WO2018221424A1 - 環境光センサー用光学フィルター - Google Patents
環境光センサー用光学フィルター Download PDFInfo
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- WO2018221424A1 WO2018221424A1 PCT/JP2018/020220 JP2018020220W WO2018221424A1 WO 2018221424 A1 WO2018221424 A1 WO 2018221424A1 JP 2018020220 W JP2018020220 W JP 2018020220W WO 2018221424 A1 WO2018221424 A1 WO 2018221424A1
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- 0 CC1(C2=*C22*)N3c4c2c(C=*)c(C(C(C[C@]2(C5C67)C5c(c(*)c5C([*+])(*)C8(*)*=C)c9N(*)*C%10%11c9c5N5C8(**8)*=CC58C%10(*)*%11)C6C7O)C2OC)c(N(*)*)c4C(*)([*+]2)C2([*+])C3(*)*=*1 Chemical compound CC1(C2=*C22*)N3c4c2c(C=*)c(C(C(C[C@]2(C5C67)C5c(c(*)c5C([*+])(*)C8(*)*=C)c9N(*)*C%10%11c9c5N5C8(**8)*=CC58C%10(*)*%11)C6C7O)C2OC)c(N(*)*)c4C(*)([*+]2)C2([*+])C3(*)*=*1 0.000 description 3
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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
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/02—Details
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J1/00—Photometry, e.g. photographic exposure meter
- G01J1/02—Details
- G01J1/04—Optical or mechanical part supplementary adjustable parts
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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
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F77/00—Constructional details of devices covered by this subclass
- H10F77/40—Optical elements or arrangements
Definitions
- the present invention relates to an optical filter for an ambient light sensor. Specifically, the present invention relates to an optical filter for an environmental light sensor that includes a compound having absorption in a specific wavelength region and has specific optical characteristics, an environmental light sensor using the optical filter, and an electronic apparatus having the optical filter.
- the ambient light sensor in the information terminal device senses the illuminance of the environment where the information terminal device is placed and controls the brightness of the display, and the ambient light sensor senses the color tone of the environment where the information terminal device is placed. It is used as a color sensor that adjusts the color tone of the image.
- the ambient light sensor can have a spectral sensitivity characteristic close to visual sensitivity by installing an optical filter such as a near infrared cut filter.
- An apparatus provided with an infrared cut filter in which a metal multilayer film is formed on a glass plate is disclosed as means for matching the spectral characteristics of an ambient light sensor with human visibility (see, for example, Patent Document 1).
- the near-infrared cut filter in which the metal multilayer thin film is formed on the glass plate has a problem that the detection accuracy of the ambient light sensor is lowered because the optical characteristics greatly change depending on the incident angle of the incident light. Further, when the metal multilayer film is formed by vapor deposition, warping or distortion may occur when the optical filter is enlarged.
- various near-infrared absorbing particles are known as materials capable of cutting broadband near-infrared rays regardless of the incident angle (see, for example, Patent Document 2 and Patent Document 3).
- the near-infrared cut filter when the addition amount of the near-infrared absorbing particles is increased, there is a problem that the visible light transmittance is lowered.
- a near-infrared absorbing filter having a norbornene-based resin substrate, a near-infrared absorbing dye having an absorption maximum at a specific wavelength, and a near-infrared reflective film has a transmittance change in the visible range when light enters from an oblique direction.
- a high incident angle such as an incident angle of 60 °.
- JP 2011-060788 A International Publication No. 2005/037932 Specification JP 2011-118255 A JP 2011-100084 A
- the present invention is capable of achieving both excellent visible light transmittance and near-infrared cut performance even when the incident angle is increased due to a reduction in the height of a device provided with various ambient light sensors, and also prevents warping and distortion.
- An object is to provide an optical filter that can be reduced and enlarged.
- An optical filter for an ambient light sensor which has a base material that satisfies the following requirement (a) and satisfies the following requirements (b), (c), and (d): (A) having a layer containing a compound (A) having an absorption maximum in a region of a wavelength of 650 nm or more and less than 800 nm and a compound (B) having an absorption maximum in a region of a wavelength of 800 nm or more and 1850 nm or less; (B) In the wavelength range of 800 to 1000 nm, the average reflectance Rfa -5 of the light incident from an oblique direction of 5 degrees with respect to the vertical direction on one surface of the optical filter and the vertical direction on the other surface On the other hand, the average value Rf b-5 of the reflectance of light incident from an oblique direction of 5 degrees is 15% or less; (C) In the wavelength range of 430 to 580 nm, the average value
- the transparent resin layer further includes a compound (B) having an absorption maximum in a wavelength region of 800 nm or more and 1850 nm or less.
- the compound (B) is composed of near-infrared absorbing fine particles, squarylium compound, phthalocyanine compound, naphthalocyanine compound, croconium compound, cyanine compound, diimonium compound, metal dithiolate compound, and pyrrolopyrrole compound.
- Item 6 The optical filter for ambient light sensors according to any one of Items [1] to [5], which is at least one compound selected from the group consisting of:
- a group in which the near-infrared absorbing fine particles are composed of first fine particles made of a compound represented by the following formula (P-1) and second fine particles made of a compound represented by the following formula (P-2).
- the optical filter for an ambient light sensor according to item [6], which is at least one selected from the group consisting of: A 1 / n CuPO 4 (P-1)
- A is at least one selected from the group consisting of alkali metals, alkaline earth metals, and NH 4
- n is 1 when A is an alkali metal or NH 4 , 2 when A is an alkaline earth metal.
- M is H, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, It is at least one element selected from Re, Be, Hf, Os, Bi and I, and x, y and z are 0.001 ⁇ x / y ⁇ 1 and 2.2 ⁇ z / y ⁇ 3.0. Satisfy the condition of
- the resin constituting the transparent resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, or an aramid resin.
- optical filter for an ambient light sensor according to Item [3] or [4], wherein the optical filter is an at least one resin selected from the group consisting of a resin mainly composed of silica formed by the above.
- the base material includes a fluorophosphate glass layer containing a copper component or a substrate made of phosphate glass.
- R transmittance ratio (R transmittance) ⁇ 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (1)
- G transmittance ratio (G transmittance) ⁇ 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (2)
- B transmittance ratio (B transmittance) ⁇ 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (3)
- the R transmittance is an average transmittance at a wavelength of 580 to 650 nm
- the G transmittance is an average transmittance at a wavelength of 500 to 580 nm
- the B transmittance is an average transmittance at a wavelength of 420 to 500 nm.
- An ambient light sensor comprising the optical filter for an ambient light sensor according to any one of items [1] to [10].
- an incident light from a vertical direction and an incident light from an oblique direction it has a high visible light transmittance and a near-infrared cut performance, and has a reduced warpage and distortion.
- An optical filter can be provided.
- An ambient light sensor using such an optical filter has a small incident angle dependency of incident light, and can measure illuminance and color temperature with high accuracy.
- up refers to a relative position with respect to the main surface of the support substrate (the light receiving surface of the sensor), and the direction away from the main surface of the support substrate is “up”.
- the upper side toward the paper surface is “upper”.
- upper includes a case where it is in contact with an object (that is, “on”) and a case where it is located above the object (that is, “over”).
- down refers to a relative position with respect to the main surface of the support substrate, and the direction approaching the main surface of the support substrate is “down”.
- the lower side is “down” toward the paper surface.
- optical filter has a base material (i) that satisfies the following requirement (a) and satisfies the following requirements (b), (c), and (d).
- the average reflectance Rf b-5 of light incident from a direction oblique to the direction by 5 degrees is 15% or less, preferably 0.1 to 12%, more preferably 1 to 10%.
- the reflectance is determined by the refractive index of the substance through which light passes, so that the average value of the reflectance within a specified range is obtained.
- the method of selecting the base material which has a refractive index to be given, or the method of providing the layer for adjusting a refractive index to a base material is mentioned.
- an optical thin film design software for example, manufactured by Essential Macleod, Thin Film Center Co.
- the average value of reflectance within a specified range is also mentioned.
- Satisfying the requirement (b) is preferable because multiple reflected light in the optical sensor module can be reduced, so that malfunction of the optical sensor can be suppressed and a highly functional optical sensor can be obtained.
- the average value Ta 0 of the transmittance of light incident from the vertical direction of the optical filter and the transmittance of light incident from an oblique direction of 30 degrees with respect to the vertical direction are both 20% or more and less than 75%, preferably 25 to 70%. It is.
- an ambient light sensor having excellent sensor sensitivity can be obtained. If the average transmittance is too high in the wavelength range of 430 to 580 nm, the intensity of the light incident on the light receiving part of the photosensor becomes excessively strong and the photosensor may saturate and may not function normally. . On the other hand, if the average value of the transmittance is too low, the intensity of the light incident on the light receiving portion of the photosensor becomes weak, and the intensity of the light passing through the filter may not be sufficiently secured.
- the average value OD a-30 of the optical density (OD value) with respect to the light and the average value OD a-60 of the optical density (OD value) with respect to the light incident from an oblique direction of 60 degrees with respect to the vertical direction are both 1 .5 or more, preferably 2.0 to 6.0.
- the light in the wavelength region is sufficient. It will enter the ambient light sensor without being cut. Since the ambient light sensor is sensitive to the light in the wavelength region, when the light in the wavelength region enters the ambient light sensor, it becomes noise and causes malfunction of color tone control.
- the values of OD a-0 , OD a-30 and OD a-60 are more than 6.0, the concentration of the compound (B) is increased or the number of layers of the dielectric multilayer film is increased. This may cause problems such as a decrease in visible light transmittance and an increase in warpage.
- a method of satisfying the requirement (d) that is, a method of adjusting the average value of the optical density, for example, the types and additions of the compound (A) and the compound (B) so that an average value of transmittance within a specified range can be obtained.
- a method of appropriately selecting and adjusting the amount for example, the types and additions of the compound (A) and the compound (B) so that an average value of transmittance within a specified range can be obtained.
- the optical filter can sufficiently cut not only near infrared rays transmitted in the vertical direction but also near infrared rays transmitted at a high incident angle.
- an optical filter is used for an optical sensor of a mobile phone or a tablet, it is possible to prevent malfunction of the screen brightness and color correction function.
- near-infrared light can be suitably cut even when a light diffusion film is provided above the optical filter of the present invention.
- the OD value is a common logarithm of transmittance, and can be calculated by the following formula (4).
- Average OD value in a certain wavelength region ⁇ Log 10 (Average transmittance in a certain wavelength region (%) / 100) Equation (4)
- the RGB balance of visible light when incident from the vertical direction of the optical filter From the viewpoint of preventing the ambient light sensor from malfunctioning, the RGB balance of visible light when incident from the vertical direction of the optical filter, the RGB balance of visible light when incident from the direction of 30 ° with respect to the vertical direction of the optical filter, it is desirable that the change in the RGB balance of the visible light when the light enters from a direction of 60 ° with respect to the vertical direction of the optical filter is small. That is, the rate of change of the R (red) transmittance ratio derived from the following equation (1), the rate of change of the G (green) transmittance ratio derived from the following equation (2), and the following equation (3):
- the change rate of the ratio of B (blue) transmittance is preferably in the range of 0.6 to 1.1. The closer the change rate is to 1.0, the smaller the incident angle dependent change of RGB balance.
- R transmittance ratio (R transmittance) ⁇ 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (1)
- G transmittance ratio (G transmittance) ⁇ 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (2)
- B transmittance ratio (B transmittance) ⁇ 100 / ((R transmittance) + (G transmittance) + (B transmittance)) (3)
- the R transmittance is an average transmittance at a wavelength of 580 to 650 nm
- the G transmittance is an average transmittance at a wavelength of 500 to 580 nm
- the B transmittance is an average transmittance at a wavelength of 420 to 500 nm.
- the ratio of the B transmittance when measured from an angle of 30 ° with respect to the vertical direction of the optical filter is divided by the ratio of the B transmittance when measured from the vertical direction of the optical filter (0 ° ⁇ 30).
- the ratio of the R transmittance when measured from an angle of 60 ° with respect to the vertical direction of the optical filter is divided by the ratio of the R transmittance when measured from the vertical direction of the optical filter (0 ° ⁇
- the rate of change in the ratio of G transmittance in the case of ° can be derived from the following equation (9).
- the rate of change in the ratio of G transmittance in the case of 0 ° to 60 ° is preferably 0.4 or more and 2.0 or less, more preferably 0.5 or more and 1.8 or less, and further preferably 0.6 or more and 1. It is 6 or less, and the closer the change rate is to 1.0, the smaller the incident angle dependent change of RGB balance.
- the optical filter of the present invention preferably does not have a dielectric multilayer film.
- an ambient light sensor of the type in which an optical filter is attached to a silicon wafer when the silicon wafer is enlarged, distortion and warpage due to vapor deposition for forming a dielectric multilayer film may become a problem.
- warpage and distortion can be reduced as compared with an optical filter having a dielectric multilayer film.
- the optical filter can be increased in size.
- the optical filter of the present invention can exhibit optical characteristics equivalent to those of a conventional ambient light sensor without having a dielectric multilayer film.
- the thickness of the optical filter of the present invention is not particularly limited, but is preferably 40 to 1000 ⁇ m, more preferably 50 to 800 ⁇ m, still more preferably 80 to 500 ⁇ m, and particularly preferably 90 to 250 ⁇ m. When the thickness of the optical filter is within the above range, the optical filter can be reduced in size and weight.
- the substrate (i) may be a single layer or multiple layers as long as it has a layer containing the compound (A) having an absorption maximum in a region of a wavelength of 650 nm or more and less than 800 nm. Moreover, it is preferable that the said base material (i) contains the compound (B) which has an absorption maximum in the wavelength range of 800 nm or more and 1850 nm or less, and the compound (B) is contained in the same layer as the compound (A). May also be included in different layers.
- a layer containing at least one compound selected from the compound (A) and the compound (B) and a transparent resin is also referred to as “transparent resin layer”, and the other resin layers are also simply referred to as “resin layers”.
- a base material composed of a transparent resin substrate containing the compound (A) and the compound (B), the compound (A) and the compound Supports such as a base material, a glass support, and a resin support as a base, in which a resin layer such as an overcoat layer made of a curable resin or a thermoplastic resin is laminated on a transparent resin substrate containing (B)
- a resin layer such as an overcoat layer made of a curable resin or a thermoplastic resin is laminated on a transparent resin substrate containing (B)
- a transparent resin layer such as an overcoat layer made of a curable resin or a thermoplastic resin containing the compound (A) and the compound (B) is laminated.
- the layer containing the compound (A) is different from the layer containing the compound (B), for example, it is made of a curable resin or thermoplastic resin containing the compound (A) on a transparent resin substrate containing the compound (B).
- a transparent resin such as an overcoat layer made of a curable resin or a thermoplastic resin containing a compound (B) on a substrate on which a transparent resin layer such as an overcoat layer is laminated, a transparent resin substrate containing the compound (A)
- a transparent resin layer such as an overcoat layer made of a curable resin or a thermoplastic resin containing the compound (A) on a base material on which layers are laminated, a support such as a glass support or a base resin support, and the like;
- the compound (A) is not particularly limited as long as it has an absorption maximum in a wavelength region of 650 nm or more and less than 800 nm, but is selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds. It is preferable that the compound is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, and cyanine compounds. In addition, a compound (A) may be used individually by 1 type, and may be used in combination of 2 or more type.
- the absorption maximum wavelength of the compound (A) is preferably 660 nm to 795 nm, more preferably 680 nm to 790 nm.
- the usage-amount of a compound (A) is suitably selected according to a desired characteristic, as the said base material, the base material which consists of a transparent resin board
- the base material which consists of a transparent resin board
- the base material which consists of a transparent resin board
- a compound
- a glass support or base is used as the base material.
- a base material in which a transparent resin layer containing the compound (A) is laminated on a support such as a resin support it is preferably 0 with respect to 100 parts by weight of the resin forming the transparent resin layer. .4 to 20.0 parts by weight, more preferably .6 ⁇ 15.0 parts by weight, more preferably 0.8 to 12.5 wt parts.
- the squarylium compound is not particularly limited, but is at least one selected from the group consisting of a squarylium compound represented by the following formula (I) and a squarylium compound represented by the following formula (II). Are preferred. Hereinafter, they are also referred to as “compound (I)” and “compound (II)”, respectively.
- R a , R b and Ya satisfy the following condition ( ⁇ ) or ( ⁇ ).
- a plurality of R a each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L 1 or —NR e R f group;
- a plurality of R b s each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L 1 or —NR g R h group;
- a plurality of Ya each independently represents a —NR j R k group;
- L 1 represents L a, L b, L c , L d, L e, L f, L g or L h;
- R e and R f each independently represents a hydrogen atom, -L a ,
- At least one of two R a on one benzene ring is bonded to Y on the same benzene ring to form a heterocycle having 5 or 6 member atoms containing at least one nitrogen atom;
- the heterocyclic ring may have a substituent, and R b and R a that is not involved in the formation of the heterocyclic ring are independently synonymous with R b and R a in the condition ( ⁇ ).
- the total number of carbon atoms including the substituents of L a to L h is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the number of carbon atoms exceeds this range, the synthesis of the compound may be difficult, and the light absorption intensity per unit weight tends to be small.
- the aliphatic hydrocarbon group L a and 1 to 12 carbon atoms in L such as a methyl group (Me), ethyl (Et), n-propyl group (n-Pr), isopropyl (i-Pr ), N-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc.
- Me methyl group
- Et ethyl
- i-Pr isopropyl
- n-Bu N-butyl group
- s-Bu sec-butyl group
- t-Bu tert-butyl group
- pentyl group hexyl group
- octyl group nonyl group
- decyl group dodecyl
- Alkyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group and octenyl group
- alkynyl groups such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group and octynyl group.
- Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms in L b and L include, for example, a trichloromethyl group, a trifluoromethyl group, a 1,1-dichloroethyl group, a pentachloroethyl group, a pentafluoroethyl group, a heptachloro group. Mention may be made of propyl and heptafluoropropyl groups.
- Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in L c and L include, for example, a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a norbornane group and an adamantane group And polycyclic alicyclic groups such as
- Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L d and L include, for example, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, Mention may be made of phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl and biphenylyl groups.
- heterocyclic group having 3 to 14 carbon atoms in Le and L examples include, for example, furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, indole, indoline, indolenine, and benzofuran.
- Examples of the alkoxy group having 1 to 12 carbon atoms in L f include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group. it can.
- Examples of the acyl group having 1 to 9 carbon atoms in L g include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.
- alkoxycarbonyl group having 1 to 9 carbon atoms in L h examples include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, and an octyl group.
- An oxycarbonyl group can be mentioned.
- L a preferably a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- butyl group, a pentyl group, a hexyl group, an octyl group, 4-phenylbutyl 2-cyclohexylethyl, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.
- L b is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, or a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, more preferably a trichloromethyl group.
- L c is preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group, or a 4-phenylcycloheptyl group, and more preferably a cyclopentyl group, a cyclohexyl group, or a 4-ethylcyclohexyl group. It is.
- the L d is preferably a phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 3,5-di-tert-butylphenyl group, 4-cyclopentylphenyl group. 2,3,6-triphenylphenyl group, 2,3,4,5,6-pentaphenylphenyl group, more preferably phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,3 , 4,5,6-pentaphenylphenyl group.
- L e preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, consisting morpholine group, more preferably furan, thiophene, pyrrole, consisting morpholine group.
- the L f is preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, methoxymethyl group, methoxyethyl group, 2-phenylethoxy group, 3-cyclohexylpropoxy group, pentyloxy group, hexyloxy Group, octyloxy group, more preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group.
- L g is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, or a trifluoromethylcarbonyl group, and more preferably an acetyl group, a propionyl group, or a benzoyl group.
- the L h is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group, more preferably A methoxycarbonyl group and an ethoxycarbonyl group;
- the L a to L h further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, and an amino group. May be. Examples include 4-sulfobutyl, 4-cyanobutyl, 5-carboxypentyl, 5-aminopentyl, 3-hydroxypropyl, 2-phosphorylethyl, 6-amino-2,2-dichloro.
- R a in the above condition ( ⁇ ) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.
- R b in the above condition ( ⁇ ) is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group T-butanoylamino group, cyclohexinoylamino group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group, dimethylamino group, nitro group Acet
- the Ya is preferably an amino group, methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-t-butylamino group, N -Ethyl-N-methylamino group, N-cyclohexyl-N-methylamino group, more preferably dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group , A di-t-butylamino group.
- At least one of two R a on one benzene ring is bonded to Y on the same benzene ring, and at least 1 nitrogen atom is formed.
- the heterocyclic ring containing 5 or 6 atoms include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine.
- a heterocyclic ring that constitutes the heterocyclic ring and in which one atom adjacent to the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.
- X independently represents O, S, Se, N—R c or C (R d R d ); a plurality of R c s independently represent a hydrogen atom, L a , L b , L c, represents L d or L e; each independently plurality of R d, a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L 1 or -NR e R f group, and adjacent R d groups may be linked to form an optionally substituted ring; L a to L e , L 1 , R e and R f are It is synonymous with L a -L e , L 1 , R e and R f defined in formula (I).
- R c in the formula (II) is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group.
- R d in the formula (II) is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl.
- n-pentyl group n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, 4-aminocyclohexyl group, more preferably hydrogen atom, chlorine atom, fluorine atom Methyl group, ethyl group, n-propyl group, isopropyl group, trifluoromethyl group and pentafluoroethyl group.
- X is preferably O, S, Se, N-Me, N-Et, CH 2 , C-Me 2 , C-Et 2 , and more preferably S, C-Me 2 , C-Et 2. It is.
- adjacent R ds may be linked to form a ring. Examples of such rings include benzoindolenin ring, ⁇ -naphthimidazole ring, ⁇ -naphthimidazole ring, ⁇ -naphthoxazole ring, ⁇ -naphthoxazole ring, ⁇ -naphthothiazole ring, ⁇ -naphthothiazole ring. , ⁇ -naphthoselenazole ring and ⁇ -naphthoselenazole ring.
- Compound (I) and Compound (II) are represented by the following formulas (I-2) and (II-2) in addition to the description methods such as the following formula (I-1) and the following formula (II-1).
- the structure can also be expressed by a description method that takes a resonance structure. That is, the difference between the following formula (I-1) and the following formula (I-2), and the difference between the following formula (II-1) and the following formula (II-2) is only the structure description method. Represents the same compound.
- the structure of the squarylium compound is represented by a description method such as the following formula (I-1) and the following formula (II-1).
- a compound represented by the following formula (I-3) and a compound represented by the following formula (I-4) can be regarded as the same compound.
- the structures of the compounds (I) and (II) are not particularly limited as long as they satisfy the requirements of the formulas (I) and (II), respectively.
- the left and right substituents bonded to the central four-membered ring may be the same or different, It is preferable that they are the same because synthesis is easy.
- compounds (I) and (II) include compounds (a-1) shown in the following Tables 1 to 3 having basic skeletons represented by the following formulas (IA) to (IH): ) To (a-36).
- the compounds (I) and (II) may be synthesized by a generally known method.
- JP-A-1-228960, JP-A-2001-40234, JP-A-3196383, etc. It can be synthesized with reference to the method described.
- the phthalocyanine compound is not particularly limited, but is preferably a compound represented by the following formula (III) (hereinafter also referred to as “compound (III)”).
- M represents a substituted metal atom including two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom
- the amino group, amide group, imide group and silyl group may have the substituent L defined in the formula (I), L 1 has the same meaning as L 1 defined in Formula (I), L 2 represents one of L a ⁇ L e as defined in the hydrogen atom or the formula (I), the L 3 represents either a hydroxyl group or the L a ⁇ L e, L 4 represents represents any of the L a ⁇ L e.
- the group and the silyl group may have the substituent L defined in the formula (I), and L 1 to L 4 have the same meanings as L 1 to L 4 defined in the formula (III).
- the amino group which may have a substituent L is an amino group, ethylamino group, dimethylamino group, methylethylamino group, dibutylamino group, diisopropylamino Group and the like.
- R a to R d and R A to R L as an amide group which may have a substituent L, an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, a diisopropylamide group, Examples thereof include a dibutylamide group, an ⁇ -lactam group, a ⁇ -lactam group, a ⁇ -lactam group, and a ⁇ -lactam group.
- the imide group that may have a substituent L is an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, a diisopropylimide group, A dibutylimide group etc. are mentioned.
- Examples of the silyl group that may have a substituent L in R a to R d and R A to R L include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a triethylsilyl group.
- —SL 2 includes thiol group, methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, isobutyl sulfide group, sec-butyl sulfide group Tert-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butylphenyl sulfide group, 2,6-diphenylphenyl sulfide group, 4-cumylphenyl sulfide group and the like.
- -SS-L 2 is a disulfide group, methyl disulfide group, ethyl disulfide group, propyl disulfide group, butyl disulfide group, isobutyl disulfide group, sec-butyl disulfide group Tert-butyl disulfide group, phenyl disulfide group, 2,6-di-tert-butylphenyl disulfide group, 2,6-diphenylphenyl disulfide group, 4-cumylphenyl disulfide group and the like.
- examples of —SO 2 -L 3 include a sulfo group, a mesyl group, an ethylsulfonyl group, an n-butylsulfonyl group, a p-toluenesulfonyl group, and the like.
- —N ⁇ N—L 4 includes a methylazo group, a phenylazo group, a p-methylphenylazo group, a p-dimethylaminophenylazo group, and the like.
- examples of the monovalent metal atom include Li, Na, K, Rb, and Cs.
- the divalent metal atoms include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, Hg, Sn, Pb etc. are mentioned.
- the substituted metal atom containing a trivalent metal atom includes Al—F, Al—Cl, Al—Br, Al—I, Ga—F, Ga—Cl, Ga—Br, Ga—I, In -F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH and the like.
- the substituted metal atom containing a tetravalent metal atom includes TiF 2 , TiCl 2 , TiBr 2 , TiI 2 , ZrCl 2 , HfCl 2 , CrCl 2 , SiF 2 , SiCl 2 , SiBr 2 , SiI 2 , GeF 2 , GeCl 2 , GeBr 2 , GeI 2 , SnF 2 , SnCl 2 , SnBr 2 , SnI 2 , Zr (OH) 2 , Hf (OH) 2 , Mn (OH) 2 , Si (OH) 2 , Ge ( OH) 2 , Sn (OH) 2 , TiR 2 , CrR 2 , SiR 2 , GeR 2 , SnR 2 , Ti (OR) 2 , Cr (OR) 2 , Si (OR) 2 , Ge (OR) 2 , Sn (OR) 2 (R represents an aliphatic group or an aromatic group),
- the M is a divalent transition metal, trivalent or tetravalent metal halide or tetravalent metal oxide belonging to Groups 5 to 11 of the periodic table and belonging to the 4th to 5th periods.
- Cu, Ni, Co, and VO are particularly preferable because high visible light transmittance and stability can be achieved.
- a method of synthesizing the phthalocyanine-based compound by a cyclization reaction of a phthalonitrile derivative such as the following formula (V) is generally known.
- the obtained phthalocyanine-based compounds are represented by the following formulas (VI-1) to (VI) It is a mixture of four isomers such as VI-4).
- VI-1 a phthalonitrile derivative
- VI-4 a phthalonitrile derivative
- the compound (III) include the basic skeletons represented by the following formulas (III-A) to (III-J) and (b-1) to (b-61) shown in Tables 4 to 7 below. ) And the like.
- Compound (III) may be synthesized by a generally known method. For example, a method described in Japanese Patent No. 4081149 or “phthalocyanine -chemistry and function” (IPC, 1997) is used. It can be synthesized by reference.
- the cyanine compound is not particularly limited, but is a compound represented by any of the following formulas (IV-1) to (IV-3) (hereinafter referred to as “compounds (IV-1) to (IV-3)”. ) ").) Is preferred.
- X a - represents a monovalent anion
- a plurality of D are independently represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom
- Represents at least one group selected from the group consisting of groups, wherein the amino group, amide group, imide group and silyl group are the substituents defined in the formula (I) It may have the L, L 1 has the same meaning as L 1 defined in Formula (I), L 2 represents one of L a ⁇ L e as defined in the hydrogen atom or the formula (I), the L 3 represents either a hydrogen atom or the L a ⁇ L e, L 4 are, represent either the L a ⁇ L e, Z a to Z c and Y a to Y d are each independently a hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L 1 ,- S-L 2, -SS-L 2, -SO 2 -L 3, -N N-L 4 (L 1 ⁇ L 4 have the same meaning as L 1 ⁇ L 4 in the R a ⁇ R
- the hydrogenation group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.
- Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z or Y in Z a to Z c and Y a to Y d include, for example, the substituent L
- the compound illustrated by the aromatic hydrocarbon group is mentioned.
- the alicyclic hydrocarbon group include compounds exemplified by the alicyclic hydrocarbon group and the heterocyclic ring in the substituent L (excluding the heteroaromatic hydrocarbon group).
- heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding Z or Y in Z a to Z c and Y a to Y d include, for example, the substituent L And the compounds exemplified as the heterocyclic group (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom or sulfur atom).
- X a ⁇ is not particularly limited as long as it is a monovalent anion, but I ⁇ , Br ⁇ , PF 6 ⁇ , N (SO 2 CF 3 ) 2 ⁇ , B (C 6 F 5 ) 4 ⁇ , nickel dithiolate. And the like, and copper dithiolate complex.
- the compounds (IV-1) to (IV-3) may be synthesized by a generally known method, for example, by the method described in JP-A-2009-108267.
- the compound (B) is not particularly limited as long as it has an absorption maximum in the wavelength region of 800 nm or more and 1850 nm or less, but near infrared absorbing fine particles, squarylium compound, phthalocyanine compound, naphthalocyanine compound, croconium compound, cyanine It is preferable that the compound is at least one compound selected from the group consisting of a compound based on a compound, a diimonium compound, a metal dithiolate compound and a pyrrolopyrrole compound.
- Ambient light sensors usually have a sensitivity up to around 1200 nm in addition to the visible light region.
- a compound having a broad absorption in the near infrared region as the compound (B), and among the above compounds, near infrared absorbing fine particles, cyanine compounds, diimonium compounds and squarylium compounds are more preferable.
- the near-infrared absorbing fine particles Cs x W y O z is most preferable.
- a compound (B) may be used individually by 1 type, and may be used in combination of 2 or more type. By using such a compound (B), absorption characteristics in a wide near infrared wavelength region and excellent visible light transmittance can be achieved.
- the absorption maximum wavelength of the compound (B) is 800 nm to 1850 nm, preferably 810 nm to 1800 nm, more preferably 820 nm to 1750 nm.
- the absorption maximum wavelength of the compound (B) other than the near-infrared absorbing fine particles is preferably 800 nm to 1200 nm, more preferably 810 nm to 1180 nm, and particularly preferably 820 nm to 1150 nm.
- the absorption maximum wavelength of the near-infrared absorbing fine particles is preferably 800 nm to 1850 nm, more preferably 840 nm to 1800 nm, and particularly preferably 870 nm to 1750 nm.
- the amount of the compound (B) (excluding near-infrared-absorbing fine particles) is appropriately selected according to the desired properties.
- the substrate include the compound (A) and the compound (B).
- a base material composed of a transparent resin substrate it is preferably 0.01 to 5.0 parts by weight, more preferably 0.02 to 3.0 parts by weight, with respect to 100 parts by weight of the transparent resin. Particularly preferably, it is 0.03 to 2.0 parts by weight, and as the substrate, a transparent material containing the compound (A) and the compound (B) on a support such as a glass support or a resin support as a base.
- the compound (A) is included. It is preferable for 100 parts by weight of the resin forming the transparent resin layer. Properly is 0.1-30.0 parts by weight, more preferably 1.0 to 28.0 parts by weight, particularly preferably 2.0 to 25.0 parts by weight.
- an optical filter having both good near infrared absorption characteristics and high visible light transmittance can be obtained.
- fine-particles as said compound (B) is mentioned later.
- the compound (B) may be synthesized by a generally known method.
- Japanese Patent No. 4168031 Japanese Patent No. 4225296, JP 2010-516823, JP-A 63-165392 It can be synthesized with reference to the method described in the publication.
- diimonium type compound is not specifically limited,
- the compound represented by a following formula (s1) is preferable.
- R 1 and R 2 are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, a —NR g R h group, —SR i Group, —SO 2 R i group, —OSO 2 R i group, or any of the following L a to L h , wherein R g and R h are each independently a hydrogen atom, —C (O) R i group or represents one of the following L a ⁇ L e, R i represents any of the following L a ⁇ L e, (L a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms (L b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atom
- the substituent L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, And at least one selected from the group consisting of an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms, and n is 0 to An integer of 4, X represents an anion necessary for neutralizing the charge.
- R 1 is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, phenyl group or benzyl group. And more preferably an isopropyl group, a sec-butyl group, a tert-butyl group, or a benzyl group.
- R 2 is preferably a chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group phenyl group, hydroxyl group, Amino group, dimethylamino group, cyano group, nitro group, methoxy group, ethoxy group, n-propoxy group, n-butoxy group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group A pentafluoroethanoylamino group, a t-butanoylamino group, a cyclohexinoylamino group, an n-butylsulfonyl group, a methylthio group, an ethylthio group, an n-prop
- X is an anion necessary for neutralizing the electric charge, and one molecule is required when the anion is divalent, and two molecules are required when the anion is monovalent.
- the two anions may be the same or different, but are preferably the same from the viewpoint of synthesis.
- X will not be restrict
- X has a tendency to improve the heat resistance of the diimonium compound when it is used as an anion of the diimonium compound as long as it has high acidity when converted to an acid, and (X-10) and (X X-16), (X-17), (X-21), (X-22), (X-24), and (X-28) are particularly preferable.
- Metal dithiolate compounds Although the said metal dithiolate type compound is not specifically limited, For example, the compound represented by a following formula (s2) is preferable.
- R 3 has the same meaning as R 1 and R 2 in the formula (s1), and adjacent R 3 may form a ring which may have a substituent L.
- Z represents D (R i ) 4 , D represents a nitrogen atom, a phosphorus atom or a bismuth atom, and y represents 0 or 1.
- R 3 is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, cyclohexyl group, n-pentyl group, n-hexyl group, n-heptyl, n-octyl, n-octyl, n-nonyl, n-decyl, phenyl, methylthio, ethylthio, n-propylthio, n-butylthio, phenylthio, benzylthio
- it is preferably a heterocyclic ring containing at least one sulfur atom or nitrogen atom in the ring.
- M is preferably a transition metal, more preferably Ni, Pd, or Pt.
- the D is preferably a nitrogen atom or a phosphorus atom, and the Ri is preferably an ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl. Group, n-hexyl group, n-heptyl group and phenyl group.
- the near-infrared absorbing fine particles are not particularly limited as long as they have absorption in a wavelength region of 800 nm to 1850 nm.
- Examples of such near-infrared absorbing fine particles include transparent conductive oxides such as ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), and GZO (gallium-doped zinc oxide), and the following formula (P-1)
- A is at least one selected from the group consisting of alkali metals, alkaline earth metals, and NH 4 , and n is 1 when A is an alkali metal or NH 4 , 2 when A is an alkaline earth metal.
- M is H, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, and when there are a plurality of M, they may be separate atoms, and x, y, and z are 0.001 ⁇ x / y ⁇ 1 and 2.2 ⁇ z / y The condition of ⁇ 3.0 is satisfied.
- the alkali metal refers to Li, Na, K, Rb, Cs
- the alkaline earth metal refers to Ca, Sr, Ba
- the rare earth element refers to Sc, Y, La, Ce
- It refers to Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.
- the average value of the particle diameter of the near-infrared absorbing fine particles is preferably 1 to 200 nm, that is, 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less.
- the diameter of the near-infrared absorbing fine particles is determined by using a dynamic light scattering photometer (model number DLS-8000HL / HH, manufactured by Otsuka Electronics Co., Ltd.) as a suspension in which the near-infrared absorbing fine particles are dispersed (hereinafter also simply referred to as “dispersion liquid”). ) Using a dynamic light scattering method (using a He—Ne laser, a cell chamber temperature of 25 ° C.).
- the average value of the particle diameter of the near-infrared absorbing fine particles is within this range, geometric scattering and Mie scattering that cause a decrease in visible light transmittance can be reduced, and a Rayleigh scattering region is obtained.
- the scattered light decreases in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the visible light transmittance is improved as the particle diameter decreases.
- the particle diameter is in the above-mentioned range since the scattered light is extremely reduced and a good visible light transmittance can be achieved.
- the particle diameter is small, but considering the ease of industrial production, production cost, etc., the lower limit of the average value of the particle diameter is preferably 1 nm or more, particularly preferably 2 nm or more. .
- the content of the near-infrared absorbing fine particles is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the resin component constituting the layer containing the near-infrared absorbing fine particles.
- the upper limit of the content is more preferably 55 parts by weight, particularly preferably 50 parts by weight.
- the lower limit of the content is more preferably 10 parts by weight, and particularly preferably 15 parts by weight. If the content of the near-infrared absorbing fine particles is less than 5 parts by weight, sufficient near-infrared absorption characteristics may not be obtained. If the content is more than 60 parts by weight, the visible transmittance decreases and the haze is caused by aggregation of the near-infrared absorbing fine particles. The value tends to increase.
- Examples of the dispersion medium for the near-infrared absorbing fine particles include water, alcohol, ketone, ether, ester, aldehyde, amine, aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic hydrocarbon.
- a dispersion medium may be used individually by 1 type, and 2 or more types may be mixed and used for it.
- the amount of the dispersion medium is preferably 50 to 95 parts by weight with respect to 100 parts by weight of the dispersion from the viewpoint of maintaining the dispersibility of the near-infrared absorbing fine particles.
- a dispersant can be blended if necessary to improve the dispersion state of the near-infrared absorbing fine particles.
- Dispersing agents that have a modifying effect on the surface of near-infrared absorbing fine particles such as surfactants, silane compounds, silicone resins, titanate coupling agents, aluminum coupling agents, zircoaluminate cups A ring agent or the like is used.
- Surfactants include anionic surfactants (special polycarboxylic acid type polymer surfactants, alkyl phosphate esters, etc.), nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxy Ethylene carboxylic acid esters, sorbitan higher carboxylic acid esters, etc.), cationic surfactants (polyoxyethylene alkylamine carboxylic acid esters, alkylamines, alkylammonium salts, etc.), and amphoteric surfactants (higher alkylbetaines, etc.). .
- silane compound examples include a silane coupling agent, chlorosilane, alkoxysilane, silazane and the like.
- silane coupling agent examples include alkoxysilanes having a functional group (glycidoxy group, vinyl group, amino group, alkenyl group, epoxy group, mercapto group, chloro group, ammonium group, acryloxy group, methacryloxy group, etc.).
- silicone resin examples include methyl silicone resin and methylphenyl silicone resin.
- titanate coupling agents include those having an acyloxy group, phosphoxy group, pyrophosphoxy group, sulfoxy group, aryloxy group, and the like.
- Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.
- Examples of the zircoaluminate coupling agent include those having an amino group, a mercapto group, an alkyl group, an alkenyl group, and the like.
- the amount of the dispersant is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the dispersion, although it depends on the type of the dispersant. If the amount of the dispersant is within the above range, the dispersibility of the near-infrared absorbing fine particles becomes good, the transparency is not impaired, and the sedimentation of the near-infrared absorbing fine particles over time can be suppressed.
- the first fine particles have near-infrared absorption characteristics due to the crystal structure (crystallite) of the compound represented by the formula (P-1).
- crystallite means a unit crystal that can be regarded as a single crystal, and “particle” is composed of a plurality of crystallites.
- the "consisting crystallites of the compound represented by formula (1)" can confirm the crystal structure of A 1 / n CuPO 4 by X-ray diffraction, the crystallite substantially A 1 / n CuPO 4 made it means that have been identified by X-ray diffraction, the term "consists crystallites substantially a 1 / n CuPO 4", crystallite sufficiently the crystal structure of a 1 / n CuPO 4 It means that impurities may be contained within a range that can be maintained (the crystal structure of A 1 / n CuPO 4 can be confirmed by X-ray diffraction).
- X-ray diffraction is measured using a X-ray diffractometer for near-infrared absorbing fine particles in a powder state.
- alkali metal Li, Na, K, Rb, Cs
- alkaline earth metal Ca, Sr, Ba
- NH 4 NH 4
- the crystal structure of the crystallites in the near-infrared absorbing fine particles is a network-like three-dimensional skeleton composed of alternating bonds of PO 4 3 ⁇ and Cu 2+, and has a space inside the skeleton.
- the size of the space is alkali metal ions (Li + : 0.090 nm, Na + : 0.116 nm, K + : 0.152 nm, Rb + : 0.166 nm, Cs + : 0.181 nm), alkaline earth metal Since the ionic radius of ions (Ca 2+ : 0.114 nm, Sr 2+ : 0.132 nm, Ba 2+ : 0.149 nm) and NH 4 + (0.166 nm) are compatible, the crystal structure can be sufficiently maintained. .
- Alkali metal ions, alkaline earth metal ions, and NH 4 + can stably exist as monovalent or divalent cations in the solution, so that a precursor is generated in the process of producing near-infrared absorbing fine particles. At this time, cations are easily incorporated into the crystal structure.
- a cation having strong coordination bond with PO 4 3- may give a crystal structure different from the crystal structure in the present embodiment that exhibits sufficient near-infrared absorption characteristics. is there.
- K is particularly preferable because it has the most suitable cation size as an ion taken into the skeleton composed of PO 4 3- and Cu 2+ and takes a thermodynamically stable structure.
- the near-infrared absorbing fine particles can exhibit sufficient near-infrared absorption characteristics when the crystallites sufficiently maintain the crystal structure of A 1 / n CuPO 4 . Therefore, when water or a hydroxyl group adheres to the surface of the crystallite, the crystal structure of A 1 / n CuPO 4 cannot be maintained, so that the difference in light transmittance between the visible light region and the near infrared wavelength region is reduced. It cannot be suitably used as an optical filter.
- the near-infrared absorbing fine particles have a wavelength of around 1600 cm ⁇ 1 attributed to water when the absorption intensity of the peak near 1000 cm ⁇ 1 attributed to the phosphate group is used as a reference (100%) in the microscopic IR spectrum.
- the peak absorption intensity is preferably 8% or less, and the peak absorption intensity near 3750 cm ⁇ 1 attributed to hydroxyl groups is preferably 26% or less.
- the peak absorption intensity near 1600 cm ⁇ 1 attributed to water is preferred. Is 5% or less, and the absorption intensity of a peak near 3750 cm ⁇ 1 attributed to a hydroxyl group is more preferably 15% or less.
- the microscopic IR spectrum is measured using a Fourier transform infrared spectrophotometer for powdered near-infrared absorbing fine particles.
- a Fourier transform infrared spectrophotometer Magna 760 manufactured by Thermo Fisher Scientific is used, and a piece of the first fine particles is placed on the diamond plate, flattened with a roller, and microscopic FT-IR method Measure with
- the composition range of the tungsten and oxygen is such that the composition ratio of oxygen to tungsten is 3 or less. Furthermore, when the tungsten oxide is described as W y O z , 2.2 ⁇ z / y ⁇ 2.999. It is preferable that If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a WO 2 crystal phase other than the target in the tungsten oxide, and to improve the chemical stability as a material. Therefore, it can be applied as an effective near-infrared absorbing material. On the other hand, if the value of z / y is 2.999 or less, the required amount of free electrons is generated in the tungsten oxide, and an efficient near-infrared absorbing material is obtained.
- a so-called “Magneli phase” having a composition ratio represented by 2.45 ⁇ z / y ⁇ 2.999 when the general formula is W y O z. Is chemically stable and has good absorption characteristics in the near-infrared region, and is therefore preferable as a near-infrared absorbing material.
- the value of x / y indicating the amount of element M added will be described. If the value of x / y is larger than 0.001, a sufficient amount of free electrons is generated and the intended infrared shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the infrared shielding efficiency also increases. However, when the value of x / y is about 1, the effect is saturated. Moreover, if the value of x / y is smaller than 1, it is preferable since an impurity phase can be prevented from being generated in the infrared shielding material, and more preferably 0.2 or more and 0.5 or less.
- the element M is H, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf , Os, Bi, I are preferably at least one selected from the group.
- the element M is an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, More preferably, the element is one or more elements selected from Ti, Nb, V, Mo, Ta, and Re. From the viewpoint of improving optical properties and weather resistance as a near-infrared absorbing material, More preferably, the element M belongs to an alkali metal, alkaline earth metal element, transition metal element, group 4 element, or group 5 element.
- the transparent resin is not particularly limited as long as it does not impair the effects of the present invention.
- the glass transition temperature (Tg) is preferably from 110 to 110 in order to ensure thermal stability and film formability. Examples thereof include resins having a temperature of 380 ° C., more preferably 110 to 370 ° C., and still more preferably 120 to 360 ° C.
- the glass transition temperature of the resin is preferably 140 ° C. or higher, and more preferably 230 ° C. or higher.
- the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95. %, Particularly preferably 80 to 95% of the resin can be used. If a resin having a total light transmittance in such a range is used, the resulting substrate exhibits good transparency as an optical film.
- the weight average molecular weight (Mw) in terms of polystyrene measured by a gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000, preferably 30,000 to 250,000.
- the average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.
- Transparent resins include, for example, cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, poly Ether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane UV curable Resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin and sol-gel method Formed Silica may be mentioned a resin as a main component was.
- cyclic polyolefin resins aromatic polyether resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polyarylate resins can be used for transparency (optical properties), heat resistance, and reflow resistance. It is preferable at the point from which the optical filter excellent in balance, etc. can be obtained.
- the cyclic polyolefin-based resin is obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (X 0 ) and a monomer represented by the following formula (Y 0 ).
- a resin and a resin obtained by hydrogenating the resin are preferable.
- R x1 to R x4 each independently represents an atom or group selected from the following (i ′) to (ix ′), and k x , mx and p x are each independently 0 Or represents a positive integer.
- R x1 and R x2 or R x3 and R x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring (provided that R x1 to R which are not involved in the bond) x4 each independently represents an atom or group selected from (i ′) to (vi ′).
- Ix ′ A monocyclic hydrocarbon ring or heterocycle formed by bonding R x2 and R x3 to each other (provided that R x1 and R x4 not involved in the bonding are each independently the above (i Represents an atom or group selected from ') to (vi').
- R y1 and R y2 each independently represent an atom or group selected from the above (i ′) to (vi ′), or R y1 and R y2 are bonded to each other formed monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or heterocyclic, k y and p y are each independently, represent 0 or a positive integer.
- the aromatic polyether-based resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).
- R 1 to R 4 each independently represents a monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represents an integer of 0 to 4.
- R 1 ⁇ R 4 and a ⁇ d independently has the same meaning as R 1 ⁇ R 4 and a ⁇ d of the formula (1)
- Y represents a single bond
- -SO 2 -Or> C O
- R 7 and R 8 each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group
- g and h each independently represent 0 to 4
- m represents 0 or 1.
- R 7 is not a cyano group.
- the aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4). Is preferred.
- R 5 and R 6 each independently represents a monovalent organic group having 1 to 12 carbon atoms
- Z represents a single bond, —O—, —S—, —SO 2 —,> C ⁇ O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms
- e and f each independently represent an integer of 0 to 4, and n represents 0 or 1.
- R 7 , R 8 , Y, m, g and h are each independently synonymous with R 7 , R 8 , Y, m, g and h in formula (2), and R 5 , R 6 , Z, n, e and f are each independently synonymous with R 5 , R 6 , Z, n, e and f in the formula (3).
- the polyimide resin is not particularly limited as long as it is a polymer compound containing an imide bond in a repeating unit.
- the method described in JP-A-2006-199945 and JP-A-2008-163107 is used. Can be synthesized.
- the fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in JP-A-2008-163194.
- the fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety.
- the fluorene polyester resin can be synthesized by the method described in JP 2010-285505 A or JP 2011-197450 A. Can do.
- the fluorinated aromatic polymer resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond.
- the polymer preferably contains a repeating unit containing at least one bond, and can be synthesized, for example, by the method described in JP-A-2008-181121.
- the acrylic ultraviolet curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic or methacrylic groups in the molecule and a compound that decomposes by ultraviolet rays to generate active radicals. Can be mentioned.
- a transparent resin layer (light absorption layer) containing a compound (A) and a curable resin is laminated on a glass support or a resin support as a base as the base (i).
- a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing the prepared base material or compound (A), it is particularly suitable as the curable resin.
- a base material in which a resin layer such as an overcoat layer made of a curable resin or the like is laminated on a transparent resin substrate containing the prepared base material or compound (A)
- it is particularly suitable as the curable resin. can be used.
- Resin mainly composed of silica formed by sol-gel process examples include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, dimethoxydiethoxylane, and methoxytriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, A compound obtained by a sol-gel reaction by hydrolysis of one or more silanes selected from phenylalkoxysilanes such as diphenyldiethoxysilane can be used as the resin.
- cyclic polyolefin resins examples include Arton manufactured by JSR Corporation, ZEONOR manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Corporation.
- polyethersulfone resins examples include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd.
- polyimide resins examples include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd.
- commercially available polycarbonate resins include Pure Ace manufactured by Teijin Limited.
- Examples of commercially available fluorene polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd.
- Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd.
- Examples of commercially available acrylic resins include NIPPON CATALYST ACRYVIEWER.
- Examples of commercially available silsesquioxane-based ultraviolet curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd.
- the base material (i) may further contain additives such as an antioxidant, a near-ultraviolet absorber, and a fluorescence quencher as long as the effects of the present invention are not impaired. These other components may be used alone or in combination of two or more.
- Examples of the near ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, and triazine compounds.
- Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2′-dioxy-3,3′-di-t-butyl-5,5′-dimethyldiphenylmethane, tetrakis [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (2,4-di-t-butylphenyl) phosphite and the like.
- additives may be mixed with the resin or the like when the transparent resin is produced, or may be added when the resin is synthesized.
- the addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2. parts by weight with respect to 100 parts by weight of the transparent resin. 0 parts by weight.
- the glass support is not particularly limited, and examples thereof include borosilicate glass, silicate glass, soda lime glass, and near infrared absorbing glass.
- the near-infrared absorbing glass is preferable in that the near-infrared cut characteristics can be improved and the incident angle dependency can be reduced.
- Specific examples thereof include a fluorophosphate glass and a phosphate system containing a copper component. Glass etc. are mentioned.
- the substrate (i) is a substrate including a transparent resin substrate containing the compound (A) or the like
- the transparent resin substrate can be formed by, for example, melt molding or cast molding, Furthermore, if necessary, a substrate on which an overcoat layer is laminated can be produced by coating a coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent after molding.
- a transparent resin layer such as an overcoat layer made of a curable resin or a thermoplastic resin containing the compound (A) or the like is laminated on a glass support or a resin support serving as a base.
- a transparent resin layer such as an overcoat layer made of a curable resin or a thermoplastic resin containing the compound (A) or the like is laminated on a glass support or a resin support serving as a base.
- a resin support or a base resin support for example, by spin-molding, slit-coating, ink-jet, etc., preferably by melt-molding or cast-molding a resin solution containing the compound (A) or the like on a glass support or a base resin support.
- the substrate in which the transparent resin layer is formed on the glass support or the resin support as the base by drying and removing the solvent after coating by the method, and further performing light irradiation and heating as necessary. Can be manufactured.
- melt molding a method of melt molding pellets obtained by melt-kneading a resin and a compound (A) or the like; a resin composition containing a resin and a compound (A) or the like; A method of melt-molding; or a method of melt-molding pellets obtained by removing the solvent from a resin composition containing a resin and a solvent such as compound (A).
- melt molding method include injection molding, melt extrusion molding, and blow molding.
- ⁇ Cast molding As the cast molding, a method of removing a solvent by casting a resin composition containing a resin and a solvent such as compound (A) on an appropriate support; or a compound (A) and the like, a photocurable resin and It can also be produced by a method in which a curable composition containing a thermosetting resin is cast on an appropriate support to remove the solvent and then cured by an appropriate method such as ultraviolet irradiation or heating. .
- the base material (i) is a base material made of a transparent resin substrate containing the compound (A) or the like
- the base material (i) peels the coating film from the support after cast molding.
- the substrate (i) is made of a curable resin containing the compound (A) or the like on a support such as a glass support or a resin support as a base.
- the substrate (i) can be obtained by not peeling the coating film after cast molding.
- the support examples include a glass plate, a steel belt, a steel drum, and a support made of a transparent resin (for example, a polyester film and a cyclic olefin resin film).
- a transparent resin for example, a polyester film and a cyclic olefin resin film.
- the optical component such as glass plate, quartz or transparent plastic is coated with the resin composition and the solvent is dried, or the curable composition is coated and cured and dried.
- a transparent resin layer can also be formed on the component.
- the amount of residual solvent in the transparent resin layer (transparent resin substrate) obtained by the above method should be as small as possible.
- the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight with respect to the weight of the transparent resin layer (transparent resin substrate). It is as follows. When the amount of residual solvent is in the above range, a transparent resin layer (transparent resin substrate) that can easily exhibit a desired function, in which deformation and characteristics hardly change can be obtained.
- the optical filter of the present invention preferably does not have a dielectric multilayer film from the viewpoint of warpage reduction, but at least one of the base materials (i) within a range not impairing the effects of the present invention.
- the surface may have a dielectric multilayer film.
- the dielectric multilayer film in the present invention is a film having the ability to reflect near infrared rays or a film having an antireflection effect in the visible range.
- the structure having an antireflection effect in the visible region of about 1 to 9 layers (antireflection film) on both surfaces of the substrate (i) is required when high visible light transmittance of the optical filter is required. Is preferable from the viewpoint that the visible light transmittance can be improved without greatly degrading the warpage.
- Examples of the dielectric multilayer film include those in which a high refractive index material layer and a low refractive index material layer are alternately laminated.
- a material constituting the high refractive index material layer a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected.
- Such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as the main components, and titanium oxide, tin oxide, and / or Alternatively, a material containing a small amount of cerium oxide or the like (for example, 0 to 10% by weight based on the main component) can be used.
- a material having a refractive index of 1.6 or less can be used, and a material having a refractive index of usually 1.2 to 1.6 is selected.
- examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium hexafluoride sodium.
- the method for laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed.
- a high-refractive index material layer and a low-refractive index material layer are alternately laminated directly on the substrate (i) by CVD, sputtering, vacuum deposition, ion-assisted deposition, or ion plating.
- a dielectric multilayer film can be formed.
- each of the high refractive index material layer and the low refractive index material layer is usually preferably from 0.1 ⁇ to 0.5 ⁇ , where ⁇ (nm) is the near infrared wavelength to be blocked.
- the value of ⁇ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm.
- the optical thickness obtained by multiplying the refractive index (n) by the thickness (d) (n ⁇ d) by ⁇ / 4 the high refractive index material layer, and the low refractive index.
- the thicknesses of the respective layers of the refractive index material layer are almost the same value, and there is a tendency that the blocking / transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection / refraction.
- the total number of high refractive index material layers and low refractive index material layers in the dielectric multilayer film is preferably 1 to 20 layers, more preferably 2 to 12 layers as a whole.
- Appropriate selection of thickness, stacking order, and number of stacks ensures sufficient transmittance in the visible range and sufficient light cut characteristics in the near-infrared wavelength range, and is close to the oblique direction. The reflectance when infrared rays are incident can be reduced.
- optical thin film design software for example, manufactured by Essential Macleod, Thin Film Center Co., Ltd.
- optical thin film design software for example, manufactured by Essential Macleod, Thin Film Center Co., Ltd.
- the target transmittance at a wavelength of 400 to 700 nm is set to 100%
- the target Tolerance value is set to 1
- the target transmittance at a wavelength of 705 to 950 nm is set to 0%.
- Parameter setting method such as setting Target Tolerance value to 0.5 can be mentioned.
- These parameters can change the value of Target Tolerance by further finely dividing the wavelength range according to various characteristics of the substrate (i).
- the optical filter of the present invention does not impair the effects of the present invention
- the optical filter is provided between the base material (i) and the dielectric multilayer film, on the side opposite to the surface on which the dielectric multilayer film is provided.
- the surface hardness of the substrate (i) or the dielectric multilayer film is improved, the chemical resistance is improved, the antistatic A functional film such as an antireflection film, a hard coat film, or an antistatic film can be appropriately provided for the purpose of scratch removal.
- the optical filter of the present invention may include one layer made of the functional film or two or more layers.
- the optical filter of the present invention may include two or more similar layers or two or more different layers.
- the method for laminating the functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melted in the base material (i) or the dielectric multilayer film as described above.
- a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melted in the base material (i) or the dielectric multilayer film as described above.
- Examples of the method include molding or cast molding.
- a curable composition containing the coating agent or the like on a substrate (i) or a dielectric multilayer film with a bar coater or the like and then curing it by ultraviolet irradiation or the like.
- the coating agent examples include ultraviolet (UV) / electron beam (EB) curable resins and thermosetting resins. Specifically, vinyl compounds, urethanes, urethane acrylates, acrylates, epoxy And epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.
- UV ultraviolet
- EB electron beam
- the curable composition may contain a polymerization initiator.
- a polymerization initiator a known photopolymerization initiator or a thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination.
- a polymerization initiator may be used individually by 1 type, and may use 2 or more types together.
- the blending ratio of the polymerization initiator in the curable composition is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, when the total amount of the curable composition is 100% by weight. More preferably, it is 1 to 5% by weight.
- a functional film such as an antireflective film, a hard coat film or an antistatic film having excellent curing characteristics and handleability of the curable composition and having a desired hardness. it can.
- organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used.
- organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, ⁇ -butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Examples include amides such as methylpyrrolidone.
- the thickness of the functional film is preferably 0.1 to 30 ⁇ m, more preferably 0.5 to 20 ⁇ m, and particularly preferably 0.7 to 5 ⁇ m.
- the base material (i) and the functional film and / or the dielectric multilayer film may be applied to the surface of the multilayer film.
- the optical filter of the present invention has excellent visible transmittance and near infrared ray cutting ability even when the incident angle is large. Therefore, it is useful for various ambient light sensors such as an illuminance sensor and a color correction sensor. In particular, it is useful for an ambient light sensor mounted on a digital still camera, a smartphone, a tablet terminal, a mobile phone, a wearable device, an automobile, a television, a game machine, or the like. Furthermore, it is useful as a heat ray cut filter mounted on a glass plate for windows of automobiles and buildings.
- the ambient light sensor is a sensor capable of detecting ambient brightness and color tone (such as strong red in the evening time zone) such as an illuminance sensor and a color correction sensor. For example, information detected by the ambient light sensor This makes it possible to control the illuminance and hue of the display mounted on the device.
- FIG. 1 shows an example of an ambient light sensor 200a that detects ambient brightness.
- the ambient light sensor 200a includes an optical filter 100 and a photoelectric conversion element 202.
- the photoelectric conversion element 202 generates a current and a voltage due to the photovoltaic effect when light enters the light receiving portion.
- the optical filter 100 is provided on the light receiving surface side of the photoelectric conversion element 202. By the optical filter 100, the light incident on the light receiving surface of the photoelectric conversion element 202 becomes light in the visible light band, and light in the near infrared band (800 nm to 2500 nm) is blocked.
- the ambient light sensor 200a outputs a signal in response to visible light.
- another light-transmitting layer may be interposed between the optical filter 100 and the photoelectric conversion element 202.
- a light-transmitting resin layer may be provided as a sealing material between the optical filter 100 and the photoelectric conversion element 202.
- the photoelectric conversion element 202 has a first electrode 206, a photoelectric conversion layer 208, and a second electrode 210. Further, a passivation film 216 is provided on the light receiving surface side.
- the photoelectric conversion layer 208 is formed using a semiconductor that exhibits a photoelectric effect. For example, the photoelectric conversion layer 208 is formed using a silicon semiconductor.
- the photoelectric conversion layer 208 is a diode-type element, and develops a photovoltaic force by a built-in electric field.
- the photoelectric conversion element 202 is not limited to a diode-type element, and is a photoconductive-type element (also referred to as a photoresistor, a light-dependent resistor, a photoconductor, or a photocell) or a phototransistor-type element. Also good.
- the photoelectric conversion layer 208 may be formed of a germanium semiconductor or a silicon / germanium semiconductor in addition to the silicon semiconductor. Further, as the photoelectric conversion layer 208, a compound semiconductor material such as GaP, GaAsP, CdS, CdTe, or CuInSe 2 may be used.
- the photoelectric conversion element 202 formed of a semiconductor material has sensitivity to light in the visible light band to the near infrared band. For example, in the case where the photoelectric conversion layer 208 is formed of a silicon semiconductor, the band gap energy of the silicon semiconductor is 1.12 eV, and thus, in principle, light having a wavelength of 700 to 1100 nm, which is near infrared light, can be absorbed.
- the ambient light sensor 200a is insensitive to near infrared light and has sensitivity to light in the visible light range.
- the photoelectric conversion element 202 is preferably surrounded by a light-shielding casing 204 so that light transmitted through the optical filter 100 is selectively irradiated.
- the ambient light sensor 200a can block ambient light and detect ambient light. Thereby, the trouble that the ambient light sensor 200a malfunctions in response to near infrared light can be solved.
- FIG. 2 shows an example of an ambient light sensor 200b that detects a color tone in addition to ambient brightness.
- the ambient light sensor 200b includes the optical filter 100, photoelectric conversion elements 202a to 202c, and color filters 212a to 212c.
- a color filter 212a that transmits light in the red light band is provided on the light receiving surface of the photoelectric conversion element 202a
- a color filter 212b that transmits light in the green light band is provided on the light receiving surface of the photoelectric conversion element 202b.
- a color filter 212c that transmits light in the blue light band is provided on the light receiving surface of the photoelectric conversion element 202c.
- the photoelectric conversion elements 202a to 202c have the same configuration as that shown in FIG.
- the photoelectric conversion elements 202a to 202c can independently detect the illuminance.
- a passivation film 216 may be provided between the color filters 212a to 212c and the photoelectric conversion elements 202a to 202c.
- the photoelectric conversion elements 202a to 202c have sensitivity over a wide range from the visible light wavelength region to the near infrared wavelength region. Therefore, by providing color filters 212a to 212c corresponding to the photoelectric conversion elements 202a to 202c in addition to the optical filter 100, the ambient light sensor 200b blocks near-infrared light and prevents malfunction of the sensor. The light corresponding to each color can be detected.
- the ambient light sensor 200b includes the optical filter 100 that blocks light in the near infrared region and the color filters 212a to 212c, so that it can not only spectroscopically detect ambient light into light of a plurality of wavelength bands,
- the conventional color sensor can be applied even in a dark environment where accurate detection is impossible due to the influence of near infrared rays.
- the electronic device of the present invention includes the above-described ambient light sensor of the present invention.
- the electronic apparatus of the present invention will be described below with reference to the drawings.
- FIG. 3A to 3C show an example of an electronic apparatus 300 having the ambient light sensor 200 according to an embodiment of the present invention.
- 3A is a front view
- FIG. 3B is a top view
- FIG. 3C is a detailed view illustrating the configuration of a region D surrounded by a dotted line in FIG. 3B.
- the electronic device 300 includes a housing 302, a display panel 304, a microphone unit 306, a speaker unit 308, and the ambient light sensor 200.
- the display panel 304 employs a touch panel and has an input function in addition to a display function.
- the ambient light sensor 200 is provided on the rear surface of the front panel 310 provided in the housing 302. That is, the ambient light sensor 200 does not appear in the appearance of the electronic device 300, and light enters through the translucent surface panel 310.
- the front panel 310 blocks light in the near infrared region by the optical filter 100, and light in the visible light region enters the photoelectric conversion element 202.
- the electronic device 300 can control the illuminance and color of the display panel 304 by the ambient light sensor 200.
- the optical filter 100 is provided close to the light receiving surface of the photoelectric conversion element 202, so that the illuminance is accurately measured even for light incident at a wide angle. be able to.
- Parts means “parts by weight” unless otherwise specified.
- the measurement method of each physical property value and the evaluation method of the physical property are as follows.
- the molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.
- A Weight average molecular weight in terms of standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS (Mw) and number average molecular weight (Mn) were measured.
- GPC gel permeation chromatography
- Tg Glass transition temperature
- DSC6200 differential scanning calorimeter
- ⁇ Spectral transmittance> The transmittance in each wavelength region of the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.
- the light 1 transmitted perpendicularly to the optical filter 2 is measured by the spectrophotometer 3 as shown in FIG.
- the spectrophotometer 3 transmits light 1 ′ transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG.
- the light 1 transmitted at an angle of 60 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. ′′ was measured with a spectrophotometer 3.
- ⁇ Spectral reflectance> The reflectance in each wavelength region of the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.
- optical density (OD value) The optical density (OD value) of the optical filter was obtained by calculation from the transmittance value measured using JASCO Corporation UV-Vis infrared spectrophotometer V-7300.
- the near-infrared absorbing dye used in the following examples was synthesized by a generally known method.
- Examples of the general synthesis method include, for example, Japanese Patent No. 336697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open No. 1-146846, JP-A-1-228960, JP-A-4081149, JP-A-63-124054, “Phthalocyanine—Chemistry and Function” (IPC, 1997), JP-A-2007-169315, JP2009. -108267, JP 2010-241873, JP 3699464, JP 4740631, and the like.
- the obtained resin A had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.
- NDM 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] dodec-3-ene
- Example 1 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- a resin composition (1) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- Resin composition (1) 60 parts by weight of tricyclodecane dimethanol acrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, near-infrared absorbing fine particle dispersion (manufactured by Sumitomo Metal Mining Co., Ltd.) YMF-02A, absorption maximum wavelength: 1715 nm, commercially available dispersion of second fine particles) 117 parts by weight (about 33 parts by weight in terms of solid content), methyl ethyl ketone (solvent, solid content concentration (TSC): 30%)
- the change rate of the ratio of B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- Example 2 an optical filter having a base material including a transparent glass substrate was produced according to the following procedure and conditions.
- the resin composition (1) was applied to one side of a near-infrared absorbing glass substrate “BS-11” (thickness 120 ⁇ m) manufactured by Matsunami Glass Industry Co., Ltd., cut into a size of 200 mm in length and 200 mm in width. And heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 4 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the glass substrate.
- BS-11 near-infrared absorbing glass substrate
- the resin solution (D-1) is applied onto the resin layer using a spin coater under conditions such that the thickness after drying is 2 ⁇ m, and heated on a hot plate at 80 ° C. for 5 minutes to remove the solvent. Volatile removal was performed to form a transparent resin layer, which was then baked in an oven at 230 ° C. for 20 minutes to obtain a 200 mm long and 200 mm wide base material.
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- Example 3 an optical filter having a base material composed of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- the resin composition (1) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 4 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- Example 4 an optical filter having a base material including a glass substrate was produced according to the following procedure and conditions.
- the resin composition (2) was applied to one side of a near-infrared absorbing glass substrate “BS-11” (thickness 120 ⁇ m) manufactured by Matsunami Glass Industry Co., Ltd., cut into a size of 200 mm in length and 200 mm in width by spin coating. Then, it was heated on a hot plate at 80 ° C. for 2 minutes to volatilize and remove the solvent, and a resin layer functioning as an adhesive layer with the transparent resin layer described later was formed. At this time, the spin coater coating conditions were adjusted so that the resin layer had a thickness of about 0.8 ⁇ m.
- the resin solution (D-2) is applied on the resin layer under the condition that the film thickness after drying is 2 ⁇ m using a spin coater, and heated on a hot plate at 80 ° C. for 5 minutes to remove the solvent. Volatile removal was performed to form a transparent resin layer.
- exposure was carried out from the glass surface side using a conveyor type exposure machine (exposure amount 1 J / cm 2 , illuminance 200 mW), and then baked at 230 ° C. for 20 minutes in an oven to obtain a 200 mm long and 200 mm wide base material.
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- Example 5 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- a resin composition (3) having the following composition was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- Resin composition (3) 60 parts by weight of tricyclodecane dimethanol diacrylate, 40 parts by weight of dipentaerythritol hexaacrylate, 5 parts by weight of 1-hydroxycyclohexyl phenyl ketone, methyl ethyl ketone (solvent, solid content concentration (TSC): 30% )
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- Example 6 an optical filter having a base material composed of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- the resin composition (1) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 6 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- Example 7 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- the resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- Example 8 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- the resin composition (1) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (1) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (1) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- a dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained base material, and a similar dielectric multilayer film (I) is formed on the other side of the base material.
- An optical filter of 0.104 mm was obtained.
- the dielectric multilayer film (I) is formed by alternately laminating a silica (SiO 2 ) layer and a titania (TiO 2 ) layer at a deposition temperature of 120 ° C. (a total of four layers).
- the silica layer and the titania layer of the dielectric multilayer film (I) are alternately laminated in the order of the titania layer, the silica layer, the titania layer, and the silica layer from the substrate side, and the outermost layer of the optical filter is a silica layer. .
- the dielectric multilayer film (I) was a multilayer deposited film having a number of stacks of 4 in which a silica layer having a thickness of 33 to 88 nm and a titania layer having a thickness of 13 to 111 nm were alternately stacked.
- An example of the film configuration is shown in Table 10 below.
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG. 13 and Table 13.
- Example 9 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- ⁇ Preparation of transparent resin substrate> In a container, 100 parts by weight of resin A obtained in Resin Synthesis Example 1, 0.10 parts of compound (a-3) as compound (A), 1.00 parts of compound (b-1) as compound (B) And 0.30 part of a compound represented by the following formula (b-2) (absorption maximum wavelength in dichloromethane: 850 nm) and dichloromethane were added to prepare a solution having a resin concentration of 20% by weight.
- the obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, then dried at 60 ° C. for 8 hours, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate.
- the peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm.
- the resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The evaluation results are shown in Table 13.
- Example 10 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- ⁇ Preparation of transparent resin substrate> In a container, 100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 0.10 parts of the compound (a-3) as the compound (A), and 1.00 parts of the compound (b-1) as the compound (B) And a compound represented by the following formula (b-3) (absorption maximum wavelength in dichloromethane: 886 nm) and dichloromethane were added to prepare a solution having a resin concentration of 20% by weight.
- the obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, then dried at 60 ° C. for 8 hours, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate.
- the peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm.
- the resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The evaluation results are shown in Table 13.
- Example 1 In the same method as in Example 1, a dielectric multilayer film (II) is formed as a first optical layer on one side of the obtained substrate, and a dielectric multilayer as a second optical layer is formed on the other side of the substrate. Film (III) was formed to obtain an optical filter having a thickness of about 0.109 mm.
- the dielectric multilayer film (II) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a deposition temperature of 120 ° C. (26 layers in total).
- the dielectric multilayer film (III) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a deposition temperature of 120 ° C. (20 layers in total).
- the silica layer and the titania layer are arranged in the order of the titania layer, the silica layer, the titania layer,..., The silica layer, the titania layer, and the silica layer from the substrate side.
- the outermost layer of the optical filter was a silica layer.
- the dielectric multilayer films (II) and (III) were designed as follows. Regarding the thickness and the number of layers, the wavelength-dependent characteristics of the base material refractive index and the applied compound (A) and compound (compound) so as to achieve a visible antireflection effect and a selective transmission / reflection performance in the near infrared region.
- the optical thin film design software (Essential Macleod, manufactured by Thin Film Center) was optimized according to the absorption characteristics of B).
- the input parameters (Target values) to the software are as shown in Table 11 below.
- the dielectric multilayer film (II) is formed by alternately laminating a silica layer having a film thickness of 31 to 155 nm and a titania layer having a film thickness of 10 to 94 nm.
- the dielectric multi-layer film (III) is a multi-layer vapor-deposited film having 20 layers, in which a silica layer having a thickness of 38 to 189 nm and a titania layer having a thickness of 11 to 109 nm are alternately stacked. It was.
- An example of the optimized film configuration is shown in Table 12 below.
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- the change rate of the R transmittance ratio, the change rate of the G transmittance ratio, and the change rate of the B transmittance ratio of the optical filter obtained in Comparative Example 1 were 0.6 or less and did not show a good RGB balance. It was. Further, the amount of warpage of the optical filter obtained in Comparative Example 1 was 17 mm, and did not show good warpage characteristics.
- Comparative Example 2 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- ⁇ Preparation of transparent resin substrate> In a container, 100 parts by weight of the resin A obtained in Resin Synthesis Example 1, 0.04 part of the compound (a-1) and 0.08 part of the compound (a-2) as the compound (A), as the compound (B) 0.15 parts of compound (b-1) and N, N-dimethylacetamide were added to prepare a solution having a resin concentration of 20% by weight.
- the obtained solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, then dried at 60 ° C. for 8 hours, further dried under reduced pressure at 140 ° C. for 8 hours, and then peeled off from the glass plate.
- the peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a transparent resin substrate having a thickness of 0.100 mm, a length of 200 mm, and a width of 200 mm.
- the resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- the optical density at 800 nm to 1200 nm of the optical filter obtained in Comparative Example 2 is 1.5 or less in any of 0 degree, 30 degrees, and 60 degrees, and does not show good near-infrared cut characteristics, and the ambient light sensor performance is also low.
- the hue control according to the external light environment was poor.
- Comparative Example 3 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was produced according to the following procedure and conditions.
- the resin composition (3) was applied to one side of the obtained transparent resin substrate with a bar coater and heated in an oven at 70 ° C. for 2 minutes to volatilize and remove the solvent. At this time, the coating conditions of the bar coater were adjusted so that the thickness after drying was 2 ⁇ m. Next, it exposed using the conveyor type exposure machine (exposure amount 500mJ / cm ⁇ 2 >, 200mW), the resin composition (3) was hardened, and the resin layer was formed on the substrate made from transparent resin. Similarly, a resin layer made of the resin composition (3) was formed on the other surface of the transparent resin substrate, and a base material having a resin layer on both surfaces of the transparent resin substrate containing the compound (A) was obtained. .
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- the optical density at 800 nm to 1200 nm of the optical filter obtained in Comparative Example 3 is 1.5 or less in all cases of 0 degree, 30 degrees, and 60 degrees, does not show good near infrared cut characteristics, and has an ambient light sensor performance.
- the hue control according to the external light environment was poor.
- the resin composition (2) was spin-coated on one side of a near-infrared absorbing glass substrate “BS-11” (thickness 120 ⁇ m) manufactured by Matsunami Glass Industry Co., Ltd., cut into a size of 200 mm in length and 200 mm in width. After coating, the mixture was heated on a hot plate at 80 ° C. for 2 minutes to volatilize and remove the solvent, thereby forming a resin layer functioning as an adhesive layer with the transparent resin layer described later. At this time, the spin coater coating conditions were adjusted so that the resin layer had a thickness of about 0.8 ⁇ m.
- the resin solution (D-3) is applied on the resin layer under the condition that the film thickness after drying is 5 ⁇ m using a spin coater, and heated on a hot plate at 80 ° C. for 5 minutes to remove the solvent. Volatile removal was performed to form a transparent resin layer.
- exposure was performed using a conveyor type exposure machine from the glass surface side (exposure amount 1 J / cm 2 , illuminance 200 mW), and then baked at 230 ° C. for 20 minutes in an oven to obtain a base material having a length of 200 mm and a width of 200 mm.
- the spectral transmittance from the angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter and the spectrum from the angle of 5 ° with respect to the vertical direction of the optical filter are measured, and the change rate of the ratio of the optical characteristics and the R transmittance and the change of the G transmittance in each wavelength region.
- the rate of change in the ratio of the transmittance and the B transmittance was evaluated. Further, the warpage characteristics and the ambient light sensor performance (color correction performance) of the obtained optical filter were evaluated. The results are shown in FIG.
- the optical density at 800 nm to 1200 nm of the optical filter obtained in Comparative Example 4 is 1.5 or less in all cases of 0 degree, 30 degrees, and 60 degrees, does not show good near-infrared cut characteristics, and has an ambient light sensor performance.
- the hue control according to the external light environment was poor.
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Abstract
Description
[1] 下記要件(a)を満たす基材を有し、かつ、下記要件(b)、(c)および(d)を満たすことを特徴とする環境光センサー用光学フィルター:
(a)波長650nm以上800nm未満の領域に吸収極大を有する化合物(A)、および波長800nm以上1850nm以下の領域に吸収極大を有する化合物(B)を含む層を有する;
(b)波長800~1000nmの領域において、光学フィルターの一方の面における垂直方向に対して5度斜め方向から入射する光の反射率の平均値Rfa-5と、他方の面における垂直方向に対して5度斜め方向から入射する光の反射率の平均値Rfb-5とが、いずれも15%以下である;
(c)波長430~580nmの領域において、光学フィルターの垂直方向から入射する光の透過率の平均値Ta-0と、垂直方向に対して30度斜め方向から入射する光の透過率の平均値Ta-30と、垂直方向に対して60度斜め方向から入射する光の透過率の平均値Ta-60とが、いずれも20%以上75%未満である;
(d)波長800nm~1200nmの領域において、光学フィルターの垂直方向から入射する光に対する光学濃度(OD値)の平均値ODa-0と、垂直方向に対して30度斜め方向から入射する光に対する光学濃度(OD値)の平均値ODa-30と、垂直方向に対して60度斜め方向から入射する光に対する光学濃度(OD値)の平均値ODa-60とが、いずれも1.5以上である。
A1/nCuPO4 ・・・(P-1)
式(P-1)中、Aは、アルカリ金属、アルカリ土類金属およびNH4からなる群より選ばれる少なくとも1種であり、nは、Aがアルカリ金属またはNH4の場合は1であり、Aがアルカリ土類金属の場合は2である。
MxWyOz ・・・(P-2)
式(P-2)中、Mは、H、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、BiおよびIから選ばれる少なくとも1種の元素であり、x、yおよびzは、0.001≦x/y≦1および2.2≦z/y≦3.0の条件を満たす。
エステル系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、アラミド系樹脂、ポリサルホン系樹脂、ポリエーテルサルホン系樹脂、ポリパラフェニレン系樹脂、ポリアミドイミド系樹脂、ポリエチレンナフタレート系樹脂、フッ素化芳香族ポリマー系樹脂、(変性)アクリル系樹脂、エポキシ系樹脂、シルセスキオキサン系紫外線硬化型樹脂、マレイミド系樹脂、脂環エポキシ熱硬化型樹脂、ポリエーテルエーテルケトン系樹脂、ポリアリレート系樹脂、アリルエステル系硬化型樹脂、アクリル系紫外線硬化型樹脂、ビニル系紫外線硬化型樹脂、およびゾルゲル法により形成されたシリカを主成分とする樹脂からなる群より選ばれる少なくとも1種の樹脂であることを特徴とする項[3]または[4]に記載の環境光センサー用光学フィルター。
下記式(1)から導かれるR(赤色)透過率の比の変化率、下記式(2)から導かれるG(緑色)透過率の比の変化率、および下記式(3)から導かれるB(青色)透過率の比の変化率が、いずれも0.6~1.1の範囲であることを特徴とする項[1]~[9]のいずれか1項に記載の環境光センサー用光学フィルター。
(R透過率の比)=(R透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(1)
(G透過率の比)=(G透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(2)
(B透過率の比)=(B透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(3)
式(1)~(3)中、R透過率は波長580~650nmにおける平均透過率、G透過率は波長500~580nmにおける平均透過率、B透過率は波長420~500nmにおける平均透過率である。
本発明の光学フィルターは、下記要件(a)を満たす基材(i)を有し、かつ、下記要件(b)、(c)および(d)を満たすことを特徴とする。
ある波長域における平均OD値=-Log10(ある波長域における平均透過率(%)/100)・・・式(4)
(G透過率の比)=(G透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(2)
(B透過率の比)=(B透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(3)
式(1)~(3)中、R透過率は波長580~650nmにおける平均透過率、G透過率は波長500~580nmにおける平均透過率、B透過率は波長420~500nmにおける平均透過率である。
(0°→30°の場合のR透過率の比の変化率)=(光学フィルターの垂直方向に対して30°の角度から入射した場合のR透過率の比)/(光学フィルターの垂直方向から入射した場合のR透過率の比)・・・式(5)
(0°→30°の場合のG透過率の比の変化率)=(光学フィルターの垂直方向に対して30°の角度から入射した場合のG透過率の比)/(光学フィルターの垂直方向から入射した場合のG透過率の比)・・・式(6)
(0°→30°の場合のB透過率の比の変化率)=(光学フィルターの垂直方向に対して30°の角度から入射した場合のB透過率の比)/(光学フィルターの垂直方向から入射した場合のB透過率の比)・・・式(7)
(0°→60°の場合のR透過率の比の変化率)=(光学フィルターの垂直方向に対して60°の角度から入射した場合のR透過率の比)/(光学フィルターの垂直方向から入射した場合のR透過率の比)・・・式(8)
(0°→60°の場合のG透過率の比の変化率)=(光学フィルターの垂直方向に対して60°の角度から入射した場合のG透過率の比)/(光学フィルターの垂直方向から入射した場合のG透過率の比)・・・式(9)
0°→60°の場合のG透過率の比の変化率は、好ましくは0.4以上2.0以下、より好ましくは0.5以上1.8以下、さらに好ましくは0.6以上1.6以下であり、該変化率が1.0に近いほど、RGBバランスの入射角依存変化が小さい。
(0°→60°の場合のB透過率の比の変化率)=(光学フィルターの垂直方向に対して60°の角度から入射した場合のB透過率の比)/(光学フィルターの垂直方向から入射した場合のB透過率の比)・・・式(9)
前記基材(i)は、波長650nm以上800nm未満の領域に吸収極大を有する化合物(A)を含む層を有していれば、単層であっても多層であってもよい。また、前記基材(i)は波長800nm以上1850nm以下の領域に吸収極大を有する化合物(B)を含有することが好ましく、化合物(B)は化合物(A)と同一の層に含まれていても異なる層に含まれていてもよい。以下、化合物(A)および化合物(B)から選ばれる少なくとも1種の化合物と透明樹脂とを含有する層を「透明樹脂層」ともいい、それ以外の樹脂層を単に「樹脂層」ともいう。
前記化合物(A)は、波長650nm以上800nm未満の領域に吸収極大があれば特に限定されないが、スクアリリウム系化合物、フタロシアニン系化合物、ナフタロシアニン系化合物、クロコニウム系化合物およびシアニン系化合物からなる群より選ばれる少なくとも1種の化合物であることが好ましく、特にスクアリリウム系化合物、フタロシアニン系化合物およびシアニン系化合物が好ましい。なお、化合物(A)は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。
前記スクアリリウム系化合物としては、特に限定されるものではないが、下記式(I)で表されるスクアリリウム系化合物および下記式(II)で表されるスクアリリウム系化合物からなる群より選ばれる少なくとも1種の化合物が好ましい。以下、それぞれ「化合物(I)」および「化合物(II)」ともいう。
複数あるRaはそれぞれ独立に、水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、-L1または-NReRf基を表し;
複数あるRbはそれぞれ独立に、水素原子、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基、-L1または-NRgRh基を表し;
複数あるYaはそれぞれ独立に、-NRjRk基を表し;
L1は、La、Lb、Lc、Ld、Le、Lf、LgまたはLhを表し;
ReおよびRfはそれぞれ独立に、水素原子、-La、-Lb、-Lc、-Ldまたは-Leを表し;
RgおよびRhはそれぞれ独立に、水素原子、-La、-Lb、-Lc、-Ld、-Leまたは-C(O)Ri基(Riは、-La、-Lb、-Lc、-Ldまたは-Leを表す。)を表し;
RjおよびRkはそれぞれ独立に、水素原子、-La、-Lb、-Lc、-Ldまたは-Leを表し;
Laは、置換基Lを有してもよい炭素数1~12の脂肪族炭化水素基を表し;
Lbは、置換基Lを有してもよい炭素数1~12のハロゲン置換アルキル基を表し;
Lcは、置換基Lを有してもよい炭素数3~14の脂環式炭化水素基を表し;
Ldは、置換基Lを有してもよい炭素数6~14の芳香族炭化水素基を表し;
Leは、置換基Lを有してもよい炭素数3~14の複素環基を表し;
Lfは、置換基Lを有してもよい炭素数1~9のアルコキシ基を表し;
Lgは、置換基Lを有してもよい炭素数1~9のアシル基を表し;
Lhは、置換基Lを有してもよい炭素数1~9のアルコキシカルボニル基を表し;
Lは、炭素数1~12の脂肪族炭化水素基、炭素数1~12のハロゲン置換アルキル基、炭素数3~14の脂環式炭化水素基、炭素数6~14の芳香族炭化水素基、炭素数3~14の複素環基、ハロゲン原子、スルホ基、水酸基、シアノ基、ニトロ基、カルボキシ基、リン酸基およびアミノ基からなる群より選ばれる少なくとも1種の置換基を表す。
1つのベンゼン環上の2つのRaのうちの少なくとも1つが、同じベンゼン環上のYと相互に結合して、窒素原子を少なくとも1つ含む構成原子数5または6の複素環を形成する;
前記複素環は置換基を有していてもよく、Rbおよび前記複素環の形成に関与しないRaは、それぞれ独立に前記条件(α)のRbおよびRaと同義である。
前記式(II)において、隣り合うRd同士は連結して環を形成してもよい。このような環としては、例えば、ベンゾインドレニン環、α-ナフトイミダゾール環、β-ナフトイミダゾール環、α-ナフトオキサゾール環、β-ナフトオキサゾール環、α-ナフトチアゾール環、β-ナフトチアダゾール環、α-ナフトセレナゾール環、β-ナフトセレナゾール環を挙げることができる。
前記フタロシアニン系化合物は、特に限定されるものではないが、下記式(III)で表される化合物(以下「化合物(III)」ともいう。)であることが好ましい。
L1は、前記式(I)において定義したL1と同義であり、
L2は、水素原子または前記式(I)において定義したLa~Leのいずれかを表し、
L3は、水酸基または前記La~Leのいずれかを表し、
L4は、前記La~Leのいずれかを表す。
前記Mにおいて、2価の金属原子としては、Be、Mg、Ca、Ba、Ti、Cr、Mn、Fe、Ru、Co、Rh、Ni、Pd、Pt、Cu、Zn、Cd、Hg、Sn、Pbなどが挙げられる。
前記シアニン系化合物は、特に限定されるものではないが、下記式(IV-1)~(IV-3)のいずれかで表される化合物(以下「化合物(IV-1)~(IV-3)」ともいう。)であることが好ましい。
L1は、前記式(I)において定義したL1と同義であり、
L2は、水素原子または前記式(I)において定義したLa~Leのいずれかを表し、
L3は、水素原子または前記La~Leのいずれかを表し、
L4は、前記La~Leのいずれかを表し、
Za~ZcおよびYa~Ydはそれぞれ独立に、水素原子、ハロゲン原子、水酸基、カルボキシ基、ニトロ基、アミノ基、アミド基、イミド基、シアノ基、シリル基、-L1、-S-L2、-SS-L2、-SO2-L3、-N=N-L4(L1~L4は、前記Ra~RiにおけるL1~L4と同義である。)、または、これらのうち隣接した二つから選ばれるZ同士もしくはY同士が相互に結合して形成される、炭素数6~14の芳香族炭化水素基;窒素原子、酸素原子もしくは硫黄原子を少なくとも1つ含んでもよい5乃至6員環の脂環式炭化水素基;もしくは、窒素原子、酸素原子もしくは硫黄原子を少なくとも1つ含む、炭素数3~14の複素芳香族炭化水素基を表し、これらの芳香族炭化水素基、脂環式炭化水素基および複素芳香族炭化水素基は、炭素数1~9の脂肪族炭化水素基またはハロゲン原子を有してもよい。
前記化合物(B)としては、波長800nm以上1850nm以下の領域に吸収極大を有すれば特に限定されないが、近赤外線吸収微粒子、スクアリリウム系化合物、フタロシアニン系化合物、ナフタロシアニン系化合物、クロコニウム系化合物、シアニン系化合物、ジイモニウム系化合物、金属ジチオラート系化合物およびピロロピロール系化合物からなる群より選ばれる少なくとも1種の化合物であることが好ましい。環境光センサーは、通常、可視光領域以外にも1200nm付近まで感度を有しており、可視光領域以外の波長の光が環境光センサーに入光すると誤作動や、周辺光環境に応じた色合い制御が適切に行われなくなる問題がある。そのため、化合物(B)としては近赤外線領域に幅広い吸収を持つ化合物を使用することが好ましく、上記化合物の中では、近赤外線吸収微粒子、シアニン系化合物、ジイモニウム系化合物およびスクアリリウム系化合物がさらに好ましく、近赤外線吸収微粒子としてはCsxWyOzが最も好ましい。なお、化合物(B)は、1種単独で用いてもよく、2種以上を組み合わせて用いてもよい。このような化合物(B)を用いることにより、幅広い近赤外波長領域における吸収特性と優れた可視光透過率を達成することができる。
前記ジイモニウム系化合物は、特に限定されるものではないが、例えば、下記式(s1)で表わされる化合物が好ましい。
(La)炭素数1~12の脂肪族炭化水素基
(Lb)炭素数1~12のハロゲン置換アルキル基
(Lc)炭素数3~14の脂環式炭化水素基
(Ld)炭素数6~14の芳香族炭化水素基
(Le)炭素数3~14の複素環基
(Lf)炭素数1~12のアルコキシ基
(Lg)置換基Lを有してもよい炭素数1~12のアシル基、
(Lh)置換基Lを有してもよい炭素数1~12のアルコキシカルボニル基
置換基Lは、炭素数1~12の脂肪族炭化水素基、炭素数1~12のハロゲン置換アルキル基、炭素数3~14の脂環式炭化水素基、炭素数6~14の芳香族炭化水素基および炭素数3~14の複素環基からなる群より選ばれる少なくとも1種であり、nは0~4の整数、Xは電荷を中和させるのに必要なアニオンを表す。
前記金属ジチオラート系化合物は、特に限定されるものではないが、例えば、下記式(s2)で表わされる化合物が好ましい。
前記Dは、好ましくは窒素原子、リン原子であり、前記Riは、好ましくはエチル基、n-プロピル基、イソプロピル基、n-ブチル基、sec-ブチル基、tert-ブチル基、n-ペンチル基、n-ヘキシル基、n-ヘプチル基、フェニル基である。
前記化合物(B)(ただし、近赤外線吸収微粒子を除く。)の市販品としては、S2058(DKSH製)、CIR-108x、CIR-96x、CIR-RL、CIR-1080(日本カーリット製)、T090821、T091021、T89021,T090721、T090122(トスコ製)、B4360、D4773、D5013(東京化成工業製)、S4253、S1426、S1445(スペクトラムインフォ製)、Excolor IR1、IR2 、IR3 、IR4(日本触媒製)などを挙げることができる。
前記近赤外線吸収微粒子は、波長800nm以上1850nm以下の領域に吸収を有するものであれば特に制限されない。このような近赤外線吸収微粒子としては、例えば、ITO(スズドープ酸化インジウム)、ATO(アンチモンドープ酸化スズ)、GZO(ガリウムドープ酸化亜鉛)などの透明導電性酸化物や、下記式(P-1)で表わされる化合物からなる第1の微粒子や下記式(P-2)で表わされる化合物からなる第2の微粒子を挙げることができ、吸収-透過特性の観点から特に第1の微粒子及び第2の微粒子が好ましい。
式(P-1)中、Aは、アルカリ金属、アルカリ土類金属およびNH4からなる群より選ばれる少なくとも1種であり、nは、Aがアルカリ金属またはNH4の場合は1であり、Aがアルカリ土類金属の場合は2である。
式(P-2)中、Mは、H、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、Bi、Iであり、Mが複数ある場合は別々の原子でもよく、x、yおよびzは、0.001≦x/y≦1および2.2≦z/y≦3.0の条件を満たす。
チタネート系カップリング剤としては、アシロキシ基、ホスホキシ基、ピロホスホキシ基、スルホキシ基、アリーロキシ基等を有するものが挙げられる。
ジルコアルミネート系カップリング剤としては、アミノ基、メルカプト基、アルキル基、アルケニル基等を有するものが挙げられる。
第1の微粒子は、上記式(P-1)で表わされる化合物の結晶構造(結晶子)に起因する近赤外線吸収特性を有する。
近赤外線吸収微粒子は、結晶子がA1/nCuPO4の結晶構造を十分に維持することによって、十分な近赤外線吸収特性を発現できる。よって、結晶子の表面に水または水酸基が付着した場合、A1/nCuPO4の結晶構造を維持できなくなるため、可視光領域と近赤外波長領域の光の透過率の差が減少し、光学フィルター用途として好適に使用できない。
三酸化タングステン(WO3)のタングステンに対する酸素の比率を3より低減し、特定の組成範囲とすることによって当該タングステン酸化物中に自由電子が生成し、近赤外線吸収材料として良好な特性を達成できることが知られている。
前記透明樹脂としては、本発明の効果を損なわないものである限り特に制限されないが、例えば、熱安定性およびフィルムへの成形性を確保するため、ガラス転移温度(Tg)が、好ましくは110~380℃、より好ましくは110~370℃、さらに好ましくは120~360℃である樹脂が挙げられる。また、リフロー工程に好適であるため前記樹脂のガラス転移温度が140℃以上であると好ましく、230℃以上であるとより好ましい。
環状ポリオレフィン系樹脂としては、下記式(X0)で表される単量体および下記式(Y0)で表される単量体からなる群より選ばれる少なくとも1種の単量体から得られる樹脂、および当該樹脂を水素添加することで得られる樹脂が好ましい。
(i')水素原子
(ii')ハロゲン原子
(iii')トリアルキルシリル基
(iv')酸素原子、硫黄原子、窒素原子またはケイ素原子を含む連結基を有する、置換または非置換の炭素数1~30の炭化水素基
(v')置換または非置換の炭素数1~30の炭化水素基
(vi')極性基(但し、(iv')を除く。)
(vii')Rx1とRx2またはRx3とRx4とが、相互に結合して形成されたアルキリデン基(但し、前記結合に関与しないRx1~Rx4は、それぞれ独立に前記(i')~(vi')より選ばれる原子または基を表す。)
(viii')Rx1とRx2またはRx3とRx4とが、相互に結合して形成された単環もしくは多環の炭化水素環または複素環(但し、前記結合に関与しないRx1~Rx4は、それぞれ独立に前記(i')~(vi')より選ばれる原子または基を表す。)
(ix')Rx2とRx3とが、相互に結合して形成された単環の炭化水素環または複素環(但し、前記結合に関与しないRx1とRx4は、それぞれ独立に前記(i')~(vi')より選ばれる原子または基を表す。)
芳香族ポリエーテル系樹脂は、下記式(1)で表される構造単位および下記式(2)で表される構造単位からなる群より選ばれる少なくとも1種の構造単位を有することが好ましい。
ポリイミド系樹脂としては、特に制限されず、繰り返し単位にイミド結合を含む高分子化合物であればよく、例えば、特開2006-199945号公報や特開2008-163107号公報に記載されている方法で合成することができる。
フルオレンポリカーボネート系樹脂としては、特に制限されず、フルオレン部位を含むポリカーボネート樹脂であればよく、例えば、特開2008-163194号公報に記載されている方法で合成することができる。
フルオレンポリエステル系樹脂としては、特に制限されず、フルオレン部位を含むポリエステル樹脂であればよく、例えば、特開2010-285505号公報や特開2011-197450号公報に記載されている方法で合成することができる。
フッ素化芳香族ポリマー系樹脂としては、特に制限されないが、フッ素原子を少なくとも1つ有する芳香族環と、エーテル結合、ケトン結合、スルホン結合、アミド結合、イミド結合およびエステル結合からなる群より選ばれる少なくとも1つの結合を含む繰り返し単位とを含有するポリマーであることが好ましく、例えば特開2008-181121号公報に記載されている方法で合成することができる。
アクリル系紫外線硬化型樹脂としては、特に制限されないが、分子内に一つ以上のアクリル基もしくはメタクリル基を有する化合物と、紫外線によって分解して活性ラジカルを発生させる化合物を含有する樹脂組成物から合成されるものを挙げることができる。アクリル系紫外線硬化型樹脂は、前記基材(i)として、ガラス支持体上やベースとなる樹脂製支持体上に化合物(A)および硬化性樹脂を含む透明樹脂層(光吸収層)が積層された基材や、化合物(A)を含有する透明樹脂製基板上に硬化性樹脂等からなるオーバーコート層などの樹脂層が積層された基材を用いる場合、該硬化性樹脂として特に好適に使用することができる。
ゾルゲル法によるシリカを主成分とする樹脂としては、テトラメトキシシラン、テトラエトキシシラン、ジメトキシジエトキシラン、メトキシトリエトキシシランなどのテトラアルコキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン、ジフェニルジメトキシシラン、ジフェニルジエトキシシランなどのフェニルアルコキシシラン等から選ばれる1種以上のシラン類の加水分解によるゾルゲル反応により得られる化合物を樹脂として使用することができる。
透明樹脂の市販品としては、以下の市販品等を挙げることができる。環状ポリオレフィン系樹脂の市販品としては、JSR(株)製アートン、日本ゼオン(株)製ゼオノア、三井化学(株)製APEL、ポリプラスチックス(株)製TOPASなどを挙げることができる。ポリエーテルサルホン系樹脂の市販品としては、住友化学(株)製スミカエクセルPESなどを挙げることができる。ポリイミド系樹脂の市販品としては、三菱ガス化学(株)製ネオプリムLなどを挙げることができる。ポリカーボネート系樹脂の市販品としては、帝人(株)製ピュアエースなどを挙げることができる。フルオレンポリカーボネート系樹脂の市販品としては、三菱ガス化学(株)製ユピゼータEP-5000などを挙げることができる。フルオレンポリエステル系樹脂の市販品としては、大阪ガスケミカル(株)製OKP4HTなどを挙げることができる。アクリル系樹脂の市販品としては、(株)日本触媒製アクリビュアなどを挙げることができる。シルセスキオキサン系紫外線硬化型樹脂の市販品としては、新日鐵化学(株)製シルプラスなどを挙げることができる。
前記基材(i)は、本発明の効果を損なわない範囲において、さらに酸化防止剤、近紫外線吸収剤および蛍光消光剤等の添加剤を含有してもよい。これらその他成分は、1種単独で用いてもよいし、2種以上を併用してもよい。
前記酸化防止剤としては、例えば2,6-ジ-t-ブチル-4-メチルフェノール、2,2'-ジオキシ-3,3'-ジ-t-ブチル-5,5'-ジメチルジフェニルメタン、テトラキス[メチレン-3-(3,5-ジ-t-ブチル-4-ヒドロキシフェニル)プロピオネート]メタン、およびトリス(2,4-ジ-t-ブチルフェニル)ホスファイトなどが挙げられる。
≪樹脂製支持体≫
前記透明樹脂基板または樹脂製支持体に用いられる樹脂は、前記透明樹脂層と同様のものを用いることができる。
前記ガラス支持体としては、特に限定されないが、例えば、ホウケイ酸塩系ガラス、ケイ酸塩系ガラス、ソーダ石灰ガラス、および近赤外線吸収ガラスなどが挙げられる。前記近赤外線吸収ガラスは、近赤外カット特性を向上できる点と入射角依存性を低減できる点で好ましく、その具体例としては、銅成分を含有するフッ素リン酸塩系ガラスおよびリン酸塩系ガラスなどが挙げられる。
前記基材(i)が、前記化合物(A)等を含有する透明樹脂製基板を含む基材である場合、該透明樹脂製基板は、例えば、溶融成形またはキャスト成形により形成することができ、さらに、必要により、成形後に、反射防止剤、ハードコート剤および/または帯電防止剤等のコーティング剤をコーティングすることで、オーバーコート層が積層された基材を製造することができる。
前記溶融成形としては、具体的には、樹脂と化合物(A)等とを溶融混練りして得られたペレットを溶融成形する方法;樹脂と化合物(A)等とを含有する樹脂組成物を溶融成形する方法;または、化合物(A)等、樹脂および溶剤を含む樹脂組成物から溶剤を除去して得られたペレットを溶融成形する方法などが挙げられる。溶融成形方法としては、射出成形、溶融押出成形またはブロー成形などを挙げることができる。
前記キャスト成形としては、化合物(A)等、樹脂および溶剤を含む樹脂組成物を適当な支持体の上にキャスティングして溶剤を除去する方法;または化合物(A)等と、光硬化性樹脂および/または熱硬化性樹脂とを含む硬化性組成物を適当な支持体の上にキャスティングして溶媒を除去した後、紫外線照射や加熱などの適切な手法により硬化させる方法などにより製造することもできる。
本発明の光学フィルターは、上述したように、反り低減の観点から誘電体多層膜を有さないことが好ましいが、本発明の効果を損なわない範囲で、前記基材(i)の少なくとも一方の面に誘電体多層膜を有してもよい。本発明における誘電体多層膜とは、近赤外線を反射する能力を有する膜または可視域における反射防止効果を有する膜である。本発明において、前記基材(i)の両面に1~9層程度の可視域の反射防止効果を有する膜(反射防止膜)を有する構成は、光学フィルターの高可視光透過率が求められる場合には、反りを大きく悪化させることなく、可視光透過率を向上させることができるという観点で好ましい。
本発明の光学フィルターは、本発明の効果を損なわない範囲において、基材(i)と誘電体多層膜との間、基材(i)の誘電体多層膜が設けられた面と反対側の面、または誘電体多層膜の基材(i)が設けられた面と反対側の面に、基材(i)や誘電体多層膜の表面硬度の向上、耐薬品性の向上、帯電防止および傷消しなどの目的で、反射防止膜、ハードコート膜や帯電防止膜などの機能膜を適宜設けることができる。
前記機能膜の厚さは、好ましくは0.1~30μm、さらに好ましくは0.5~20μm、特に好ましくは0.7~5μmである。
本発明の光学フィルターは、入射角度が大きい場合においても優れた可視透過率と近赤外線カット能を有する。したがって、照度センサーや色補正用センサーなどの各種環境光センサー用として有用である。特に、デジタルスチルカメラ、スマートフォン、タブレット端末、携帯電話、ウェアラブルデバイス、自動車、テレビ、ゲーム機等に搭載される環境光センサー用として有用である。さらに、自動車や建物等の窓用ガラス板等に装着される熱線カットフィルターなどとしても有用である。
上述した本発明の光学フィルターと、光電変換素子を組み合わせて環境光センサーとして用いることができる。ここで、環境光センサーとは、照度センサーや色補正用センサーなど周囲の明るさや色調(夕方の時間帯で赤色が強いなど)を感知可能なセンサーであり、例えば、環境光センサーで感知した情報により機器に搭載されているディスプレイの照度や色合いを制御することが可能である。
本発明の電子機器は上述した本発明の環境光センサーを含む。以下、図面を参照しながら、本発明の電子機器について説明する。
樹脂の分子量は、各樹脂の溶剤への溶解性等を考慮し、下記の(a)または(b)の方法にて測定を行った。
エスアイアイ・ナノテクノロジーズ株式会社製の示差走査熱量計(DSC6200)を用いて、昇温速度:毎分20℃、窒素気流下で測定した。
光学フィルターの各波長域における透過率は、株式会社日立ハイテクノロジーズ製の分光光度計(U-4100)を用いて測定した。
光学フィルターの各波長域における反射率は、株式会社日立ハイテクノロジーズ製の分光光度計(U-4100)を用いて測定した。
光学フィルターの光学濃度(OD値)は、日本分光株式会社 紫外可視赤外分光光度計V-7300を用いて測定した透過率の値から計算により求めた。
縦200mm×横200mmの光学フィルターを平らなガラス板上に静置し、光学フィルターの角がガラス板上から反りあがった垂直高さを反りとして、定規を用いて測定した。光学フィルターの四隅について、反りを測定し、四隅の反りの平均値を反り量とした。反り量が10mm以下の場合、反り特性「○」と評価し、10mm以上の場合、反り特性「×」と評価した。
Apple社製「iPad(登録商標) Pro 9.7インチ」の環境光センサーモジュールの近赤外線カットフィルターを取り出し、代わりに、後述の実施例および比較例で作製した光学フィルターを環境光センサーモジュールに組み込み、日中の外光、夕方の外光、明るい室内、および暗い室内で画面の色調変化を観察し、外光環境(明るさ、色調)に応じた色合いの制御具合によって環境光センサー性能を評価した。外光環境に応じて適切に色合い制御ができる場合を「○」、一部色合い制御に問題がある場合を「△」、色合い制御が不良である場合を「×」とした。
3Lの4つ口フラスコに2,6-ジフルオロベンゾニトリル35.12g(0.253mol)、9,9-ビス(4-ヒドロキシフェニル)フルオレン87.60g(0.250mol)、炭酸カリウム41.46g(0.300mol)、N,N-ジメチルアセトアミド(以下「DMAc」ともいう。)443gおよびトルエン111gを添加した。続いて、4つ口フラスコに温度計、撹拌機、窒素導入管付き三方コック、ディーンスターク管および冷却管を取り付けた。次いで、フラスコ内を窒素置換した後、得られた溶液を140℃で3時間反応させ、生成する水をディーンスターク管から随時取り除いた。水の生成が認められなくなったところで、徐々に温度を160℃まで上昇させ、そのままの温度で6時間反応させた。室温(25℃)まで冷却後、生成した塩をろ紙で除去し、ろ液をメタノールに投じて再沈殿させ、ろ別によりろ物(残渣)を単離した。得られたろ物を60℃で一晩真空乾燥し、白色粉末(以下「樹脂A」ともいう。)を得た(収率95%)。得られた樹脂Aは、数平均分子量(Mn)が75,000、重量平均分子量(Mw)が188,000であり、ガラス転移温度(Tg)が285℃であった。
下記式(8)で表される8-メチル-8-メトキシカルボニルテトラシクロ[4.4.0.12,5.17,10]ドデカ-3-エン(以下「DNM」ともいう。)100部、1-ヘキセン(分子量調節剤)18部およびトルエン(開環重合反応用溶媒)300部を、窒素置換した反応容器に仕込み、この溶液を80℃に加熱した。次いで、反応容器内の溶液に、重合触媒として、トリエチルアルミニウムのトルエン溶液(0.6mol/リットル)0.2部と、メタノール変性の六塩化タングステンのトルエン溶液(濃度0.025mol/リットル)0.9部とを添加し、この溶液を80℃で3時間加熱攪拌することにより開環重合反応させて開環重合体溶液を得た。この重合反応における重合転化率は97%であった。
実施例1では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例1で得られた樹脂A 100重量部、化合物(A)として
下記式(a-1)で表わされる化合物(a-1)(ジクロロメタン中での吸収極大波長713nm)0.04部、
下記式(a-2)で表わされる化合物(a-2)(ジクロロメタン中での吸収極大波長736nm)0.08部、および
下記式(a-3)で表わされる化合物(a-3)(ジクロロメタン中での吸収極大波長776nm)0.10部、
化合物(B)として、日本カーリット社製の光吸収剤「CIR-RL」(吸収極大波長;1095nm、以下「化合物(b-1)」ともいう。)1.50部、
ならびにN,N-ジメチルアセトアミドを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、下記組成の樹脂組成物(1)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(1)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(1)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
実施例2では、透明ガラス基板を含む基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例2で得られた樹脂B 100重量部、化合物(A)として、
化合物(a-1)2.00部、
化合物(a-2)4.00部、および
化合物(a-3)5.00部、
化合物(B)として、化合物(b-1)15.00部、
ならびにジクロロメタンを加えて樹脂濃度が10重量%の溶液を調製した。その後、孔径5μmのミリポアフィルタでろ過して樹脂溶液(D-1)を得た。
続いて、縦200mm、横200mmの大きさにカットした、松波硝子工業(株)製近赤外線吸収ガラス基板「BS-11」(厚み120μm)の片面に、前記樹脂組成物(1)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが4μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(1)を硬化させ、ガラス基板上に樹脂層を形成した。
実施例3では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例2で得られた樹脂B 100重量部、化合物(A)として、化合物(a-3)0.04部、化合物(B)として、化合物(b-1)0.15部、およびジクロロメタンを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、前記樹脂組成物(1)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが4μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(1)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(1)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
実施例4では、ガラス基板を含む基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例1で得られた樹脂A 100重量部、化合物(A)として、化合物(a-3)10.00部、化合物(B)として、化合物(b-1)22.50部、およびジクロロメタンを加えて樹脂濃度が10重量%の溶液を調製した。その後、孔径5μmのミリポアフィルタでろ過して樹脂溶液(D-2)を得た。
イソシアヌル酸エチレンオキサイド変性トリアクリレート(商品名:アロニックスM-315、東亜合成化学(株)製)30重量部、1,9-ノナンジオールジアクリレート20重量部、メタクリル酸20重量部、メタクリル酸グリシジル30重量部、3-グリシドキシプロピルトリメトキシシラン5重量部、1-ヒドロキシシクロヘキシルベンゾフェノン(商品名:IRGACURE184、チバ・スペシャリティ・ケミカル(株)製)5重量部およびサンエイドSI-110主剤(三新化学工業(株)製)1重量部を混合し、固形分濃度が50wt%になるようにプロピレングリコールモノメチルエーテルアセテートに溶解した後、孔径0.2μmのミリポアフィルタでろ過し、樹脂組成物(2)を調製した。
続いて、縦200mm、横200mmの大きさにカットした、松波硝子工業(株)製近赤外線吸収ガラス基板「BS-11」(厚み120μm)の片面に樹脂組成物(2)をスピンコートで塗布した後、ホットプレート上80℃で2分間加熱し溶剤を揮発除去し、後述する透明樹脂層との接着層として機能する樹脂層を形成した。この際、該樹脂層の膜厚が0.8μm程度となるようにスピンコーターの塗布条件を調整した。次に、樹脂層上に、スピンコーターを用いて樹脂溶液(D-2)を乾燥後の膜厚が2μm となるような条件で塗布し、ホットプレート上80℃で5分間加熱し、溶剤を揮発除去して透明樹脂層を形成した。次いで、ガラス面側からコンベア式露光機を用いて露光(露光量1J/cm2、照度200mW)し、その後オーブン中230℃で20分間焼成して縦200mm、横200mmの基材を得た。
実施例5では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例2で得られた樹脂B 100重量部、化合物(A)として、化合物(a-3)0.10部、化合物(B)として、化合物(b-1)1.50部、およびジクロロメタンを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、下記組成の樹脂組成物(3)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(3)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(3)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
実施例6では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例1で得られた樹脂A 100重量部、化合物(A)として、化合物(a-1)0.02部および化合物(a-2)0.04部、ならびにN,N-ジメチルアセトアミドを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、前記樹脂組成物(1)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが6μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(1)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(1)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
実施例7では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例1で得られた樹脂B 100重量部、化合物(A)として、化合物(a-1)0.03部および化合物(a-2)0.06部、化合物(B)として化合物(b-1)0.60部、ならびにジクロロメタンを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、前記樹脂組成物(3)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(3)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(3)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
実施例8では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例1で得られた樹脂B 100重量部、化合物(A)として
化合物(a-1)0.04部、
化合物(a-2)0.08部、および
化合物(a-3)0.10部、
化合物(B)として化合物(b-1)1.50部、
ならびにジクロロメタンを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、前記樹脂組成物(1)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(1)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(1)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
得られた基材の片面に第一光学層として誘電体多層膜(I)を形成し、さらに基材のもう一方の面にも同様の誘電体多層膜(I)を形成し、厚さ約0.104mmの光学フィルターを得た。
実施例9では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例1で得られた樹脂A 100重量部、化合物(A)として、化合物(a-3)0.10部、化合物(B)として、化合物(b-1)1.00部と下記式(b-2)で表わされる化合物(ジクロロメタン中での吸収極大波長850nm)0.30部およびジクロロメタンを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、前記樹脂組成物(3)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(3)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(3)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
実施例10では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例2で得られた樹脂B 100重量部、化合物(A)として、化合物(a-3)0.10部、化合物(B)として、化合物(b-1)1.00部と下記式(b-3)で表わされる化合物(ジクロロメタン中での吸収極大波長886nm)0.10部およびジクロロメタンを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、前記樹脂組成物(3)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(3)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(3)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
実施例1と同様の方法において、得られた基材の片面に第一光学層として誘電体多層膜(II)を形成し、さらに基材のもう一方の面に第二光学層として誘電体多層膜(III)を形成し、厚さ約0.109mmの光学フィルターを得た。
各層の厚さと層数については、可視域の反射防止効果と近赤外域の選択的な透過・反射性能を達成できるよう基材屈折率の波長依存特性や、適用した化合物(A)および化合物(B)の吸収特性に合わせて光学薄膜設計ソフト(Essential Macleod、Thin Film Center社製)を用いて最適化を行った。最適化を行う際、本実施例においてはソフトへの入力パラメーター(Target値)を下記表11の通りとした。
比較例2では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例1で得られた樹脂A 100重量部、化合物(A)として、化合物(a-1)0.04部および化合物(a-2)0.08部、化合物(B)として化合物(b-1)0.15部、ならびにN,N-ジメチルアセトアミドを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、前記樹脂組成物(3)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(3)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(3)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
比較例3では、両面に樹脂層を有する透明樹脂製基板からなる基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例2で得られた樹脂B 100重量部、化合物(A)として、化合物(a-1)0.04部および(a-2)0.08部、およびジクロロメタンを加えて樹脂濃度が20重量%の溶液を調製した。得られた溶液を平滑なガラス板上にキャストし、60℃で8時間乾燥した後、60℃で8時間乾燥、さらに減圧下140℃で8時間乾燥した後、ガラス板から剥離した。剥離した塗膜をさらに減圧下100℃で8時間乾燥して、厚さ0.100mm、縦200mm、横200mmの透明樹脂製基板を得た。
得られた透明樹脂製基板の片面に、前記樹脂組成物(3)をバーコーターで塗布し、オーブン中70℃で2分間加熱し、溶剤を揮発除去した。この際、乾燥後の厚みが2μmとなるように、バーコーターの塗布条件を調整した。次に、コンベア式露光機を用いて露光(露光量500mJ/cm2,200mW)を行い、樹脂組成物(3)を硬化させ、透明樹脂製基板上に樹脂層を形成した。同様に、透明樹脂製基板のもう一方の面にも樹脂組成物(3)からなる樹脂層を形成し、化合物(A)を含む透明樹脂製基板の両面に樹脂層を有する基材を得た。
比較例では、ガラス基板を含む基材を有する光学フィルターを以下の手順および条件で作製した。
容器に、樹脂合成例2で得られた樹脂B 100重量部、化合物(A)として、化合物(a-1)0.8部および化合物(a-2)1.6部、およびジクロロメタンを加えて樹脂濃度が10重量%の溶液を調製した。その後、孔径5μmのミリポアフィルタでろ過して樹脂溶液(D-3)を得た。
続いて、縦200mm、横200mmの大きさにカットした、松波硝子工業(株)製近赤外線吸収ガラス基板「BS-11」(厚み120μm)の片面に前記樹脂組成物(2)をスピンコートで塗布した後、ホットプレート上80℃で2分間加熱し溶剤を揮発除去し、後述する透明樹脂層との接着層として機能する樹脂層を形成した。この際、該樹脂層の膜厚が0.8μm程度となるようにスピンコーターの塗布条件を調整した。次に、樹脂層上に、スピンコーターを用いて樹脂溶液(D-3)を乾燥後の膜厚が5μm となるような条件で塗布し、ホットプレート上80℃で5分間加熱し、溶剤を揮発除去して透明樹脂層を形成した。次いで、ガラス面側からコンベア式露光機を用いて露光(露光量1J/cm2、照度200mW)し、その後オーブン中230℃で20分間焼成して縦200mm、横200mmの基材を得た。
200・・・環境光センサー
202・・・光電変換素子
204・・・筐体
206・・・第1電極
208・・・光電変換層
210・・・第2電極
212・・・カラーフィルタ
214・・・素子分離絶縁層
216・・・パッシベーション膜
300・・・電子機器
302・・・筐体
304・・・表示パネル
306・・・マイクロホン部
308・・・スピーカ部
310・・・表面パネル
Claims (12)
- 下記要件(a)を満たす基材を有し、かつ、下記要件(b)、(c)および(d)を満たすことを特徴とする環境光センサー用光学フィルター:
(a)波長650nm以上800nm未満の領域に吸収極大を有する化合物(A)、および波長800nm以上1850nm以下の領域に吸収極大を有する化合物(B)を含む層を有する;
(b)波長800~1000nmの領域において、光学フィルターの一方の面における垂直方向に対して5度斜め方向から入射する光の反射率の平均値Rfa-5と、他方の面における垂直方向に対して5度斜め方向から入射する光の反射率の平均値Rfb-5とが、いずれも15%以下である;
(c)波長430~580nmの領域において、光学フィルターの垂直方向から入射する光の透過率の平均値Ta-0と、垂直方向に対して30度斜め方向から入射する光の透過率の平均値Ta-30と、垂直方向に対して60度斜め方向から入射する光の透過率の平均値Ta-60とが、いずれも20%以上75%未満である;
(d)波長800nm~1200nmの領域において、光学フィルターの垂直方向から入射する光に対する光学濃度(OD値)の平均値ODa-0と、垂直方向に対して30度斜め方向から入射する光に対する光学濃度(OD値)の平均値ODa-30と、垂直方向に対して60度斜め方向から入射する光に対する光学濃度(OD値)の平均値ODa-60とが、いずれも1.5以上である。 - 誘電体多層膜を有さないことを特徴する請求項1に記載の環境光センサー用光学フィルター。
- 前記化合物(A)を含む層が透明樹脂層であることを特徴とする請求項1または2に記載の環境光センサー用光学フィルター。
- 前記透明樹脂層が、前記化合物(B)をさらに含むことを特徴とする請求項3に記載の環境光センサー用光学フィルター。
- 前記化合物(A)が、スクアリリウム系化合物、フタロシアニン系化合物およびシアニン系化合物からなる群より選ばれる少なくとも1種の化合物であることを特徴とする請求項1~4のいずれか1項に記載の環境光センサー用光学フィルター。
- 前記化合物(B)が、近赤外線吸収微粒子、スクアリリウム系化合物、フタロシアニン系化合物、ナフタロシアニン系化合物、クロコニウム系化合物、シアニン系化合物、ジイモニウム系化合物、金属ジチオラート系化合物およびピロロピロール系化合物からなる群より選ばれる少なくとも1種の化合物であることを特徴とする請求項1~5のいずれか1項に記載の環境光センサー用光学フィルター。
- 前記近赤外線吸収微粒子が、下記式(P-1)で表わされる化合物からなる第1の微粒子と、下記式(P-2)で表わされる化合物からなる第2の微粒子とからなる群より選ばれる少なくとも1種であることを特徴とする請求項6に記載の環境光センサー用光学フィルター。
A1/nCuPO4 ・・・(P-1)
[式(P-1)中、Aは、アルカリ金属、アルカリ土類金属およびNH4からなる群より選ばれる少なくとも1種であり、nは、Aがアルカリ金属またはNH4の場合は1であり、Aがアルカリ土類金属の場合は2である。]
MxWyOz ・・・(P-2)
[式(P-2)中、Mは、H、アルカリ金属、アルカリ土類金属、希土類元素、Mg、Zr、Cr、Mn、Fe、Ru、Co、Rh、Ir、Ni、Pd、Pt、Cu、Ag、Au、Zn、Cd、Al、Ga、In、Tl、Si、Ge、Sn、Pb、Sb、B、F、P、S、Se、Br、Te、Ti、Nb、V、Mo、Ta、Re、Be、Hf、Os、BiおよびIから選ばれる少なくとも1種の元素であり、x、yおよびzは、0.001≦x/y≦1および2.2≦z/y≦3.0の条件を満たす。] - 前記透明樹脂層を構成する樹脂が、環状ポリオレフィン系樹脂、芳香族ポリエーテル系樹脂、ポリイミド系樹脂、フルオレンポリカーボネート系樹脂、フルオレンポリエステル系樹脂、ポリカーボネート系樹脂、ポリアミド系樹脂、アラミド系樹脂、ポリサルホン系樹脂、ポリエーテルサルホン系樹脂、ポリパラフェニレン系樹脂、ポリアミドイミド系樹脂、ポリエチレンナフタレート系樹脂、フッ素化芳香族ポリマー系樹脂、(変性)アクリル系樹脂、エポキシ系樹脂、シルセスキオキサン系紫外線硬化型樹脂、マレイミド系樹脂、脂環エポキシ熱硬化型樹脂、ポリエーテルエーテルケトン系樹脂、ポリアリレート系樹脂、アリルエステル系硬化型樹脂、アクリル系紫外線硬化型樹脂、ビニル系紫外線硬化型樹脂、およびゾルゲル法により形成されたシリカを主成分とする樹脂からなる群より選ばれる少なくとも1種の樹脂であることを特徴とする請求項3または4に記載の環境光センサー用光学フィルター。
- 前記基材が、銅成分を含有するフッ素リン酸塩系ガラス層又はリン酸塩系ガラスからなる基板を含むことを特徴とする請求項1~8のいずれか1項に記載の環境光センサー用光学フィルター。
- 前記環境光センサー用光学フィルターに、垂直方向から入射した場合、垂直方向に対して30°の方向から入射した場合および垂直方向に対して60°の方向から入射した場合において、
下記式(1)から導かれるR(赤色)透過率の比の変化率、下記式(2)から導かれるG(緑色)透過率の比の変化率、および下記式(3)から導かれるB(青色)透過率の比の変化率が、いずれも0.6~1.1の範囲であることを特徴とする請求項1~9のいずれか1項に記載の環境光センサー用光学フィルター。
(R透過率の比)=(R透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(1)
(G透過率の比)=(G透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(2)
(B透過率の比)=(B透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(3)
[式(1)~(3)中、R透過率は波長580~650nmにおける平均透過率、G透過率は波長500~580nmにおける平均透過率、B透過率は波長420~500nmにおける平均透過率である。] - 請求項1~10のいずれか1項に記載の環境光センサー用光学フィルターを具備することを特徴とする環境光センサー。
- 請求項11に記載の環境光センサーを有することを特徴とする電子機器。
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2019028433A (ja) * | 2018-01-24 | 2019-02-21 | 日本板硝子株式会社 | 光学フィルタ |
| JP2019174833A (ja) * | 2019-06-19 | 2019-10-10 | 日本板硝子株式会社 | 光学フィルタ及びカメラ付き情報端末 |
| CN111983743A (zh) * | 2019-05-21 | 2020-11-24 | Jsr株式会社 | 光学滤波器、摄像装置与照相机模块 |
| KR20210001993A (ko) * | 2019-06-27 | 2021-01-06 | 제이에스알 가부시끼가이샤 | 광학 필터 및 그의 용도 |
| US11585968B2 (en) | 2017-07-27 | 2023-02-21 | Nippon Sheet Glass Company, Limited | Optical filter and camera-equipped information device |
| US11592603B2 (en) | 2017-07-27 | 2023-02-28 | Nippon Sheet Glass Company, Limited | Optical filter |
| US12287501B2 (en) | 2019-05-23 | 2025-04-29 | Nippon Sheet Glass Company, Limited | Light-absorbing composition, light-absorbing film, and optical filter |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008303130A (ja) * | 2007-06-11 | 2008-12-18 | Asahi Glass Co Ltd | 撮像装置用近赤外線カットフィルタおよび撮像装置 |
| JP2011070031A (ja) * | 2009-09-25 | 2011-04-07 | Panasonic Electric Works Co Ltd | 近赤外吸収粘着フィルム、近赤外吸収粘着層付き反射防止フィルム、近赤外吸収粘着層付き電磁波シールドフィルム、プラズマディスプレイ用フィルター |
| JP2012021066A (ja) * | 2010-07-13 | 2012-02-02 | Kaneka Corp | 近赤外線吸収能を有する硬化性コーティング剤、および近赤外線吸収材 |
| WO2013054864A1 (ja) * | 2011-10-14 | 2013-04-18 | Jsr株式会社 | 光学フィルターならびに該光学フィルターを用いた固体撮像装置およびカメラモジュール |
| WO2014192714A1 (ja) * | 2013-05-29 | 2014-12-04 | Jsr株式会社 | 光学フィルターおよび前記フィルターを用いた装置 |
| WO2017006571A1 (ja) * | 2015-07-09 | 2017-01-12 | 日本板硝子株式会社 | 赤外線カットフィルタ、撮像装置、及び赤外線カットフィルタの製造方法 |
| WO2017018419A1 (ja) * | 2015-07-28 | 2017-02-02 | Jsr株式会社 | 光学フィルター及び光学フィルターを具備する環境光センサー |
| WO2017094672A1 (ja) * | 2015-11-30 | 2017-06-08 | Jsr株式会社 | 光学フィルター、環境光センサーおよびセンサーモジュール |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100444332B1 (ko) * | 1999-12-20 | 2004-08-16 | 도요 보세키 가부시키가이샤 | 적외선 흡수필터 |
| BRPI0407265B1 (pt) | 2003-10-20 | 2018-01-09 | Sumitomo Metal Mining Co., Ltd. | Dispersão de partículas finas de material de proteção contra infravermelho |
| JP5489669B2 (ja) | 2008-11-28 | 2014-05-14 | Jsr株式会社 | 近赤外線カットフィルターおよび近赤外線カットフィルターを用いた装置 |
| JP5198394B2 (ja) | 2009-09-04 | 2013-05-15 | シャープ株式会社 | 近接照度センサおよびその製造方法 |
| JP5454111B2 (ja) | 2009-12-07 | 2014-03-26 | 旭硝子株式会社 | 近赤外線カットフィルタおよび撮像装置・表示装置 |
| WO2012169447A1 (ja) * | 2011-06-06 | 2012-12-13 | 旭硝子株式会社 | 光学フィルタ、固体撮像素子、撮像装置用レンズおよび撮像装置 |
| JP2013155353A (ja) * | 2012-01-31 | 2013-08-15 | Fujifilm Corp | 赤外線吸収性液状組成物、これを用いた赤外線カットフィルタ及びその製造方法、並びに、カメラモジュール及びその製造方法 |
| KR102056613B1 (ko) * | 2012-08-23 | 2019-12-17 | 에이지씨 가부시키가이샤 | 근적외선 커트 필터 및 고체 촬상 장치 |
| KR101724562B1 (ko) * | 2013-02-14 | 2017-04-07 | 후지필름 가부시키가이샤 | 적외선 흡수 조성물 내지는 적외선 흡수 조성물 키트, 이것을 사용한 적외선 커트 필터 및 그 제조방법, 및 카메라 모듈 및 그 제조방법 |
| CN104159085A (zh) * | 2014-08-21 | 2014-11-19 | 中南林业科技大学 | 一种基于新型监控镜头和双图像传感器的监控系统 |
-
2018
- 2018-05-25 KR KR1020237011610A patent/KR102619325B1/ko active Active
- 2018-05-25 JP JP2019522201A patent/JP7031665B2/ja active Active
- 2018-05-25 WO PCT/JP2018/020220 patent/WO2018221424A1/ja not_active Ceased
- 2018-05-25 KR KR1020197034856A patent/KR102575309B1/ko active Active
- 2018-05-25 CN CN201880034851.4A patent/CN110678785B/zh active Active
- 2018-05-29 TW TW107118205A patent/TWI756436B/zh active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008303130A (ja) * | 2007-06-11 | 2008-12-18 | Asahi Glass Co Ltd | 撮像装置用近赤外線カットフィルタおよび撮像装置 |
| JP2011070031A (ja) * | 2009-09-25 | 2011-04-07 | Panasonic Electric Works Co Ltd | 近赤外吸収粘着フィルム、近赤外吸収粘着層付き反射防止フィルム、近赤外吸収粘着層付き電磁波シールドフィルム、プラズマディスプレイ用フィルター |
| JP2012021066A (ja) * | 2010-07-13 | 2012-02-02 | Kaneka Corp | 近赤外線吸収能を有する硬化性コーティング剤、および近赤外線吸収材 |
| WO2013054864A1 (ja) * | 2011-10-14 | 2013-04-18 | Jsr株式会社 | 光学フィルターならびに該光学フィルターを用いた固体撮像装置およびカメラモジュール |
| WO2014192714A1 (ja) * | 2013-05-29 | 2014-12-04 | Jsr株式会社 | 光学フィルターおよび前記フィルターを用いた装置 |
| WO2017006571A1 (ja) * | 2015-07-09 | 2017-01-12 | 日本板硝子株式会社 | 赤外線カットフィルタ、撮像装置、及び赤外線カットフィルタの製造方法 |
| WO2017018419A1 (ja) * | 2015-07-28 | 2017-02-02 | Jsr株式会社 | 光学フィルター及び光学フィルターを具備する環境光センサー |
| WO2017094672A1 (ja) * | 2015-11-30 | 2017-06-08 | Jsr株式会社 | 光学フィルター、環境光センサーおよびセンサーモジュール |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11585968B2 (en) | 2017-07-27 | 2023-02-21 | Nippon Sheet Glass Company, Limited | Optical filter and camera-equipped information device |
| US12072517B2 (en) | 2017-07-27 | 2024-08-27 | Nippon Sheet Glass Company, Limited | Light-absorbing composition and method of manufacturing |
| US11885993B2 (en) | 2017-07-27 | 2024-01-30 | Nippon Sheet Glass Company, Limited | Optical filter and method of manufacturing |
| US11592603B2 (en) | 2017-07-27 | 2023-02-28 | Nippon Sheet Glass Company, Limited | Optical filter |
| JP2019028433A (ja) * | 2018-01-24 | 2019-02-21 | 日本板硝子株式会社 | 光学フィルタ |
| TWI845685B (zh) * | 2019-05-21 | 2024-06-21 | 日商Jsr股份有限公司 | 光學濾波器、攝像裝置與照相機模塊 |
| CN111983743B (zh) * | 2019-05-21 | 2024-02-27 | Jsr株式会社 | 光学滤波器、摄像装置与照相机模块 |
| CN111983743A (zh) * | 2019-05-21 | 2020-11-24 | Jsr株式会社 | 光学滤波器、摄像装置与照相机模块 |
| US12287501B2 (en) | 2019-05-23 | 2025-04-29 | Nippon Sheet Glass Company, Limited | Light-absorbing composition, light-absorbing film, and optical filter |
| JP2019174833A (ja) * | 2019-06-19 | 2019-10-10 | 日本板硝子株式会社 | 光学フィルタ及びカメラ付き情報端末 |
| JP2021006901A (ja) * | 2019-06-27 | 2021-01-21 | Jsr株式会社 | 光学フィルターおよびその用途 |
| KR20210001993A (ko) * | 2019-06-27 | 2021-01-06 | 제이에스알 가부시끼가이샤 | 광학 필터 및 그의 용도 |
| JP7540208B2 (ja) | 2019-06-27 | 2024-08-27 | Jsr株式会社 | 光学フィルターおよびその用途 |
| KR102867615B1 (ko) * | 2019-06-27 | 2025-10-10 | 제이에스알 가부시키가이샤 | 광학 필터 및 그의 용도 |
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| TWI756436B (zh) | 2022-03-01 |
| KR20200011944A (ko) | 2020-02-04 |
| JP7031665B2 (ja) | 2022-03-08 |
| CN110678785B (zh) | 2022-04-05 |
| TW201901198A (zh) | 2019-01-01 |
| CN110678785A (zh) | 2020-01-10 |
| KR20230051613A (ko) | 2023-04-18 |
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