Patent Application
20230145740
The present invention relates to an optical filter that transmits light in a visible wavelength range and interrupts light in an ultraviolet wavelength range and a near-infrared wavelength range.
To reproduce colors satisfactorily and obtain a clear image, an optical filter that transmits light in a visible range (hereinafter also referred to as “visible light”) and that interrupts light in an ultraviolet wavelength range (hereinafter also referred to as “ultraviolet light” or “UV light”) and light in a near-infrared wavelength range (hereinafter also referred to as “near-infrared light” or “NIR light”) is used in imaging apparatus provided with a solid-state imaging device.
Examples of such an optical filter include various types of optical filters such as a reflection optical filter in which dielectric thin-films having different refractive indices are laid alternately (to form a dielectric multilayer film) on one or both surfaces of a transparent substrate and that thereby reflects light to be interrupted utilizing light interference. In an optical filter including such a dielectric multilayer film, the optical thickness of the dielectric multilayer film varies depending on the light incident angle. The optical filter therefore has problems such as an incident angle-dependent variation of a spectral transmittance curve, light leakage in which ultraviolet light that should be high in reflectance is increased in transmittance at a large incident angle, and occurrence of noise due to ultraviolet light reflected by the dielectric multilayer film. In the case where such a filter is used, the spectral sensitivity of a solid-state imaging device may be affected by the incident angle. An optical filter was therefore desired that can interrupt ultraviolet light with causing almost no influence on the visible light transmittance and with no dependence on the incident angle.
In this connection, Patent documents 1 to 4 disclose optical filters whose dependence on the incident angle of light in a wavelength range of 370 to 425 nm is low and that has both a UV cutting ability and an NIR cutting ability as a result of a combination of a dielectric multilayer film and an absorption layer that contains a UV absorbing dye and an NIR absorbing dye in a transparent resin.
Patent document 1: JP-A-2019-16649
Patent document 2: Japanese Patent No. 6,504,176
Patent document 3: Japanese Patent No. 6,020,740
Patent document 4: Japanese Patent No. 6,256,335
However, the optical filters disclosed in Patent documents 1-4 have room for improvement in the transparency of visible light, in particular, blue light, and the ultraviolet light shieldability at large incident angles.
An object of the present invention is therefore to provide an optical filter that exhibits high visible light transparency and high near-infrared light and ultraviolet light shieldability, in particular, an optical filter that exhibits high blue light transparency and that is suppressed in the reduction of ultraviolet light shieldability at large incident angles.
The present invention provides optical filters having the following configurations:
[1] An optical filter including:
a substrate; and
a dielectric multilayer film laid on or above at least one major surface of the substrate, as an outermost layer, in which:
the substrate includes a resin film containing a dye (U) having a maximum absorption wavelength in a range of 360 to 395 nm in dichloromethane, a dye (A) having a maximum absorption wavelength in a range of 600 to 800 nm in dichloromethane, and a resin; and
the optical filter satisfies all of the following spectral characteristics (i-1) to (i-5):
(i-1) an average transmittance T440-480 of a spectral transmittance curve in a wavelength range of 440 to 480 nm is 86% or more;
(i-2) an absolute value of a difference between UV10(0deg) and UV10(50deg) is 3 nm or less, an absolute value of a difference between UV20(0deg) and UV20(50deg) is 4 nm or less, and an absolute value of a difference between UV50(0deg) and uV50(50deg) is 4 nm or less, where UV10(0deg), UV20(0deg), and UV50(0deg) represent wavelengths at which transmittances are 10%, 20%, and 50%, respectively, at an incident angle of 0° in a wavelength range of 350 to 450 nm, and UV10(50deg), UV20(50deg), and UV50(50deg) represent wavelengths at which transmittances are 10%, 20%, and 50%, respectively, at an incident angle of 50° in a wavelength range of 350 to 450 nm;
(i-3) an average transmittance T400-440 of a spectral transmittance curve in a wavelength range of 400 to 440 nm is 40% or more;
(i-4) an average transmittance T370-400(0deg) of a spectral transmittance curve at an incident angle of 0° in a wavelength range of 370 to 400 nm is 1% or less; and
(i-5) an average transmittance T370-400(50deg) of a spectral transmittance curve at an incident angle of 50° in a wavelength range of 370 to 400 nm is 0.5% or less.
The present invention can provide an optical filter that exhibits high visible light transparency and high near-infrared light and ultraviolet light shieldability, in particular, an optical filter that exhibits high blue light transparency and that is suppressed in the reduction of ultraviolet light shieldability at large incident angles.
An embodiment of the present invention will be described below. In this specification, a near-infrared absorbing dye and an ultraviolet light absorbing dye may be abbreviated as “NIR dye” and “UV dye,” respectively. In this specification, a compound represented by formula (I) will be referred to as a “compound (I)” and similar notations will be used for compounds represented by other formulae. A dye made of a compound (I) will also be referred to as a “dye (I)” and similar notations will be used for other dyes. Furthermore, a group represented by formula (1) will also be referred to as a “group (I)” and similar notations will be used for groups represented by other formulae.
In this specification, the “internal transmittance” means transmittance obtained by subtracting influence of interface reflection from measured transmittance and is represented by an equation (measured transmittance)/(100-reflectance).
In this specification, as for a transmittance of a substrate and a transmittance of a resin film including a case that a dye is contained in a resin, an “internal transmittance” is meant in all cases including a case that only a word “transmittance” is used. On the other hand, a transmittance that is measured by dissolving a dye in a solvent such as dichloromethane and a transmittance of an optical filter having a dielectric multilayer film are each measured transmittance.
In this specification, for example, the expression “the transmittance is 90% or more in a particular wavelength range” means that the transmittance is not less than 90% in the whole of that wavelength range, that is, the smallest transmittance in that wavelength range is 90% or more. Likewise, for example, the expression “the transmittance is 1% or less in a particular wavelength range” means that the transmittance is not more than 1% in the whole of that wavelength range, that is, the highest transmittance in that wavelength range is 1% or less. The same is true of the internal transmittance. An average transmittance or an average internal transmittance in a particular wavelength range is an arithmetic average of transmittance values or internal transmittance values every 1 nm wavelength in that wavelength range.
In this specification, the symbol “-” or the word “to” used to indicate a numerical value range is used to include numerical values written before and after it as a upper limit value and a lower limit value, respectively.
<Optical filter>
An optical filter according to one embodiment of the present invention (hereinafter also referred to as “the present filter”) includes a substrate and a dielectric multilayer film laid on or above at least one major surface of the substrate, as an outermost layer and the optical filter satisfies particular spectral characteristics described later. The substrate includes a resin film that contains a dye (U) having a maximum absorption wavelength in a range of 360 to 395 nm in dichloromethane, a dye (A) having a maximum absorption wavelength in a range of 600 to 800 nm in dichloromethane, and a resin.
Examples of configurations of the present filter will be described with reference to the drawings.
An optical filter lA illustrated in
The substrate of the optical filter according to the present invention includes a dye (U) having a maximum absorption wavelength in a range of 360 to 395 nm in dichloromethane, a dye (A) having a maximum absorption wavelength in a range of 600 to 800 nm in dichloromethane, and a resin. The dye (U) is a UV dye and the dye (A) is an NIR dye. In the case where the substrate includes dyes that absorb ultraviolet light or near-infrared light, deterioration of the spectral characteristics of the dielectric multilayer film at large incident angles, such as light leakage in an ultraviolet range or a near-infrared range and generation of noise etc., can be suppressed by the absorption property of the substrate. The individual dyes and the resin will be described later.
The optical filter according to the present invention satisfies all of the following spectral characteristics (i-1) to (i-5):
(i-1) an average transmittance T440-480 of a spectral transmittance curve in a wavelength range of 440 to 480 nm is 86% or more;
(i-2) an absolute value of a difference between UV10(0deg) and UV10(50deg) is 3 nm or less, an absolute value of a difference between UV20(0deg) and UV20(50deg) is 4 nm or less, and an absolute value of a difference between UV50(0deg) and UV50(50deg) is 4 nm or less, where UV10(0deg), UV20(0deg), and UV50(0deg) represent wavelengths at which transmittances are 10%, 20%, and 50%, respectively, at an incident angle of 0° in a wavelength range of 350 to 450 nm, and UV10(50deg), UV20(50deg), and UV50(50deg) represent wavelengths at which transmittances are 10%, 20%, and 50%, respectively, at an incident angle of 50° in a wavelength range of 350 to 450 nm;
(i-3) an average transmittance T400-440 of a spectral transmittance curve in a wavelength range of 400 to 440 nm is 40% or more;
(i-4) an average transmittance T370-400(0deg) of a spectral transmittance curve at an incident angle of 0° in a wavelength range of 370 to 400 nm is 1% or less; and
(i-5) an average transmittance T370-400(50deg) of a spectral transmittance curve at an incident angle of 50° in a wavelength range of 370 to 400 nm is 0.5% or less.
The present optical filter that satisfies all of the spectral characteristics (i-1) to (i-5) is an optical filter in which the ultraviolet light shieldability is high, in particular, the reduction of ultraviolet light shieldability at large incident angles is suppressed while the visible light transparency, particularly the blue light transparency, is kept high.
The satisfaction of the spectral characteristic (i-1) means that the transparency in a visible range is high. In the spectral characteristic (i-1), it is preferable that T440-480 be 87% or more, even preferably 89% or more.
The satisfaction of the spectral characteristic (i-2) means that the shift is small even at large incident angles in a wavelength range of 350 to 450 nm (i.e., in and around a UV absorption start band) and hence the color reproducibility is high. In the spectral characteristic (i-2), the absolute value of the difference between UV10(0deg) and UV10(50deg) is preferably 2.5 nm or less, the absolute value of the difference between UV20(0deg) and UV20(50deg) is preferably 3 nm or less, and the absolute value of the difference between UV50(0deg) and UV50(50deg) is preferably 3 nm or less.
The satisfaction of the spectral characteristic (i-3) means that the blue light transmittance is high in a wavelength range of 400 to 440 nm (i.e., in a wavelength range that is a little longer than the UV absorption start band). In the spectral characteristic (i-3), it is preferable that T400-440 be 45% or more, even preferably 50% or more.
The satisfaction of the spectral characteristic (i-4) means that the light shieldability is high in a wavelength range of 370 to 470 nm (UV absorption band). In the spectral characteristic (i-4), it is preferable that T370-400(0deg) be 0.5% or less.
The satisfaction of the spectral characteristic (i-5) means that light leakage is not prone to occur, that is, the light shieldability is high, even at large incident angles in a wavelength range of 370 to 400 nm (UV absorption band). In the spectral characteristic (i-5), it is preferable that T370-400(50deg) be 0.1% or less.
It is preferable that the optical filter according to the present invention further satisfy the following spectral characteristic (i-6):
(i-6) an absolute value of a difference between UV10(0deg) and UV70(0deg) is 16 nm or less, where UV10(0deg) and UV70(0deg) represent wavelengths at which transmittances are 10% and 70%, respectively, at an incident angle of 0° in a wavelength range of 350 to 450 nm.
The satisfaction of the spectral characteristic (i-6) means that the slope of a spectral transmittance curve is steep in a wavelength range of 350 to 450 nm (i.e., in and around a UV absorption start band). It is even preferable that the absolute value mentioned in the spectral characteristic (i-6) be 14 nm or less, particularly preferably 13 nm or less.
The substrate and the dielectric multilayer film will be described below. For example, the present filter is designed so that the substrate has ultraviolet light and near-infrared light absorption ability and the above-mentioned spectral characteristics (i-1) to (i-5) are satisfied by the absorption property of the substrate and the reflection property of the dielectric multilayer film.
<Sub strate>
In the optical filter according to the present invention, the substrate includes the resin film that contains the dye (U), the dye (A) (described later), and the resin.
<UV Dye>
The dye (U) is a UV dye having a maximum absorption wavelength in a range of 360 to 395 nm in dichloromethane. Having this dye, the optical filter can cut ultraviolet light effectively.
It is preferable that the dye (U) have particular spectral characteristics in a resin. Specifically, it is preferable that the dye (U), in a spectral transmittance curve of a coated film formed by coating an alkali glass plate with a solution obtained by dissolving the dye (U) in a resin, satisfy all of the following spectral characteristics (ii-1) to (ii-6). It is preferable that the resin be the same as a resin contained in the substrate.
(ii-1) an average transmittance T400-440 in a wavelength range of 400 to 440 nm is 40% or more;
(ii-2) an average transmittance T370-400 in a wavelength range of 370 to 400 nm is 5% or less;
(ii-3) a transmittance T400 at a wavelength of 400 nm is 7% or less;
(ii-4) a transmittance T390 at a wavelength of 390 nm is 5% or less;
(ii-5) a transmittance T380 at a wavelength of 380 nm is 5% or less; and
(ii-6) a transmittance T370 at a wavelength of 370 nm is 5% or less.
The satisfaction of the optical characteristic (ii-1) means that the blue light transmittance is high in a wavelength range of 400 to 440 nm (i.e., in a wavelength range that is a little longer than the UV absorption start band). It is even preferable that T400-440 of the optical characteristic (ii-1) be 45% or more, particularly preferably 50% or more.
The satisfaction of the optical characteristic (ii-2) means that the light shieldability is high in a wavelength range of 370 to 400 nm (UV absorption band). It is even preferable that T370-400 of the optical characteristic (ii-2) be 3% or less, particularly preferably 2% or less.
In the case where the optical characteristic (ii-3) is satisfied, the transmittance is low at a wavelength of 400 nm which is a UV absorption start wavelength, which means that the light shieldability is high in a wavelength range that is shorter than this wavelength. It is even preferable that the transmittance T400 of the optical characteristic (ii-3) be 5% or less, particularly preferably 2% or less.
The satisfaction of the optical characteristics (ii-4) to (ii-6) means that necessary light shieldability can be secured by absorption in a wavelength range of 370 to 390 nm in which light leakage is prone to occur because a dielectric multilayer film cannot interrupt light entering at a large incident angle sufficiently.
It is even preferable that T390 of the optical characteristics (ii-4) be 3% or less, particularly preferably 1% or less.
It is even preferable that T380 of the optical characteristics (ii-5) be 3% or less, particularly preferably 1% or less.
It is even preferable that T370 of the optical characteristics (ii-6) be 3% or less, particularly preferably 1% or less.
It is preferable that the dye (U), in the spectral transmittance curve of the coated film, further satisfy the following spectral characteristic (ii-7):
(ii-7): an average internal transmittance T440-480 in a wavelength range of 440 to 480 nm is 79% or more.
The satisfaction of the optical characteristic (ii-7) means that absorption by the dye itself does not cause a loss of transmittance in a visible range. It is even preferable that T440-480 of the optical characteristic (ii-7) be 80% or more, particularly preferably 81% or more.
Furthermore, it is preferable that the dye (U) satisfy the following spectral characteristic (iii-1):
(iii-1) an absolute value of a difference between UV10 and UV70 is 25 nm or less, where UV10 and UV70 represent wavelengths at which transmittances are 10% and 70%, respectively, in a wavelength range of 350 to 450 nm in a spectral transmittance curve that is measured by dissolving the dye (U) in dichloromethane so that a transmittance at a maximum absorption wavelength becomes 10%.
The satisfaction of the spectral characteristic (iii-1) means that the slope of the spectral transmittance curve is steep in a wavelength range of 350 to 450 nm (i.e., in and around a UV absorption start band). This makes it possible to transmit necessary blue light more and efficiently interrupt ultraviolet light to be interrupted.
It is even preferable that the absolute value mentioned in the spectral characteristic (iii-1) be 22 nm or less.
One kind of the dye (U) may be used in the substrate singly or two or more kinds of the dye (U) may be used in the substrate in combination. From the viewpoint of enabling more efficient light shielding of ultraviolet light with a small content, it is preferable to use two or more kinds of the dye (U) having different maximum absorption wavelengths in combination. In the case where two or more kinds of the dye (U) are used in combination, it is not necessary that each compound exhibit the properties of the dye (U); it suffices that a mixture exhibits the properties of the dye (U).
It is even preferable to use, as the dye (U), a dye (U1) having a maximum absorption wavelength in a range of 370 to 385 nm in dichloromethane. Furthermore, in the case where the substrate contains the dye (U1), it is preferable that the substrate further contain a dye (U2) having a maximum absorption wavelength in a range of 385 to 405 nm in dichloromethane. It is preferable that the dyes (U1) and (U2) have different maximum absorption wavelengths in a resin, and it is preferable that the absolute value of the difference between the maximum absorption wavelengths of the dye (U1) and the dye (U2) in the resin be 10 nm or more and 15 nm or less, even preferably 10 nm or more and 14 nm or less.
Using UV dyes having different maximum absorption wavelengths in combination enables light shielding of ultraviolet light with small contents.
Examples of the dye (U) include an oxazole dye, a merocyanine dye, a cyanine dye, a naphthalimide dye, an oxadiazole dye, an oxazine dye, an oxazolidine dye, a naphthalic acid dye, a styryl dye, an anthracene dye, a cyclic carbonyl dye, and a triazole dye. Among these examples, an oxazole dye and a merocyanine dye are preferable and a merocyanine dye is even preferable.
Furthermore, from the viewpoint of obtaining an optical filter that is superior in light resistance, it is particularly preferable to use two or more kinds of merocyanine dyes having different maximum absorption wavelengths. The NIR dye (A) is prone to deteriorate when used together with a UV dye, but this can be prevented by using two or more kinds of merocyanine dyes as UV dyes in combination.
A merocyanine dye represented by the following Formula (M) is particularly preferable as the dye (U):
The symbols in Formula (M) have the following meanings:
R1 represents a monovalent hydrocarbon group having a carbon number of 1 to 12 that may include a substituent.
Preferable examples of the substituent include an alkoxy group, an acyl group, an acyloxy group, a cyano group, a dialkylamino group, and a chlorine atom. It is preferable that the carbon number of the alkoxy group, the acyl group, the acyloxy group, and the dialkylamino group be 1 to 6.
Specific, preferable examples of R1 including no substituent include an alkyl group having a carbon number of 1 to 12 part of whose hydrogen atoms may be replaced by an aliphatic ring, an aromatic ring, or an alkenyl group, a cycloalkyl group having a carbon number of 3 to 8 part of whose hydrogen atoms may be replaced by an aromatic ring, an alkyl group, or an alkenyl group, and an aryl group having a carbon number of 6 to 12 part of whose hydrogen atoms may be replaced by an aliphatic ring, an alkyl group, or an alkenyl group.
In the case where R1 is an unsubstituted alkyl group, that alkyl group may be either linear or branched and its carbon number is even preferably 1 to 6.
In the case where R1 is an alkyl group having a carbon number of 1 to 12 part of whose hydrogen atoms are replaced by an aliphatic ring, an aromatic ring, or an alkenyl group, it is even preferably an alkyl group having a carbon number of 1 to 4 and having a cycloalkyl group having a carbon number of 3 to 6 or a phenyl-group-replaced alkyl group having a carbon number of 1 to 4, and particularly preferably a phenyl-group-replaced alkyl group having a carbon number of 1 or 2. The phrase “ phenyl-group-replaced alkyl group” or “alkyl group replaced by an alkenyl group” means a group that is a phenyl or an alkenyl group as a whole but has no unsaturated bond between position 1 and position 2, examples of which include an aryl group and a 3-butenyl group.
Preferable examples of R1 include an alkyl group having a carbon number of 1 to 6 part of whose hydrogen atoms may be replaced by a cycloalkyl group or a phenyl group. Particularly preferable examples of le include an alkyl group having a carbon number of 1 to 6, specific examples of which include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group.
R2 to R5 represent, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 10, or an alkoxy group having a carbon number of 1 to 10. It is preferable that the carbon number of the alkyl group and the alkoxy group be 1 to 6, even preferably 1 to 4.
It is preferable that at least one of R2 and R3 be an alkyl group and it is even preferable that both of them be an alkyl group. In the case where R2 or R3 is not an alkyl group, it is preferable that R2 or R3 be a hydrogen atom. It is particularly preferable that both of R2 and R3 be an alkyl group having a carbon number of 1 to 6.
It is preferable that at least one of R4 and R5 be a hydrogen atom and it is even preferable that both of them be a hydrogen atom. In the case where R4 or R5 is not a hydrogen atom, it is preferable that R4 or R5 be an alkyl group having a carbon number of 1 to 6.
Y represents a methylene group replaced by R6 and R7, or an oxygen atom.
R6 and R7 represent, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 10, or an alkoxy group having a carbon number of 1 to 10.
X represents one of divalent groups represented by (X1) to (X5).
R8 and R9 represent, independently of each other, a monovalent hydrocarbon group having a carbon number of 1 to 12 that may include a substituent, and R10 to R19 represent, independently of each other, a hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 12 that may include a substituent:
Examples of the substituents for R8 to R19 are the same as those for R1, and preferable modes of the former are the same as those of the latter. In the case where each of R8 to R19 represents a hydrocarbon group not including a substituent, they may be in the same mode as R1 not including a sub stituent.
In Formula (X1), R8 and R9 may be different groups but it is preferable that R8 and R9 be the same group. In the case where R8 and R9 are unsubstituted alkyl groups, R8 and R9 may be either linear or branched and their carbon number is preferably 1 to 6.
It is preferable that each of R8 and R9 be an alkyl group having a carbon number of 1 to 6 part of whose hydrogen atoms may be replaced by a cycloalkyl group or a phenyl group. It is particularly preferable that each of le and R9 be an alkyl group having a carbon number of 1 to 6, specific examples of which include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n-butyl group, an isobutyl group, and a t-butyl group.
In Formula (X2), it is preferable that each of R10 and R11 be an alkyl group having a carbon number of 1 to 6 and it is particularly preferable that they be the same alkyl group.
In Formula (X3), it is preferable that each of R12 and R15 be a hydrogen atom or an alkyl group having a carbon number of 1 to 6 that does not include a substituent. It is preferable that R13 and R14 which are two groups connected to the same carbon atom each be a hydrogen atom or an alkyl group having a carbon number of 1 to 6.
In Formula (X4), it is preferable that each of two groups R16 and R17 which are connected to the same carbon atom and each of two groups R18 and R19 which are connected to the same carbon atom be a hydrogen atom or an alkyl group having a carbon number of 1 to 6.
Preferable examples of a compound represented by Formula (M) include a compound in which Y is an oxygen atom and X is the group (X1), (X2), or (X5), and a compound in which Y is an unsubstituted methylene group and X is the group (X1), (X2), or (X5).
Specific examples of the compound (M) that can be used as the dye (U) include compounds shown in the following tables.
Specific examples of the compound (M) that can be used as the dye (U1) include compounds shown in the following table.
Specific examples of the compound (M) that can be used as the dye (U2) include compounds shown in the following table.
Among the above examples of the compound (M), the compounds (M-1-2), (M-1-10), (M-1-24), (M-1-28), etc. are preferable from the viewpoints of solubility in resin or a solvent, visible light transparency, and, in particular, satisfaction of the optical characteristic (iii-1). In the case where two kinds of compounds (M) having different maximum absorption wavelengths are used in combination, a combination of the compounds (M-1-28) and (M-1-2), a combination of the compounds (M-1-28) and (M-1-10), a combination of the compounds (M-1-24) and (M-1-2), and a combination of the compounds (M-1-24) and (M-1-10) are preferable. It is noted that the compound (M) can be manufactured by a known method.
It is preferable that the content of the UV dye (U) in the resin film be in such a range that the product of the total content of the dye (U) and the dye (A) and the thickness of the resin film be 100 (mass %·μm) or less, even preferably 80 (mass %˜μm) or less, further preferably 70 (mass %˜μm) or less, and particularly preferably 50 (mass %˜μm) or less. As the addition amount of the UV dye increases, the resin properties deteriorate, resulting in reduction of the adhesion to the dielectric multilayer film. Furthermore, the glass transition temperature of the resin lowers, posing a concern about heat resistance. These problems can be prevented if the product of the total content of the dyes and the thickness of the resin film is in the above range. Furthermore, from the viewpoint of satisfying desired spectral characteristics, it is preferable that the product of the total content and the thickness be 10 (mass %·μm) or more, even preferably 15 (mass %˜μm) or more.
To allow the product to fall within the above range, it is preferable that the content of the UV dye (U) in the resin film be 5 to 25 parts by mass with respect to 100 parts by mass of the resin, even preferably 5 to 20 parts by mass. In the case where the content of the UV dye (U) is in this range, the above problems can be avoided without lowering the resin properties.
<NIR Dye>
In the optical filter according to the present invention, the substrate includes the above-described dye (U) and dye (A).
The dye (A) is an NIR dye having a maximum absorption wavelength in a range of 600 to 800 nm in dichloromethane. Having such a dye, the optical filter can cut infrared light effectively.
It is preferable that the dye (A) be at least one kind selected from the group consisting of a squarylium dye, a cyanine dye, a phthalocyanine dye, a naphthalocyanine dye, a dithiol metal complex dye, an azo dye, a polymethine dye, a phthalide dye, a naphthoquinone dye, an anthraquinone dye, an indophenol dye, a pyrylium dye, a thiopyrylium dye, a croconium dye, a tetradehydrocholine dye, a triphenyl methane dye, an aminium dye, and diimonium dye.
It is preferable that the dye (A) contain at least one dye selected from a squarylium dye, a phthalocyanine dye, and a cyanine dye. Among these NIR dyes, a squarylium dye and a cyanine dye are preferable from the spectral point of view, and a phthalocyanine dye is preferable from the viewpoint of durability.
It is preferable that the squarylium dye be a compound represented by the following Formula (I):
Symbols in Formula (1) have the following meanings:
R24 and R26 represent, independently of each other, a hydrogen atom, a halogen atom, an hydroxyl group, an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, an acyloxy group having a carbon number of 1 to 10, —NR27R28 (R27 and R28 represent, independently of each other, a hydrogen atom, an alkyl group having a carbon number of 1 to 20, —C(═O)—R29 (R29 represents a hydrogen atom, an alkyl group having a carbon number of 1 to 20 that may include a substituent, an aryl group having a carbon number of 6 to 11 that may include a sub stituent, or an alaryl group having a carbon number of 7 to 18 that may include a substituent and may have an oxygen atom between carbon atoms), —NHR30 or SO2—R30 (each R30 represents a hydrocarbon group having a carbon number of 1 to 25 whose one or more hydrogen atoms may be replaced by a halogen atom, an hydroxy group, a carboxy group, a sulfo group, or a cyano group and that may include an unsaturated bond, an oxygen atom, or a saturated or unsaturated ring structure between carbon atoms), or a group represented by the following Formula (S) (R41 and R42 represent, independently of each other, a hydrogen atom, a halogen atom, or an alkyl group having a carbon number of 1 to 10 or an alkoxy group having a carbon number of 1 to 10 and k represents 2 or 3).
R21 and R22, R22 and R25, and R21 and R23 may form a heterocycle A, a heterocycle B, and a heterocycle C each having five or six members, respectively, together with a nitrogen atom by connecting to each other.
R21 and R22 form, in the case where the heterocycle A is formed, as a divalent group -Q- as a result of their connection, an alkylene group or an alkyleneoxy group whose hydrogen atom may be replaced by an alkyl group having a carbon number of 1 to 6, an aryl group having a carbon number of 6 to 10, or an acyloxy group having a carbon number of 1 to 10 that may include a substituent.
R22 and R25 form, in the case where the heterocycle B is formed, as a result of their connection, and R21 and R23 form, in the case where the heterocycle C is formed, as a result of their connection, divalent groups —X1—Y1— and —X2—Y2—(X1 and X2 connect the nitrogen), respectively, and each of X1 and X2 is represented by the' following Formula (1x) or (2x) and each of Y1 and Y2 is represented by one of the following Formulae (1y) to (5y), and in the case where each of X1 and X2 is a group represented by the following Formula (2x), each of Y1 and Y2 may be a single bond in which case an oxygen atom may exist between carbon atoms.
In Formula (1x), four Zs represent, independently of each other, a hydrogen atom, an hydroxy group, an alkyl group having a carbon number of 1 to 6, an alkoxy group having a carbon number of 1 to 6, or —NR38R39 (R38 and R39 represent, independently of each other, a hydrogen atom or an alkyl group having a carbon number of 1 to 20), R31 to R36 represent, independently of each other, a hydrogen atom, an alkyl group having a carbon number of 1 to 6, or an aryl group having a carbon number of 6 to 10, and R37 represents an alkyl group having a carbon number of 1 to 6 or an aryl group having a carbon number of 6 to 10.
R27, R28, R29, R31 to R37, R21 to R23 not forming a heterocycle, and R25 may form a 5-membered ring or a 6-membered ring by connecting to one of the others, and R31 and R36 or R31 and R37 may connect to each other directly.
R21 and R22 not forming a heterocycle represent, independently of each other, a hydrogen atom, an alkyl group having a carbon number of 1 to 6 and that may include a substituent, an allyl group that may include a substituent, an aryl group having a carbon number of 6 to 11 and that may include a substituent, or an alaryl group having a carbon number of 6 to 11 and that may include a substituent, and R23 and R25 not forming a heterocycle represent, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 6, or an alkoxy group having a carbon number of 1 to 6.
From the viewpoint that the visible light transmittance can be made high, it is preferable that the compound (I) be, for example, a compound represented by the following Formula (I-1):
The symbols used in Formula (I-1) have the same meanings as the same symbols used in Formula (1) and preferable modes of what are represented by the former are also the same as those of the latter.
In the compound (I-1), X1 is preferably the group (2x) and Y1 is preferably a single bond or the group (1y). In this case, R31 to R36 are preferably a hydrogen atom or an alkyl group having a carbon number of 1 to 3, and even preferably a hydrogen atom or a methyl group. Specific examples of —Y1—X1— include divalent organic groups represented by the following Formulae (11-1) to (12-3).
—C(CH3)2—CH(CH3)— (11-1)
—C(CH3)2—CH2— (11-2)
—C(CH3)2—CH(C2H5)— (11-3)
—C(CH3)2—C(CH3)(nC3H7)— (11-4)
—C(CH3)2—CH2—CH2 (12-1)
—C(CH3)2—CH2—CH(CH3)— (12-2)
—C(CH3)2—CH(CH3)—CH2— (12-3)
In the compound (1-1), from the viewpoints of solubility, heat resistance, and the steepness of a variation around the boundary between a visible range and a near-infrared range of a spectral transmittance curve, it is even preferable that R21's be, independently of each other, a group represented by the following Formula (4-1) or (4-2):
In Formulae (4-1) and (4-2), R71 to R75 represent, independently of each other, a hydrogen atom, a halogen atom, or an alkyl group having a carbon number of 1 to 4.
In the compound (I-1), from the viewpoint of increasing the transmittance of visible light, in particular, light in a wavelength range of 430 to 550 nm, it is preferable that R24′s be —NH—SO2—R30.
Formula (I-12) shows a compound in which R24's in the compound (I-1) are —NH—SO2—R30.
It is preferable that R23 and R26 of the compound (1-12) be, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 6, or an alkoxy group having a carbon number of 1 to 6. It is even preferable that each of R23 and R26 be a hydrogen atom.
In the compound (I-12), from the viewpoint of weatherability, it is preferable that R30's be, independently of each other, an alkyl group having a carbon number of 1 to 12 that may have a branch, an alkoxy group having a carbon number of 1 to 12 that may have a branch, or a hydrocarbon group having a carbon number of 6 to 16 that includes an unsaturated ring structure. Examples of the unsaturated ring structure include benzene, toluene, xylene, furan, and benzofuran. It is even preferable that R30's be, independently of each other, an alkyl group having a carbon number of 1 to 12 that may have a branch or an alkoxy group having a carbon number of 1 to 12 that may have a branch. It is noted that in each group represented by R30 all or part of the hydrogen atoms may be replaced by a halogen atom, in particular, a fluorine atom.
The compound (I) can be manufactured by known methods described in U.S. Pat. No. 5,543,086, US-A-2014/0061505, and WO 2014/088063.
Examples of the phthalocyanine dye include ones described in Japanese Patent No. 5,884,953 and WO 2019/168090.
Preferable examples of the cyanine dye include a compound represented by the following Formula (A1) or (A2):
The symbols in Formulae (A1) and (A2) have the following meanings:
R101 to R109 and R121 to R131 represent, independently of each other, a hydrogen atom. a halogen atom, an alkyl group having a carbon number of 1 to 15 and that may include a substituent, an alkoxy group having a carbon number of 1 to 15 and that may include a substituent, or an aryl group having a carbon number of 5 to 20. R110 to R114 and R132 to R136 represent, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 15, or an alkoxy group having a carbon number of 1 to 15.
X− represents a monovalent anion.
Symbols n1 and n2 represent, independently of each other, 0 or 1. A hydrogen atom connected to the carbon ring including —(CH2)n1— or the carbon ring including —(CH2)n2— may be replaced by a halogen atom, an alkyl group having a carbon number of 1 to 15 that may include a substituent, or an aryl group having a carbon number of 5 to 20 that may include a substituent.
In Formulae (A1) and (A2), it is preferable that R102 to R105, R108, R109, R122 to R127, R130, and R131 be, independently of each other, a hydrogen atom, an alkyl group having a carbon number of 1 to 15, an alkoxy group having a carbon number of 1 to 15, or an aryl group having a carbon number of 5 to 20. Among these examples, a hydrogen atom is even preferable from the viewpoint that high visible light transmittance can be obtained.
In Formulae (A1) and (A2), it is preferable that R110 to R114 and R132 to R136 be, independently of each other, a hydrogen atom or an alkyl group having a carbon number of 1 to 15. Among these examples, a hydrogen atom is even preferable from the viewpoint that high visible light transmittance can be obtained.
It is preferable that R106, R107, R128, and R129 be, independently of each other, a hydrogen atom, an alkyl group having a carbon number of 1 to 15, or an aryl group having a carbon number of 5 to 20 (it may include a chain, cyclic, or branched alkyl group), even preferably a hydrogen atom or an alkyl group having a carbon number of 1 to 15. It is preferable that R106 and R107 be the same group and R128 and R129 be the same group.
It is preferable that R101 and R121 be an alkyl group having a carbon number of 1 to 15 or an aryl group having a carbon number of 5 to 20. From the viewpoint of maintaining high visible light transmittance in a transparent resin as in a solution, it is preferable that R101 and R121 be an alkyl group having a carbon number of 1 to 15.
Examples of X− include I−, BF4−, PF6−, ClO4−, and anions represented by the following Formula (X1) or (X2), among which BF4−and PF6− are preferable.
In the following description, the portion of the dye (A1) excluding R101 to R114 is also referred to as a framework (A1). This kind of notification also applies to the other dyes.
A compound in which n1 in Formula (A1) is 1 is represented by the following Formula (A11) and a compound in which n1 in Formula (A1) is 0 is represented by the following Formula (A12):
In Formulae (A11) and (A12), R101 to R114 and X− are the same as in Formula (A1). R115 to R120 represent, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 15 and that may include a substituent, an alkoxy group having a carbon number of 1 to 15 and that may include a substituent, or an aryl group having a carbon number of 5 to 20. It is preferable that R115 to R120 be, independently of each other, a hydrogen atom, an alkyl group having a carbon number of 1 to 15, or an aryl group having a carbon number of 5 to 20 (it may include a chain, cyclic, or branched alkyl group), even preferably a hydrogen atom or an alkyl group having a carbon number of 1 to 15. It is preferable that R115 to R120 be the same group.
A compound in which n2 in Formula (A2) is 1 is represented by the following Formula (A21) and a compound in which n2 in Formula (A2) is 0 is represented by the following Formula (A22):
In Formulae (A21) and (A22), R121 to R136 and X− are the same as in Formula (A2). R137 to R142 represent, independently of each other, a hydrogen atom, a halogen atom, an alkyl group having a carbon number of 1 to 15 and that may include a substituent, an alkoxy group having a carbon number of 1 to 15 and that may include a substituent, or an aryl group having a carbon number of 5 to 20. It is preferable that R137 to R142 be, independently of each other, a hydrogen atom, an alkyl group having a carbon number of 1 to 15, or an aryl group having a carbon number of 5 to 20 (it may include a chain, cyclic, or branched alkyl group), even preferably a hydrogen atom or an alkyl group having a carbon number of 1 to 15. It is preferable that R137 to R142 be the same group.
The dyes (A1) and (A2) can be manufactured by, for example, known methods described in “Dyes and Pigments,” 73 (2007), pp. 344-352 and J. Heterocyclic Chem., 42, 959 (2005).
As described above, it is preferable that the content of the NIR dye (A) in the substrate be such that the product of the total content of the dye (U) and the dye (A) and the thickness of the resin film is in the particular range.
From the viewpoint of satisfying the above range requirement, it is preferable that the content of the NIR dye (A) in the resin film be 5 to 25 parts by mass with respect to 100 parts by mass of the resin, even preferably 5 to 20 parts by mass.
The substrate of the present filter may have either a single-layer structure or a multilayer structure. There are no particular limitations on the material of the substrate; the material may be either an organic material or an inorganic material as long as it is a transparent material that transmits visible light in a range of 400 to 700 nm.
In the case where the substrate has a single-layer structure, it is preferable that the substrate be a resin substrate that is made of a resin film containing a resin, the UV dye (U), and the NIR dye (A).
In the case where the substrate has a multilayer structure, it is preferable that the substrate have a structure that a resin film containing the UV dye (U) and the NIR dye (A) is laid on or above at least one major surface of a support body. In this structure, it is preferable that the support body be made of a transparent resin or a transparent inorganic material.
It is preferable that the resin be a transparent resin, examples of which include a polyester resin, an acrylic resin, an epoxy resin, an en thiol resin, a polycarbonate resin, a polyether resin, a polyarylate resin, a polysulfone resin, a polyether sulfone resin, a polyparaphenylene resin, a polyarylene ether phosphine oxide resin, a polyamide resin, a polyimide resin, a polyamideimide resin, a polyolefin resin, a cyclic olefin resin, a polyurethane resin, and a polystyrene resin. These resins may be used singly or two or more kinds of them may be used in mixture. Among these examples, a polyimide resin is preferable from the viewpoints that it is high in visible light transmittance and its glass transition temperature is so high that the dyes are made less prone to thermal deterioration.
Preferable examples of the transparent inorganic materials include glass and a crystal material.
Examples of glass that can be used as the support body include an absorption glass (a near-infrared light absorption glass) obtained by making copper ions be contained in a fluorophosphate glass, a phosphate glass, or the like, a soda-lime glass, a borosilicate glass, an alkali-free glass, and a quartz glass. It is preferable that the glass be an absorption glass that is suitable for a purpose; from the viewpoint of absorbing infrared light, a phosphate glass and a fluorophosphate glass are preferable. An alkali glass, an alkali-free glass, and a quartz glass are preferable when it is desired to take in a large amount of red light (600 to 700 nm). It is noted that the term “phosphate glass” includes a silicophosphate glass in which part of its glass framework is made of SiO2.
A chemically strengthened glass, obtained by replacing alkali metal ions (e.g., Li ions and/or Na ions) having a small ion radius that exist adjacent to a major surface of a glass plate with alkali ions (e.g., Na ions or K ions for Li ions and K ions for Na ions) having a large ion radius by ion exchange at a glass transition temperature or lower, can be used as the glass.
Examples of the crystal materials that can be used to form the support body include birefringent crystals such as quartz, lithium niobate and sapphire.
From the viewpoints of the shape stability that relates to the long-term reliability of optical characteristics, mechanical properties, etc. and the ease of handling during filter manufacture, it is preferable that the support body be made of an inorganic material, particularly preferably glass or sapphire.
The resin film can be formed by preparing a coating liquid by dissolving or dispersing, in a solvent, the dye (U) and the dye (A), a resin or material components of a resin, and components that are mixed when necessary, and applying it to the support body and drying it, and, if necessary, curing it. The support body may be either one included in the present filter or a peelable one that is used only in forming the resin film. It suffices that the solvent be a dispersion medium that enables stable dispersion or a solvent capable of dissolution.
The coating liquid may contain a surfactant to improve voids formed by minute babbles, depressions due to sticking of foreign substances etc., and cissing etc. in a drying step. The coating liquid can be applied by, for example, an immersion coating method, a cast coating method, or spin coating method. The resin film is formed by applying the above-mentioned coating liquid to the support body and then drying it. In the case where the coating liquid contains material components of a transparent resin, curing treatment is performed further such as thermal curing or photocuring.
The resin film can also be manufactured so as to have a film shape by extrusion molding. In the case where the substrate has a single-layer structure made of a resin film containing the dye (U) and the dye (A) (resin substrate), the resin film itself can be used as the substrate. In the case where the substrate has a multilayer structure including the support body, and the resin film containing the dye (U) and the dye (A) and laid on or above at least one major surface of the support body (composite substrate), the substrate can be manufactured by integrating this film with the support body by, for example, thermocompression bonding.
The optical filter may include either one or two or more resin films. In the case where the optical filter includes two or more resin films, the resin films may have either the same structure or different structures.
It is preferable that the thickness of the resin film be 10 μm or less, even preferably 5 μm or less.
In the case where the substrate has a single-layer structure made of a resin film containing the dye (U) and the dye (A) (resin substrate), it is preferable that the thickness of the resin film be 10 μm or less, even preferably 5μm or less.
In the case where the substrate has a multilayer structure including the support body, and the resin film containing the dye (U) and the dye (A) (composite substrate), it is preferable that the thickness of the resin film be 10 μm or less, even preferably 5μm or less. In the case where the resin film includes plural layers, it is preferable that the total thickness of those layers be 20 μm or less, even preferably 10 μm or less.
There are no particular limitations on the shape of the substrate; it may have a block shape, a plate shape, or a film shape.
Furthermore, from the viewpoints of warp deformation that occurs due to a reliability-related variation when a dielectric multilayer film is formed or the ease of handling, it is preferable that the thickness of the substrate be 300 μm or less, even preferably 50 to 300 pm and particularly preferably 70 to 300 μm.
In the case where the substrate is a resin substrate containing a resin and the dyes, it is preferable that the thickness of the substrate be 120 μm or less from the viewpoint of an advantage of height reduction, and 50 μm or more from the viewpoint of reduction of a warp that may occur at the time of formation of a multilayer film. In the case where the substrate is a composite substrate containing a support body and a resin film, it is preferable that the thickness of the substrate be 70 to 110 μm.
In the present filter, the dielectric multilayer film serves as an outermost layer and is laid on or above at least one major surface of the substrate.
In the present filter, it is preferable that at least one dielectric multilayer film be designed as a near-infrared light reflection layer (hereinafter also referred to as an “NIR reflection layer”). It is preferable that other dielectric multilayer film(s) be designed as an NIR reflection layer, a reflection layer having a reflection range other than a near-infrared range, or an anti-reflection layer.
The NIR reflection layer is a dielectric multilayer film that is designed so as to interrupt near-infrared light. For example, the NIR reflection layer has such wavelength selectivity as to transmit visible light and reflect mainly light in a near-infrared range other than a light interruption range of the resin film. The reflection range of the NIR reflection layer may include a near-infrared light interruption range of the resin film. The NIR reflection layer may be designed appropriately so as to interrupt light in a wavelength range other than a near-infrared range, such as light in a near-ultraviolet range, regardless of the characteristics of the NIR reflection.
For example, the NIR reflection layer is a dielectric multilayer film that is formed by laying a dielectric film having a lower refractive index (low refractive index films) and a dielectric film having a higher refractive index (high refractive index films) alternately. It is preferable that the refractive index of the high refractive index films be 1.6 or more, even preferably 2.2 to 2.5. Examples of a material of the high refractive index films include Ta2O5, TiO2, and Nb2O5, among which TiO2 is preferable from the viewpoints of the ease of film formation, the reproducibility of a refractive index etc., and stability.
On the other hand, it is preferable that the refractive index of the low refractive index films be less than 1.6, even preferably 1.45 or more and less than 1.55. Examples of a material of the low refractive index films include SiO2 and SiOxNy. SiO2 is preferable from the viewpoints of reproducibility in film formation, stability, and economy.
Furthermore, it is preferable that the transmittance of the NIR reflection layer vary steeply in a boundary wavelength range between a transmission range and an interruption range. To this end, it is preferable that the total number of lamination layers of the dielectric multilayer film constituting the reflection layer be 15 or more, even preferably 25 or more, and further preferably 30 or more. However, since a warp or the like occurs or the thickness increases unduly if the total number of lamination layers is too large, it is preferable that the total number of lamination layers be 100 or less, even preferably 75 or less, and further preferably 60 or less. It is preferable that the total thickness of the reflection layer be 2 to 10 um.
If the total number of lamination layers and the thickness of the dielectric multilayer film are within the above ranges, the NIR reflection layer satisfies a requirement of miniaturization and makes it possible to suppress the incident angle dependence while maintaining high productivity. Incidentally, vacuum film forming processes such as a CVD method, a sputtering method, and a vacuum vapor deposition method and wet film forming processes such as a spray method and a dip method can be used for formation of the dielectric multilayer film.
The NIR reflection layer may accomplish prescribed optical characteristics by either a single layer (one dielectric multilayer film) or two or more layers. In the case where two or more reflection layers are provided, they may be either the same or different in structure. In the case where two or more reflection layers are provided, usually plural reflection layers having different reflection bands are employed as them. In the case where two reflection layers are provided, they may be such that one is a near-infrared reflection layer that interrupts light in a shorter wavelength band of a near-infrared range, and the other is a near-infrared/near-ultraviolet reflection layer that interrupts light in both of a longer wavelength band of that near-infrared range and a near-ultraviolet range.
Examples of the anti-reflection layer include a dielectric multilayer film, an intermediate refractive index medium, and a moss eye structure in which the refractive index varies gradually. Among these examples, a dielectric multilayer film is preferable from the viewpoints of optical efficiency and productivity. The anti-reflection layer is formed by laying dielectric films alternately like the reflection layer is.
For example, the present filter may be equipped with, as another constituent element, a constituent element (layer) that provides absorption by inorganic fine particles or the like to control transmission and absorption of light in a particular wavelength range. Specific examples of a material of the inorganic fine particles include ITO (indium tin oxides), ATO (antimony-doped tin oxides), cesium tungstate, and lanthanum boride. Since ITO fine particles and cesium tungstate fine particles are high in visible light transmittance and are light absorptive in a wide infrared wavelength range that is longer than 1,200 nm, they can be used in a case that such infrared light needs to be interrupted.
In the case where the present filter is used in, for example, an imaging apparatus such as a digital still camera, it can provide an imaging apparatus that is superior in color reproducibility. An imaging apparatus provided with the present filter is equipped with a solid-state imaging device, an imaging lens, and the present filter. For example, the present filter can be used in such a manner as to be disposed between the imaging lens and the solid-state imaging device or directly stuck to, for example, the solid-state imaging device or the imaging lens of the imaging apparatus via an adhesive layer.
Next, the present invention will be described in more detail using Inventive Examples.
An ultraviolet/visible spectral photometer (type “UH-4150” produced by Hitachi High-Tech Corporation) was used for measurement of various optical characteristics.
It is noted that values of spectral characteristics for which no particular incident angle is specified are measured at an incident angle of 0° (i.e., from a direction that is perpendicular to the major surface).
Dyes used in each Example are as follows.
Compounds 1-17 are UV dyes and compound 18 is an NIR dye.
Compound 1 (merocyanine compound): Synthesized by reference to Japanese Patent No. 6,504,176
Compound 2: “Nikkafluor U1” produced by Nippon Chemical Industrial Co., Ltd. was used.
Compound 3 (cyanine compound): “SMP-416” produced by Hayashibara Chemical Laboratories was used.
Compound 4 (cyanine compound): “SMP-370” produced by Hayashibara Chemical Laboratories was used.
Compound 5 (cyanine compound): “SMP-471” produced by Hayashibara Chemical Laboratories was used.
Compound 6: “Kayalight 408” produced by Nippon Kayaku Co., Ltd. was used.
Compound 7: “Kayalight B” produced by Nippon Kayaku Co., Ltd. was used.
Compound 8: “Nikkafluor MCT” produced by Nippon Chemical Industrial Co., Ltd. was used.
Compound 9 (merocyanine compound): Synthesized by reference to Japanese Patent No. 6,504,176
Compound 10 (merocyanine compound): Synthesized by reference to Japanese Patent No. 6,504,176
Compound 11 (benzoxazole compound): “UVITEX OB” produced by Tokyo Chemical Industry Co., Ltd.
Compound 12 (merocyanine compound): Synthesized by reference to Japanese Patent No. 6,504,176
Compound 13 (merocyanine compound): Synthesized by reference to Japanese Patent No. 6,504,176
Compound 14 (azo compound): Synthesized by reference to Japanese Patent No. 6,256,335
Compound 15 (merocyanine compound): Synthesized by reference to Japanese Patent No. 6,504,176
Compound 16 (triazine compound): Synthesized by reference to Japanese Patent No. 6,256,335
Compound 17 (merocyanine compound): Synthesized by reference to Japanese Patent No. 6,504,176
Compound 18 (squarylium compound); Synthesized by reference to Japanese Patent No. 6,197,940
<Test A: Spectral Characteristics of UV Dye in dichloromethane>
Each dye was dissolved in dichloromethane uniformly. For each obtained solution, a maximum absorption wavelength (λmax), and the absolute value (UV70-UV10) of the difference between a wavelength UV10 at which the transmittance was 10% and a wavelength UV70 at which the transmittance was 70% in a wavelength range of 350 to 450 nm were measured using the spectrophotometer. Results are shown in the following table.
A UV dye of compound 1 (2.5 mass %), an NIR dye of compound 18 (2.3 mass %), and a polyimide resin (polyimide varnish “C-3G30G” produced by Mitsubishi Gas Chemical Company, Inc.) diluted with an organic solvent (a mixed solvent of y-butyrolactone and cyclohexanone) were mixed together, and the dyes were dissolved sufficiently in the polyimide solution.
A resulting resin solution was applied to a glass substrate (alkali glass “D263” produced by Schott AG) by spin coating and the organic solvent was removed by sufficient heating, whereby a 5-μm-thick dye-containing polyimide thin-film was produced.
The thin-film obtained was subjected to a transmission spectral measurement at an incident direction 0° in a wavelength range of 350 to 1,200 nm using the spectrophotometer. Results are shown in the following table.
Each dye-containing resin thin-film was produced in the same manner as in Example 1-1 except that a type and an addition amount of the UV dye, an addition amount of the NIR dye and a thickness of a resin thin-film were set to a type and at values shown in the following table, and was subjected to a transmission spectral measurement.
Results are shown in the following table.
Examples 1-2, 1-5 to 1-11, 1-15, and 1-16 are Inventive Examples and Examples 1-1, 1-3, 1-4, and 1-12 to 1-14 are Comparative Examples.
T440-480: Average transmittance (%) of a spectral transmittance curve in a wavelength range of 440 to 480 nm
T400-440: Average transmittance (%) of the spectral transmittance curve in a wavelength range of 400 to 440 nm
T370-400: Average transmittance (%) of the spectral transmittance curve in a wavelength range of 370 to 400 nm
T400: Transmittance (%) at a wavelength of 400 nm of the spectral transmittance curve
T390: Transmittance (%) at a wavelength of 390 nm of the spectral transmittance curve
T380: Transmittance (%) at a wavelength of 380 nm of the spectral transmittance curve
T370: Transmittance (%) at a wavelength of 370 nm of the spectral transmittance curve
70-400(0deg) (%)
90 (%)
80 (%)
70 (%)
indicates data missing or illegible when filed
As is understood from the above results, Examples 1-2, 1-5 to 1-11, 1-15, and 1-16 each of which employed a UV dye(s) whose maximum absorption wavelength in dichloromethane was in a range of 360 to 395 nm showed high blue light transparency and ultraviolet light shieldability, that is, superior spectral characteristics. Example 1-16 that employed two kinds of UV dyes in combination exhibited particularly superior spectral characteristics. Although Example 1-2 showed superior spectral characteristics, to obtain desired spectral characteristics it was necessary to set the content of the UV dye and the thickness of the resin film high or large.
An ultraviolet/infrared-cutting multilayer film having a passband in a range of 400 to 700 nm was formed on a glass substrate (alkali glass “D263” produced by Schott AG). The same resin thin-film (absorption film) as employed in Example 1-1 was formed on the multilayer film by spin coating. Subsequently, a dielectric multilayer film (anti-reflection film) made of SiO2 and TiO2 was formed on the resin thin-film by vapor deposition, whereby an absorption infrared cutting filter was produced. The produced infrared cutting filter was subjected to a transmission spectral measurement at incident directions 0° and 50° in a wavelength range of 350 to 1,200 nm using the spectrophotometer. Results are shown in the following table.
Each infrared cutting filter was produced by the same method as in Example 2-1 except that a type and an addition amount of the UV dye, an addition amount of the NIR dye, and a thickness of the resin thin-film were set to a type and at values shown in the following table, and subjected to a transmission spectral measurement.
Results are shown in the following table.
Furthermore, spectral transmittance curves of the infrared cutting filters of Examples 2-14 and 2-15 are shown in
Examples 2-5, 2-6, 2-9, 2-10, and 2-15 are Inventive Examples and Examples 2-1 to 2-4, 2-7, 2-8, and 2-11 to 2-14 are Comparative Examples.
λmax: Maximum absorption wavelength (nm)
T440-480: Average transmittance (%) of a spectral transmittance curve in a wavelength range of 440 to 480 nm
T400-440: Average transmittance (%) of a spectral transmittance curve in a wavelength range of 400 to 440 nm
T370-400(odeg): Average transmittance (%) of a spectral transmittance curve at an incident angle of 0° in a wavelength range of 370 to 400 nm
T370-400(50deg): Average transmittance (%) of a spectral transmittance curve at an incident angle of 50° in a wavelength range of 370 to 400 nm
UV10(0deg): Wavelength (nm) at which the transmittance was 10% at an incident angle of 0° in a wavelength range of 350 to 450 nm
UV10(50deg): Wavelength (nm) at which the transmittance was 10% at an incident angle of 50° in a wavelength range of 350 to 450 nm
UV20(0deg): Wavelength (nm) at which the transmittance was 20% at an incident angle of 0° in a wavelength range of 350 to 450 nm
UV20(50deg): Wavelength (nm) at which the transmittance was 20% at an incident angle of 50° in a wavelength range of 350 to 450 nm
UV50(0deg): Wavelength (nm) at which the transmittance was 50% at an incident angle of 0° in a wavelength range of 350 to 450 nm
UV50(50deg): Wavelength (nm) at which the transmittance was 50% at an incident angle of 50° in a wavelength range of 350 to 450 nm
UV70(0deg): Wavelength (nm) at which the transmittance was 70% at an incident angle of 0° in a wavelength range of 350 to 450 nm
|UV70(0deg)-UV10(0deg)|: Absolute value (nm) of the difference between UV10(0deg) and UV70(0deg)
|UV10(50deg)-UV10(0deg)|: Absolute value (nm) of the difference between UV10(0deg) and UV10(50deg)
|UV20(50deg)-UV20(0deg)|: Absolute value (nm) of the difference between UV20(0deg) and UV20(50deg)
|UV50(50deg)-UV50(0deg)|: Absolute value (nm) of the difference between UV50(0deg) and UV50(50deg)
0-
(%)
0deg) −
0-
(%)
0deg) −
indicates data missing or illegible when filed
As is understood from the above results, the optical filters of Examples 2-5, 2-6,2-9, 2-10, and 2-15 each of which employed a UV dye in which the maximum absorption wavelength in dichloromethane was in a range of 360 to 395 nm and the spectral characteristics in a solution (UV70-UV10) in test A and the spectral characteristics in a resin in test B were in the prescribed ranges were high in blue light transparency and were high in the ultraviolet light shieldability even at large incident angles, that is, showed superior spectral characteristics. The optical filter of Example 2-15 that employed the two kinds of UV dyes in combination exhibited particularly superior spectral characteristics.
On the other hand, the optical filters of Examples 2-1, 2-3, 2-4, 2-12, 2-13, and 2-14 in each of which the maximum absorption wavelength was not in the prescribed range, and the optical filters of Examples 2-2, 2-7, 2-8, and 2-11 in each of which the spectral characteristics in a solution in test A were not in the prescribed ranges were low in blue light transparency or the ultraviolet light shieldability at large incident angles.
A UV dye of compound 1 (7.5 mass %), a UV dye of compound 13 (3.5 mass %), an NIR dye of compound 18 (7 mass %), and a polyimide resin (polyimide varnish “C-3G30G” produced by Mitsubishi Gas Chemical Company, Inc.) diluted with an organic solvent (a mixed solvent of γ-butyrolactone and cyclohexanone) were mixed together, and the dyes were dissolved sufficiently in the polyimide solution. The addition amounts of the dyes are addition amounts with respect to the resin.
A resulting solution was applied to a glass substrate (alkali glass “D263” produced by Schott A G) by spin coating and the organic solvent was removed by sufficient heating, whereby a 1.5-μm-thick dye-containing polyimide film was produced.
The same anti-reflection film as employed in in Example 2-1 was formed on the produced polyimide film by vapor deposition. An optical sample obtained was subjected to a light resistance test using a super xenon weather meter produced by Suga Test Instruments Co., Ltd. The light incident surface was the anti-reflection film surface.
A light quantity was set so as to become 80,000 J/mm2 as an accumulated light quantity in a wavelength range of 300 to 2,450 nm. NIR dye survival rates were calculated on the basis of absorption coefficients at 400 nm and 680 nm obtained before and after the sample was subjected to the light resistance test. Results are shown in the following table.
The light resistance was judged high if the survival rate at 400 nm (T400-nm survival rate) was 85% or more and the survival rate at 680 nm (T680-nm survival rate) was 75% or more.
Each light resistance test was performed in the same manner as in Example 3-1 except that the dye types and their contents were set to types and at values shown in the following table.
Results are shown in the following table.
Examples 3-1 to 3-4, 3-5, and 3-7 to 3-10 are Inventive Examples and Example 3-6 is a Comparative Example.
A tendency is found from the above results (i.e., comparison between Example 3-6 and Examples 3-4 and 3-5) that coexistence of a UV dye and an NIR dye results in degradation of the NIR dye. As seen from Examples 3-1 to 3-3, using plural merocyanine compounds in combination as UV dyes can suppress degradation of an NW dye.
Although the present invention has been described above in detail with reference to the particular embodiment, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. The present application is based on Japanese Patent Application No. 2020-126700 filed on Jul. 27, 2020, the disclosure of which is incorporated herein by reference.
The optical filter according to the present invention exhibits an excellent ultraviolet light shieldability property in which, in particular, the reduction of ultraviolet light shieldability at large incident angles is suppressed while the near-infrared light shieldability and the visible light transparency, in particular, the blue light transparency, is kept high. The optical filter according to the present invention is useful when used in, for example, information acquisition devices such as cameras and sensors for transport machines that have been being increased in performance in recent years.
1A, 1B, 1C, 1D . . . Optical filter; 10 . . . Substrate; 11 . . . Support body; 12 . . . Resin film; 30 . . . Dielectric multilayer film.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2020-126700 | Jul 2020 | JP | national |
This is a bypass continuation of International Patent Application No. PCT/JP2021/026882, filed on Jul. 16, 2021, which claims priority to Japanese Patent Application No. 2020-126700, filed on Jul. 27, 2020. The contents of these applications are hereby incorporated by reference in their entireties.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2021/026882 | Jul 2021 | US |
| Child | 18155319 | US |
