18 2021-04-30 キヤノン株式会社 プロセスカートリッジ及び電子写真装置
WO2022239590A1 (fr) * 2021-05-14 2022-11-17 日本板硝子株式会社 Composition d'absorption de lumière, film d'absorption de lumière, procédé de fabrication de film d'absorption de lumière et filtre optique

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