WO2017094672A1 - 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 - Google Patents
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 Download PDFInfo
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- WO2017094672A1 WO2017094672A1 PCT/JP2016/085210 JP2016085210W WO2017094672A1 WO 2017094672 A1 WO2017094672 A1 WO 2017094672A1 JP 2016085210 W JP2016085210 W JP 2016085210W WO 2017094672 A1 WO2017094672 A1 WO 2017094672A1
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Images
Classifications
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- H01L31/12—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto
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- H01L31/12—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto
- H01L31/16—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the semiconductor device sensitive to radiation being controlled by the light source or sources
- H01L31/167—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the semiconductor device sensitive to radiation being controlled by the light source or sources the light sources and the devices sensitive to radiation all being semiconductor devices characterised by potential barriers
- H01L31/173—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof structurally associated with, e.g. formed in or on a common substrate with, one or more electric light sources, e.g. electroluminescent light sources, and electrically or optically coupled thereto the semiconductor device sensitive to radiation being controlled by the light source or sources the light sources and the devices sensitive to radiation all being semiconductor devices characterised by potential barriers formed in, or on, a common substrate
Definitions
- the present invention relates to an optical filter, an ambient light sensor, and a sensor module. Specifically, the present invention relates to an optical filter containing a dye compound having absorption in a specific wavelength range, an ambient light sensor using the optical filter, and a sensor module including 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.
- 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 region when light enters from an oblique direction (See Patent Document 4).
- 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
- An optical filter having a substrate (i) having a light absorption layer and transmitting visible light, wherein the light absorption layer has an absorption maximum in a wavelength region of 750 to 1150 nm, and has a wavelength of 850 In an area of ⁇ 1050 nm, the average OD value when measured from the vertical direction of the optical filter is 2.0 or more, and the average OD when measured from an angle of 60 ° with respect to the vertical direction of the optical filter An optical filter having a value of 2.0 or more.
- the compound (S) is a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a croconium compound, a cyanine compound, a diimonium compound, a metal dithiolate compound, a copper phosphate complex compound, or a pyrrolopyrrole compound.
- Item 3 The optical filter according to Item [3], which is at least one compound selected from the group consisting of compounds.
- the optical filter according to any one of [1] to [5], wherein the light absorption layer further includes a compound (A) having an absorption maximum in a wavelength region of 650 to 750 nm. .
- the compound (A) is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds.
- the optical filter according to [6] is at least one compound selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds.
- the light absorbing layer is a cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, polysulfone resin.
- Resin polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester curable type At least one resin selected from the group consisting of a resin, a silsesquioxane-based UV-curable resin, an acrylic UV-curable resin, a vinyl-based UV-curable resin, and a silica-based resin formed by a sol-gel method Including the term [1 The optical filter according to any one of - [7].
- optical filter according to any one of items [1] to [9], which is used for an ambient light sensor.
- An ambient light sensor comprising the optical filter according to any one of items [1] to [9].
- a photoelectric conversion element that generates a photocurrent by light incident on the light receiving surface and measures illuminance and color temperature, and the items [1] to [9] disposed on the light receiving surface side of the photoelectric conversion element
- An ambient light sensor comprising the optical filter according to claim 1.
- a photoelectric conversion element that generates a photocurrent by light incident on the light receiving surface and measures illuminance and color temperature; and an optical filter disposed on the light receiving surface side of the photoelectric conversion element, and the optical filter Is an ambient light sensor comprising a near-infrared absorbing layer and a near-infrared reflecting layer.
- the resin of the resin layer is cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, polyarylate resin, polysulfone.
- Term [14] characterized by Ambient light sensor described.
- optical filter includes a glass substrate, and the near-infrared absorbing layer is provided on at least one surface of the glass substrate.
- the ambient light sensor according to any one of items [13] to [19], wherein the optical filter satisfies the following conditions (A) to (C): (A) In the wavelength range of 430 to 580 nm, the transmittance when measured from the vertical direction of the optical filter is 50% or more; (B) In the wavelength range of 800 to 1000 nm, the average value of transmittance when measured from the vertical direction of the optical filter is 15% or less; (C) In the wavelength range of 560 to 800 nm, measured from a wavelength value (Xa) at which the transmittance is 50% when measured from the vertical direction of the optical filter and an angle of 30 ° with respect to the vertical direction of the optical filter.
- ) of the difference between the wavelength values (Xb) at which the transmittance is 50% is less than 20 nm.
- Item 1 The ambient light sensor according to item 1.
- the near-infrared absorption layer has an absorption maximum in a wavelength region of 750 to 1150 nm, and an average OD value when measured from the vertical direction of the optical filter at a wavelength of 850 to 1050 nm is 2.0 or more, The average OD value when measured from an angle of 60 ° with respect to the vertical direction of the optical filter is 2.0 or more, [13] to [21], Ambient light sensor.
- a proximity sensor having a light emitting element that emits near infrared light and a second photoelectric conversion element that detects near infrared light.
- a sensor module comprising the optical filter according to any one of items [1] to [10].
- an optical filter that has high visible light transmittance and near-infrared cut performance for both incident light from a vertical direction and incident light from an oblique direction, and can be suitably used as an ambient light sensor application.
- 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.
- the optical filter of the present invention has a configuration described later, and its use is not particularly limited, but is suitable for use as an ambient light sensor.
- the ambient light sensor of the present invention is not particularly limited as long as it includes an optical filter to be described later.
- a photoelectric conversion element that generates a photocurrent by light incident on a light receiving surface and measures illuminance and color temperature.
- an optical filter disposed on the light receiving surface side of the photoelectric conversion element.
- the optical filter of the present invention will be described by being divided into a first aspect (hereinafter also referred to as “first optical filter”) and a second aspect (hereinafter also referred to as “second optical filter”).
- first optical filter a first aspect
- second optical filter a second aspect
- the description of one aspect can be applied to the other aspect as long as the effects of the present invention are not impaired.
- the optical filter of the present invention in principle, it includes both the first optical filter and the second optical filter.
- a first optical filter according to the present invention is an optical filter having a base material (i) having a light absorption layer and transmitting visible light, wherein the light absorption layer has a wavelength of 750 to 1150 nm. It has an absorption maximum, has an average OD value (hereinafter also referred to as “OD A ”) of 2.0 or more when measured from the vertical direction of the optical filter at a wavelength of 850 to 1050 nm, and The average OD value (hereinafter also referred to as “OD B ”) when measured from an angle of 60 ° with respect to the vertical direction is 2.0 or more.
- OD value is a common logarithm of transmittance and can be calculated by the following formula (1).
- the average OD value in the specified wavelength range is high, it indicates that the optical filter has high light cut characteristics in the wavelength region.
- the OD A is preferably 2.3 to 10, more preferably 2.5 to 9.
- the OD B is preferably 2.3 to 10, more preferably 2.5 to 9.
- an average OD value (hereinafter also referred to as “OD D ”) measured at an angle of 30 ° with respect to the vertical direction of the optical filter at a wavelength of 850 to 1050 nm is preferably 2.0 or more, more preferably. Is 2.3 or more and 10 or less, more preferably 2.5 or more and 9 or less.
- the optical filter is not only near infrared rays transmitted through the vertical, near infrared can be cut sufficiently transmitted through at high angles of incidence.
- 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 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, In addition, 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.
- R (red) transmittance is the average transmittance at wavelengths of 580 to 650 nm
- G (green) transmittance is the average transmittance at wavelengths of 500 to 580 nm
- B (blue) transmittance is the average transmittance at wavelengths of 420 to 500 nm
- R transmittance ratio, G transmittance ratio, and B transmittance ratio can be derived from the following equations (2) to (4).
- the rate of change in the ratio of R transmittance in the case of 0 ° ⁇ 30 ° is preferably 0.5 or more and 2.0 or less, more preferably 0.6 or more and 1.8 or less, and further preferably 0.8 or more and 1. It is 4 or less, and the closer the change rate is to 1.0, the smaller the incident angle dependent change of RGB balance.
- the rate of change of the ratio of G transmittance in the case of ° can be derived from the following formula (6).
- the rate of change in the G transmittance ratio when 0 ° ⁇ 30 ° is preferably 0.5 or more and 2.0 or less, more preferably 0.6 or more and 1.8 or less, and even more preferably 0.8 or more and 1. It is 4 or less, and the closer the change rate is to 1.0, the smaller the incident angle dependent change of RGB balance.
- 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 change rate of the ratio of the B transmittance in the case of ° can be derived from the following formula (7).
- the rate of change in the ratio of B transmittance in the case of 0 ° ⁇ 30 ° is preferably from 0.5 to 2.0, more preferably from 0.6 to 1.8, still more preferably from 0.8 to 1. It is 4 or less, and the closer the change rate is to 1.0, the smaller the incident angle dependent change of RGB balance.
- 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 R transmittance at 60 ° can be derived from the following equation (8).
- the rate of change in the ratio of R 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 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 rate of change in the ratio of B transmittance in the case of 0 ° to 60 ° is preferably 0.4 to 2.0, more preferably 0.5 to 1.8, and still more preferably 0.6 to 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 first optical filter of the present invention in the wavelength range of 430 ⁇ 580 nm, the average value of the transmittance as measured in the vertical direction of the optical filter (hereinafter referred to as "T A".) Is preferably 30% or more It is desirable that it is 80% or less, more preferably 30% or more and 75% or less, and still more preferably 33% or more and 70% or less. Further, in the wavelength region of 430 to 580 nm, the average value of transmittance (hereinafter also referred to as “T B ”) measured from an angle of 30 ° with respect to the vertical direction of the optical filter is preferably 30% or more and 80 % Or less, preferably 30% or more and 75% or less, and more preferably 33% or more and 70% or less.
- the average value of transmittance (hereinafter also referred to as “T C ”) when measured from an angle of 60 ° with respect to the vertical direction of the optical filter is preferably 20% or more and 78. % Or less, more preferably 25% or more and 75% or less, and further preferably 30% or more and 70% or less.
- the average transmittance (T A ) 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 will become excessively high, and the photosensor will function satisfactorily. It may disappear.
- the average value (T A ) 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 is not sufficiently secured, so that it is suitably used for the above application. It may not be possible.
- 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.
- the optical filter can be reduced in size and weight, and can be suitably used for various applications such as an optical sensor.
- the substrate (i) may be a single layer or a multilayer, and may contain a light absorption layer having an absorption maximum in a wavelength region of 750 to 1150 nm.
- the light absorption layer preferably contains a compound (S) having an absorption maximum in a wavelength region of 750 to 1150 nm.
- a substrate made of a transparent resin substrate (ii) containing the compound (S) and a substrate made of a near infrared absorbing glass substrate (iii) containing a copper component are used.
- the transparent resin substrate (ii) or the glass substrate (iii) serves as the light absorption layer.
- a base in which a transparent resin layer such as an overcoat layer made of a curable resin containing the compound (S) is laminated on a support such as a glass support or a resin support serving as a base examples thereof include a base material obtained by laminating a resin layer such as an overcoat layer made of a curable resin on a transparent resin substrate (ii) containing a material and the compound (S). From the viewpoints of manufacturing cost and ease of optical property adjustment, and further, it is possible to achieve a scratch-removing effect on the resin support and the transparent resin substrate (ii) and the improvement of scratch resistance of the substrate (i).
- a substrate in which a resin layer such as an overcoat layer made of a curable resin is laminated on a transparent resin substrate (ii) containing) is particularly preferable.
- the light absorption layer is not particularly limited as long as it has an absorption maximum in a wavelength region of 750 to 1150 nm.
- an average OD value (measured from a direction perpendicular to the substrate (i) in a wavelength region of 850 to 1050 nm ( (Hereinafter also referred to as “OD C ”) is preferably 1.0 or more, more preferably 1.1 or more and 10 or less, and further preferably 1.3 or more and 9 or less.
- the thickness of the light absorption layer is not particularly limited, but is preferably 50 to 500 ⁇ m, more preferably 50 to 300 ⁇ m, and still more preferably 50 to 200 ⁇ m.
- the optical filter using the light absorption layer can be reduced in size and weight, and can be suitably used for various applications such as an optical sensor.
- a metal complex compound, a dye or a pigment that acts as a dye that absorbs near infrared rays can be used.
- a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound, a croconium There may be mentioned at least one compound selected from the group consisting of a compound, a cyanine compound, a diimonium compound, a metal dithiolate complex compound, a copper phosphate complex compound and a pyrrolopyrrole compound.
- a diimonium compound represented by the following formula (s1) and a metal dithiolate complex compound represented by the following formula (s2) are preferable.
- R 1 to R 3 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 phosphate group, —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 ) represents any R i groups or 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
- 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, It is 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 adjacent R 3 They may form a ring which may have a substituent L.
- n represents an integer of 0 to 4
- X represents an anion necessary for neutralizing the charge.
- M represents a metal atom.
- Z represents D (R i ) 4 , D represents a nitrogen atom, a phosphorus atom or a bismuth atom, and y represents 0 or 1.
- the R 1 in the diimonium compound represented by the above formula (s1) is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group.
- a butyl group, a cyclohexyl group, a phenyl group and a benzyl group more preferably an isopropyl group, a sec-butyl group, a tert-butyl group and a benzyl group.
- R 2 is preferably a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or a 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, pentafluoroethanoylamino group, t-butanoylamino group, cyclohexinoylamino group, n-butylsulfonyl group, methylthio group, ethylthio group, n-propylthio group N-butylthio group, more preferably a chlorine atom, a fluorine atom, Tyl, ethyl, n-propyl, isopropyl, tert-butyl, hydroxyl, dimethylamino,
- 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 if it has a high acidity when converted to an acid.
- (X-10) and (X in Table 1 above) X-16), (X-17), (X-21), (X-22), (X-24), and (X-28) are particularly preferable.
- the R 3 in the metal dithiolate complex compound represented by the formula (s2) is preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl.
- M is preferably a transition metal, more preferably Ni, Pd, or Pt.
- Z represents D (R i ) 4
- D is preferably a nitrogen atom or a phosphorus atom
- R i is preferably an ethyl group, n-propyl.
- the absorption maximum wavelength of the compound (S) is from 750 nm to 1150 nm, preferably from 760 nm to 1140 nm, more preferably from 770 nm to 1130 nm, and particularly preferably from 780 nm to 1120 nm.
- the absorption maximum wavelength of the compound (S) is in such a range, unnecessary near-infrared rays can be efficiently cut, and the incident angle dependency of incident light can be reduced.
- the compound (S) may be synthesized by a generally known method.
- Japanese Patent No. 4168031 Japanese Patent No. 4225296, JP-T 2010-516823, JP-A No. 63-165392 It can be synthesized with reference to the method described in the publication.
- S Commercially available compounds
- S include S2058 (manufactured by DKSH), CIR-108x, CIR-96x, CIR-RL, CIR-1080 (manufactured by Nippon Carlit), T090821, T091021, T89021, T090721, T090122, (Tosco) B4360, D4773, D5013 (manufactured by Tokyo Chemical Industry Co., Ltd.), S4253, S1426, S1445 (manufactured by Spectrum Info), Excolor IR1, IR2 IR, IR3 IR, IR4 (manufactured by Nippon Shokubai).
- the amount of the compound (S) used is appropriately selected according to the desired properties, but is preferably 0.01 to 20.0 parts by weight, more preferably 100 parts by weight of the transparent resin used in the present invention.
- the amount is 0.01 to 15.0 parts by weight, more preferably 0.01 to 10.0 parts by weight.
- the amount of the compound (S) used is larger than the above range, an optical filter in which the characteristics of the compound (S) are more strongly exhibited may be obtained, but a transmittance in the range of 430 to 580 nm is preferable as an optical sensor. If the amount of the compound (S) used is less than the above range, an optical filter having an excessively high transmittance can be obtained, and the optical sensor can be obtained. It may be difficult to limit the amount of light incident on the.
- the light absorption layer may further include a compound (A) having an absorption maximum in a wavelength region of 650 to 750 nm.
- the light absorbing layer containing the compound (S) and the light absorbing layer containing the compound (A) may be the same layer or different layers. Further, the compound (A) contained in the light absorption layer may be one kind alone or two or more kinds.
- the compound (A) is not particularly limited as long as it has an absorption maximum in the wavelength region of 650 to 750 nm, but is selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds. At least one compound is preferable, and squarylium compounds and phthalocyanine compounds are particularly preferable.
- 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.
- 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 2 to 4 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 monovalent metal atoms 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 5 to 8 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
- 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, represents any of the L a ⁇ L e
- 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 addition amount of the compound (A) is appropriately selected according to the desired properties, but is usually 0.01 to 20.0 parts by weight, preferably 0.03 to 100 parts by weight with respect to 100 parts by weight of the transparent resin.
- the amount is desirably 10.0 parts by weight.
- the transparent resin used for the light absorbing layer is not particularly limited as long as it does not impair the effects of the present invention. For example, thermal stability and film formability are ensured, and a deposition temperature of 100 ° C. or higher.
- the glass transition temperature (Tg) is preferably 110 to 380 ° C., more preferably 110 to 370 ° C., and even more preferably 120 to 360 ° C. in order to obtain a film capable of forming a dielectric multilayer film by high-temperature vapor deposition performed in Resin. Further, it is particularly preferable that the glass transition temperature of the resin is 140 ° C. or higher because a film capable of depositing a dielectric multilayer film at a higher temperature can be obtained.
- 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 examples include cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, and polysulfones.
- Resin polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl
- examples thereof include an ester curable resin, a silsesquioxane ultraviolet curable resin, an acrylic ultraviolet curable resin, a vinyl ultraviolet curable resin, and a resin mainly composed of silica formed by a sol-gel method.
- the use of cyclic polyolefin resins, aromatic polyether resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, and polyarylate resins helps balance transparency (optical properties), heat resistance, etc. This is preferable in that an excellent optical filter 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 are each independently the following (i ′) to (ix ′) Represents an atom or group selected from the above, k x , mx and p x each independently represents 0 or 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 (S) and a curable resin is laminated on a glass support or a resin support as a base as the base (i).
- the curable resin It can be particularly preferably 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 light-absorbing layer 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, triazine compounds, and the like.
- antioxidants examples 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.
- Glass support for example, a colorless and transparent glass substrate, a glass substrate containing a copper component, or a fluorophosphate glass substrate can be used.
- fluorophosphate glass containing a copper component as an absorbent is preferable because it can improve near-infrared cutting ability.
- the transparent resin substrate (ii) can be formed by, for example, melt molding or cast molding, 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 coating agent such as an antireflection agent, a hard coat agent and / or an antistatic agent after molding.
- a transparent resin layer (light absorbing layer) such as an overcoat layer made of a curable resin containing the compound (S) is laminated on a glass support or a resin support as a base.
- a resin solution containing the compound (S) is melt-molded or cast-molded on a glass support or a resin support serving as a base, and preferably spin coating, slit coating, inkjet, etc. After coating by the method, the solvent is dried and removed, and if necessary, the substrate on which the transparent resin layer is formed on the glass support or the base resin support is further obtained by performing light irradiation or heating. Can be manufactured.
- the melt molding is a method of melt-molding pellets obtained by melt-kneading a resin and a compound (S) or the like; melting a resin composition containing the resin and the compound (S) A method of molding; or a method of melt-molding pellets obtained by removing the solvent from the resin composition containing the compound (S), the resin and the solvent.
- the 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 the compound (S), a resin and a solvent on an appropriate support; or the compound (S) and a photocurable resin and / or 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 (ii) containing the compound (S)
- the base material (i) is coated with a coating film from the support after cast molding. It can be obtained by peeling, and the base material (i) is made from a curable resin containing the compound (S) 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 (ii)) 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 0.8% by weight with respect to the weight of the transparent resin layer (transparent resin substrate (ii)). 5% by weight or less.
- the amount of residual solvent is in the above range, a transparent resin layer (transparent resin substrate (ii)) that can easily exhibit a desired function is obtained, in which deformation and characteristics are hardly changed.
- the first optical filter according to the present invention preferably has a dielectric multilayer film on at least one surface of the substrate (i).
- 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. By having a dielectric multilayer film, a better visible light transmittance and near-infrared radiation are obtained. Cut characteristics can be achieved.
- the dielectric multilayer film may be provided on one side of the substrate or on both sides.
- the optical filter When it is provided on one side, it is possible to obtain an optical filter that is excellent in production cost and manufacturability and has high strength and is less likely to warp or twist when provided on both sides.
- the optical filter When the optical filter is applied to a solid-state imaging device, it is preferable that the optical filter is less warped or twisted. Therefore, it is preferable to provide a dielectric multilayer film on both surfaces of the resin substrate.
- the dielectric multilayer film preferably has reflection characteristics over the entire wavelength range of 700 to 1100 nm, more preferably 700 to 1150 nm, and even more preferably 700 to 1200 nm.
- 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 with respect to 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 16 to 70 layers, more preferably 20 to 60 layers, as a whole. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and the warpage of the optical filter and cracks in the dielectric multilayer film can be reduced. can do.
- 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.
- solvents may be used alone or in combination of two or more.
- 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 second optical filter according to the present invention includes a near-infrared absorbing layer (light absorbing layer) and a near-infrared reflecting layer.
- the near-infrared absorbing layer examples include an embodiment that is a resin layer containing a near-infrared absorbing dye, an embodiment that is a fluorophosphate glass layer or a phosphate glass layer containing a copper component, and the like.
- the second optical filter according to the present invention includes, for example, a glass substrate, the embodiment in which the near infrared absorption layer is provided on at least one surface of the glass substrate, a resin substrate, and the near infrared ray Examples include an aspect in which an absorption layer is provided on at least one surface of the resin substrate.
- the near-infrared reflective layer may be a dielectric multilayer film.
- the transmittance of the second optical filter according to the present invention satisfies the following conditions (A) to (C).
- the transmittance when measured from the vertical direction of the optical filter is 50% or more, preferably 60% or more, more preferably 70% or more.
- a filter can be obtained.
- the average value of the transmittance when measured from the vertical direction of the optical filter is 15% or less, preferably 10% or less, more preferably 5% or less, and still more preferably 1. % Or less.
- ) of the difference in wavelength value (Xb) at which the transmittance when measured from an angle of 30 ° is 50% is less than 20 nm, preferably less than 15 nm, more preferably less than 10 nm. It is.
- the change in the spectral sensitivity characteristic of the ambient light sensor due to the incident angle of the incident light is reduced, and the decrease in sensitivity of the ambient light sensor and the occurrence of malfunction are suppressed.
- Ambient light sensor sensitivity close to human visual sensitivity characteristics can be achieved regardless of the angle, and high sensor sensitivity characteristics can be obtained.
- the optical filter 104 includes a layer or member that reflects near infrared rays and a layer or member that absorbs near infrared rays.
- FIG. 1 shows an embodiment in which the optical filter 104 includes a near infrared reflection layer 118 and a near infrared absorption layer 120.
- the near-infrared reflective layer 118 has a characteristic of reflecting light in the near-infrared wavelength band.
- the near-infrared reflective layer 118 is formed of a dielectric multilayer film.
- the dielectric multilayer film has a structure in which dielectric films having a relatively high refractive index and dielectric films having a relatively low refractive index are alternately stacked.
- the dielectric multilayer film has a characteristic of transmitting light in the visible light band and reflecting light in the near-infrared wavelength band due to the light interference effect.
- the dielectric multilayer film exhibits a steep rise (or fall) in spectral transmission characteristics.
- the dielectric multilayer film has a characteristic that the spectral transmission spectrum is different between vertically incident light and incident light from an oblique direction (obliquely incident light). That is, with only the dielectric multilayer film, a spectral transmission spectrum as designed can be obtained only with normal incident light, but the optical path length changes with respect to oblique incident light, and the spectral transmission spectrum differs from the designed value. For this reason, in the optical filter using only the dielectric multilayer film, when outside light is incident at a wide angle, the transmission spectrum of the incident light deviates from the visibility characteristic of the photoelectric conversion element 102, and thus malfunction occurs. Problems arise.
- the optical filter 104 is provided with a near-infrared absorbing layer 120 in addition to the near-infrared reflecting layer 118.
- the near-infrared absorbing layer 120 has a characteristic of transmitting light in the visible light band and absorbing light in the near-infrared wavelength band.
- the near-infrared absorbing layer 120 contains a compound that absorbs near-infrared rays and has at least one absorption peak in the near-infrared wavelength band.
- the compound that absorbs near infrared rays preferably has a maximum absorption within a wavelength range of 600 nm to 1500 nm, more preferably has a maximum absorption within a wavelength range of 650 nm to 1200 nm, and a maximum within a wavelength range of 650 nm to 800 nm. It is more preferable to have absorption, and it is particularly preferable to have maximum absorption within a wavelength range of 650 nm to 750 nm.
- a compound having a maximum absorption in this wavelength range a highly accurate ambient light sensor with a small change in sensor sensitivity due to an incident angle can be obtained.
- a near-infrared absorbing dye can be used as a compound that absorbs near-infrared rays.
- Such a near-infrared absorbing layer 120 is formed using a near-infrared absorbing composition containing a compound that absorbs near-infrared rays and at least one selected from a binder resin and a polymerizable compound.
- a compound that absorbs near-infrared light is included in a resin layer that is transparent to visible light.
- the optical filter 104 has a near infrared absorption layer 120 disposed on the back surface of the near infrared reflection layer 118.
- the near-infrared reflecting layer 118 reflects near-infrared light, but when the transmitted light includes light in the near-infrared wavelength band, the near-infrared absorbing layer 120 absorbs light in the near-infrared wavelength band included in the transmitted light.
- the light (obliquely incident light) incident from the oblique direction of the optical filter 104 changes as compared with the case where the transmission spectrum is perpendicularly incident because the near-infrared reflective layer 118 is a dielectric multilayer film.
- the near-infrared absorption layer 120 absorbs the light component, so that the near-infrared wavelength band Can be prevented from remaining.
- the optical filter 104 can improve the performance of blocking near-infrared light by providing the near-infrared reflecting layer 118 and the near-infrared absorbing layer 120 so as to overlap each other. Thereby, when the ambient light sensor 100a measures the illuminance, it is possible to accurately detect the illuminance by the light in the visible light band even when light is incident from an oblique direction.
- At least one of the absorption peak wavelengths of the near-infrared absorbing layer 120 has such a characteristic that it overlaps with the cutoff wavelength in the near-infrared reflecting layer 118. Even when the cut-off wavelength of the transmitted light spectrum is changed by light incident on the near-infrared reflecting layer 118 from an oblique direction, the near-infrared absorbing layer 120 can reduce the influence of the shift of the cut-off wavelength.
- the optical filter 104 according to this embodiment has a transmittance of 50% or more in the wavelength range of 430 nm to 580 nm when measured from the vertical direction. Further, the transmittance when measured from the vertical direction of the optical filter 104 according to the present embodiment is 15% or less in the wavelength range of 800 nm to 1000 nm.
- the optical filter 104 according to this embodiment has a wavelength (Xa) at which the transmittance is 50% when measured from the vertical direction in the wavelength range of 560 nm to 800 nm, and an angle of 30 ° with respect to the vertical direction of the optical filter 104.
- the absolute value of the difference in wavelength (Xb) at which the transmittance when measured is 50% is less than 20 nm.
- the optical filter 104 according to the present embodiment desirably satisfies the above conditions at the same time.
- optical filter 104 Since the optical filter 104 has such optical characteristics, not only the light incident from the vertical direction but also the light incident from the oblique direction is blocked from the near infrared light, and the same regardless of the incident angle. Light in the visible light band of optical characteristics can be transmitted.
- the second optical filter according to the present invention includes a near-infrared reflecting layer and a near-infrared absorbing layer, but various modifications are allowed as its form.
- FIG. 2A shows an optical filter 104a provided with a first near-infrared reflecting layer 118a, a near-infrared absorbing layer 120, and a second near-infrared reflecting layer 118b from the light incident side.
- the first near-infrared reflective layer 118a has a structure in which dielectric films having different refractive indexes are stacked.
- the second near-infrared reflective layer 118b may have the same dielectric multilayer structure as the first near-infrared reflective layer 118a, or may have a different dielectric multilayer structure.
- the near-infrared absorbing layer 120 contains a compound that absorbs near-infrared rays in a translucent resin layer. Examples of the compound that absorbs near infrared rays include near infrared absorbing dyes.
- the near-infrared absorbing layer 120 includes a compound that absorbs near-infrared rays in a translucent resin layer. In the optical filter 104a, this resin layer may have a function as a base material. By using the near-infrared absorbing layer 120 itself as a structural material, the optical filter 104a can be thinned.
- a near infrared absorption layer 120 is interposed in a structure in which a dielectric multilayer film is formed as the first near infrared reflection layer 118a and the second near infrared reflection layer 118b.
- FIG. 2A shows a mode in which the near-infrared reflective layer is provided on both sides of the near-infrared absorbing layer, but the optical filter 104a is not limited to this mode.
- the near infrared reflection layer may be provided only on one side of the near infrared absorption layer.
- the optical filter 104a may be configured by the first near-infrared reflecting layer 118a and the near-infrared absorbing layer 120. Even with such a configuration, the synergistic effect of the near-infrared reflecting layer and the near-infrared absorbing layer described above can be exhibited.
- the structure which replaced either the 1st near-infrared reflective layer and the 2nd near-infrared reflective layer with the antireflection layer can also be used.
- optical filter 2 ⁇ glass that absorbs near infrared light may be used for the near infrared absorbing layer 120. That is, instead of the resin layer containing a compound that absorbs near infrared rays, the optical filter 104 may be configured using a glass substrate containing a substance that absorbs near infrared rays.
- the glass material may be a fluorine phosphate glass layer or a phosphate glass layer containing a copper component. Since the glass layer has higher heat resistance and is harder than the resin layer, the heat resistance and structural stability of the optical filter 104 can be improved.
- the first resin layer 122a is provided between the first near-infrared reflecting layer 118a and the near-infrared absorbing layer 120, and the second near-infrared reflecting layer 118b and the near-infrared absorbing layer 120 are provided.
- the optical filter 104b provided with the second resin layer 122b is shown.
- the near-infrared absorbing layer 120 a layer containing a compound that absorbs near-infrared in the above-described translucent resin layer or a glass substrate containing a substance that absorbs near-infrared can be used.
- the resin layer 122 may be provided with only one of the first resin layer 122a and the second resin layer 122b.
- FIG. 2B illustrates an embodiment in which the near-infrared reflecting layer is provided on both surfaces of the near-infrared absorbing layer, but the optical filter 104b is not limited to this embodiment.
- the near infrared reflection layer may be provided only on one side of the near infrared absorption layer.
- the resin layers 122a and 122b may or may not contain a near infrared absorber.
- the structure which replaced either the 1st near-infrared reflective layer and the 2nd near-infrared reflective layer with the antireflection layer can also be used.
- the optical filter 104b shown in FIG. 2B has the same effect as the optical filter 104a shown in FIG. 2A by having a combination of a near-infrared reflecting layer and a near-infrared absorbing layer.
- FIG. 3A shows an optical filter 104 c configured using a transparent glass substrate 124.
- the optical filter 104c is provided with a near-infrared absorbing layer 120 on one surface of a glass substrate 124, and a first near-infrared reflecting layer 118a is provided on the upper surface thereof.
- a near-infrared absorbing layer 120 a layer containing a compound that absorbs near-infrared rays in a translucent resin layer is used.
- a second near-infrared reflective layer 118b is provided on the other surface of the glass substrate 124.
- the transparent glass substrate 124 can be used as a base material for the optical filter 104.
- the rigidity of the optical filter 104 can be increased.
- the second near-infrared reflective layer 118 b shown in FIG. 3A may be provided between the glass substrate 124 and the near-infrared absorbing layer 120.
- the near-infrared absorbing layers 120 may be provided on both surfaces of the glass substrate 124. Moreover, you may provide the group of the 1st near-infrared reflective layer 118a and the near-infrared absorption layer 120 in multiple steps. Furthermore, instead of the transparent glass substrate 124, a glass substrate containing a substance that absorbs near infrared rays may be used. Furthermore, the near-infrared reflecting layer may be provided only on one side of the near-infrared absorbing layer.
- the optical filter 104c may be configured by the first near-infrared reflecting layer 118a, the near-infrared absorbing layer 120, and the glass substrate 124. Moreover, the structure which replaced either the 1st near-infrared reflective layer and the 2nd near-infrared reflective layer with the antireflection layer can also be used.
- 3A has the same effect as the optical filter 104a shown in FIG. 2A by having a combination of a near-infrared reflecting layer and a near-infrared absorbing layer.
- FIG. 3B shows an optical filter 104 d configured using a transparent resin substrate 125.
- the optical filter 104d is provided with a near-infrared absorbing layer 120 on one surface of a resin substrate 125, and a first near-infrared reflecting layer 118a is provided on the upper surface thereof.
- a second near-infrared reflective layer 118 b is provided on the other surface of the resin substrate 125.
- the resin substrate 125 can be used as a base material for the optical filter 104. By using the resin substrate 125 as a base material, the workability and flexibility of the optical filter 104 can be improved. Note that the second near-infrared reflective layer 118b shown in FIG.
- the resin substrate 124 may be provided between the resin substrate 124 and the near-infrared absorbing layer 120.
- the near-infrared absorbing layer 120 a layer containing a compound that absorbs near-infrared rays in a translucent resin layer is used.
- the near-infrared absorbing layer 120 may be provided on both surfaces of the resin substrate 125. Moreover, you may provide the group of the 1st near-infrared reflective layer 118a and the near-infrared absorption layer 120 in multiple steps. Furthermore, the near-infrared reflecting layer may be provided only on one side of the near-infrared absorbing layer.
- the optical filter 104d may be configured by the first near-infrared reflecting layer 118a, the near-infrared absorbing layer 120, and the resin substrate 125. Moreover, the structure which replaced either the 1st near-infrared reflective layer and the 2nd near-infrared reflective layer with the antireflection layer can also be used.
- the optical filter 104d shown in FIG. 3B has the same effect as the optical filter 104a shown in FIG. 2A by having a combination of a near-infrared reflecting layer and a near-infrared absorbing layer.
- the near-infrared reflective layer 118 is designed to transmit visible light having a wavelength of at least 400 nm to 600 nm and reflect near-infrared having a wavelength of 750 nm or more.
- the near-infrared reflective layer 118 preferably has a high transmittance in the visible region, and has an average spectral transmittance of 90% or more in a wavelength band of at least a wavelength of 400 nm to 600 nm.
- it is preferable that the near-infrared reflective layer 118 has a spectral transmittance of less than 2% in the near-infrared wavelength band having a wavelength of 750 nm or more. This is because near-infrared light is not incident on the photoelectric conversion element 102 while light in the visible light band is detected with high sensitivity.
- the near-infrared reflective layer 118 preferably has a steep rising (or falling) characteristic (cut-off characteristic) in spectral transmission characteristics. This is because the near-infrared reflective layer 118 has a steep cut-off characteristic, and thus acts advantageously in optical design in combination with the near-infrared absorbing layer 120. That is, even when the transmission spectrum changes with respect to obliquely incident light on the near-infrared reflecting layer 118, if the cutoff characteristic is steep, it is easy to match the cutoff wavelength to the absorption peak of the near-infrared absorbing layer 120. It is because it becomes.
- the near-infrared reflective layer 118 is formed of a dielectric multilayer film.
- the details of the dielectric multilayer film are as described in the first optical filter.
- the physical film thickness of each of the high refractive index material layer and the low refractive index material layer is preferably 5 to 500 nm, although it depends on the refractive index of each layer, and is the total physical film thickness of the dielectric multilayer film.
- the value is preferably 1.0 to 8.0 ⁇ m for the entire optical filter.
- the warp of the optical filter is small. Therefore, it is preferable to provide a dielectric multilayer film on both sides of the substrate, and the dielectric multilayer provided on both sides.
- the films may have the same or different spectral characteristics.
- the spectral characteristics of the dielectric multilayer films provided on both surfaces are the same, the transmittance of the light blocking zones Za and Zc can be efficiently reduced in the near-infrared wavelength region, and the spectral characteristics of the dielectric multilayer films provided on both surfaces.
- the values are different, there is a tendency that the light blocking band Zc can be easily extended to the longer wavelength side.
- Transparent resin can be used as the resin used for the near-infrared absorbing layer 120 and the resin used for the transparent resin substrate 125 containing the near-infrared absorbing dye.
- the details of the transparent resin are as described in the first optical filter.
- the thickness of the resin layer containing the near-infrared absorbing dye is preferably 10 when the near-infrared absorbing dye-containing resin layer also has a function as a resin substrate, as in “optical filter 1” and “optical filter 3”. It is preferably from 300 to 300 ⁇ m, more preferably from 20 to 200 ⁇ m, still more preferably from 25 to 150 ⁇ m, particularly preferably from 30 to 120 ⁇ m.
- the optical filter can be reduced in weight and size, and the height of the ambient light sensor can be reduced. If the thickness of the resin layer is larger than the above range, the original purpose of reducing the height of the ambient light sensor cannot be achieved. On the other hand, when the thickness of the resin layer is thinner than the above range, there is a problem that the warp of the optical filter becomes large.
- the thickness of the near-infrared absorbing dye-containing resin layer is preferably Is 0.5 to 150 ⁇ m, more preferably 0.7 to 100 ⁇ m, still more preferably 1 to 50 ⁇ m, and particularly preferably 2 to 30 ⁇ m.
- the optical filter can be reduced in weight and size, and the height of the ambient light sensor can be reduced. If the thickness of the resin layer is larger than the above range, the original purpose of reducing the height of the ambient light sensor cannot be achieved.
- the thickness of the resin layer is thinner than the above range, there is a limit to the solubility of the near-infrared absorbing dye in the resin layer. Optical properties cannot be obtained.
- the thickness of the glass that absorbs near-infrared rays used in the near-infrared absorbing layer of the “optical filter 2” is preferably 30 to 1000 ⁇ m, more preferably 35 to 500 ⁇ m, still more preferably 40 to 300 ⁇ m, and particularly preferably 45 to 210 ⁇ m. is there.
- Near-infrared absorbing glass is very fragile, and when the thickness of the glass is thinner than the above range, it is difficult to use because there are problems such as cracking, chipping and warping when used.
- the thickness of the transparent glass substrate used for the “optical filter 4” is preferably 20 to 1000 ⁇ m, more preferably 25 to 500 ⁇ m, still more preferably 30 to 300 ⁇ m, and particularly preferably 35 to 210 ⁇ m.
- the optical filter can be reduced in weight and size, and the ambient light sensor can be reduced in height. If the thickness of the transparent glass is thicker than the above range, the original purpose of reducing the height of the ambient light sensor cannot be achieved.
- the thickness of the transparent glass is thinner than the above range, it is difficult to use due to problems such as large warpage, cracking and chipping because the glass layer is brittle.
- a resin substrate such as “optical filters 1, 3, 5” is used from the viewpoint of reducing the height of the ambient light sensor. It is preferable.
- the resin layer containing the near-infrared absorbing dye can be used as a film substrate as the resin layer itself, or can be used in the form of coating this resin layer on another film substrate, and the resin layer on the glass substrate. It can also be used in the form of a coated layer.
- the film substrate can be produced by the above-described solution casting method or extrusion molding method.
- a resin film made of the transparent resin can be used as the film substrate.
- the transparent resin layer may contain additives such as an antioxidant, a near-ultraviolet absorber, a fluorescence quencher, and a metal complex compound in addition to the near-infrared absorbing dye, as long as the effects of the present invention are not impaired. .
- manufacture of a base material can be made easy by adding a leveling agent and an antifoamer. These components may be used alone or in combination of two or more.
- the substrate may be a single layer or a multilayer, and the layer containing a near infrared absorbing dye may be formed by multilayering transparent resin layers containing different near infrared absorbing dyes, or a near infrared ray.
- a layer containing an absorbing dye and a layer not containing a near-infrared absorbing dye can be multilayered.
- dye can also be laminated
- a resin layer such as an overcoat layer containing a curable resin can be laminated on the substrate.
- This curable resin layer can also contain a near infrared absorbing dye.
- a transparent resin layer on the transparent resin substrate containing near-infrared absorbing dyes, from the viewpoints of manufacturing cost and ease of adjustment of optical characteristics, and improvement in scratch resistance of the transparent resin resin substrate It is particularly preferable to use a substrate on which a resin layer such as an overcoat layer made of a curable resin is laminated.
- the transparent resin substrate can be manufactured by the method described in the first optical filter.
- a near-infrared absorbing glass containing a copper component (hereinafter also referred to as “Cu-containing glass”) can be used.
- Cu-containing glass a near-infrared absorbing glass containing a copper component
- the phosphate glass includes silicic acid phosphate glass in which a part of the glass skeleton is composed of SiO 2 .
- a Cu containing glass the thing of the following compositions is mentioned, for example.
- (GL1) is NF50-E, NF50-EX (manufactured by Asahi Glass Co., Ltd.)
- (GL2) is BG-60, BG-61 (manufactured by SHOTTT)
- (GL3) is CD5000 (manufactured by HOYA), etc. Is mentioned.
- the Cu-containing glass may further contain a metal oxide.
- a metal oxide contains, for example, one or more of Fe 2 O 3 , MoO 3 , WO 3 , CeO 2 , Sb 2 O 3 , V 2 O 5, etc.
- the Cu-containing glass has ultraviolet absorption characteristics. .
- the thickness of the Cu-containing glass is preferably in the range of 0.03 to 5 mm, and more preferably in the range of 0.05 to 1 mm from the viewpoint of strength, weight reduction, and low profile.
- the glass substrate without absorption is not particularly limited as long as it is a substrate containing silicate as a main component, and examples thereof include a quartz glass substrate having a crystal structure.
- borosilicate glass substrates, soda glass substrates, and colored glass substrates can be used.
- glass substrates such as non-alkali glass substrates and low ⁇ -ray glass substrates have little influence on sensor elements, preferable.
- the near-infrared absorbing layer and the glass substrate have different chemical compositions and thermal linear expansion coefficients. For this reason, it is preferable to provide an adhesion layer between the near-infrared absorbing layer and the glass substrate to ensure their sufficient adhesion.
- the adhesion layer used in the present invention is not particularly limited as long as it is made of a material that can ensure adhesion between the near-infrared absorbing layer and the glass substrate.
- a structural unit derived from a (meth) acryloyl group-containing compound It is preferable to have (b) a structural unit derived from a carboxylic acid group-containing compound and (c) a structural unit derived from an epoxy group-containing compound, since the adhesion between the near-infrared absorbing layer and the glass substrate is increased.
- the structural unit (a) is not particularly limited as long as it is a structural unit derived from a (meth) acryloyl group-containing compound.
- the (meth) acryloyl group-containing compound for example, monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters are preferable from the viewpoint of good polymerizability.
- (meth) acryl means “acryl” or “methacryl”.
- Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl) Mention may be made of phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate and ⁇ -carboxypolycaprolactone monoacrylate.
- Aronix M-101, M-111, M-114, M-5300 above, manufactured by Toagosei Co., Ltd.
- KAYARAD TC-110S, TC -120S Nippon Kayaku Co., Ltd.
- Biscote 158, 2311 Osaka Organic Chemical Co., Ltd.
- bifunctional (meth) acrylic acid ester examples include ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 9, 9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate and 1,9-nonanediol Mention may be made of dimethacrylate.
- Aronix M-210, M-240, M-6200 manufactured by Toagosei Co., Ltd.
- KAYARAD HDDA As mentioned above, Nippon Kayaku Co., Ltd.
- Biscote 260, 312 and 335HP Osaka Organic Chemical Co., Ltd.
- Light acrylate 1,9-NDA Korean Organic Chemical Co., Ltd.
- trifunctional or higher functional (meth) acrylic acid ester examples include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol.
- polyfunctional urethane acrylate compounds obtained by reacting with compounds having 3, 4 or 5 (meth) acryloyloxy groups obtained by reacting with compounds having 3, 4 or 5 (meth) acryloyloxy groups.
- these (meth) acryloyl group-containing compounds may be used alone or in combination of two or more.
- the structural unit (b) is not particularly limited as long as it is a structural unit derived from a compound containing a carboxylic acid group.
- the carboxylic acid group-containing compound include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, and polymers having carboxylic acid groups.
- Examples of monocarboxylic acids include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid and 2-methacryloyloxyethyl hexahydrophthalic acid. Mention may be made of acids.
- dicarboxylic acid examples include maleic acid, fumaric acid, and citraconic acid.
- dicarboxylic acid anhydride examples include the above dicarboxylic acid anhydrides.
- the polymer having a carboxylic acid group is a compound having a carboxylic acid group, for example, a compound having at least one polymer selected from acrylic acid, methacrylic acid, maleic acid, maleic anhydride and the like.
- a polymer or a copolymer of these compounds and the (meth) acryloyl group-containing compound can be preferably used.
- acrylic acid methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride is preferred from the viewpoint of copolymerization reactivity.
- the structural unit (c) is not particularly limited as long as it is a structural unit derived from an epoxy group-containing compound.
- the epoxy group (oxiranyl group) -containing compound include oxiranyl groups such as (meth) acrylic acid oxiranyl (cyclo) alkyl ester, ⁇ -alkylacrylic acid oxiranyl (cyclo) alkyl ester, and glycidyl ether compound having an unsaturated bond.
- An unsaturated compound having an oxetanyl group such as a (meth) acrylic acid ester having an oxetanyl group.
- Examples of (meth) acrylic acid oxiranyl (cyclo) alkyl esters include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid 3,4 -Epoxybutyl, (meth) acrylic acid 6,7-epoxyheptyl, (meth) acrylic acid 3,4-epoxycyclohexyl and (meth) acrylic acid 3,4-epoxycyclohexylmethyl.
- Acid oxiranyl (cyclo) alkyl esters such as glycidyl ⁇ -ethyl acrylate, glycidyl ⁇ -n-propyl acrylate, glycidyl ⁇ -n-butyl acrylate, 6,7-epoxyheptyl ⁇ -ethyl acrylate and ⁇ -ethyl Acrylic acid 3, -Epoxycyclohexyl can be mentioned, and examples of glycidyl ether compounds having an unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether, which have an oxetanyl group.
- Examples of (meth) acrylic acid esters include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, 3-((meth) acryloyloxymethyl) -2- Methyl oxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyloxymethyloxetane
- Preliminary 3-ethyl-3- (meth) acrylate can be given acryloyloxy methyl oxetane.
- glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl- 3-Methacryloyloxymethyloxetane or 3-ethyl-3-methyloxetane is preferred from the viewpoint of polymerizability.
- Arbitrary components such as an acid generator, a close_contact
- These addition amounts are appropriately selected according to the desired properties, and are usually each based on a total of 100 parts by weight of the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound and the epoxy group-containing compound. It is desirable that the amount be 0.01 to 15.0 parts by weight, preferably 0.05 to 10.0 parts by weight.
- the polymerization initiator is a component that generates active species capable of initiating polymerization of monomer components in response to light rays such as ultraviolet rays and electron beams.
- a polymerization initiator is not particularly limited, and examples thereof include an O-acyloxime compound, an acetophenone compound, a biimidazole compound, an alkylphenone compound, and a benzophenone compound. Specific examples thereof include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl- 6-Benzoyl-9. H.
- the adhesion layer is, for example, a pellet obtained by melt-kneading the composition (G) containing the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound, the epoxy group-containing compound and, if necessary, the optional component.
- a method of melt-molding pellets obtained by removing the solvent from the liquid composition containing the composition (G) and the solvent, or a method of casting (cast molding) the above-mentioned liquid composition Can be manufactured. Examples of the melt molding method and the cast molding method include the same methods as described above.
- the amount of the (meth) acryloyl group-containing compound is preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight per 100 parts by weight of the composition (G).
- the amount is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight per 100 parts by weight of the composition (G), and the amount of the epoxy group-containing compound is 100 parts by weight of the composition (G).
- the amount is preferably 15 to 50 parts by weight, more preferably 20 to 40 parts by weight.
- the blending amount of the optional component is appropriately selected according to the desired characteristics, but is preferably 0.01 to 15.0 parts by weight, more preferably 0.05 to 100 parts by weight per 100 parts by weight of the composition (G). 10.0 parts by weight.
- the thickness of the adhesion layer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0.1 to 5.0 ⁇ m, more preferably 0.2 to 3.0 ⁇ m.
- ⁇ Near-infrared absorbing dye> As near-infrared absorbing dyes, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, octaphyrin compounds, hexaphyrin compounds, cyanine compounds, diimonium compounds, aminium compounds, iminium compounds, And anthraquinone compounds. One or more compounds selected from these compounds can be used, and two or more compounds can also be mixed and used. Among these, squarylium compounds, phthalocyanine compounds, or cyanine compounds are preferably used from the viewpoints of transmittance characteristics and thermal stability.
- the near infrared absorbing dye is preferably the compound (A).
- 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 ambient light sensor 100a according to an embodiment of the present invention.
- the ambient light sensor 100 a includes an optical filter 104 and a photoelectric conversion element 102.
- the photoelectric conversion element 102 generates current and voltage due to the photovoltaic effect when light enters the light receiving portion.
- FIG. 1 shows a photoelectric conversion element 102 having a first electrode 106, a photoelectric conversion layer 108, and a second electrode 114 as an example.
- the photoelectric conversion layer 108 is formed using a semiconductor that exhibits a photoelectric effect.
- the photoelectric conversion layer 108 is formed using a silicon semiconductor.
- the optical filter 104 is provided on the light receiving surface side of the photoelectric conversion element 102.
- the light receiving surface of the photoelectric conversion element 102 is irradiated with light that has passed through the optical filter 104.
- the ambient light sensor 100a is sensitive to light in the visible light band and detects external light intensity corresponding to the visibility.
- the optical filter 104 includes a near infrared reflection layer 118 and a near infrared absorption layer 120.
- the light incident on the optical filter 104 is affected by the near-infrared reflecting layer 118 and the near-infrared absorbing layer 120, and the light intensity in the near-infrared band is sufficiently reduced.
- the near-infrared reflecting layer 118 and the near-infrared absorbing layer 120 are provided so as to overlap each other. In other words, the near-infrared reflecting layer 118 and the near-infrared absorbing layer 120 are arranged in series on the optical axis of incident light.
- the ambient light sensor 100a includes the optical filter 104, the ambient light sensor 100a can receive light at a wide angle, and even in this case, it is possible to detect the intensity of external light that matches the visibility.
- another light-transmitting layer may be interposed between the optical filter 104 and the photoelectric conversion element 102.
- a light-transmitting resin layer may be provided as a sealing material between the optical filter 104 and the photoelectric conversion element 102.
- FIG. 4 shows an example of a cross-sectional structure of the ambient light sensor 100a including the illuminance sensor light receiving element 102a and the optical filter 104.
- the ambient light sensor 100a functions as an illuminance sensor by detecting the intensity of external light with the illuminance sensor light receiving element 102a.
- An optical filter 104 is provided on the upper surface of the illuminance sensor light receiving element 102a. The optical filter 104 blocks light in the near-infrared wavelength region from light incident on the light receiving surface of the illuminance sensor light receiving element 102a, and can detect external light intensity corresponding to the visibility characteristics of the illuminance sensor light receiving element.
- the optical filter 104 composed of the near-infrared reflecting layer 118 and the near-infrared absorbing layer 120, light in the visible light region with a small change depending on the incident angle is incident on the illuminance sensor light-receiving element in accordance with the visibility characteristics of the illuminance sensor. Therefore, an illuminance sensor with few malfunctions can be obtained.
- FIGS. 5A and 5B show an example of an ambient light sensor 100 b including an illuminance sensor light receiving element 102 a, a proximity sensor light receiving element 102 b, a light emitting diode 130, and an optical filter 104.
- 5A shows a plan view of the ambient light sensor 100b
- FIG. 5B shows a cross-sectional structure taken along line IJ.
- the ambient light sensor 100b detects the intensity of external light by the illuminance sensor light receiving element 102a and functions as an illuminance sensor.
- the light emitting diode 130 emits infrared light
- the proximity sensor light receiving element 102b receives the reflected light. That is, the light emitting diode 130 and the proximity sensor light receiving element 102b cooperate to function as a proximity sensor.
- the illuminance sensor light receiving element 102a and the proximity sensor light receiving element 102b are separated from the light emitting diode 130 by a light shielding member 132 so that light emitted from the light emitting diode 130 does not enter as stray light.
- the light shielding member 132 is made of a curable resin such as an epoxy-based resin, and is molded so as to surround each of the illuminance sensor light receiving element 102a, the proximity sensor light receiving element 102b, and the light emitting diode 130, and the upper surface portion can enter or emit light. It is open like this.
- An optical filter 104 is provided on the upper surface of the illuminance sensor light receiving element 102a.
- the optical filter 104 blocks light in the near-infrared wavelength region from light incident on the light receiving surface of the illuminance sensor light receiving element 102a, and can detect external light intensity corresponding to the visibility characteristics of the illuminance sensor light receiving element.
- the optical filter 104 composed of the near-infrared reflecting layer 118 and the near-infrared absorbing layer 120, light in the visible light region with a small change depending on the incident angle is incident on the illuminance sensor light-receiving element in accordance with the visibility characteristics of the illuminance sensor. Therefore, an illuminance sensor with few malfunctions can be obtained.
- the illuminance sensor light receiving element 102a is sensitive to light in the visible light wavelength band of the external light and functions as an illuminance sensor.
- a near infrared pass filter 134 is provided on the light receiving surface of the proximity sensor light receiving element 102b.
- the near-infrared pass filter 134 is a pass filter that transmits light in the near-infrared wavelength region.
- the near-infrared pass filter 134 is formed by adding a pigment (pigment or dye) having absorption at a wavelength in the visible light wavelength region to a binder resin or a polymerizable compound.
- the near-infrared pass filter 134 absorbs (cuts) light having a wavelength of approximately less than 700 nm, preferably less than 750 nm, more preferably less than 800 nm, and transmits light having a wavelength of 700 nm or more, preferably 750 nm or more, more preferably 800 nm or more. It has transmission characteristics.
- the near-infrared pass filter 134 blocks the light having a wavelength less than a predetermined wavelength (for example, a wavelength less than 750 nm) and transmits the near-infrared light in a predetermined wavelength region (for example, 750 to 950 nm).
- a predetermined wavelength for example, a wavelength less than 750 nm
- Near-infrared rays can be incident on 102b.
- the proximity sensor light receiving element 102b can detect near infrared rays with high accuracy without being affected by noise or the like caused by visible light.
- the near-infrared pass filter 134 can be formed using, for example, a photosensitive composition described in JP-A-2014-130332.
- Such an ambient light sensor 100b is mounted on an electronic device, detects the brightness of ambient light by a function as an illuminance sensor, and detects an object close to the main body of the electronic device by a function as a proximity sensor. It becomes possible.
- an electronic device having a touch panel integrated display screen controls the brightness of the screen according to the brightness of the surrounding environment, turns off the display screen according to the distance from the object, and the touch panel. It is possible to support the operation of stopping the function and turning off the screen.
- a color sensor light receiving element in which an RGB color filter is installed on a photodiode may be provided instead of the illuminance sensor light receiving element.
- the spectral intensity ratio (RGB ratio) of ambient light can be detected, and the brightness and image quality of the screen can be finely controlled.
- the function as a color sensor makes it possible to detect ambient light by dividing it into light of a plurality of wavelength bands.
- the optical filter 104 provided on the light receiving surface of the illuminance sensor light receiving element 102a is incident from an oblique direction by combining the near infrared reflecting layer 118 and the near infrared absorbing layer 120. It is possible to effectively block near-infrared rays against the light that is transmitted. Thereby, it is possible to realize a proximity sensor integrated illuminance sensor with little change in sensor sensitivity due to an incident angle and few malfunctions.
- a sensor module can be formed by combining the optical filter of the present invention, another optical filter, a lens, a photoelectric conversion element, and the like.
- FIG. 17 and 18 show schematic diagrams of the optical sensor module.
- the optical filter 203 of the present invention is used between the optical sensor 207 and the light diffusion film 202.
- an IR cut film 204 having near infrared absorption characteristics in addition to the optical filter 203 of the present invention is used between the optical sensor 207 and the optical filter 203.
- 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. 6A to 6C show examples of the electronic device 136.
- FIG. 6A is a front view of the electronic device 136
- FIG. 6B is a plan view
- FIG. 6C is a cross-sectional view illustrating details of a region D surrounded by a dotted line in FIG. 6B.
- the electronic device 136 includes a housing 138, a display panel 140, a microphone unit 142, and a speaker unit 144, and further includes an ambient light sensor 100 (an ambient light sensor 100 a or “ambient light sensor 2” described as “ambient light sensor 1”). Including an ambient light sensor 100b).
- the ambient light sensor 100 includes an optical filter 104 and a photoelectric conversion element 102.
- the display panel 140 employs a touch panel and has an input function in addition to a display function.
- the light enters the ambient light sensor 100 through an optical window 145 provided in the housing 138.
- the ambient light sensor 100 detects the intensity of ambient light on which the electronic device 136 is placed.
- the ambient light sensor 100 has a function of a proximity sensor, the distance to an object close to the surface panel of the electronic device 136 is measured in addition to the measurement of ambient light.
- the electronic device 136 controls the brightness of the display panel 140 by the ambient light sensor 100, and controls on / off of the display panel and on / off of the input function.
- the electronic device 136 emphasizes the design of the appearance, and does not provide an opening for allowing external light to enter the ambient light sensor 100, but allows the ambient light sensor 100 to pass through the optical window 145 of the housing 138.
- a structure that is exposed to light is adopted.
- the optical window 145 is, for example, a member used as a surface panel of the electronic device 136, or a part thereof, and has translucency.
- the front panel is a member that constitutes the external appearance of the electronic device 136, it is usually colored. In this case, the optical window 145 has a problem that the amount of transmitted visible light is reduced and is buried in near-infrared information.
- the optical filter 104 is provided in the ambient light sensor 100, visible light can be detected by removing near-infrared noise. Therefore, even when the ambient light sensor 100b having a function as a color sensor is used, a shift in color tone can be suppressed and ambient light can be accurately detected.
- the optical filter 104 is provided close to the light receiving surface of the photoelectric conversion element 102, so that the illuminance is accurately measured even for light incident at a wide angle. be able to.
- Parts and % mean “parts by weight” and “% by weight” unless otherwise specified.
- 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), (b) or (c) 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
- ⁇ ⁇ ln (ts / t0) ⁇ / C t0: Flowing time of solvent ts: Flowing time of dilute polymer solution C: 0.5 g / dL ⁇ Glass transition temperature (Tg)> Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.
- the spectrophotometer 3 transmits light 1 ′ transmitted at an angle of 30 ° with respect to the vertical direction of the optical filter 2 as shown in FIG.
- the light 1 transmitted at an angle of 60 ° with respect to the vertical direction of the optical filter 2 as shown in FIG. ′′ was measured with a spectrophotometer 3.
- the transmittance is such that light is incident on the substrate and the filter perpendicularly except when measuring (T B ), (T C ), (OD B ), (OD D ), and (Xb). It was measured using the spectrophotometer under conditions.
- the spectrophotometer is used under the condition of incidence at an angle of 60 ° with respect to the vertical direction of the optical filter.
- the measurement was performed using the spectrophotometer under the condition that light was incident at an angle of 30 ° with respect to the vertical direction of the filter. It is.
- ⁇ Illuminance sensor sensitivity characteristics The optical characteristics of the optical filter (the optical characteristics of the light that passes through the optical filter) are compared with the illuminance sensor and the human visual sensitivity characteristics. Evaluation was performed. Evaluation was made based on the following criteria.
- the incident light to the illuminance sensor can be light that is close to human visual sensitivity characteristics, and high sensor sensitivity characteristics can be obtained.
- Xx Since the optical characteristics of incident light to the illuminance sensor change depending on the incident angle, human visual sensitivity characteristics and errors occur, the sensor sensitivity characteristics are low, and the obtained optical filter has a wavelength of 800 to 1000 nm. Since the transmittance is high, the near-infrared cut by the optical filter is insufficient, and the incident light is greatly deviated from the human visual sensitivity characteristic, which causes the illuminance sensor to malfunction.
- DCM dodec-3-ene
- reaction A hydrogenated polymer solution
- Mn number average molecular weight
- Mw weight average molecular weight
- Tg glass transition temperature
- the autoclave was heated to 75 ° C., and the catalyst component palladium 2-ethylhexanoate (as Pd atoms); 0.003 milligram atoms and tricyclohexylphosphine; 0.0015 mmol toluene; 1 in 10 ml at 25 ° C. Polymerization was initiated by adding the total amount of the solution reacted for a time, triphenylcarbenium pentafluorophenylborate; 0.00315 mmol in this order.
- addition polymer B having a solid content of 19.9% by weight was obtained.
- a part of the solution of addition polymer B was put in isopropanol, solidified, and dried to obtain addition polymer B (hereinafter also referred to as “resin B”).
- polyimide solution C an N-methyl-2-pyrrolidone solution of polyimide
- the obtained resin D 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.
- ⁇ Resin synthesis example 5> In a 500 mL five-necked flask equipped with a thermometer, stirrer, nitrogen inlet tube, dropping funnel with side tube, Dean-Stark tube and condenser tube, 1,4-bis (4-amino- ⁇ , ⁇ -Dimethylbenzyl) benzene (27.66 g, 0.08 mol) and 4,4′-bis (4-aminophenoxy) biphenyl (7.38 g, 0.02 mol) were added, and ⁇ -butyrolactone (68.65 g) and N, It was dissolved in 17.16 g of N-dimethylacetamide. The obtained solution was cooled to 5 ° C.
- resin E A part of this polyimide resin solution was poured into 1 L of methanol to precipitate the polyimide.
- the IR spectrum of the obtained resin E was measured, 1704 cm -1 characteristic of imido group, absorption of 1770 cm -1 were observed.
- Resin E had a glass transition temperature (Tg) of 310 ° C. and a logarithmic viscosity of 0.87.
- Example A1 100 parts by weight of resin A obtained in Resin Synthesis Example 1, 0.050 part by weight of compound (x) (absorption maximum wavelength; 704 nm) having the following structure, and compound (y) having the following structure (absorption maximum wavelength: 737 nm) 0.056 parts by weight, a light absorber “CIR-RL” (maximum absorption wavelength: 1095 nm) manufactured by Nippon Carlit Co., Ltd., and further dissolved by adding toluene to a solution having a solid content of 30% Got. Subsequently, the solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, and at 100 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side of 60 mm.
- the average OD value (OD C ) at 850 to 1050 nm of the obtained substrate was 2.1.
- the results are shown in Table 11.
- a dielectric multilayer film (III) is formed on one surface of the obtained base material, and a dielectric multilayer film (IV) is further formed on the other surface of the base material.
- a filter was obtained.
- the dielectric multilayer film (III) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a deposition temperature of 100 ° C. (total number of layers: 26 layers).
- the dielectric multilayer film (IV) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a deposition temperature of 100 ° C. (total number of layers: 20 layers).
- the silica layer and the titania layer are 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 (III) and (IV) were designed as follows.
- Optimization was performed using optical thin film design software (Essential Macleod, Thin Film Center) according to the characteristics.
- the input parameters (Target values) to the software are as shown in Table 10 below.
- the average value (T A ) of transmittance at wavelengths of 430 to 580 nm of the obtained optical filter was 67%, and the average OD value (OD A ) at 850 to 1050 nm was 4.7.
- the average transmittance (T B ) when measured from an angle of 30 ° with respect to the vertical direction of the optical filter is 66%, and measured from an angle of 60 ° with respect to the vertical direction of the optical filter.
- the average transmittance (T C ) is 51%
- the average OD value (OD D ) when measured from an angle of 30 ° with respect to the vertical direction of the optical filter at a wavelength of 850 to 1050 nm is 4.9.
- the average OD value (OD B ) when measured from an angle of 60 ° with respect to the vertical direction of the optical filter was 3.9. Further, the rate of change of the ratio of R transmittance when 0 ° ⁇ 30 ° is 1.0, and the rate of change of the ratio of G transmittance when 0 ° ⁇ 30 ° is 1.0, 0 ° ⁇ 30 °.
- the change rate of the B transmittance ratio in the case is 1.0
- the change rate of the R transmittance ratio in the case of 0 ° ⁇ 60 ° is 0.6
- the change rate of the G transmittance in the case of 0 ° ⁇ 60 ° The rate of change in the ratio was 1.3
- the rate of change in the ratio of the B transmittance in the case of 0 ° ⁇ 60 ° was 1.0.
- Example A2 Other than changing the light absorber “CIR-RL” manufactured by Nippon Carlit Co., Ltd. to 0.6 parts by weight and the dye “S2058” (absorption maximum wavelength; 980 nm) manufactured by DKSH, to 0.3 parts by weight. Produced a substrate having a thickness of 0.1 mm and a side of 60 mm in the same manner as in Example A1. Furthermore, using the obtained base material, an optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A3 A base material having a thickness of 0.1 mm and a side of 60 mm was obtained in the same manner as in Example A1, except that the resin B obtained in Resin Synthesis Example 2 was used instead of the resin A, and cyclohexane was used instead of toluene. It was. Furthermore, using the obtained base material, an optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A4 100 parts by weight of norbornene resin “Arton G” manufactured by JSR Corporation, 0.050 parts by weight of the compound (x), 0.056 parts by weight of the compound (y), and a light absorber manufactured by Nippon Carlit Co., Ltd. 0.6 part by weight of “CIR-RL” was added and further methylene chloride was added and dissolved to obtain a solution having a solid content of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side of 60 mm.
- Example A1 an optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A5 100 parts by weight of norbornene-based resin “ZEONOR 1400R” manufactured by Nippon Zeon Co., Ltd., 0.050 parts by weight of the compound (x), 0.056 parts by weight of the compound (y), light absorption manufactured by Nippon Carlit
- the agent “CIR-RL” was added by 0.6 parts by weight, and a 7: 3 mixed solution of cyclohexane and xylene was further added and dissolved to obtain a solution having a solid content of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 60 ° C. for 8 hours, and at 80 ° C. for 8 hours, and then peeled off from the glass plate.
- the peeled resin was further dried under reduced pressure at 100 ° C. for 24 hours to obtain a substrate having a thickness of 0.1 mm and a side of 60 mm. Furthermore, using the obtained base material, an optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A6 100 parts by weight of norbornene resin “APEL # 6015” manufactured by Mitsui Chemicals, Ltd., 0.050 parts by weight of the compound (x), 0.056 parts by weight of the compound (y), and Hikari manufactured by Nippon Carlit 0.6 part by weight of the absorbent “CIR-RL” was added, and further a 99: 1 mixed solution of cyclohexane and methylene chloride was added and dissolved to obtain a solution having a solid content of 20%. Then, the solution was cast on a smooth glass plate, dried at 40 ° C. for 4 hours and 60 ° C. for 4 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C.
- Example A1 An optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A7 100 parts by weight of polycarbonate resin “Pure Ace” manufactured by Teijin Limited, 0.050 part by weight of the compound (x), 0.056 parts by weight of the compound (y), and a light absorber “Nippon Carlit” CIR-RL "was added in an amount of 0.6 part by weight, and further methylene chloride was added and dissolved to obtain a 20% solid content solution. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side of 60 mm.
- Example A1 an optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A8 100 parts by weight of polyethersulfone “FS-1300” manufactured by Sumitomo Bakelite Co., Ltd., 0.050 parts by weight of the compound (x), 0.056 parts by weight of the compound (y), manufactured by Nippon Carlit Co., Ltd. 0.6 part by weight of the absorbent “CIR-RL” was added, and further N-methyl-2-pyrrolidone was added and dissolved to obtain a solution having a solid content of 20%. Then, the solution was cast on a smooth glass plate, dried at 60 ° C. for 4 hours and at 80 ° C. for 4 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 120 ° C.
- Example A1 An optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A9 100 parts by weight of the polyimide solution C obtained in Resin Synthesis Example 3, 0.050 parts by weight of the compound (x), 0.056 parts by weight of the compound (y), a light absorber “CIR” manufactured by Nippon Carlit Co., Ltd. -RL "was added in an amount of 0.6 part by weight to obtain a solution having a solid content of 20%. Then, the solution was cast on a smooth glass plate, dried at 60 ° C. for 4 hours and at 80 ° C. for 4 hours, and then peeled off from the glass plate. The peeled resin was further dried under reduced pressure at 120 ° C. for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side of 60 mm.
- Example A1 an optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A10 To 100 parts by weight of norbornene-based resin “Arton G” manufactured by JSR Corporation, 0.050 part by weight of the compound (x), 0.056 part by weight of the compound (y), and a light absorber “Nippon Carlit” 0.9 part by weight of “CIR-RL” was added, and further methylene chloride was added and dissolved to obtain a 20% solid content solution. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm and a side of 60 mm.
- Example A1 an optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A11 To 100 parts by weight of norbornene-based resin “Arton G” manufactured by JSR Corporation, 0.050 part by weight of the compound (x), 0.056 part by weight of the compound (y), and 0 of the dye “S2058” manufactured by DKSH .3 parts by weight, 3.2 parts by weight of cesium tungsten oxide (Cs 0.33 WO 3 ) were added, and further methylene chloride was added and dissolved to obtain a solution having a solid content of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled resin was further dried at 100 ° C.
- Example A1 An optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A12 To the container, 100 parts of the resin A obtained in Resin Synthesis Example 1 and methylene chloride 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 20 ° 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 support having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
- a resin composition (1) having the following composition was applied to one side of the obtained transparent resin support 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 transparent resin support body. Similarly, the resin layer which consists of resin composition (1) was formed also in the other surface of the transparent resin support body, and the base material which has a resin layer on both surfaces of a transparent resin support body was obtained. Furthermore, using the obtained base material, an optical filter having a thickness of 0.107 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured to evaluate optical characteristics. The results are shown in Table 11.
- 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, and 2.5 parts by weight of the compound (x) 2.8 parts by weight of the compound (y), 30 parts by weight of an absorbent “CIR-RL” manufactured by Nippon Carlit Co., Ltd., methyl ethyl ketone (solvent, solid content concentration (TSC): 30%).
- Example A13 In a container, 100 parts of the resin A obtained in Resin Synthesis Example 1, 2.5 parts by weight of the compound (x), 2.8 parts by weight of the compound (y), a light absorber “Nippon Carlit” 30 parts by weight of “CIR-RL” was added, and methylene chloride was added to prepare a solution having a resin concentration of 20% by weight. The resulting solution was cast on a transparent glass substrate “OA-10G” (thickness 200 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd. cut to a size of 60 mm in length and 60 mm in width, and dried at 20 ° C. for 8 hours.
- OA-10G thickness 200 ⁇ m
- Example A14 To the container, 100 parts of the resin A obtained in Resin Synthesis Example 1, 6.5 parts by weight of DKSH dye “S2058”, and methylene chloride were added to prepare a solution having a resin concentration of 20% by weight.
- the obtained solution was cast on a blue plate glass substrate “BS-6” (thickness: 210 ⁇ m) manufactured by Matsunami Glass Industry Co., Ltd. cut to a size of 60 mm in length and 60 mm in width, and dried at 20 ° C. for 8 hours. Furthermore, it dried at 100 degreeC under pressure reduction for 8 hours, and obtained the base material which has a transparent resin layer and glass support of thickness 0.216mm, length 60mm, and width 60mm.
- Example A1 an optical filter having a thickness of 0.220 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A15 100 parts by weight of norbornene-based resin “Arton G” manufactured by JSR Corporation, 0.075 parts by weight of the compound (x), 0.085 parts by weight of the compound (y), a light absorber manufactured by Nippon Carlit 0.9 parts by weight of “CIR-RL” and 0.10 parts by weight of compound (z) having the following structure were added, and methylene chloride was further added and dissolved to obtain a solution having a solid content of 20%.
- the solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate.
- the peeled resin was further dried under reduced pressure at 100 ° C. for 8 hours to obtain a transparent resin substrate having a thickness of 0.1 mm and a side of 60 mm.
- the spectral transmittance of the obtained transparent resin substrate was measured in the same manner as in Example A1, and the optical characteristics were evaluated. The results are shown in Table 11.
- Example A16 An optical filter having a thickness of 0.214 mm was obtained in the same manner as in Example A1, except that a blue plate glass substrate “BS-6” (thickness: 210 ⁇ m) manufactured by Matsunami Glass Industry Co., Ltd. was used as the substrate. The spectral transmittance of the substrate and the obtained optical filter was measured in the same manner as in Example A1, and the optical characteristics were evaluated. The results are shown in Table 11.
- a multilayer deposited film reflecting a near infrared ray at a deposition temperature of 150 ° C. silicon (SiO 2 : film thickness 120 to 190 nm) layer and titania (TiO 2 : film thickness 70 to 120 nm)
- SiO 2 film thickness 120 to 190 nm
- TiO 2 film thickness 70 to 120 nm
- an optical filter having a thickness of 0.105 mm was obtained.
- the spectral transmittance of the obtained optical filter was measured in the same manner as in Example A1, and the optical characteristics were evaluated. The results are shown in Table 11.
- Example A2 A base having a thickness of 0.1 mm and a side of 60 mm, as in Example A1, except that the light absorber “CIR-RL” manufactured by Nippon Carlit Co., Ltd. was changed from 0.6 parts by weight to 0.05 parts by weight. I got the material. Furthermore, using the obtained base material, an optical filter having a thickness of 0.105 mm was obtained in the same manner as in Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example A3 A substrate having a thickness of 0.1 mm and a side of 60 mm was obtained in the same manner as in Example A1, except that the light absorber “CIR-RL” manufactured by Nippon Carlit Co., Ltd. was not used. Furthermore, using the obtained base material, an optical filter having a thickness of 0.106 mm was obtained in the same manner as in Comparative Example A1. Spectral transmittances of the obtained substrate and optical filter were measured in the same manner as in Example A1, and optical characteristics were evaluated. The results are shown in Table 11.
- Example B1 an optical filter having a base material made of a transparent resin substrate was prepared according to the following procedure and conditions.
- a base material composed of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
- the spectral transmittance of this substrate was measured, and measured in the region where the wavelength was 600 nm or more and less than 750 nm, the lowest transmittance (Ta) measured from the vertical direction of the optical filter and the substrate in the region where the wavelength was 600 nm or more.
- the shortest wavelength (Xc) at which the transmittance was from more than 50% to 50% or less was determined. The results are shown in FIG.
- the dielectric multilayer film (I) is formed on one surface of the obtained base material, and the dielectric multilayer film (II) is further formed on the other surface of the base material, so that the optical thickness is about 0.104 mm.
- a filter was obtained.
- the dielectric multilayer film (I) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a deposition temperature of 100 ° C. (total number of layers: 26 layers).
- the dielectric multilayer film (II) is formed by alternately laminating silica (SiO 2 ) layers and titania (TiO 2 ) layers at a deposition temperature of 100 ° C. (total number of layers: 20 layers).
- the silica layer and the titania layer are in 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 (I) and (II) were designed as follows.
- the wavelength-dependent characteristics of the substrate refractive index and the absorption characteristics of the applied compound (A) so as to achieve the visible antireflection effect and the selective transmission / reflection performance in the near infrared range was optimized using optical thin film design software (Essential Macleod, Thin Film Center).
- the input parameters (Target values) to the software are as shown in Table 12 below.
- the spectral transmittance measured from the vertical direction of the obtained optical filter and an angle of 30 ° from the vertical direction was measured, and the optical characteristics in each wavelength region were evaluated.
- the results are shown in FIG.
- the average value of transmittance at wavelengths of 430 to 580 nm was 90%
- the average value of transmittance at wavelengths of 800 to 1000 nm was 1% or less
- was 3 nm.
- FIG. 15 shows spectral sensitivity characteristics of a general illuminance sensor
- FIG. 16 shows human visual sensitivity characteristics.
- the obtained optical filter has a small change in optical characteristics depending on the incident angle and can cut near-infrared light of 700 nm or more. By setting it on the upper side (light incident side), the incident light to the illuminance sensor can be made light close to human visual sensitivity characteristics regardless of the incident angle, and high sensor sensitivity characteristics can be obtained.
- Example B2 an optical filter having a base material made of a transparent resin substrate having a resin layer on both sides was prepared according to the following procedure and conditions.
- Example B1 as compound (A), 0.03 part of compound (a-3) (absorption maximum wavelength 703 nm in dichloromethane) represented by the following formula (a-3) and the following formula (a-4): From the transparent resin substrate containing the compound (A) in the same procedure and conditions as in Example B1, except that 0.07 part of the compound (a-4) represented (absorption maximum wavelength 736 nm in dichloromethane) was used. A base material was obtained.
- a resin composition (G-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, exposure (exposure amount: 500 mJ / cm 2 , 200 mW) was performed using a conveyor type exposure machine, the resin composition (G-1) was cured, and a resin layer was formed on a transparent resin substrate. Similarly, a resin layer made of the resin composition (G-1) is 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) is provided. Obtained. The spectral transmittance of this substrate was measured to determine (Ta) and (Xc). The results are shown in FIG.
- Resin composition (G-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, methyl ethyl ketone (solvent, solid content concentration (TSC): 30 %).
- Example B1 a dielectric multilayer film (total number of layers: 26) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on one side of the obtained base material. And forming a dielectric multilayer film (total number of layers: 20) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on the other surface of the substrate, and having a thickness of about An optical filter of 0.104 mm was obtained.
- the dielectric multilayer film was designed using the same design parameters as in Example B1 in consideration of the wavelength dependency of the base material refractive index. The spectral transmittance of the obtained optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.
- the obtained optical filter has a small change in optical characteristics depending on the incident angle and can cut near infrared light of 700 nm or more.
- the incident light to the illuminance sensor can be made light close to human visual sensitivity characteristics regardless of the incident angle, and high sensor sensitivity characteristics can be obtained.
- Example B3 an optical filter having a base material composed of a near-infrared absorbing glass substrate was prepared according to the following procedure and conditions.
- a silica (SiO 2 ) layer is formed on one side of the base material in the same manner as in Example B1, except that a near-infrared absorbing glass substrate “BS-6” (thickness 210 ⁇ m) manufactured by Matsunami Glass Industrial Co., Ltd. was used as the base material. And a titania (TiO 2 ) layer are alternately laminated to form a dielectric multilayer film (total number of layers: 26), and a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are formed on the other surface of the substrate.
- BS-6 near-infrared absorbing glass substrate manufactured by Matsunami Glass Industrial Co., Ltd.
- a dielectric multilayer film (total number of layers: 20) formed by alternately laminating layers was formed, and an optical filter having a thickness of about 0.216 mm was obtained.
- the dielectric multilayer film was designed using the same design parameters as in Example B1 in consideration of the wavelength dependency of the base material refractive index. The spectral transmittance of this optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG.
- the obtained optical filter is inferior in incident angle dependency in the region of 650 to 700 nm as compared with the optical filter of Example B1 and Example B2, the change in the optical characteristics depending on the incident angle. Because it is small and can cut near-infrared light of 700 nm or more, by installing this optical filter on the upper side (light incident side) of the illuminance sensor, the incident light to the illuminance sensor is independent of the incident angle. Can be made light that is close to human visual sensitivity characteristics, and high sensor sensitivity characteristics can be obtained.
- Example B4 an optical filter having a base material composed of a transparent glass substrate having a transparent resin layer containing the compound (A) on one side was prepared according to the following procedure and conditions.
- a resin composition (G-2) having the following composition was applied to a transparent glass substrate “OA-10G” (thickness: 200 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd., cut to a size of 60 mm in length and 60 mm in width with a spin coater. Then, the solvent was volatilized and removed by heating on a hot plate at 80 ° C. for 2 minutes. Under the present circumstances, the application
- Resin composition (G-2) 20 parts by weight of tricyclodecane dimethanol acrylate, 80 parts by weight of dipentaerythritol hexaacrylate, 4 parts by weight of 1-hydroxycyclohexyl phenyl ketone, 1.5 parts by weight of compound (a-1), Compound (a-2) 1.5 parts by weight, methyl ethyl ketone (solvent, TSC: 35%) Subsequently, as in Example B1, a dielectric multilayer film (total number of layers: 26) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on one side of the obtained base material.
- a dielectric multilayer film total number of layers: 26
- dielectric multilayer film (total number of layers: 20) in which a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated on the other surface of the substrate, and having a thickness of about
- An optical filter of 0.108 mm was obtained.
- the dielectric multilayer film was designed using the same design parameters as in Example B1 after considering the wavelength dependence of the refractive index of the base material in the same manner as in Example B1. The spectral transmittance of this optical filter was measured, and the optical characteristics in each wavelength region were evaluated. The results are shown in Table 13.
- the obtained optical filter has a small change in optical characteristics depending on the incident angle and can cut near-infrared light of 700 nm or more.
- the incident light to the illuminance sensor can be made to be close to human visual sensitivity characteristics regardless of the incident angle, and high sensor sensitivity characteristics can be obtained.
- Examples B5 to B7 A substrate and an optical filter were prepared in the same manner as in Example B2, except that the transparent resin species and the compound (A) were changed as shown in Table 13. Table 13 shows the optical characteristics of the obtained substrate and optical filter.
- the optical filters obtained in Examples B5 to B7 have little change in optical characteristics depending on the incident angle, and can cut near infrared light of 700 nm or more. Is placed on the upper side of the illuminance sensor (on the light incident side), the incident light to the illuminance sensor can be made light close to human visual sensitivity characteristics regardless of the incident angle, and high sensor sensitivity characteristics can be obtained.
- Example B1 In Example B1, a substrate and an optical filter were prepared in the same manner as in Example B1, except that the compound (A) was not used. The optical characteristics of the obtained optical filter are shown in FIG.
- the obtained optical filter has a large change in optical characteristics depending on the incident angle, and when this optical filter is installed on the upper side (light incident side) of the illuminance sensor, the illuminance sensor depends on the incident angle. Since the optical characteristics of the incident light on the surface change, human visual sensitivity characteristics and errors occur, and the sensor sensitivity characteristics are low.
- Example B2 An optical filter was prepared in the same manner as in Example B1, except that a transparent glass substrate “OA-10G” (thickness: 200 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd. was used instead of the transparent resin substrate. Table 13 shows the optical characteristics of the obtained optical filter.
- the obtained optical filter has a large change in the optical characteristics depending on the incident angle, and when this optical filter is installed on the upper side of the illuminance sensor (on the light incident side), the optical characteristics of the incident light to the illuminance sensor change depending on the incident angle. Therefore, an error occurs with human visibility characteristics, and the sensor sensitivity characteristics are low.
- Example B3 In Example B1, the compound (A) was not used, and instead of the dielectric multilayer film (I), a silica (SiO 2 ) layer and a titania (TiO 2 ) layer were alternately laminated at a deposition temperature of 100 ° C. In place of the dielectric multilayer film (total number of layers 6) and dielectric multilayer film (II), a silica (SiO 2 ) layer and a titania (TiO 2 ) layer are alternately laminated at a deposition temperature of 100 ° C. A substrate and an optical filter were prepared in the same manner as in Example B1, except that the dielectric multilayer film (total number of layers: 6) was used. The optical characteristics of the obtained optical filter are shown in FIG.
- the obtained optical filter has a large change in optical characteristics depending on the incident angle.
- the illuminance sensor depends on the incident angle. Since the optical characteristics of the incident light to the light change, human visual sensitivity characteristics and errors occur, and the sensor sensitivity characteristics are low.
- the obtained optical filter has a high transmittance of 800 to 1000 nm, so the near-infrared cut by the optical filter is insufficient, and when this optical filter is installed on top of the illuminance sensor, the incident light is human visibility The illuminance sensor malfunctions due to a large deviation from the characteristics.
- Glass substrate (2) Transparent glass substrate “OA-10G” (thickness: 200 ⁇ m) manufactured by Nippon Electric Glass Co., Ltd. cut to a size of 60 mm in length and 60 mm in width ⁇ Near-infrared absorbing dye> ⁇ Compound (A) >> Compound (a-1): Compound (a-1) (absorption maximum wavelength in dichloromethane 698 nm) Compound (a-2): Compound (a-2) (absorption maximum wavelength in dichloromethane: 733 nm) Compound (a-3): Compound (a-3) (absorption maximum wavelength in dichloromethane 703 nm) Compound (a-4): Compound (a-4) above (maximum absorption wavelength 736 nm in dichloromethane) ⁇ Solvent> Solvent (1): Methylene chloride Solvent (2): N, N-dimethylacetamide Solvent (3): Cyclohexane / xylene (weight ratio: 7/3) In Table 13, the
- Optical filter 3 Spectrophotometer 100: Ambient light sensor 102: Photoelectric conversion element 104: Optical filter 106: First electrode 108: Photoelectric conversion layer 110: p-type semiconductor region 112: n-type semiconductor region 114: Second electrode 116: Insulating layer 118: Near-infrared reflecting layer 120: Near-infrared absorbing layer 122: Resin layer 124: Glass substrate 126: Color filter 128: Element isolation insulating layer 130: Light-emitting diode 132: Light shielding member 134: Near-infrared path Filter 136: Electronic device 138: Housing 140: Display panel 142: Microphone unit 144: Speaker unit 145: Optical window 201: Sensor module 202: Light diffusion film 203: Optical filter 204: IR cut film 205: Light shielding plate 206: Light shielding Spacer 207: Light sensor
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Abstract
Description
(A)波長430~580nmの範囲において、光学フィルターの垂直方向から測定した場合の透過率が50%以上である;
(B)波長800~1000nmの範囲において、光学フィルターの垂直方向から測定した場合の透過率の平均値が15%以下である;
(C)波長560~800nmの範囲において、光学フィルターの垂直方向から測定した場合の透過率が50%となる波長の値(Xa)と、光学フィルターの垂直方向に対して30°の角度から測定した場合の透過率が50%となる波長の値(Xb)の差の絶対値(|Xa-Xb|)が20nm未満である。
本発明に係る第一の光学フィルターは、光吸収層を有する基材(i)を有し、かつ、可視光を透過する光学フィルターであって、前記光吸収層が波長750~1150nmの領域に吸収極大を有し、波長850~1050nmにおいて、前記光学フィルターの垂直方向から測定した場合の平均OD値(以下「ODA」ともいう。)が2.0以上であり、かつ、前記光学フィルターの垂直方向に対して60°の角度から測定した場合の平均OD値(以下「ODB」ともいう。)が2.0以上であることを特徴とする。
前記ODAは、好ましくは2.3以上10以下、より好ましくは2.5以上9以下である。前記ODBは、好ましくは2.3以上10以下、より好ましくは2.5以上9以下である。
(G透過率の比)=(G透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(3)
(B透過率の比)=(B透過率)×100/((R透過率)+(G透過率)+(B透過率))・・・式(4)
光学フィルターの垂直方向に対して30°の角度から測定した場合のR透過率の比を、光学フィルターの垂直方向から測定した場合のR透過率の比で割った値(0°→30°の場合のR透過率の比の変化率)は下記式(5)から導くことができる。
0°→30°の場合のR透過率の比の変化率は、好ましくは0.5以上2.0以下、より好ましくは0.6以上1.8以下、さらに好ましくは0.8以上1.4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°→30°の場合のG透過率の比の変化率は、好ましくは0.5以上2.0以下、より好ましくは0.6以上1.8以下、さらに好ましくは0.8以上1.4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°→30°の場合のB透過率の比の変化率は、好ましくは0.5以上2.0以下、より好ましくは0.6以上1.8以下、さらに好ましくは0.8以上1.4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R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。
前記基材(i)は、単層であっても多層であってもよく、波長750~1150nmの領域に吸収極大を有する光吸収層を含有すればよい。また、前記光吸収層は、波長750~1150nmの領域に吸収極大を有する化合物(S)を含有することが好ましい。基材(i)が単層の場合は、例えば、化合物(S)を含む透明樹脂製基板(ii)からなる基材、銅成分を含有する近赤外線吸収ガラス基板(iii)からなる基材を挙げることができ、この透明樹脂製基板(ii)、またはガラス基板(iii)が前記光吸収層となる。多層の場合は、例えば、ガラス支持体やベースとなる樹脂製支持体などの支持体上に化合物(S)を含有する硬化性樹脂等からなるオーバーコート層などの透明樹脂層が積層された基材、化合物(S)を含む透明樹脂製基板(ii)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などを挙げることができる。製造コストや光学特性調整の容易性、さらに、樹脂製支持体や透明樹脂製基板(ii)の傷消し効果を達成できることや基材(i)の耐傷つき性向上等の点から、化合物(S)を含有する透明樹脂製基板(ii)上に硬化性樹脂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が特に好ましい。
前記光吸収層は、波長750~1150nmの領域に吸収極大を有すれば特に限定されないが、波長850~1050nmの領域において、前記基材(i)の垂直方向から測定した場合の平均OD値(以下「ODC」ともいう。)が、好ましくは1.0以上、より好ましくは1.1以上10以下、さらに好ましくは1.3以上9以下であることが望ましい。
前記化合物(S)としては、近赤外線を吸収する色素として作用する金属錯体系化合物、染料または顔料を用いることができ、具体的には、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、金属ジチオラート錯体系化合物、リン酸銅錯体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種の化合物を挙げることができる。特に下記式(s1)で表されるジイモニウム系化合物および下記式(s2)で表される金属ジチオラート錯体系化合物が好ましい。このような化合物(S)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。また、前記光吸収層に含まれる化合物(S)は、1種単独でもよく、2種以上でもよい。
(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、隣り合うR3同士は置換基Lを有してもよい環を形成してもよい。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。Mは金属原子を表す。ZはD(Ri)4を表し、Dは窒素原子、リン原子またはビスマス原子を表し、yは0もしくは1を表す。
前記光吸収層は、波長650~750nmの領域に吸収極大を有する化合物(A)をさらに含むことができる。前記化合物(S)を含む光吸収層と、前記化合物(A)を含む光吸収層は、同一の層であってもよく、異なる層であってもよい。また、前記光吸収層に含まれる化合物(A)は、1種単独でもよく、2種以上でもよい。
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。
前記光吸収層に用いる透明樹脂としては、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し、かつ、100℃以上の蒸着温度で行う高温蒸着により誘電体多層膜を形成しうるフィルムとするため、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、前記樹脂のガラス転移温度が140℃以上であると、誘電体多層膜をより高温で蒸着形成しえるフィルムが得られるため、特に好ましい。
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。
より選ばれる原子または基を表し、kx、mxおよびpxはそれぞれ独立に、0または正の整数を表す。
(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(S)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(S)を含有する透明樹脂製基板(ii)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。
前記光吸収層は、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。
≪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、例えば、無色透明のガラス基板、銅成分を含有するガラス基板、またはフツリン酸塩ガラス基板を用いることができる。特に、吸収剤として銅成分を含むフツリン酸ガラスは近赤外線カット能を向上させられるため好ましい。
前記基材(i)が、前記透明樹脂製基板(ii)を含む基材である場合、該透明樹脂製基板(ii)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(S)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(S)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(S)、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(S)、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(S)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。
本発明に係る第一の光学フィルターは、前記基材(i)の少なくとも一方の面に誘電体多層膜を有することが好ましい。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り、誘電体多層膜を有することでより優れた可視光透過率と近赤外線カット特性を達成することができる。
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。
本発明に係る第二の光学フィルターは、近赤外線吸収層(光吸収層)と、近赤外線反射層とを含むことを特徴とする。
本発明に係る第二の光学フィルターは、近赤外線反射層及び近赤外線吸収層を含むが、その形態として様々な変形が許容される。
図2(A)は、光入射側から、第1近赤外線反射層118a、近赤外線吸収層120、第2近赤外線反射層118bが設けられた光学フィルター104aを示す。第1近赤外線反射層118aは屈折率の異なる誘電体膜が積層された構造を有する。第2近赤外線反射層118bは、第1近赤外線反射層118aと同じ誘電体多層構造を有していてもよいし、異なる誘電体多層構造を有していてもよい。
図2(A)で示す光学フィルター104aにおいて、近赤外線吸収層120に近赤外線を吸収するガラスを用いてもよい。すなわち、近赤外線を吸収する化合物を含む樹脂層に代えて、近赤外線を吸収する物質を含むガラス基板を用いて光学フィルター104を構成してもよい。ガラス素材としては、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層であってもよい。ガラス層は樹脂層に比べて耐熱性が高く、硬質であるので、光学フィルター104の耐熱性や構造安定性を高めることができる。
図2(B)は、第1近赤外線反射層118aと近赤外線吸収層120との間に第1樹脂層122aが設けられ、第2近赤外線反射層118bと近赤外線吸収層120との間に第2樹脂層122bが設けられた光学フィルター104bを示す。近赤外線反射層と近赤外線吸収層との間に樹脂層を設けることで、光学フィルター104bの薄型化を図りつつ強度を高めることが可能となる。近赤外線吸収層120としては、上述の透光性の樹脂層の中に近赤外線を吸収する化合物を含む層、あるいは近赤外線を吸収する物質を含むガラス基板を用いることができる。なお、樹脂層122は、第1樹脂層122a及び第2樹脂層122bの一方のみが設けられていてもよい。また、図2(B)は、近赤外線反射層が近赤外線吸収層の両面に設けられる態様を示すが、光学フィルター104bはこの態様に限定されない。近赤外線反射層は、近赤外線吸収層の片面のみに設けられていてもよい。なお、樹脂層122aおよび122bには近赤外線吸収剤が含まれてもよいし、含まれていなくてもよい。また、第1近赤外線反射層と第2近赤外線反射層のどちらかを反射防止層に代えた構成を用いることもできる。
図3(A)は、透明なガラス基板124を用いて構成される光学フィルター104cを示す。光学フィルター104cは、ガラス基板124の一方の面に近赤外線吸収層120を設け、その上面に第1近赤外線反射層118aが設けられている。近赤外線吸収層120としては、透光性の樹脂層の中に近赤外線を吸収する化合物を含む層が用いられる。また、ガラス基板124の他方の面に第2近赤外線反射層118bが設けられている。透明なガラス基板124は、光学フィルター104の基材として用いることができる。ガラス基板124を基材として用いることで、光学フィルター104の剛性を高めることができる。なお、図3(A)において示される第2近赤外線反射層118bを、ガラス基板124と近赤外線吸収層120との間に設けてもよい。
図3(B)は、透明な樹脂基板125を用いて構成される光学フィルター104dを示す。光学フィルター104dは、樹脂基板125の一方の面に近赤外線吸収層120を設け、その上面に第1近赤外線反射層118aが設けられている。また、樹脂基板125の他方の面に第2近赤外線反射層118bが設けられている。樹脂基板125は、光学フィルター104の基材として用いることができる。樹脂基板125を基材として用いることで、光学フィルター104の加工性、柔軟性を高めることができる。なお、図3(B)において示される第2近赤外線反射層118bを、樹脂基板124と近赤外線吸収層120との間に設けてもよい。近赤外線吸収層120としては、透光性の樹脂層の中に近赤外線を吸収する化合物を含む層が用いられる。
近赤外線反射層118は、少なくとも波長400nm~600nmの帯域の可視光線を透過するとともに、少なくとも波長750nm以上の近赤外線を反射するように設計される。近赤外線反射層118は、可視領域の透過率が高く、少なくとも波長400nm~600nmの波長帯域において90%以上の平均分光透過率を有することが好ましい。また、近赤外線反射層118は、波長750nm以上の近赤外線波長帯域においては2%未満の分光透過率を有していることが好ましい。これは、光電変換素子102に近赤外線が入射されず、一方で可視光線帯域の光を高感度で検知するためである。
近赤外線吸収層120を構成するための近赤外線吸収色素を含有させる樹脂および透明樹脂基板125に用いられる樹脂としては、透明樹脂を用いることができる。透明樹脂の詳細については、前記第一の光学フィルターにおいて説明した通りである。
前記基材が近赤外線吸収色素を含有する透明樹脂製基板を含む場合、該透明樹脂製基板は、前記第一の光学フィルターで説明した方法で製造することができる。
近赤外線吸収層として、銅成分を含む近赤外線吸収ガラス(以下「Cu含有ガラス」ともいう。)を用いることができる。Cu含有ガラスを用いることで、可視光に対する高透過性を有するとともに、近赤外線に対しても高い遮蔽性を有する。なお、リン酸塩ガラスには、ガラス骨格の一部がSiO2で構成されるケイリン酸塩ガラスも含むものとする。Cu含有ガラスとしては、例えば、以下の組成のものが挙げられる。
吸収の無いガラス基板としては、主成分として、珪酸塩を含む基板であれば、特に限定されるものではなく、結晶構造を有する石英ガラス基板等が挙げられる。ほかに、ホウ珪酸ガラス基板、ソーダガラス基板および色ガラス基板等を用いることができるが、とりわけ、無アルカリガラス基板、低α線ガラス基板等のガラス基板は、センサー素子への影響が少ないため、好ましい。
本発明において、近赤外線吸収層と近赤外線反射膜の間には樹脂層があってもよい。特に、前記基材としてガラス基材を使用し、ガラス基板上に近赤外線吸収層を積層する場合には、前記近赤外線吸収層とガラス基板は、互いに化学的な組成、および熱線膨張率が異なるため、近赤外線吸収層とガラス基板との間に密着層を設けて、それらの十分な密着性を確保することが好ましい。本発明に用いる密着層は近赤外線吸収層とガラス基板との間の密着性を確保できる材料からなれば、特に限定されないが、例えば、(a)(メタ)アクリロイル基含有化合物に由来する構造単位、(b)カルボン酸基含有化合物に由来する構造単位、および(c)エポキシ基含有化合物に由来する構造単位を有すると、近赤外線吸収層とガラス基板との密着性が高くなるため好ましい。
構造単位(a)としては、(メタ)アクリロイル基含有化合物に由来する構造単位であれば特に限定されるものではない。(メタ)アクリロイル基含有化合物としては、例えば、単官能、2官能または3官能以上の(メタ)アクリル酸エステルが、重合性が良好である点から好ましい。本発明において、「(メタ)アクリル」は、「アクリル」または「メタクリル」を意味する。
構造単位(b)としては、カルボン酸基を含有する化合物に由来する構造単位であれば特に限定されるものではない。カルボン酸基含有化合物としては、例えばモノカルボン酸、ジカルボン酸、ジカルボン酸の無水物およびカルボン酸基を有する重合体を挙げることができる。
構造単位(c)としては、エポキシ基含有化合物に由来する構造単位であれば特に限定されるものではない。エポキシ基(オキシラニル基)含有化合物としては、例えば、(メタ)アクリル酸オキシラニル(シクロ)アルキルエステル、α-アルキルアクリル酸オキシラニル(シクロ)アルキルエステルおよび不飽和結合を有するグリシジルエーテル化合物等のオキシラニル基を有する不飽和化合物;オキセタニル基を有する(メタ)アクリル酸エステル等のオキセタニル基を有する不飽和化合物を挙げることができる。
前記密着層には、本発明の効果を損なわない範囲において、酸発生剤、密着助剤、界面活性剤、重合開始剤等の任意成分を添加することができる。これらの添加量は、所望の特性に応じて適宜選択されるが、前記(メタ)アクリロイル基含有化合物、前記カルボン酸基含有化合物および前記エポキシ基含有化合物の合計100重量部に対して、それぞれ通常0.01~15.0重量部、好ましくは0.05~10.0重量部であることが望ましい。
前記重合開始剤は、紫外線や電子線等の光線に感応してモノマー成分の重合を開始しうる活性種を生じる成分である。このような重合開始剤としては特に限定されるものではないが、O-アシルオキシム化合物、アセトフェノン化合物、ビイミダゾール化合物、アルキルフェノン化合物、ベンゾフェノン化合物などを挙げることができる。これらの具体例としては、エタノン-1-〔9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、1-〔9-エチル-6-ベンゾイル-9.H.-カルバゾール-3-イル〕-オクタン-1-オンオキシム-O-アセテート、1-〔9-エチル-6-(2-メチルベンゾイル)-9.H.-カルバゾール-3-イル〕-エタン-1-オンオキシム-O-ベンゾエート、1-〔9-n-ブチル-6-(2-エチルベンゾイル)-9.H.-カルバゾール-3-イル〕-エタン-1-オンオキシム-O-ベンゾエート、エタノン-1-[9-エチル-6-(2-メチル-4-テトラヒドロフラニルベンゾイル)-9.H.-カルバゾール-3-イル]-1-(O-アセチルオキシム)、1,2-オクタンジオン-1-[4-(フェニルチオ)-2-(O-ベンゾイルオキシム)]、エタノン-1-〔9-エチル-6-(2-メチル-4-テトラヒドロピラニルベンゾイル)-9.H.-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-(2-メチル-5-テトラヒドロフラニルベンゾイル)-9.H.-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、エタノン-1-〔9-エチル-6-{2-メチル-4-(2,2-ジメチル-1,3-ジオキソラニル)メトキシベンゾイル}-9.H.-カルバゾール-3-イル〕-1-(O-アセチルオキシム)、2-ベンジル-2-ジメチルアミノ-1-(4-モルホリノフェニル)-ブタン-1-オン、2-ジメチルアミノ-2-(4-メチルベンジル)-1-(4-モルフォリン-4-イル-フェニル)-ブタン-1-オン、2-メチル-1-(4-メチルチオフェニル)-2-モルフォリノプロパン-1-オン、1-フェニル-2-ヒドロキシ-2-メチルプロパン-1-オン、1-(4-i-プロピルフェニル)-2-ヒドロキシ-2-メチルプロパン-1-オン、4-(2-ヒドロキシエトキシ)フェニル-2-ヒドロキシ-2-プロピル)ケトン、1-ヒドロキシシクロヘキシルベンゾフェノン、1-ヒドロキシシクロヘキシルフェニルケトンなどを挙げることができる。これらの重合開始剤は単独で、または2種以上を混合して使用することができる。
本発明に係る第二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、前記第一の光学フィルターと同様に、基材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。
近赤外線吸収色素としては、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、オクタフィリン系化合物、ヘキサフィリン系化合物、シアニン系化合物、ジイモニウム系化合物、アミニウム系化合物、イミニウム系化合物、アントラキノン系化合物等が挙げられる。これらの化合物から選ばれる1種以上の化合物を使用することができ、2種以上の化合物を混合して使用することもできる。これらの中では、透過率特性および熱安定性の観点から、スクアリリウム系化合物、フタロシアニン系化合物、またはシアニン系化合物が好適に使用される。また、前記近赤外線吸収色素は前記化合物(A)であることが好ましい。
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。
図1は、本発明の一実施形態に係る環境光センサー100aを示す。環境光センサー100aは、光学フィルター104及び光電変換素子102を備える。光電変換素子102は、受光部に光が入射すると光起電力効果により電流や電圧を発生する。図1は、一例として、第1電極106、光電変換層108、第2電極114を有する光電変換素子102を示す。光電変換層108は光電効果を発現する半導体で形成される。例えば、光電変換層108は、シリコン半導体を用いて形成される。光学フィルター104は光電変換素子102の受光面側に設けられている。光電変換素子102の受光面には光学フィルター104を通過した光が照射される。
図4は、照度センサー受光素子102aおよび光学フィルター104を備えた環境光センサー100aの断面構造の一例を示す。環境光センサー100aは、照度センサー受光素子102aで外光の強度を検知し、照度センサーとして機能する。照度センサー受光素子102aの上面には、光学フィルター104が設けられる。光学フィルター104により、照度センサー受光素子102aの受光面に入射する光から、近赤外線波長領域の光が遮断され、照度センサー受光素子の視感度特性に対応した外光強度を検知することができる。近赤外線反射層118と近赤外線吸収層120からなる光学フィルター104を使用することにより、照度センサーの視感度特性に合わせた、入射角度による変化が小さい可視光線領域の光が照度センサー受光素子に入射するため、誤作動が少ない照度センサーを得ることができる。
図5(A)及び(B)は、照度センサー受光素子102a、近接センサー受光素子102b、発光ダイオード130および光学フィルター104を備えた環境光センサー100bの一例を示す。なお、図5(A)は環境光センサー100b平面図を示し、図5(B)はI-J線に沿った断面構造を示す。
本発明の光学フィルター、他の光学フィルター、レンズ、および光電変換素子等を組み合わせてセンサーモジュールとすることができる。
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)、(b)または(c)の方法にて測定を行った。
t0:溶媒の流下時間
ts:希薄高分子溶液の流下時間
C:0.5g/dL
<ガラス転移温度(Tg)>
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。
ASTM D570に準拠し、試験片を23℃の水中に1週間浸漬させた後、試験片の重量変化より吸水率を測定した。
各種透過率および波長等は、日本分光株式会社製の分光光度計(V-7200)を用いて測定した。
光学フィルターの光学特性(光学フィルターを透過する光の光学特性)と照度センサーおよび人間の視感度特性との比較を行い、図4と同様の構成の照度センサーを作成した場合の照度センサー感度特性の評価を行った。評価判断は下記の基準に基づいて行った。
下記実施例および比較例で用いた化合物(A)は、一般的に知られている方法で合成した。一般的合成方法としては、例えば、特許第3366697号公報、特許第2846091号公報、特許第2864475号公報、特許第3703869号公報、特開昭60-228448号公報、特開平1-146846号公報、特開平1-228960号公報、特許第4081149号公報、特開昭63-124054号公報、「フタロシアニン -化学と機能―」(アイピーシー、1997年)、特開2007-169315号公報、特開2009-108267号公報、特開2010-241873号公報、特許第3699464号公報、特許第4740631号公報などに記載されている方法を挙げることができる。
下記式(2)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部と、1-ヘキセン(分子量調節剤)18部と、トルエン(開環重合反応用溶媒)300部とを、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。
十分に乾燥し、窒素置換した1リットルのステンレス製オートクレーブに水分6ppmの脱水されたシクロヘキサン;420.4g、p-キシレン;180.2g、5-トリメトキシシリル-ビシクロ[2.2.1]ヘプタ-2-エン;48.75ミリモル(10.43g)、ビシクロ[2.2.1]ヘプタ-2-エン;1,425ミリモル(134.1g)を仕込み、ガス状のエチレンをオートクレーブ内圧が0.1MPaになるように仕込んだ。
温度計、撹拌器、窒素導入管、側管付き滴下ロート、ディーンスターク、冷却管を備えた500mLの5つ口フラスコに、窒素気流下、4,4'-ジアミノジフェニルエーテル 10.0重量部(0.05モル)と、溶剤としてN-メチル-2-ピロリドン 85重量部を仕込んで溶解させた後、1,2,4,5-シクロヘキサンテトラカルボン酸二無水物 11.2重量部(0.05モル)を室温にて固体のまま1時間かけて分割投入し、室温下2時間撹拌した。
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D」ともいう。)を得た(収率95%)。得られた樹脂D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。
温度計、撹拌器、窒素導入管、側管付き滴下ロート、ディーンスターク管および冷却管を備えた500mLの5つ口フラスコに、窒素気流下、1,4-ビス(4-アミノ-α,α-ジメチルベンジル)ベンゼン27.66g(0.08モル)および4,4’-ビス(4-アミノフェノキシ)ビフェニル7.38g(0.02モル)を入れて、γ―ブチロラクトン68.65g及びN,N-ジメチルアセトアミド17.16gに溶解させた。得られた溶液を、氷水バスを用いて5℃に冷却し、同温に保ちながら1,2,4,5-シクロヘキサンテトラカルボン酸二無水物22.62g(0.1モル)およびイミド化触媒としてトリエチルアミン0.50g(0.005モル)を一括添加した。添加終了後、180℃に昇温し、随時留出液を留去させながら、6時間還流させた。反応終了後、内温が100℃になるまで空冷した後、N,N-ジメチルアセトアミド143.6gを加えて希釈し、攪拌しながら冷却し、固形分濃度20重量%のポリイミド樹脂溶液264.16gを得た。このポリイミド樹脂溶液の一部を1Lのメタノール中に注ぎいれてポリイミドを沈殿させた。濾別したポリイミドをメタノールで洗浄した後、100℃の真空乾燥機中で24時間乾燥させて白色粉末(以下「樹脂E」ともいう。)を得た。得られた樹脂EのIRスペクトルを測定したところ、イミド基に特有の1704cm-1、1770cm-1の吸収が見られた。樹脂Eはガラス転移温度(Tg)が310℃であり、対数粘度を測定したところ、0.87であった。
樹脂合成例1で得た樹脂Aを100重量部に、下記構造の化合物(x)(吸収極大波長;704nm)を0.050重量部、下記構造の化合物(y)(吸収極大波長;737nm)を0.056重量部、日本カーリット社製の光吸収剤「CIR-RL」(吸収極大波長;1095nm)を0.6重量部加え、さらにトルエンを加えて溶解し、固形分が30%の溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、60℃で8時間、100℃で8時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下100℃で8時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。
光吸収剤として、日本カーリット社製の光吸収剤「CIR-RL」を0.6重量部、DKSH社製色素「S2058」(吸収極大波長;980nm)を0.3重量部に変更したこと以外は実施例A1と同様にして、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
樹脂Aの代わりに樹脂合成例2で得た樹脂Bを用い、トルエンの代わりにシクロヘキサンを用いたこと以外は実施例A1と同様にして、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
JSR株式会社製のノルボルネン系樹脂「アートンG」を100重量部に、前記化合物(x)を0.050重量部、前記化合物(y)を0.056重量部、日本カーリット社製の光吸収剤「CIR-RL」を0.6重量部加え、さらに塩化メチレンを加えて溶解し、固形分が20%の溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、20℃で8時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下100℃で8時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
日本ゼオン株式会社製のノルボルネン系樹脂「ゼオノア1400R」を100重量部に、前記化合物(x)を0.050重量部、前記化合物(y)を0.056重量部、日本カーリット社製の光吸収剤「CIR-RL」を0.6重量部加え、さらにシクロヘキサンとキシレンの7:3混合溶液を加えて溶解し、固形分が20%の溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、60℃で8時間、80℃で8時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下100℃で24時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
三井化学株式会社製のノルボルネン系樹脂「APEL#6015」を100重量部に、前記化合物(x)を0.050重量部、前記化合物(y)を0.056重量部、日本カーリット社製の光吸収剤「CIR-RL」を0.6重量部加え、さらにシクロヘキサンと塩化メチレンの99:1混合溶液を加えて溶解し、固形分が20%の溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、40℃で4時間、60℃で4時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下100℃で8時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
帝人株式会社製のポリカーボネート樹脂「ピュアエース」を100重量部に、前記化合物(x)を0.050重量部、前記化合物(y)を0.056重量部、日本カーリット社製の光吸収剤「CIR-RL」を0.6重量部加え、さらに塩化メチレンを加えて溶解し、固形分が20% 溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、20℃で8時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下100℃で8時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
住友ベークライト株式会社製のポリエーテルサルホン「FS-1300」を100重量部に、前記化合物(x)を0.050重量部、前記化合物(y)を0.056重量部、日本カーリット社製の吸収剤「CIR-RL」を0.6重量部加え、さらにN-メチル-2-ピロリドンを加えて溶解し、固形分が20%の溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、60℃で4時間、80℃で4時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下120℃で8時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
樹脂合成例3で得たポリイミド溶液Cを100重量部に、前記化合物(x)を0.050重量部、前記化合物(y)を0.056重量部、日本カーリット社製の光吸収剤「CIR-RL」を0.6重量部加え、固形分が20%の溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、60℃で4時間、80℃で4時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下120℃で8時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
JSR株式会社製のノルボルネン系樹脂「アートンG」100重量部に、前記化合物(x)を0.050重量部、前記化合物(y)を0.056重量部、日本カーリット社製の光吸収剤「CIR-RL」を0.9重量部加え、さらに塩化メチレンを加えて溶解し、固形分が20% 溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、20℃で8時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下100℃で8時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
JSR株式会社製のノルボルネン系樹脂「アートンG」100重量部に、前記化合物(x)を0.050重量部、前記化合物(y)を0.056重量部、DKSH社製色素「S2058」を0.3重量部、セシウム酸化タングステン(Cs0.33WO3)3.2重量部加え、さらに塩化メチレンを加えて溶解し、固形分が20% 溶液を得た。次いで、係る溶液を平滑なガラス板上にキャストし、20℃で8時間乾燥した後、ガラス板から剥離した。剥離した樹脂をさらに減圧下100℃で8時間乾燥して、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
容器に、樹脂合成例1で得られた樹脂Aを100部および塩化メチレ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、20℃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0.1mm、縦60mm、横60mmの透明樹脂製支持体を得た。
容器に、樹脂合成例1で得られた樹脂Aを100部、前記化合物(x)を2.5重量部、前記化合物(y)を2.8重量部、日本カーリット社製の光吸収剤「CIR-RL」を30重量部加え、および塩化メチレ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、縦60mm、横60mmの大きさにカットした日本電気硝子(株)製透明ガラス基板「OA-10G」(厚み200um)上にキャストし、20℃で8時間乾燥した後、さらに減圧下100℃で8時間乾燥して、厚さ0.202mm、縦60mm、横60mmの透明樹脂製層とガラス支持体を有する基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.207mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
容器に、樹脂合成例1で得られた樹脂Aを100部、DKSH社製色素「S2058」を6.5重量部、および塩化メチレ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、縦60mm、横60mmの大きさにカットした、松浪硝子工業(株)製青板ガラス基板「BS-6」(厚み210μm)上にキャストし、20℃で8時間乾燥した後、さらに減圧下100℃で8時間乾燥して、厚さ0.216mm、縦60mm、横60mmの透明樹脂製層とガラス支持体を有する基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.220mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
JSR株式会社製のノルボルネン系樹脂「アートンG」を100重量部に、前記化合物(x)を0.075重量部、前記化合物(y)を0.085重量部、日本カーリット社製の光吸収剤「CIR-RL」を0.9重量部、下記構造の化合物(z)を0.10重量部加え、さらに塩化メチレンを加えて溶解し、固形分が20%の溶液を得た。
基材として、松浪硝子工業(株)製青板ガラス基板「BS-6」(厚み210μm)を用いたこと以外は、実施例A1と同様にして厚さ0.214mmの光学フィルターを得た。基材および得られた光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
容器に、樹脂合成例1で得られた樹脂Aを100部および塩化メチレ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、20℃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0.1mm、縦60mm、横60mmの基材を得た。得られた基材の分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
日本カーリット社製の光吸収剤「CIR-RL」を0.6重量部から0.05重量部に変更したこと以外は実施例A1と同様にして、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、実施例A1と同様にして、厚さ0.105mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
日本カーリット社製の光吸収剤「CIR-RL」を用いなかったこと以外は実施例A1と同様にして、厚さ0.1mm、一辺が60mmの基材を得た。さらに、得られた基材を用いて、比較例A1と同様にして、厚さ0.106mmの光学フィルターを得た。得られた基材および光学フィルターの分光透過率を実施例A1と同様に測定し、光学特性を評価した。結果を表11に示す。
実施例B2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成した。
実施例B3では、近赤外線吸収ガラス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成した。
実施例B4では、片面に化合物(A)を含む透明樹脂層を有する透明ガラス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成した。
続いて、実施例B1と同様に、得られた基材の片面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる誘電体多層膜(合計層数26)を形成し、さらに基材のもう一方の面にシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる誘電体多層膜(合計層数20)を形成し、厚さ約0.108mmの光学フィルターを得た。誘電体多層膜の設計は、実施例B1と同様に基材屈折率の波長依存性等を考慮した上で、実施例B1と同じ設計パラメーターを用いて行った。この光学フィルターの分光透過率を測定し、各波長領域における光学特性を評価した。結果を表13に示す。
透明樹脂種、および化合物(A)を表13に示すように変更したこと以外は、実施例B2と同様にして、基材および光学フィルターを作成した。得られた基材および光学フィルターの光学特性を表13に示す。
実施例B1において、化合物(A)を用いなかったこと以外は実施例B1と同様にして基材および光学フィルターを作成した。得られた光学フィルターの光学特性を図13および表13に示す。
透明樹脂基材に替えて日本電気硝子(株)製透明ガラス基板「OA-10G」(厚み200μm)を用いたこと以外は、実施例B1と同様に光学フィルターを作成した。得られた光学フィルターの光学特性を表13に示す。
実施例B1において、化合物(A)を用いなかったことと、誘電体多層膜(I)の代わりに、蒸着温度100℃でシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる誘電体多層膜(合計層数6)、誘電体多層膜(II)の代わりに、蒸着温度100℃でシリカ(SiO2)層とチタニア(TiO2)層とが交互に積層されてなる誘電体多層膜(合計層数6)を用いたこと以外は、実施例B1と同様にして基材および光学フィルターを作成した。得られた光学フィルターの光学特性を図14および表13に示す。
形態(1):化合物(A)を含む透明樹脂製基板
形態(2):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
形態(3):近赤外線吸収ガラス基板
形態(4):ガラス基板の片方の面に化合物(A)を含む透明樹脂層を有する
形態(5):化合物(A)を含まない透明樹脂製基板(比較例)
形態(6):ガラス基板(比較例)
<透明樹脂>
樹脂A:環状オレフィン系樹脂(樹脂合成例1)
樹脂D:芳香族ポリエーテル系樹脂(樹脂合成例4)
樹脂E:ポリイミド系樹脂(樹脂合成例5)
樹脂F:環状オレフィン系樹脂「ゼオノア 1420R」(日本ゼオン(株)製)
<ガラス基板>
ガラス基板(1): 縦60mm、横60mmの大きさにカットした、松浪硝子工業(株)製近赤外線吸収ガラス基板「BS-6」(厚み210μm)
ガラス基板(2): 縦60mm、横60mmの大きさにカットした、日本電気硝子(株)製透明ガラス基板「OA-10G」(厚み200μm)
<近赤外線吸収色素>
≪化合物(A)≫
化合物(a-1):上記化合物(a-1)(ジクロロメタン中での吸収極大波長698nm)
化合物(a-2):上記化合物(a-2)(ジクロロメタン中での吸収極大波長733nm)
化合物(a-3):上記化合物(a-3)(ジクロロメタン中での吸収極大波長703nm)
化合物(a-4):上記化合物(a-4)(ジクロロメタン中での吸収極大波長736nm)
<溶媒>
溶媒(1):塩化メチレン
溶媒(2):N,N-ジメチルアセトアミド
溶媒(3):シクロヘキサン/キシレン(重量比:7/3)
表13における、実施例および比較例の(透明)樹脂製基板乾燥条件は以下の通りである。なお、減圧乾燥前に、塗膜をガラス板から剥離した。
条件(1):20℃/8hr→減圧下 100℃/8hr
条件(2):60℃/8hr→80℃/8hr→減圧下 140℃/8hr
条件(3):60℃/8hr→80℃/8hr→減圧下 100℃/24hr
2:光学フィルター
3:分光光度計
100:環境光センサー
102:光電変換素子
104:光学フィルター
106:第1電極
108:光電変換層
110:p型半導体領域
112:n型半導体領域
114:第2電極
116:絶縁層
118:近赤外線反射層
120:近赤外線吸収層
122:樹脂層
124:ガラス基板
126:カラーフィルター
128:素子分離絶縁層
130:発光ダイオード
132:遮光部材
134:近赤外線パスフィルター
136:電子機器
138:筐体
140:表示パネル
142:マイクロホン部
144:スピーカ部
145:光学窓
201:センサーモジュール
202:光拡散フィルム
203:光学フィルター
204:IRカットフィルム
205:遮光板
206:遮光スペーサー
207:光センサー
Claims (26)
- 光吸収層を含む基材(i)を有し、かつ、可視光を透過する光学フィルターであって、
前記光吸収層が波長750~1150nmの領域に吸収極大を有し、
波長850~1050nmの領域において、前記光学フィルターの垂直方向から測定した場合の平均OD値が2.0以上であり、かつ、前記光学フィルターの垂直方向に対して60°の角度から測定した場合の平均OD値が2.0以上であることを特徴とする光学フィルター。 - 波長430~580nmの領域において、前記光学フィルターの垂直方向から測定した場合の透過率の平均値が30%以上80%以下であることを特徴とする請求項1に記載の光学フィルター。
- 前記光吸収層が、波長750~1150nmの領域に吸収極大を有する化合物(S)を含むことを特徴とする請求項1または2に記載の光学フィルター。
- 前記化合物(S)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、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、 リン酸銅錯体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3に記載の光学フィルター。
- 波長850~1050nmの領域において、前記基材(i)の垂直方向から測定した場合の平均OD値が1.0以上であることを特徴とする請求項1~4のいずれか1項に記載の光学フィルター。
- 前記光吸収層が、波長650~750nmの領域に吸収極大を有する化合物(A)をさらに含むことを特徴とする請求項1~5のいずれか1項に記載の光学フィルター。
- 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、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を特徴とする請求項6に記載の光学フィルター。
- 前記光吸収層が、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、ポリアリレート系樹脂、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、アリルエステル系硬化型樹脂、シルセスキオキサン系紫外線硬化型樹脂、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種の樹脂を含むことを特徴とする請求項1~7のいずれか1項に記載の光学フィルター。
- 前記基材(i)の少なくとも一方の面に誘電体多層膜を有することを特徴とする請求項1~8のいずれか1項に記載の光学フィルター。
- 環境光センサー用であることを特徴とする請求項1~9のいずれか1項に記載の光学フィルター。
- 請求項1~9のいずれか1項に記載の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。
- 受光面に入射する光により光電流を生成し照度や色温度を測定する光電変換素子と、前記光電変換素子の前記受光面側に配置された、請求項1~9のいずれか1項に記載の光学フィルターとを有することを特徴とする環境光センサー。
- 受光面に入射する光により光電流を生成し照度や色温度を測定する光電変換素子と、前記光電変換素子の前記受光面側に配置された光学フィルターとを有し、
前記光学フィルターは、近赤外線吸収層と、近赤外線反射層とを含むことを特徴とする環境光センサー。 - 前記近赤外線吸収層は、近赤外線吸収色素を含む樹脂層であることを特徴とする請求項13に記載の環境光センサー。
- 前記樹脂層の樹脂が、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、ポリアリレート系樹脂、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、アリルエステル系硬化型樹脂、シルセスキオキサン系紫外線硬化型樹脂、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14に記載の環境光センサー。
- 前記近赤外線吸収層は、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層であることを特徴とする請求項13に記載の環境光センサー。
- 前記光学フィルターはガラス基板を含み、前記近赤外線吸収層は前記ガラス基板の少なくとも一方の面に設けられていることを特徴とする請求項13~15のいずれか1項に記載の環境光センサー。
- 前記光学フィルターは樹脂製基板を含み、前記近赤外線吸収層は前記樹脂基板の少なくとも一方の面に設けられていることを特徴とする請求項13~15のいずれか1項に記載の環境光センサー。
- 前記近赤外線反射層が誘電体多層膜であることを特徴とする請求項13~18のいずれか1項に記載の環境光センサー。
- 前記光学フィルターは、透過率が下記条件(A)~(C)を満たすことを特徴とする請求項13~19のいずれか1項に記載の環境光センサー:
(A)波長430~580nmの範囲において、光学フィルターの垂直方向から測定した場合の透過率が50%以上である;
(B)波長800~1000nmの範囲において、光学フィルターの垂直方向から測定した場合の透過率の平均値が15%以下である;
(C)波長560~800nmの範囲において、光学フィルターの垂直方向から測定した場合の透過率が50%となる波長の値(Xa)と、光学フィルターの垂直方向に対して30°の角度から測定した場合の透過率が50%となる波長の値(Xb)の差の絶対値(|Xa-Xb|)が20nm未満である。 - 前記光学フィルターは、光入射面側から、前記近赤外線反射層および前記近赤外線吸収層がこの順に配置された構造を含むことを特徴とする請求項13~20のいずれか1項に記載の環境光センサー。
- 前記近赤外線吸収層が波長750~1150nmの領域に吸収極大を有し、
波長850~1050nmの領域において、前記光学フィルターの垂直方向から測定した場合の平均OD値が2.0以上であり、かつ、前記光学フィルターの垂直方向に対して60°の角度から測定した場合の平均OD値が2.0以上であることを特徴とする請求項13~21のいずれか1項に記載の環境光センサー。 - 近赤外光を出射する発光素子と、近赤外光を検知する第2光電変換素子とを有する近接センサーをさらに含むことを特徴とする請求項12~22のいずれか1項に記載の環境光センサー。
- さらに、光散乱フィルムを具備することを特徴とする請求項11~23のいずれか1項に記載の環境光センサー。
- 請求項1~10のいずれか1項に記載の光学フィルターを具備することを特徴とするセンサーモジュール。
- 請求項11~24のいずれか1項に記載の環境光センサーを含むことを特徴とする電子機器。
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US20200278243A1 (en) | 2020-09-03 |
KR20180087265A (ko) | 2018-08-01 |
US20180364095A1 (en) | 2018-12-20 |
US10996105B2 (en) | 2021-05-04 |
CN108449956A (zh) | 2018-08-24 |
TWI720073B (zh) | 2021-03-01 |
TW201721188A (zh) | 2017-06-16 |
JPWO2017094672A1 (ja) | 2018-09-13 |
JP2021015298A (ja) | 2021-02-12 |
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