Optical filter and imaging device

Abstract

To provide an infrared cut filter including a resin film having high adhesion to an absorption glass substrate consisting of phosphate based glass or fluorophosphate glass.SOLUTION: An optical filter includes a resin film through a bonding layer having a layer structure including a Si atom, and one or more kinds selected from a Ti atom, a Zr atom and an Al atom to an absorption glass substrate consisting of phosphate based glass or fluorophosphate based glass, or an optical filter includes a resin film including a Si atom, and one or more kinds selected from a Ti atom, a Zr atom and an Al atom to the absorption glass substrate consisting of phosphate based glass or fluorophosphate based glass.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an optical filter and an imaging device. [Background technology]

[0002] Digital still cameras such as compact digital cameras and digital single-lens reflex cameras (DS CCD or CMOS image mounted on a digital still camera In an imaging device using a solid-state imaging element such as a sensor, color tones can be reproduced well and a clear image can be produced. In order to obtain the desired color, an infrared cut filter ( The filter used is called IRCF (InfraRed Cut Filter). (For example, see Patent Document 1 (JP 2014-148567 A)).

[0003] FIG. 1 is a schematic diagram of a camera module that constitutes a DSC. FIG. 1(a) shows a smart FIG. 1 is a schematic diagram of a camera module for a compact digital camera mounted on a smartphone or the like. FIG. 1(b) is a schematic explanatory diagram of a camera module for a digital single-lens reflex camera. In the camera module shown in FIG. 1(a), the infrared light is transmitted through the lens L. The infrared reflector filter (IRCF)1 selectively reflects ultraviolet and near infrared light to reduce the visible light intensity of the human eye. Only light in the visible light range that matches the sensitivity characteristics is selectively introduced into the module, and the image sensor The same is true for the camera module shown in Figure 1(b). Among the light transmitted through the lens L, the infrared cut filter (IRCF) 1 cuts out the ultraviolet light and The cover glass CG selectively reflects infrared light and near-infrared light, and removes alpha rays while preventing the intrusion of dust. This suppresses the penetration of light into the module, and selectively transmits only light in the visible light range, which matches the human visual sensitivity characteristics. This has been introduced and incorporated into the image sensor IC.

[0004] The infrared cut filter (IRCF) is a filter that is attached to the upper surface of the glass substrate (light incident surface). A reflective film (UVIR film) is provided on the bottom surface (light exit surface) of the glass substrate. The mainstream was those with an anti-reflection coating (AR coating) on ​​the front (front side). Figure 2(a) is a schematic diagram showing the structure of a conventional infrared cut filter (IRCF)1. In the infrared cut filter (IRCF) 1 shown in FIG. 2(a), a glass substrate 3 A reflective film (UVIR film) 2 is provided on the upper surface side (light incident surface side) of the glass substrate 3. An anti-reflection film (AR film) 4 is provided on the lower surface (light exit surface) of the The ultraviolet light and near infrared light are selectively reflected by the reflective film 2 to match the human visual sensitivity characteristics. Only the light in the visible light region is transmitted through the glass substrate 3 and the anti-reflection film (AR film) 4, and the reflected light is The light is emitted from the bottom of the anti-reflection film (AR film) 4.

[0005] However, with the demand for thinner digital still cameras, the various components are becoming smaller. The optical design has been improved to allow light to enter the image sensor at a more oblique angle. On the other hand, the above-mentioned reflective infrared cut filter (IRCF) is designed to Since the optical fiber has high optical stability, the cutoff frequency shifts to the short wavelength side when the angle of incidence of light increases. This causes a phase shift, cutting infrared rays between the light that passes through the center of the lens and the light that passes through the peripheral areas. Color reproduction due to interference shift caused by different angles of incidence of light rays entering the filter (IRCF) This can easily result in a decrease in sexual function.

[0006] For this reason, infrared cut filters (IRCFs) are not only made of reflective films (UVIR films). It is not recommended to use a glass substrate that has a light absorbing resin film or a glass substrate that has light absorbing properties (such as an absorbing glass substrate). By using the same plate, the burden on the reflective film (UVIR film) is reduced, and the ultraviolet and A hybrid type that can effectively reduce infrared and near infrared light while exhibiting excellent oblique incidence characteristics. Infrared cut filters (IRCFs) for optical fiber are being considered.

[0007] Figure 2(b) shows the structure of the hybrid type infrared cut filter (IRCF) 1. FIG. 2(b) is a schematic diagram showing an example of an infrared cut filter (IRCF) 1. In this case, an absorbing glass substrate 3' that absorbs at least one of ultraviolet light and near infrared light is used. A reflective film (UVIR film) 2 is provided on the upper surface side (light incident surface side) of the above-mentioned absorbing glass. The lower surface (light emitting surface) of the substrate 3' is further provided with an absorbing resin film for absorbing ultraviolet light or near infrared light. 5 and an anti-reflection film (AR film) 4 are provided in this order. By using the absorbing glass substrate 3' and the absorbing resin film 5 in combination, ultraviolet and near infrared light in the incident light can be absorbed. While effectively reducing external light, it transmits only visible light downward under high oblique incidence characteristics. The structure allows light to pass through and exit the device. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] JP 2014-148567 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0009] However, the inventors of the present invention have found that there are no absorbents that absorb ultraviolet or near infrared light. The material of the glass substrate is usually phosphate glass or fluorophosphate glass. Phosphate-based glass is used, while various polymeric materials are used as the constituent materials of the above-mentioned absorption resin membrane. However, the adhesion between the two is not necessarily sufficient, especially when it comes into contact with moisture. It was found that adhesion in the presence of both substances is easily insufficient.

[0010] Under such circumstances, the present invention provides a glass made of phosphate-based glass or fluorophosphate-based glass. To provide an optical filter having a resin film having high adhesion to an absorbing glass substrate. Another object of the present invention is to provide an imaging device having such an optical filter. [Means for solving the problem]

[0011] In order to achieve the above object, the present inventors have conducted extensive research and have found that phosphate-based glass or The absorbing glass substrate is made of phosphate glass, and Si atoms, Ti atoms, Zr atoms, and A resin film is provided using a bonding component containing at least one selected from the group consisting of aluminum and silicon. It was found that the above technical problems can be solved by using an optical filter, and the present invention was developed based on this finding. This led to the completion of the project.

[0012] That is, the present invention provides (1) For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, A single layer structure containing at least one selected from Ti atoms, Zr atoms, and Al atoms together with i atoms. An optical filter (hereinafter referred to as a filter) characterized in that a resin film is provided via a bonding layer having a structure. Hereinafter, this will be referred to as the optical filter 1 of the present invention. (2) In the bonding layer, the ratio of the total number of Si atoms, Ti atoms, Zr atoms and Al atoms to the total number of The ratio of the total number of Ti atoms, Zr atoms and Al atoms to the total number of Ti atoms, Zr atoms and Al atoms is greater than 0 atomic %. The optical filter according to (1) above, wherein the content is 33.3 atomic % or less. (3) For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, General formula (I) M(OSiR 1 R 2 R 3 ) n (I) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 1 , R 2 and R 3 is acid Straight or branched chain hydrocarbons having 1 to 10 carbon atoms which may contain hydrogen or nitrogen atoms. groups, which may be the same or different, and n is a group in which M is a Ti atom or a Zr When M is an Al atom, it is 4, and when M is an Al atom, it is 3, and when M is an Al atom, it is 4. 1 R 2 R 3 The groups may be the same or different. and a compound represented by the following general formula (II): (Ti k O k-1 )(OSiR 4 R 5 R 6 ) 2k+2 (II) (However, R 4 , R 5 and R 6 is a group having 1 to 2 carbon atoms which may contain an oxygen atom or a nitrogen atom. 10 linear or branched hydrocarbon groups, which may be the same or different from each other k is a real number between 2 and 15, and multiple -OSiR 4 R 5 R 6 The groups are the same They may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: Through the bonding layer A resin film is provided The optical filter according to the above (1) or (2) (hereinafter, appropriately, the optical filter of the present invention) 1-1), (4) For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, General formula (III) M{OSi(OR 7 ) (OR 8 ) (OR 9 )} n (III) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 7 , R 8 and R 9 Charcoal A linear or branched hydrocarbon group having a prime number of 1 to 10, which may be the same or different. n may be 4 when M is a Ti atom or a Zr atom, and n may be 4 when M is an Al atom. 3 if multiple -OSi(OR 7 ) (OR 8 ) (OR 9 ) groups are identical to each other. may be the same or different.) and a compound represented by the following general formula (IV): (Ti k O k-1 ){OSi(OR 10 ) (OR 11 ) (OR 12 )} 2k+2 (IV) (However, R 10 , R 11 and R 12 is a linear or branched chain carbon with 1 to 10 carbon atoms. k is a hydrogen atom, which may be the same or different, and k is 2 or more and 15 or less. It is a real number and multiple -OSi(OR10 ) (OR 11 ) (OR 12 ) groups are identical to each other may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: Through the bonding layer A resin film is provided The optical filter according to any one of the above (1) to (3) (hereinafter, appropriately referred to as the optical filter of the present invention) Luther 1-2), (5) The coupling agent represented by the general formula (III) is represented by the following general formula (V): Si(OR 7 )(OR 8 ) (OR 9 )OH (V) (However, R 7 , R 8 and R 9 is a straight or branched chain hydrocarbon with 1 to 10 carbon atoms groups, which may be the same or different. and a silicon compound represented by the following general formula (VI): Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) (VI) (However, R 13 , R 14 , R 15 and R 16 is a linear or branched chain with 1 to 10 carbon atoms They are chain-like hydrocarbon groups and may be the same or different from each other, and are represented by the following general formula: (VII) Zr(OR 17 )(OR 18 )(OR 19 )(OR 20 ) (VII) (However, R 17 , R 18 , R 19 and R 20is a linear or branched chain with 1 to 10 carbon atoms ) and one of the following: General formula (VIII) Al(OR 21 )(OR 22 )(OR 23 ) (VIII) (However, R 21 , R 22 and R 23 is a linear or branched chain carbon with 1 to 10 carbon atoms. and aryl groups, which may be the same or different. One or more metal alkoxides represented by the formula: The optical filter according to (4) above, which is a reaction product of (6) Any of the above (1) to (5), wherein the bonding layer further contains a dehydration condensate of silanol. The optical filter according to (7) For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, General formula (V) Si(OR 7 )(OR 8 ) (OR 9 )OH (V) (However, R 7 , R 8 and R 9 is a straight or branched chain hydrocarbon with 1 to 10 carbon atoms groups, which may be the same or different. and 50 mol % or more but less than 100 mol % of a silicon compound represented by the following general formula (VI): Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) (VI) (However, R 13 , R 14 , R 15 and R 16 is a linear or branched chain with 1 to 10 carbon atoms They are chain-like hydrocarbon groups and may be the same or different from each other, and are represented by the following general formula: (VII) Zr(OR 17 )(OR 18 )(OR 19 )(OR 20 ) (VII) (However, R 17 , R 18 , R 19 and R 20 is a linear or branched chain with 1 to 10 carbon atoms ) and one of the following: General formula (VIII) Al(OR 21 )(OR 22 )(OR 23 ) (VIII) (However, R 21 , R 22 and R 23 is a linear or branched chain carbon with 1 to 10 carbon atoms. and aryl groups, which may be the same or different. A reaction product of more than 0 mol % and 50 mol % or less of a metal alkoxide selected from the group consisting of Through a bonding layer containing a hydrolysis and dehydration condensation product of a coupling agent composition containing The above (1) to ( 6 2. An optical filter according to any one of claims 1 to 11, (8) The coupling agent composition contains 80 moles of the silicon compound represented by the general formula (V). % but less than 100 mol % and one or more selected from the general formulae (VI) to (VIII). The optical composition according to the above (7), which is a reaction product of more than 0 mol % and less than 20 mol % of a metal alkoxide. Filters, (9) The coupling agent composition contains 85 to 9 silicon compounds represented by the general formula (V). 4 mol % and one or more metal alkoxy groups selected from the general formulas (VI) to (VIII). The optical filter according to the above (7), which is a reaction product with 6 to 15 mol % of a silane. (10) For an absorbing glass substrate made of phosphate-based glass or fluorophosphate-based glass, A resin containing Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms. The optical filter having an oil film (hereinafter, appropriately, referred to as the optical filter of the present invention) Luther II), (11) In the resin film, the total number of Si atoms, Ti atoms, Zr atoms and Al atoms is The ratio of the total number of Ti atoms, Zr atoms and Al atoms contained in the alloy is greater than 0 atomic%. The optical filter according to (10) above, wherein the content is 33.3 atomic % or less. (12) For an absorbing glass substrate made of phosphate-based glass or fluorophosphate-based glass, The following general formula (I) M(OSiR 1 R 2 R 3 ) n (I) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 1 , R 2 and R 3 is acid Straight or branched chain hydrocarbons having 1 to 10 carbon atoms which may contain hydrogen or nitrogen atoms. groups, which may be the same or different, and n is a group in which M is a Ti atom or a Zr When M is an Al atom, it is 4, and when M is an Al atom, it is 3, and when M is an Al atom, it is 4. 1 R 2 R 3 The groups may be the same or different. and a compound represented by the following general formula (II): (Ti k O k-1 )(OSiR 4 R 5 R 6 ) 2k+2 (II) (However, R 4 , R 5 and R 6 is a group having 1 to 2 carbon atoms which may contain an oxygen atom or a nitrogen atom. 10 linear or branched hydrocarbon groups, which may be the same or different from each other k is a real number between 2 and 15, and multiple -OSiR 4 R 5 R 6 The groups are the same They may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: A resin film is provided The optical filter according to the above (10) or (11) (hereinafter, appropriately, the optical filter of the present invention) (hereinafter referred to as Tur2-1) (13) For an absorbing glass substrate made of phosphate-based glass or fluorophosphate-based glass, The following general formula (III) M{OSi(OR 7 ) (OR 8 ) (OR 9 )} n (III) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 7 , R 8 and R 9 Charcoal A linear or branched hydrocarbon group having a prime number of 1 to 10, which may be the same or different. n may be 4 when M is a Ti atom or a Zr atom, and n may be 4 when M is an Al atom. 3 if multiple -OSi(OR 7 ) (OR 8 ) (OR 9 ) groups are identical to each other. may be the same or different.) and a compound represented by the following general formula (IV): (Ti k O k-1 ){OSi(OR 10 )(OR 11) (OR 12 )} 2k+2 (IV ) (However, R 10 , R 11 and R 12 is a linear or branched chain carbon with 1 to 10 carbon atoms. k is a hydrogen atom, which may be the same or different, and k is 2 or more and 15 or less. It is a real number and multiple -OSi(OR 10 )(OR 11 ) (OR 12 ) groups are identical to each other may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: A resin film is provided The optical filter according to any one of the above (10) to (12) (hereinafter, appropriately referred to as the optical filter of the present invention) Filter 2-2), (14) The coupling agent represented by the general formula (III) is represented by the following general formula (V): Si(OR 7 )(OR 8 ) (OR 9 )OH (V) (However, R 7 , R 8 and R 9 is a straight or branched chain hydrocarbon with 1 to 10 carbon atoms groups, which may be the same or different. and a silicon compound represented by the following general formula (VI): Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) (VI) (However, R 13 , R 14 , R 15 and R 16 is a linear or branched chain with 1 to 10 carbon atoms They are chain-like hydrocarbon groups and may be the same or different from each other, and are represented by the following general formula: (VII) Zr(OR 17 )(OR 18 )(OR 19 )(OR 20 ) (VII) (However, R 17 , R 18 , R 19 and R 20 is a linear or branched chain with 1 to 10 carbon atoms ) and one of the following: General formula (VIII) Al(OR 21 )(OR 22 )(OR 23 ) (VIII) (However, R 21 , R 22 and R 23 is a linear or branched chain carbon with 1 to 10 carbon atoms. and aryl groups, which may be the same or different. One or more metal alkoxides represented by the formula: The optical filter according to (13) above, which is a reaction product of (15) Any one of the above (10) to (14), wherein the resin film further contains a dehydration condensate of silanol. The optical filter according to any one of the preceding claims. (16) For an absorbing glass substrate made of phosphate-based glass or fluorophosphate-based glass, The following general formula (V) Si(OR 7 )(OR 8 ) (OR 9 )OH (V) (However, R 7 , R 8 and R 9 is a straight or branched chain hydrocarbon with 1 to 10 carbon atoms groups, which may be the same or different. and 50 mol % or more but less than 100 mol % of a silicon compound represented by the following general formula (VI): Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) (VI) (However, R 13 , R 14 , R 15 and R 16 is a linear or branched chain with 1 to 10 carbon atoms They are chain-like hydrocarbon groups and may be the same or different from each other, and are represented by the following general formula: (VII) Zr(OR 17 )(OR 18 )(OR 19 )(OR 20 ) (VII) (However, R 17 , R 18 , R 19 and R 20 is a linear or branched chain with 1 to 10 carbon atoms ) and one of the following: General formula (VIII) Al(OR 21 )(OR 22 )(OR 23 ) (VIII) (However, R 21 , R 22 and R 23 is a linear or branched chain carbon with 1 to 10 carbon atoms. and aryl groups, which may be the same or different. Reaction with more than 0 mol % and not more than 50 mol % of a metal alkoxide selected from the group consisting of A coupling agent composition containing a hydrolysis and dehydration condensation product The optical filter according to any one of the above (10) to (15), which is provided with a resin film. (17) The coupling agent composition contains 80 molybdenum silicon compounds represented by the general formula (V). % or more but less than 100 mol % and one or more of the general formulae (VI) to (VIII) The photocatalytic reaction product according to the above (16) is a reaction product of more than 0 mol % and less than 20 mol % of a metal alkoxide. Learning filters, (18) The coupling agent composition comprises a silicon compound 85 to 86 represented by the general formula (V). 94 mol % and one or more metal alkoxy groups represented by the general formulas (VI) to (VIII). The optical filter according to (16) above, which is a reaction product with 6 to 15 mol % of azide, (19) A solid-state imaging element, an imaging lens, and the optical filter according to any one of (1) to (18) above. An imaging device comprising: This provides: Effect of the Invention

[0013] According to the invention, an absorbing glass substrate made of phosphate-based glass or fluorophosphate glass is provided. It is possible to provide an optical filter having a resin film having high adhesion to the It is therefore possible to provide an imaging device having such an optical filter. [Brief description of the drawings]

[0014] [Figure 1] 1A is a schematic explanatory diagram of a camera module related to a compact digital camera, and FIG. 1B is a schematic explanatory diagram of a camera module related to a digital single-lens reflex camera. [Diagram 2] 2A and 2B are schematic diagrams showing the structure of an infrared cut filter (IRCF) 1. FIG. 2(a) is a schematic diagram of a reflective type IRCF that reflects ultraviolet light and near-infrared light using a reflective film (UVIR film). FIG. 2(b) is a schematic diagram of a hybrid type IRCF that has an absorbing glass substrate that absorbs ultraviolet light or near-infrared light together with the reflective film (UVIR film) and an absorbing resin film that absorbs ultraviolet light or near-infrared light. [Diagram 3] 1 is a cross-sectional image (image contrast) of an example of an optical filter according to the present invention, taken by a scanning transmission electron microscope-energy dispersive X-ray spectrometer (STEM-EDX). [Figure 4] FIG. 2 is a diagram showing STEM-EDX lines (EDX ray (K ray) detection intensity lines in the depth direction of each element constituting the optical filter) in an example of the optical filter according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] The optical filter 1 of the present invention is made of phosphate glass or fluorophosphate glass. The absorbing glass substrate is coated with Si atoms and Ti atoms, Zr atoms, and Al atoms. The resin film is provided via a bonding layer having a single layer structure containing one or more of the following: Specific embodiments thereof include the optical filters 1-1 and 1-2 of the present invention described later. Alternatively, the optical filter 1-2 of the present invention can be mentioned. The optical filter 2 of the present invention is made of phosphate glass or fluorophosphate glass. The absorption of Ti, Zr and Al atoms was observed in addition to Si atoms on the absorbing glass substrate. and one or more resin films selected from the group consisting of As a specific embodiment, the optical filter 2-1 of the present invention or the optical filter 2-2 of the present invention described later is One example is Tar 2-2.

[0016] The optical filter 1 of the present invention and the optical filter 2 of the present invention are, with respect to an absorbing glass substrate, A single layer containing Si atoms and at least one selected from Ti atoms, Zr atoms, and Al atoms. A resin film is provided through a bonding layer having a structure, or a Si atom and Also, a resin film containing one or more selected from Ti atoms, Zr atoms, and Al atoms is provided. They differ in that they are made up of the same material, but have other commonalities. Therefore, unless otherwise specified, the following description of the optical filter of the present invention is based on the present invention. This is common to the optical filter 1 of the present invention and the optical filter 2 of the present invention.

[0017] [Glass substrate] The optical filter according to the present invention is made of a glass substrate made of phosphate glass or futurin glass. The optical fiber has an absorbing glass substrate made of an acid salt glass.

[0018] In the optical filter according to the present invention, the absorbing glass substrate has a thickness of 0.01 to Preferably, it is 1.50 mm, more preferably, it is 0.01 to 0.70 mm, and 0.0 A thickness of 1 to 0.30 mm is more preferable. By setting the thickness of the absorbing glass substrate within the above range, it is possible to easily reduce the thickness of the optical filter. can be achieved.

[0019] In the optical filter according to the present invention, the absorbing glass substrate is made of phosphate glass or fluorine. It is made of phosphate glass.

[0020] The phosphate-based glass in the present invention is composed of P and O as essential components and other optional components. The glass containing CuO is particularly preferred. By using the phosphate glass, near infrared light can be absorbed more effectively. Optional components include, for example, Ca, Mg, Sr, Ba, Li, Na, K, and Cs. can be.

[0021] The fluorophosphate glass in the present invention is composed of essential components P, O, and F, and other optional components. Glass containing an organic component, and glass containing CuO is particularly preferred. Fluorophosphate-based glass By including CuO, near infrared light can be absorbed more effectively. Other optional components of salt-based glasses include, for example, Ca, Mg, Sr, Ba, Li, Na, K, Examples include Cs.

[0022] The phosphate-based glass may be P2O: more than 50% by mass but not more than 70% by mass Al2O30~40% by mass, BaO 0~40% by mass, CuO 0~40% by mass It is preferred that the compound contains

[0023] The phosphate-based glass may be P2O520~60% by mass, Al2O30~10% by mass, BaO 0~10 mass%, CuO 0~10% by mass More preferably, it contains:

[0024] The phosphate-based glass may be P2O520~60% by mass, Al2O31~10% by mass, BaO 1~10% by mass, CuO 1~10% by mass More preferably, it comprises:

[0025] The fluorophosphate glass may be P2O: more than 50% by mass but not more than 70% by mass Al2O30~40% by mass, BaO 0~40% by mass, CuO 0~40% by mass and further contains more than 0 mass% and up to 40 mass% fluoride. The one is preferred.

[0026] The fluorophosphate glass may be P2O520~60% by mass, Al2O30~10% by mass, BaO 0~10% by mass, CuO 0~10% by mass and further contains 1 to 30 mass% of fluoride. Things are more preferable.

[0027] The fluorophosphate glass may be P2O520~60% by mass, Al2O31~10% by mass, BaO 1~10% by mass, CuO 1~10% by mass and further contains 2 to 30 mass% of fluoride. It is even more preferable.

[0028] The fluoride may be one or more selected from MgF2, CaF2, SrF2, etc. can be done.

[0029] The optical filter 1 of the present invention is a glass substrate having Ti atoms, Si atoms, and A bond layer having a single layer structure containing at least one selected from Zr atoms and Al atoms is formed on the bond layer. It is characterized by being provided with an oil film.

[0030] In the optical filter 1 of the present invention, the bonding layer is formed by hydrolysis of a coupling agent described later. Examples include decomposition products and dehydration condensation products.

[0031] In the optical filter 1 of the present invention, the bonding layer contains Ti atoms and Zr atoms in addition to Si atoms. The SiO2-containing nanotube has a single layer structure containing at least one selected from the group consisting of a SiO2 atom and an Al atom. In the present application, the term "single-layer structure" refers to a structure obtained by scanning transmission electron microscope-energy spectrometry under the following conditions: The image obtained when measuring with a beam dispersive X-ray spectrometer (STEM-EDX) The images (image contrast) or elemental analysis results show that the materials are made of the same composition. means a layer structure in which <Measurement conditions> Scanning transmission electron microscope: JEOL Ltd. ARM200F Energy dispersive X-ray spectrometer: JED-2300T manufactured by JEOL Ltd. Sample preparation: Focused ion beam processing (FIB) Acceleration voltage: 200 kV Elemental analysis: EDX mapping (resolution: 256 x 256)

[0032] FIG. 3 shows the S obtained under the above measurement conditions in an example of the optical filter according to the present invention. This is a TEM-EDX image (image contrast). From this figure, it is clear that the optical filter is an absorbing glass. A resin film R is provided on a substrate G via a bonding layer B, and the bonding layer B has a single-layer structure. I know it will be.

[0033] In the optical filter 1 of the present invention, the thickness of the bonding layer is 1000 nm or less. It is preferably 10 to 500 nm, more preferably 30 to 300 nm. Even more preferred. By making the thickness of the bonding layer 1000 nm or less, This makes it easier to prevent unevenness from occurring, and makes it easier to make the film surface of the bonding layer uniform. In addition, when the thickness of the bonding layer is 10 nm or more, the bonding layer is likely to exhibit sufficient bonding strength. As a result, the mechanical strength of the optical filter can be easily improved.

[0034] In the present application, the thickness of the bonding layer was measured using the above-mentioned STEM-EDX. In the measured image (image contrast) of the optical filter cross section obtained at times, This refers to the arithmetic average value when the thickness of the bonding layer was measured at 50 points.

[0035] In the optical filter 1 of the present invention, the bonding layer contains Ti atoms and Zr atoms in addition to Si atoms. The bonding layer contains one or more atoms selected from the group consisting of silicon atoms and aluminum atoms. The one or more atoms selected from Ti atoms, Zr atoms and Al atoms are preferably Ti atoms. is preferred.

[0036] FIG. 4 shows the STEM-E spectra of the optical filter 1 according to the present invention, measured under the above-mentioned conditions. DX line (EDX line (K line) detection in the depth direction of each element that makes up the optical filter In the example shown in FIG. 4, the distance from the surface is 0 to 98 A resin film containing C atoms and O atoms as main components (described later) is provided in the 0 nm region, The main components of the atom distribution are Si, Ti and O atoms in the region 980 to 1150 nm from the surface. and a bonding layer including P atoms in a region having a distance from the surface of the bonding layer of greater than 1150 nm. It can be seen that an absorbing glass substrate containing F atoms and O atoms as main components is provided. The STEM-EDX line allows the constituent elements of each region to be identified. It is also possible to check the thickness of layers, etc. In the example shown in FIG. 4, the bonding layer of the optical filter 1 contains Ti atoms as well as Si atoms. It is clear that it includes

[0037] In the bonding layer constituting the optical filter 1 of the present invention, Si atoms, Ti atoms, and Zr atoms and the total number of Ti atoms, Zr atoms, and Al atoms in the total number of Al atoms (total number of atoms) The atomic percentage α (atomic%) is greater than 0 atomic% and is 33.3 atomic%. It is preferable that the content is 9 to 33.3 atomic % or less, and more preferable that the content is 1 It is more preferable that the content is 2 to 33.3 atomic %.

[0038] In the present application, the Si atoms, Ti atoms, Zr atoms and Al atoms constituting the bonding layer The ratio of the total number of Ti atoms, Zr atoms, and Al atoms to the total number of atoms (total number of atoms) In this case, α (atomic %) means a value calculated by the following method. (1) STEM-EDX measurement of the optical filter was performed under the above-mentioned measurement conditions, and the results are shown in Figure 4. As shown in the example, STEM-EDX lines (in the depth direction of each element that constitutes the optical filter) The EDX line (K line) detection intensity line at 100 nm is obtained. (2) EDX line integrated intensity X of Si atoms in the region that constitutes the bonding layer Si , Ti atoms EDX ray integrated intensity X Ti , the integrated EDX line intensity of Zr atom X Zr and EDX lines of Al atoms Accumulative Intensity X Al We ask for the following respectively. (3) The k-factor (which depends on the accelerating voltage and detection efficiency) is added to each EDX line integrated intensity obtained in (2). The k-factor of the Si atom is hereafter referred to as K Si , The k factor of Ti atoms is K Ti , the k-factor of Zr atom is K Zr , the k-fa of Al atoms Kuta K Al The value multiplied by (1) can be considered to correspond to the weight ratio of each constituent element. For this reason, for example, the weight ratio A of Ti atoms constituting the bonding layer Ti (% by weight) is calculated using the following formula: It can be put out.

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number

[0039] As an embodiment of the optical filter 1 of the present invention, the optical filter 1-1 of the present invention and An example of the optical filter of the present invention is optical filter 1-2.

[0040] The optical filter 1-1 of the present invention is a compound represented by the following general formula (I) for the above absorbing glass substrate: M(OSiR 1 R 2 R 3 ) n (I) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 1 , R 2 and R 3 is acid Straight or branched chain hydrocarbons having 1 to 10 carbon atoms which may contain hydrogen or nitrogen atoms. groups, which may be the same or different, and n is a group in which M is a Ti atom or a Zr When M is an Al atom, it is 4, and when M is an Al atom, it is 3, and when M is an Al atom, it is 4. 1 R 2 R 3 The groups may be the same or different. and a compound represented by the following general formula (II): (Ti k O k-1 )(OSiR 4 R 5 R 6 ) 2k+2 (II) (However, R 4 , R 5 and R 6 is a group having 1 to 2 carbon atoms which may contain an oxygen atom or a nitrogen atom. 10 linear or branched hydrocarbon groups, which may be the same or different from each other k is a real number between 2 and 15, and multiple -OSiR 4 R 5 R 6 The groups are the same They may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: Through the bonding layer A resin film is provided It is something. The optical filter 1-2 of the present invention is made of phosphate glass or fluorophosphate glass. The absorbent glass substrate is coated with a compound represented by the following general formula (III): M{OSi(OR 7 ) (OR 8 ) (OR 9 )} n (III) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 7 , R 8 and R 9 Charcoal A linear or branched hydrocarbon group having a prime number of 1 to 10, which may be the same or different. n may be 4 when M is a Ti atom or a Zr atom, and n may be 4 when M is an Al atom. 3 if multiple -OSi(OR 7 ) (OR 8 ) (OR 9 ) groups are identical to each other. may be the same or different.) and a compound represented by the following general formula (IV): (Ti k O k-1 ){OSi(OR 10 ) (OR 11 ) (OR 12 )} 2k+2 (IV) (However, R 10 , R 11 and R 12 is a linear or branched chain carbon with 1 to 10 carbon atoms. k is a hydrogen atom, which may be the same or different, and k is 2 or more and 15 or less. It is a real number and multiple -OSi(OR 10 ) (OR 11 ) (OR 12 ) groups are identical to each other may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: Through the bonding layer A resin film is provided It is something.

[0041] The compound represented by the general formula (III), which is a component of the bonding layer, is represented by the general formula (I). The compounds that are used are more limited, and the general components of the bonding layer are The compound represented by formula (IV) is a more specific example of the compound represented by the above general formula (II). It is. Therefore, in the following, the structure of the bonding layer of the optical filter 1 of the present invention will be described. The compound represented by the general formula (I) and the compound represented by the general formula (III) are the components, The compounds represented by the general formula (II) and the general formula (IV) are sequentially explained. The formation method will now be described.

[0042] In the optical filter 1 of the present invention, M(OSiR 1 R 2 R 3 ) n (I) M constituting the compound represented by the formula (1) is a Ti atom, a Zr atom or an Al atom, and the Ti atom It is preferable that:

[0043] In the compound represented by the above general formula (I), R 1 , R 2 and R 3 is an oxygen atom or is a linear or branched hydrocarbon group having 1 to 10 carbon atoms which may contain a nitrogen atom, Straight or branched chain hydrocarbons having 1 to 4 carbon atoms which may contain oxygen or nitrogen atoms It is preferably a linear group having 1 to 3 carbon atoms which may contain an oxygen atom or a nitrogen atom. Or, it is more preferably a branched hydrocarbon group.

[0044] R 1 , R2 and R 3 Specifically, methyl, ethyl, propyl, butyl linear alkyl groups such as pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; Branched or cyclic hydrocarbon groups, -C3H6(COO)CHCH2, -CH2(CO O)CHCH2, -C2H4(COO)CHCH2, -C4H8(COO)CHCH2, -C 5H 10 (COO)CHCH2, -CH 12 (COO)CHCH2, -C7H 14 (COO )CHCH2, -C8H 16 (COO)CHCH2, -C9H 18 (COO)CHCH2, - C 10 H 20 From linear, branched or cyclic hydrocarbon groups such as (COO)CHCH2 You can name a selection.

[0045] In the optical filter 1 according to the present invention, R 1 , R 2 and R 3 The number of carbon atoms is within the above range. By setting the above condition, it becomes easier to maintain a suitable reaction rate between the silicon compound and the metal alkoxide. This makes it easier to prepare a more homogeneous coupling agent. In addition, in the compound represented by the general formula (I), R bonded to a silicon atom 1 , R 2 Oh BiR 3 The functional group represented by the formula (I) may affect the adhesiveness between the resin film and the adhesive layer. Depending on the resin film to be applied on the laminate, an appropriate R 1 , R 2 and R 3 By selecting the group, The adhesiveness between the resin film and the adhesive layer can be adjusted.

[0046] Above R 1 , R 2 and R 3 may be the same or different from each other. In addition, n is 4 when M is a Ti atom or a Zr atom, and n is 5 when M is an Al atom. The total number of -OSiRs is 3, and 1 R 2 R 3 The groups may be the same or different. This is also fine.

[0047] In the optical filter 1 of the present invention, the compound represented by the general formula (I) is any one of the following: General formula (III) M{OSi(OR 7 ) (OR 8 ) (OR 9 )} n (III) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 7 , R 8 and R 9 Charcoal A linear or branched hydrocarbon group having a prime number of 1 to 10, which may be the same or different. n may be 4 when M is a Ti atom or a Zr atom, and n may be 4 when M is an Al atom. 3 if multiple -OSi(OR 7 ) (OR 8 ) (OR 9 ) groups are identical to each other. It may be the same or different. Examples of the compound include compounds represented by the following formula:

[0048] In the compound represented by the above general formula (III), M is a Ti atom, a Zr atom, or an Al atom. It is preferably a Ti atom.

[0049] In the compound represented by the above general formula (III), R 7 , R 8 and R 9 has 1 to 10 carbon atoms 10 straight-chain or branched-chain hydrocarbon groups having 1 to 4 carbon atoms. and preferably a linear or branched hydrocarbon group having 1 to 3 carbon atoms. It is more preferable that:

[0050] R 7 , R 8 and R 9 Specifically, methyl, ethyl, propyl, butyl linear or hexyl groups, pentyl groups, hexyl groups, heptyl groups, octyl groups, nonyl groups, and decyl groups The alkyl group may be selected from the group consisting of branched and cyclic hydrocarbon groups. R 7 , R 8 and R 9 may be the same or different from each other.

[0051] In the optical filter 1 according to the present invention, R 7 , R 8 and R 9 The number of carbon atoms is within the above range. By setting the above condition, it becomes easier to maintain a suitable reaction rate between the silicon compound and the metal alkoxide. This makes it easier to prepare a more homogeneous coupling agent.

[0052] Above R 7 , R 8 and R 9 may be the same or different from each other. In addition, n is 4 when M is a Ti atom or a Zr atom, and n is 5 when M is an Al atom. In this case, the number is 3, and multiple -OSi(OR 7 ) (OR 8 ) (OR 9 ) groups may be the same as each other. Or it may be different.

[0053] The coupling agent represented by the above general formula (III) is represented by the following general formula (V): Si(OR7 )(OR 8 ) (OR 9 )OH (V) (However, R 7 , R 8 and R 9 is a straight or branched chain hydrocarbon with 1 to 10 carbon atoms groups, which may be the same or different. and a silicon compound represented by the following general formula (VI): Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) (VI) (However, R 13 , R 14 , R 15 and R 16 is a linear or branched chain with 1 to 10 carbon atoms They are chain-like hydrocarbon groups and may be the same or different from each other, and are represented by the following general formula: (VII) Zr(OR 17 )(OR 18 )(OR 19 )(OR 20 ) (VII) (However, R 17 , R 18 , R 19 and R 20 is a linear or branched chain with 1 to 10 carbon atoms ) and one of the following: General formula (VIII) Al(OR 21 )(OR 22 )(OR 23 ) (VIII) (However, R 21 , R 22 and R 23 is a linear or branched chain carbon with 1 to 10 carbon atoms. and aryl groups, which may be the same or different. One or more metal alkoxides represented by the formula: It is preferable that the compound is a reaction product of

[0054] In the silicon compound represented by the general formula (V), 7 , R 8 and R 9 Carbon The numbers and specific examples are as described above. 7 , R 8 and R 9 are identical to each other. They may be different.

[0055] The silicon compound represented by the above general formula (V) can be prepared by reacting the corresponding silane alkoxy group with the silicon compound represented by the following general formula (V): It can be easily produced by partial hydrolysis of Si(OR 7 )(OR 8 ) (OR 9 ) (OR a )+H2O → Si(OR 7 )(OR 8 ) (OR 9 )OH+R a OH (However, R 7 , R 8 , R 9 and R a is a linear or branched chain carbon with 1 to 10 carbon atoms. and aryl groups, which may be the same or different. The above-mentioned hydrocarbon group R 7 , R 8 and R 9 Preferred embodiments of are as described above, and R a The preferred embodiment of the hydrocarbon group R 7 , R 8 and R 9 This is similar to the preferred embodiment of the above. When silane alkoxide is completely hydrolyzed, the reaction proceeds as follows: This produces silanol Si(OH)4. Si(OR 7 )(OR8 ) (OR 9 ) (OR a )+4H2O → Si(OH)4+R 7 OH+R 8 OH+R 9 OH+R a OH On the other hand, by controlling the amount of water for hydrolyzing silane alkoxide, As a result, the silicon compound represented by the general formula (V) can be obtained as described above.

[0056] General formula (VI)Ti(OR) 13 )(OR 14 )(OR 15 )(OR 16 ) Titanium Alkoxides, Zr(OR 17 )(OR 18 )(OR 19 )(OR 20 )in and zirconium alkoxides represented by the above general formula (VIII) Al(OR 21 )(OR 2 2 )(OR 23 In the aluminum alkoxide represented by the formula: 13 ~R 23 (R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 ) is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, It is preferably a linear or branched hydrocarbon group having 3 to 8 carbon atoms. A branched hydrocarbon group is more preferred.

[0057] R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 or R 23 Specifically, methyl, ethyl, propyl, butyl, pentyl, linear or branched chain of aryl, hexyl, heptyl, octyl, nonyl, or decyl groups Examples of the alkyl group include those selected from cyclic and rectangular hydrocarbon groups. R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 and R 23 may be the same or different from each other.

[0058] In the optical filter 1 according to the present invention, R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 or R 23 The number of carbon atoms is 2 or more. As a result, the stability of the metal alkoxide against moisture can be effectively improved, and the moisture content can be reduced to 9 or less. This suppresses the increase in viscosity of the metal alkoxide and effectively improves handling. It can be improved.

[0059] The above general formula Si(OR 7 ) (OR 8 ) (OR9 )OH and the silicon compound represented by the above general formula Titanium alkoxide Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) Taking the above as an example, the reaction between the two is thought to proceed as follows: 4Si(OR 7 ) (OR 8 ) (OR 9 )OH+Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) →Ti{OSi(OR 7 ) (OR 8 ) (OR 9 )}4+R 13 OH+R 14 OH+R 15 O H+R 16 OH In the reaction system, the general formula Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) Titanium represented by For 1 mole of alkoxide, the compound of the general formula Si(OR 7 ) (OR 8 ) (OR 9 )OH By reacting in the presence of an excess of silicon compound (4 moles or more), It is believed that all titanium alkoxides present in the reaction system react according to the above reaction scheme.

[0060] The optical filter 1 according to the present invention is a filter having a structure in which a compound represented by the following general formula (III) is added to an absorbing glass substrate. M{OSi(OR 7 ) (OR 8 ) (OR 9 )} n (III) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 7 , R 8 and R 9 Charcoal A linear or branched hydrocarbon group having a prime number of 1 to 10, which may be the same or different. n may be 4 when M is a Ti atom or a Zr atom, and n may be 4 when M is an Al atom. 3 if multiple -OSi(OR 7 ) (OR 8 ) (OR 9 ) groups are identical to each other. may be the same or different.) After passing through a bonding layer containing a hydrolysis and dehydration condensation product of a coupling agent containing a compound represented by the formula: Examples of the resin film include the resin film described above.

[0061] The coupling agent comprising the compound represented by the general formula (III) is Ti{OSi(OR 7 ) (OR 8 ) (OR 9 )}4 is taken as an example, the coupling agent is As shown in the following reaction formula, the hydrolysis reaction proceeds by adding water to the system. Ti{OSi(OR 7 ) (OR 8 ) (OR 9 )}4+12H2O → Ti{OSi(OH)3 }4+4R 7 OH+4R 8 OH+4R 9 OH The hydrolysis reaction is carried out, for example, at a temperature of 10 to 40° C. using a catalyst such as HCl. The reaction can be carried out in the presence of a suitable amount of water. Next, the hydrolyzate of the coupling agent composed of the compound represented by the above general formula (III) is A coating solution containing the compound is applied to an absorbing glass substrate to form a coating film. The content of the coupling agent composed of the compound represented by the general formula (III) in the coating liquid is The content of the coating liquid is preferably 0.1 to 10.0% by mass. The application rate is 0.01-0.10ml / cm 2 It is preferable that: As a method for applying the coating solution containing the hydrolysate of the coupling agent, a dip coating method is used. Coating method, cast coating method, spray coating method, spin coating method The coating method may include one or more coating methods selected from the following: Then, a resin film forming coating liquid described later is applied onto the coating film to form an absorbent resin coating film. After the synthesis, the resulting mixture is appropriately heated to obtain a dehydration condensation product of the hydrolyzate of the coupling agent, [-Ti(OSiO3)3―] n (where n is a positive integer) can be obtained.

[0062] The dehydrated condensate is a mixture of the coupling agent and the absorbing glass or It is believed that the resin film is strongly bonded to the phosphate glass. A resin film having high adhesion is provided on an absorbing glass substrate made of fluorophosphate glass. Therefore, the optical filter 1 can be easily provided.

[0063] In the optical filter 1 of the present invention, the bonding layer further contains a hydrolysis and dehydration condensation product of silanol. It may also be something like that.

[0064] That is, by appropriately heating silanol Si(OH)4, the reaction shown in the following formula can be obtained. As shown, a dehydration condensation product (Si-O-Si)2 is produced. Si(OH)4 → (Si-O-Si)2 + 2H2O According to the investigations of the present inventors, the above-mentioned dehydration condensation product of silanol alone does not have a sufficient ability to react with water, particularly in the presence of water. In the above-mentioned general formula (I) or A compound represented by the general formula (III) is a coupling agent having a hydrolyzate thereof, which is obtained by dehydration condensation. It is believed that by using it in combination with a dehydrated condensation product, the two products complement each other and improve the above-mentioned adhesion. can be obtained.

[0065] The silanol is a compound represented by the general formula (I) or (III). The hydrolyzate of the coupling agent is added to a coating solution containing the hydrolyzate, and the coating solution is then coated with an absorbing glass substrate. The coating is applied to a plate to form a coating film, and then the above-mentioned heat treatment is appropriately performed to form a coupling. Dehydration condensation product of hydrolyzate of the coating agent [-Ti(OSiO3)3―] n (where n is a positive integer. ) and a dehydration condensation product of silanol can be produced.

[0066] The optical filter 1 of the present invention is made of phosphate glass or fluorophosphate glass. The following general formula (V) is applied to an absorbing glass substrate. Si(OR 7 )(OR 8 ) (OR 9 )OH (V) (However, R 7 , R 8 and R 9 is a straight or branched chain hydrocarbon with 1 to 10 carbon atoms groups, which may be the same or different. and 50 mol % or more but less than 100 mol % of a silicon compound represented by the following general formula (VI): Ti(OR 13 )(OR 14 )(OR 15 )(OR 16 ) (VI) (However, R13 , R 14 , R 15 and R 16 is a linear or branched chain with 1 to 10 carbon atoms They are chain-like hydrocarbon groups and may be the same or different from each other, and are represented by the following general formula: (VII) Zr(OR 17 )(OR 18 )(OR 19 )(OR 20 ) (VII) (However, R 17 , R 18 , R 19 and R 20 is a linear or branched chain with 1 to 10 carbon atoms ) and one of the following: General formula (VIII) Al(OR 21 )(OR 22 )(OR 23 ) (VIII) (However, R 21 , R 22 and R 23 is a linear or branched chain carbon with 1 to 10 carbon atoms. and aryl groups, which may be the same or different. A reaction product of more than 0 mol % and 50 mol % or less of a metal alkoxide selected from the group consisting of A resin film is provided via a bonding layer containing a hydrolysis and dehydration condensation product of a coupling agent composition containing the It is preferable that the above-mentioned composition is a composition comprising: By containing the metal alkoxide in an amount of 50 mol % or less, the coupling agent obtained The coatability can be effectively improved.

[0067] In the optical filter 1 according to the present invention, the coupling agent composition is represented by the above general formula (V) and 50 mol % or more but less than 100 mol % of a silicon compound represented by the above general formula (VI) or general formula ( VII) and one or more metal alkoxides represented by general formula (VIII) It is preferable that the reaction composition is a reaction composition containing more than 50 mol % or less of the ketone represented by the above general formula (V). More than 80 mol % and less than 100 mol % of an isopropyl compound and the above general formula (VI), general formula (VII) and At least one metal alkoxide selected from the group consisting of metal alkoxides represented by the general formula (VIII) in an amount of more than 0 mol % and less than 20 mol % More preferably, it is a reaction composition with a silicon compound represented by the above general formula (V): 85 to 94 mol % and metals represented by general formula (VI), general formula (VII) and general formula (VIII) It is more preferable that the composition is a reaction composition containing 6 to 15 mol % of one or more selected from alkoxides. I wish. A silicon compound represented by the above general formula (V) and the above general formula (VI), general formula (VII) and The reaction ratio with one or more metal alkoxides represented by the general formula (VIII) is within the above range. By being within this range, it is easy to form a homogeneous, smooth film that is not prone to peeling. It is possible.

[0068] The above-mentioned absorbing glass substrate, the silicon compound represented by the general formula (V), the silicon compound represented by the general formula (VI), The details of the metal alkoxides represented by the formula (VII) and the general formula (VIII) are as described above. It is.

[0069] In the optical filter 1 according to the present invention, the coupling agent composition is represented by the general formula (V): The silicon compounds represented by the general formula (VI), the general formula (VII) and the general formula (VIII) are The coupling agent is a reaction product obtained by reacting the metal alkoxide with the metal alkoxide in the above ratio. A uniform coating solution containing the composition can be easily prepared, and a uniform film can be easily formed. This can be done.

[0070] As described above, the above general formula (V) Si(OR 7 )(OR 8 ) (OR 9 )OH A silicon compound and a titanium alkoxide Ti(OR) represented by the above general formula (VI) 13 )(OR 14 )(OR 15 )(OR 16 ) For example, the reaction between the two proceeds as follows: 4Si(OR 7 )(OR 8 ) (OR 9 )OH+Ti(OR 13 )(OR 14 )(OR 15 )(OR 1 6 ) →Ti{OSi(OR 7 ) (OR 8 ) (OR 9 )}4+R 13 OH+R 14 OH+R 15 O H+R 16 OH

[0071] A silicon compound in which 4 moles or more of the silicon compound exist per mole of the titanium alkoxide. When the reaction is carried out in the presence of an excess of the above, all of the titanium alkoxides present in the system are reacted with the above formula. Therefore, it is thought that the reaction occurs, whereas the reaction rate of the above silicon is 1 mole for the above titanium alkoxide. When the amount of the elemental compound is less than 4 moles, the amount of alkoxy groups (OR 13 base, OR 14 Group, OR 15 Group, OR 16 The alkoxy group remains. If a large amount of titanium compounds are present, the titanium compounds will precipitate in the coating solution, resulting in a uniform coating. Therefore, the reaction is carried out in the presence of an excess of silicon compound compared to the theoretical amount. It is preferable to use a coupling composition having the above structure.

[0072] As described above, the Ti{OSi(OR 7 ) (OR 8 ) (OR 9 )}4 is By hydrolyzing the compound in the presence of a catalyst such as an inorganic acid, the compound can be reacted as shown in the following reaction formula: This causes a hydrolysis reaction. Ti{OSi(OR 7 ) (OR 8 ) (OR 9 )}4+12H2O → Ti{OSi(OH)3 }4+4R 7 OH+4R 8 OH+4R 9 OH In addition, if an excess amount of the silicon compound represented by the general formula (V) is present in the system, the following occurs: Hydrolysis occurs according to the above reaction formula to produce silanol Si(OH)4. Si(OR 7 )(OR 8 ) (OR 9 )OH+3H2O→Si(OH)4+R 7 OH+R 8 OH +R 9 OH

[0073] As described above, the hydrolyzate Ti{OSi(OH)3}4 can be heated appropriately to obtain As a result, the dehydration condensation product of the hydrolyzate was [-Ti(OSiO3)3―] n (however, where n is a positive integer.) can be obtained. As described above, the silanol Si(OH)4 produced by the hydrolysis is also heated appropriately. By carrying out the treatment, the dehydration condensation reaction shown in the following reaction formula occurs to produce a dehydration condensation product (Si-OS i) 2 is produced. Si(OH)4 → (Si-O-Si)2 + 2H2O The above-mentioned silanol dehydration condensation product alone is difficult to form on an absorbing glass substrate or resin, especially in the presence of moisture. Although adhesion to the film is easily insufficient, the hydrolysis product of the above coupling agent, Ti{OSi(OH) 3) By using it in combination with the dehydration condensation product of 4, they complement each other and improve the adhesion to the absorbing glass substrate, etc. It is believed that adhesion will be improved.

[0074] The coupling agent composition comprises a silicon compound represented by the general formula (V) and a silicon compound represented by the general formula (V) (VI), reaction product with a metal alkoxide represented by general formula (VII) or general formula (VIII) In addition to the above, it contains optional ingredients such as reaction catalysts, pH adjusters, leveling agents, and defoamers. It may be possible.

[0075] In the optical filter 1 of the present invention, (Ti k O k-1 )(OSiR 4 R 5 R 6 ) 2k+2 (II) (However, R 4 , R 5 and R 6 is a group having 1 to 2 carbon atoms which may contain an oxygen atom or a nitrogen atom. 10 linear or branched hydrocarbon groups, which may be the same or different from each other k is a real number between 2 and 15, and multiple -OSiR 4 R 5 R 6 The groups are the same They may be the same or different.) The compound represented by the formula (I) is different from the compound represented by the formula (I) in that it contains two or more Ti atoms. It has a polymer structure (-Ti-O-Ti-) containing the above in the molecule.

[0076] In the compound represented by the general formula (II), R 4 , R 5 and R 6 is an oxygen or nitrogen atom A linear or branched hydrocarbon group having 1 to 10 carbon atoms which may contain oxygen atoms. A linear or branched hydrocarbon group having 1 to 4 carbon atoms which may contain a cyclic or nitrogen atom. It is preferable that the alkyl group is a straight-chain alkyl group having 1 to 3 carbon atoms which may contain an oxygen atom or a nitrogen atom. is more preferably a branched chain hydrocarbon group.

[0077] R 4 , R 5 and R 6 Specifically, methyl, ethyl, propyl, butyl linear alkyl groups such as pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups; Branched or cyclic hydrocarbon groups, -C3H6(COO)CHCH2, -CH2(CO O)CHCH2, -C2H4(COO)CHCH2, -C4H8(COO)CHCH2, -C 5H 10 (COO)CHCH2, -CH 12 (COO)CHCH2, -C7H 14 (COO )CHCH2, -C8H 16 (COO)CHCH2, -C9H 18 (COO)CHCH2, - C 10 H 20 From linear, branched or cyclic hydrocarbon groups such as (COO)CHCH2 You can name a selection.

[0078] In the compound represented by the general formula (II), R 4 , R 5 and R 6 The number of carbon atoms is within the above range. By setting the above condition, it becomes easier to maintain a suitable reaction rate between the silicon compound and the metal alkoxide. This makes it easier to prepare a more homogeneous coupling agent. In addition, in the compound represented by the general formula (II), R bonded to a silicon atom 4 , R 5 Oh BiR 6 The functional group represented by the formula (I) may affect the adhesiveness between the resin film and the adhesive layer. Depending on the resin film to be applied on the laminate, an appropriate R 4 , R 5 and R 6 By selecting the group, The adhesiveness between the resin film and the adhesive layer can be adjusted.

[0079] In the compound represented by the general formula (II), k is a real number of 2 to 15, and More preferably, it is a real number equal to or less than 10, and particularly preferably 4, 7 or 10. .

[0080] In the compound represented by the general formula (II), k is within the above range, so that the phosphate A resin having high adhesion to an absorbing glass substrate made of fluorophosphate glass or fluorophosphate glass. An oil film can be easily formed.

[0081] In the compound represented by the general formula (II), R 4 , R 5 and R 6 are identical to each other. may be the same or different. In addition, multiple -OSiR 4 R 5 R 6 The groups may be the same or different. stomach.

[0082] In the optical filter 1 of the present invention, the compound represented by the general formula (II) is any one of the following: General formula (IV) (Ti k O k-1){OSi(OR 10 )(OR 11 ) (OR 12 )} 2k+2 (IV) (However, R 10 , R 11 and R 12 is a linear or branched chain carbon with 1 to 10 carbon atoms. k is a hydrogen atom, which may be the same or different, and k is 2 or more and 15 or less. Real number, multiple -OSi(OR 10 )(OR 11 ) (OR 12 ) groups are identical to each other. may be the same or different.) Examples of the compound include compounds represented by the following formula:

[0083] R constituting the compound represented by general formula (IV) 10 , R 11 and R 12 has 1 to 10 carbon atoms 10 straight-chain or branched-chain hydrocarbon groups having 1 to 4 carbon atoms. and preferably a linear or branched hydrocarbon group having 1 to 3 carbon atoms. It is more preferable that:

[0084] R 10 , R 11 and R 12 Specifically, the alkyl group includes a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl groups Examples of the hydrocarbon group include linear, branched, and cyclic hydrocarbon groups. R 10 , R 11 and R 12 may be the same or different from each other.

[0085] In the compound represented by the general formula (IV), R 10 , R 11 and R12 The number of carbon atoms is as above By being within this range, a favorable reaction rate between the silicon compound and the metal alkoxide can be maintained. This makes it easier to prepare a more homogeneous coupling agent.

[0086] In the compound represented by the general formula (IV), k is a real number of 2 to 15, and More preferably, it is a real number equal to or less than 10, and particularly preferably 4, 7, or 10. stomach. In addition, multiple -OSi (OR 10 )(OR 11 ) (OR 12 ) groups may be identical to each other. It may be good or different.

[0087] In the compound represented by the general formula (IV), k is within the above range, so that the phosphate A resin having high adhesion to an absorbing glass substrate made of fluorophosphate glass or fluorophosphate glass. An oil film can be easily formed.

[0088] In the compound represented by the general formula (IV), when k is 2, the compound represented by the following structural formula It is possible.

[0089] [ka] (However, multiple R 10 , R 11 and R 12 may be the same or different. Also, multiple -OSi(OR 10 ) (OR 11 ) (OR 12 ) groups are identical to each other may be the same or different.)

[0090] In the compound represented by the general formula (IV), when k is 3, the compound represented by the following structural formula It is possible.

[0091] [ka] (However, multiple R 10 , R 11 and R 12 may be the same or different. Also, multiple -OSi(OR 10 ) (OR 11 ) (OR 12 ) groups are identical to each other may be the same or different.)

[0092] The coupling agent represented by the above general formula (IV) is represented by the following general formula (IX): Si(OR 10 )(OR 11 ) (OR 12 )OH (IX) (However, R 10 , R 11 and R 12 is a linear or branched chain carbon with 1 to 10 carbon atoms. and aryl groups, which may be the same or different. and a silicon compound represented by the following formula: Ti(OH)4 It is preferable that the reactant is a reaction product with tetrahydroxytitanium represented by the formula:

[0093] In the silicon compound represented by the general formula (IX), 10 , R 11 and R 12 The carbon number and specific examples of R are as described above. 10 , R 11 and R 12 are the same as each other They may be the same or different.

[0094] General formula (IX)Si(OR) 10 ) (OR 11 ) (OR 12 Silicon compounds represented by OH The reaction of with tetrahydroxytitanium represented by the above formula Ti(OH)4 can be carried out, for example, as follows: It is thought that the situation will progress as follows. 6Si(OR 10 ) (OR 11 ) (OR 12 )OH+2Ti(OH)4 →Ti2O{OSi(OR 10 ) (OR 11 ) (OR 12 )}6+4H2O The general formula TiO{OSi(OR 10 ) (OR 11 ) (OR 12 ) The compound represented by}6 is a compound represented by the above general formula (IV), in which k is 2. This is equivalent to a union. In the reaction system, 2 moles of tetrahydroxytitanium (Ti(OH)4) are mixed with the compound of the general formula Si(OR 10 ) (OR 11 ) (OR 12 Silicon compounds represented by OH are present in an amount of 6 moles or more. By reacting in the presence of an excess of the compound, the tetrahydroxytitanium present in the system It is believed that all reactions follow the above formula.

[0095] The optical filter 1 according to the present invention is a filter having a structure in which a compound represented by the following general formula (IV) is added to an absorbing glass substrate. (Ti k O k-1 ){OSi(OR 10 )(OR 11 ) (OR 12 )} 2k+2 (IV) (However, R 10 , R 11 and R 12 is a linear or branched chain carbon with 1 to 10 carbon atoms. k is a hydrogen atom, which may be the same or different, and k is 2 or more and 15 or less. Real number, multiple -OSi(OR 10 )(OR 11 ) (OR 12 ) groups are identical to each other. may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: It is preferable that a resin film, which will be described later, is provided via a bonding layer.

[0096] The coupling agent consisting of the compound represented by the general formula (IV) is TiO{OSi(OR 10 ) (OR 11 ) (OR 12 ) In the case of}6 (in the compound represented by the above general formula (IV) For example, when k is 2, the above coupling agent can be reacted with As shown in the formula, the hydrolysis reaction proceeds by adding water to the system. TiO{OSi(OR 10 ) (OR 11 ) (OR 12 )}6+18H2O→ Ti2O{OSi(OH)3}6+6R 10 OH+6R 11 OH+6R 12 OH The hydrolysis reaction is carried out, for example, at a temperature of 10 to 40° C. using a catalyst such as HCl. The reaction can be carried out in the presence of a suitable amount of water. Next, a coupling agent comprising a hydrolyzate of the compound represented by the above general formula (IV) is The coating solution is applied to an absorbent glass substrate to form a coating film. The content of the coupling agent composed of the compound represented by the general formula (IV) in the coating liquid is The content is preferably 0.5 to 20% by mass. The amount is 0.005~0.5ml / cm2 It is preferable that: As a method for applying the coating solution containing the hydrolysate of the coupling agent, a dip coating method is used. Coating method, cast coating method, spray coating method, spin coating method The coating method may include one or more coating methods selected from the following: Then, a resin film forming coating liquid described later is applied onto the coating film to form an absorbent resin coating film. After synthesis, by heating appropriately, the hydrolyzate is dehydrated and condensed to give [-(TiO3) 2(SiO3)5-] m (where m is a positive integer) to obtain a reactant represented by can be done.

[0097] The dehydrated condensate is a mixture of the coupling agent and the absorbing glass or It is believed that the resin film is strongly bonded to the phosphate glass. A resin film having high adhesion is provided on an absorbing glass substrate made of fluorophosphate glass. Therefore, the optical filter 1 can be easily provided.

[0098] In the optical filter 1 of the present invention, as described above, the bonding layer further comprises a silanol. The polyolefin may contain hydrolysis and dehydration condensation products of the above-mentioned copolymers.

[0099] That is, by appropriately heating silanol Si(OH)4, the reaction shown in the following formula can be obtained. As shown, a dehydration condensation product (Si-O-Si)2 is produced. Si(OH)4 → (Si-O-Si)2 + 2H2O According to the investigations of the present inventors, the above-mentioned dehydration condensation product of silanol alone does not have a sufficient ability to react with water, particularly in the presence of water. In the above-mentioned general formula (II) or A coupling agent comprising a compound represented by general formula (IV) and a hydrolyzate thereof is subjected to dehydration condensation. It is believed that by using it in combination with a dehydrated condensation product, the two products complement each other and improve the adhesion. can be done.

[0100] The silanol is a carboxyl group consisting of a compound represented by the general formula (II) or (IV). The hydrolyzate of the coupling agent is added to a coating solution containing the hydrolyzate, and the coating solution is then applied to an absorbent glass substrate. The coating is applied to the substrate to form a coating film, and then the above-mentioned heat treatment is appropriately performed to form a coupling agent. It is possible to generate a dehydration condensation product of silanol together with a dehydration condensation product of the hydrolysis product of the binder. .

[0101] Next, the optical filter 2 of the present invention will be described. The optical filter 2 of the present invention is made of phosphate glass or fluorophosphate glass. The absorbing glass substrate is coated with Si atoms and Ti atoms, Zr atoms, and Al atoms. The present invention is characterized in that the resin film contains one or more of the following: As an embodiment, the optical filter 2-1 of the present invention or the optical filter 2-2 of the present invention can be mentioned. It can be done.

[0102] The optical filter 2-1 of the present invention is made of phosphate glass or fluorophosphate glass. The following general formula (I) was added to an absorbing glass substrate: M(OSiR 1 R 2 R 3 ) n (I) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 1 , R 2 and R 3 is acid Straight or branched chain hydrocarbons having 1 to 10 carbon atoms which may contain hydrogen or nitrogen atoms. groups, which may be the same or different, and n is a group in which M is a Ti atom or a Zr When M is an Al atom, it is 4, and when M is an Al atom, it is 3, and when M is an Al atom, it is 4. 1 R 2 R 3 The groups may be the same or different. and a compound represented by the following general formula (II): (Ti k O k-1 )(OSiR 4 R 5 R 6 ) 2k+2 (II) (However, R 4 , R 5 and R 6 is a group having 1 to 2 carbon atoms which may contain an oxygen atom or a nitrogen atom. 10 linear or branched hydrocarbon groups, which may be the same or different from each other k is a real number between 2 and 15, and multiple -OSiR 4 R 5 R 6 The groups are the same They may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: A resin film is provided.

[0103] The optical filter 2-2 of the present invention is made of phosphate glass or fluorophosphate glass. The absorbent glass substrate is coated with a compound represented by the following general formula (III): M{OSi(OR 7 ) (OR 8 ) (OR 9 )} n (III) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R 7 , R 8 and R 9 Charcoal A linear or branched hydrocarbon group having a prime number of 1 to 10, which may be the same or different. n may be 4 when M is a Ti atom or a Zr atom, and n may be 4 when M is an Al atom. 3 if multiple -OSi(OR 7 ) (OR 8 ) (OR 9 ) groups are identical to each other. may be the same or different.) and a compound represented by the following general formula (IV): (Ti k O k-1 ){OSi(OR 10 )(OR 11 ) (OR 12 )} 2k+2 (IV ) (However, R 10 , R 11 and R 12 is a linear or branched chain carbon with 1 to 10 carbon atoms. k is a hydrogen atom, which may be the same or different, and k is 2 or more and 15 or less. Real number, multiple -OSi(OR 10 )(OR 11 ) (OR 12 ) groups are identical to each other may be the same or different.) The compound contains one or more hydrolysis and dehydration condensation products of coupling agents selected from the compounds represented by the formula: The resin film is provided to cover the surface of the substrate.

[0104] In relation to the optical filter 1 of the present invention, the optical filter 2 of the present invention has a bonding layer Constituent (e.g., hydrolysis, dehydration condensation product of coupling agent or coupling agent composition) ) in the resin film described later, but other Therefore, the details of the common points are explained as above. It is.

[0105] In addition, in the resin film constituting the optical filter 2 of the present invention, Si atoms, Ti atoms, Z Ti atoms, Zr atoms, and Al atoms in the total number of R atoms and Al atoms (total number of atoms) The ratio α (atomic%) of the total number of atoms is also over 0 atomic%, at 33.3atom. ic% or less, and more preferably 9 to 33.3 atomic %. It is more preferable that the content is 12 to 33.3 atomic %. In the present application, the Ti atoms, Zr atoms and Al atoms constituting the resin film The ratio α (atomic%) of the total number of atoms in the bonding layer is also The ratio α (atomic%) of the total number of Al atoms and Al atoms was measured under the same conditions. The values ​​were calculated by STEM-EDX measurement of an optical filter.

[0106] The optical filter 2 of the present invention can be produced, for example, by using phosphate glass or phosphate-based glass. The above coupling agent composition is hydrolyzed on an absorbing glass substrate made of phosphate-based glass. A resin film-forming liquid containing the above-mentioned substances (described later) is applied to form a coating film, and then heated appropriately. The present production method can be exemplified by a method in which the above-mentioned cuprate is subjected to a dehydration condensation reaction by treating the cuprate with a solvent or the like. The coupling agent strongly bonds with the coupling agent or the coupling agent is hydrolyzed or decomposed. The water condensate and the absorbing glass substrate are firmly bonded to form the desired optical filter. can be done.

[0107] [Resin film] In the optical filter according to the present invention, the resin film is, for example, a film that is resistant to ultraviolet light or near infrared light. Light absorbing resin film, anti-reflection film, reflection amplification film, protective film to prevent glass from fading, Examples of such films include a reinforcement film for improving the strength of glass and a water-repellent film. The resin film that absorbs ultraviolet or near infrared light includes a near infrared absorbing dye and a transparent resin. The near-infrared absorbing dye is uniformly dissolved or dispersed in the transparent resin. It is preferable that:

[0108] As the near-infrared absorbing dye constituting the absorbing resin film, a conventionally known dye can be used. cyanine dyes, polymethine dyes, squarylium dyes, porphyrin dyes, Metal dithiol complex dyes, phthalocyanine dyes, diimonium dyes and inorganic oxides Preferably, the pigment is one or more selected from the group consisting of squarylium-based pigments, cyanine-based pigments, and phthalocyanine-based pigments. More preferably, one or more dyes selected from cyanine dyes are used.

[0109] The resin constituting the resin film can be a conventionally known transparent resin, such as acrylic. Resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, Polyarylate resin, polysulfone resin, polyethersulfone resin, polyparaphenylene Polyarylene ether phosphine oxide resin, polyimide resin, polyamine Select from diimide resin, polyolefin resin, cyclic olefin resin and polyester resin. There are at least one type that can be identified. For transparent resins, the transparency, solubility of the near infrared absorbing dye in the transparent resin, and heat resistance are required. From this viewpoint, it is preferable that the glass transition point (Tg) is high. Specifically, polyester resin is preferable. Grease, polycarbonate resin, polyethersulfone resin, polyarylate resin, polyimide Preferably, the resin is at least one selected from the group consisting of polyester resin, polyamide resin, and epoxy resin. More preferably, the resin is one or more selected from imide resins. Polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, It is preferable to use one or more resins selected from the group consisting of olefin copolymers, ... and olefin copolymers.

[0110] In addition to the near infrared absorbing dye and the transparent resin, the resin film may further include any other material that does not impair the effects of the present invention. To the extent that it does not cause any damage, color correction dyes, leveling agents, antistatic agents, heat stabilizers, light stabilizers, antioxidants The composition may contain optional components such as an antibacterial agent, a dispersant, a flame retardant, a lubricant, a plasticizer, etc.

[0111] As described above, when the optical filter according to the present invention is the optical filter 1 of the present invention, In this case, for example, on an absorbing glass substrate made of phosphate glass or fluorophosphate glass. a hydrolysis-formed film is formed by hydrolyzing a liquid containing the coupling agent composition; A resin film-forming liquid that absorbs at least one of ultraviolet light and near-infrared light is applied thereon. A coating film is formed. In addition, when the optical filter according to the present invention is the optical filter 2 of the present invention, for example, The above-mentioned carbon nanotube is applied to an absorbing glass substrate made of phosphate-based glass or fluorophosphate-based glass. A resin film-forming liquid containing the coupling agent composition is applied to form a coating film.

[0112] The resin film may be, for example, a dye, a transparent resin, and an infrared cutoff film according to the second embodiment of the present invention. When forming a filter, the coupling agent and the optional ingredients are dissolved or dispersed in a solvent. The resin film forming liquid is prepared by dispersing the resin, which is then coated and dried, and further cured as necessary. It can be formed by:

[0113] The resin film forming liquid contains a known surfactant such as a cationic, anionic, or nonionic surfactant. It may also be something like that.

[0114] There are several methods for applying the resin film forming liquid, including dip coating, cast coating, and spray coating. One or more coating methods selected from the group consisting of a coating method, a spin coating method, etc. are used. It is possible.

[0115] The resin film forming liquid is applied onto a substrate, and then dried to form a resin film. can.

[0116] The optical filter according to the present invention may be, for example, an infrared cut filter (IRCF). Some examples include:

[0117] When the optical filter according to the present invention is an infrared cut filter (IRCF), for example As shown in FIG. 2(b), an absorbing glass substrate 3' that absorbs ultraviolet light or near infrared light is used. The lower surface (light emitting surface) of the infrared ray lamp further includes an absorbing resin film 5 that absorbs ultraviolet light or near infrared light. An example of such a filter is an outer cut filter (IRCF).

[0118] In the embodiment illustrated in FIG. 2(b), an absorbing glass group that absorbs ultraviolet or near infrared light is used. A reflective film (UVIR film) 2 is provided on the upper surface side (light incident surface side) of the plate 3', and the above-mentioned ultraviolet IR film is An anti-reflection film (AR film) 4 is further provided on the lower surface side of the absorptive resin film 5 that absorbs external light or near infrared light. It has been established.

[0119] In the above example, the reflective film (UVIR film) transmits visible light and reflects ultraviolet and near infrared light. Anything that blocks light in the infrared region is acceptable. Examples of such reflective films (UVIR films) include: One example is a dielectric multilayer film. The dielectric multilayer film is made up of a dielectric film with a low refractive index (low refractive index film) and a dielectric film with a high refractive index (high refractive index film). It is composed of a dielectric multilayer film in which a high refractive index film is made by alternately laminating a dielectric film and a ferroelectric film. can be one or more selected from Ta2O5, TiO2, Nb2O5, etc., and T iO2 is preferred. The low refractive index film is made of SiO2, SiO x N y One or more selected from the above The above can be mentioned, with SiO2 being preferred.

[0120] An example of an anti-reflection film (AR film) is a dielectric multilayer film.

[0121] According to the invention, an absorbing glass substrate made of phosphate-based glass or fluorophosphate glass is provided. It is possible to provide an infrared cut filter having a resin film having high adhesion to the .

[0122] Next, an image pickup device according to the present invention will be described. The imaging device according to the present invention comprises a solid-state imaging device, an imaging lens, and the optical filter according to the present invention. The present invention is characterized by having the above. The solid-state imaging element is a CCD (Charge-Coupled Device) sensor. Complementary Metal Oxide Semiconductor CMOS (Complementary Metal Oxide Semiconductor) Examples of image sensors include a 3D image sensor and a 3D image sensor.

[0123] An example of the configuration of an imaging device according to the present invention is a camera module as shown in FIG. This can be done. FIG. 1(a) shows a camera related to a compact digital camera mounted on a smartphone or the like. FIG. 1(a) is a schematic diagram of a camera module. The lens L (or lenses L1...Ln) (the integer n above), the optical filter 1 according to the present invention, and an image sensor IC. FIG. 1(b) is a schematic diagram of a camera module for a digital single-lens reflex camera. The camera module shown in FIG. 1(b) includes a lens L and an optical filter 1 according to the present invention. , a cover glass CG, and an image sensor IC.

[0124] According to the invention, an absorbing glass substrate made of phosphate-based glass or fluorophosphate glass is provided. To provide an imaging device having an optical filter provided with a resin film having high adhesion to the This can be done. EXAMPLES

[0125] The present invention will be further described below with reference to examples and comparative examples. However, the present invention is not limited to the following examples. It is not something that is done.

[0126] (Examples 1 to 7, Comparative Example 1) 1. Preparation of coating solution containing coupling agent (1) Put 0.3 mL of 0.5N (mol / L) HCl solution and 2-methoxyethanol into a container. 2.2 mL of the solution was weighed out and mixed in a sealed container. (2) Add tetraethyl orthosilicate (Si(OC2H5)4) to the container and seal it. The mixture was mixed at 40° C. for 30 minutes to cause the reaction represented by the following reaction formula. Si(OC2H5)4+H2O → HO-Si(OC2H5)3+C2H5OH The above reaction consumes all water and produces hydroxyl groups, so the alumina of Ti, which has a high hydrolysis rate, It was expected that the addition of hydroxide would not result in precipitation of hydroxide and the solution would become homogeneous. (3) Add titanium (IV) n-butoxide (Ti(OC4H9)4) (see Table 1) to the container. Add each component in the ratio shown in the table, and mix in a sealed container for 30 minutes to obtain a coupling solution. A coating solution containing a blocking agent was prepared. Table 1 shows the results of the coating of HO-Si(OC2H5)3 and Ti(OC4H 9)4 is taken as 100 mol % in total, 4H9)Indicate the addition ratio of each of 4. At this time, it is believed that the reaction represented by the following reaction formula occurred inside the container. 4OH-Si(OC2H5)3+Ti(OC4H9)4→Ti(O-Si(OC2H5) )3)4+4C4H9OH

[0127] 2. Formation of coating film The coupling agent-containing coating solution was further mixed with 0.5N aqueous HCl solution. Weigh out 1.2 mL of the liquid, 4.7 mL of water, and 8.1 mL of 2-methoxyethanol, and place them in a sealed container. The mixture was mixed for 30 minutes at RT to prepare a coating film forming solution. At this time, it is believed that the reaction represented by the following reaction formula occurred inside the container. Ti{(O-Si(OC2H5)3}4+12H2O→Ti{(O-Si(OH)3} 4+12C2H5OH HO-Si(OC2H5)3+3H2O→ Si(OH)4+ 3C2H5OH The obtained coating film forming solution was applied to an absorbent material made of fluorophosphate glass using a spin coater. On a glass substrate (HOYA Corporation CD700, thickness 0.59 mm), 0.03 mL / c m 2 The coating was applied so that the result was as follows. The absorbent glass substrate on which the coating film forming solution was applied was placed on a hot plate heated to 250°C. The absorbent material is placed on the substrate and heated for 30 minutes to dehydrate and condense, forming a hardened film (bonding layer) on the surface. A glass substrate (hereinafter referred to as "evaluation substrate 1") was prepared.

[0128] In each of the above examples and comparative examples, a plurality of evaluation substrates 1 were fabricated and evaluated as follows. (1) Untreated, (2) Boiled, (3) Highly Accelerated Life Test Equipment (PCT) (3) treated with high temperature and humidity. The above boiling treatment, highly accelerated life test equipment treatment (PCT treatment) and high temperature and humidity treatment are as follows: , respectively, as follows:

[0129] (Boiling treatment) The evaluation board was immersed in a boiling water bath and boiled for 60 minutes, after which the evaluation board was removed and Blow dry with nitrogen. (Processed with highly accelerated life test equipment (PCT processing)) The evaluation board is placed in a highly accelerated life test device (Espec Corp. EHS-411M), After pressure treatment at 0.13 MPa for 72 hours under conditions of 135°C and 85% humidity, Remove the plate. (High temperature and humidity treatment) The evaluation board was placed in a high-temperature, high-humidity tester (Espec Corporation PL-2KPH) and heated to a temperature of 85 After processing for 1000 hours under conditions of 50°C and humidity of 85%, the evaluation substrate is taken out.

[0130] (1) Untreated evaluation board, (2) Boiling-treated evaluation board, (3) Highly accelerated life test Regarding the evaluation board that was subjected to (1) the equipment treatment (PCT treatment) and (2) the evaluation board that was subjected to the high temperature and humidity treatment, The adhesive properties of the cured film were measured according to the JIS 5600-5-6 standard. A loss cut test was conducted. The test results were classified according to the following evaluation criteria of 0 to 5. The results are shown in Table 1. 0: The edges of the cut are completely smooth and there are no peeling marks on any of the grids. 1: Small separation of laminate at the intersection of cuts. Less than 5% separation per unit area. 2: The coating is peeling along the edges of cuts and / or at intersections. Or peeling of 5% or more but less than 15%. 3: The coating has peeled off in large areas, either partially or completely, along the edges of the cuts and / or Various parts of the eye are partially or completely peeled off. More than 15% per unit area Less than 35% peeling. 4: The coating has peeled off in large areas, either partially or completely, along the edges of the cut, and / or Or several holes are partially or completely peeled off. Less than 35% of the unit area Peeling. 5: Peeling of 35% or more per unit area.

[0131] Example 8 In Example 6, titanium (IV) n-butoxide (Ti(OC4H9)4) was replaced with Example 6, except that zirconium(IV) n-butoxide (Zr(OC4H9)4) was used In the same manner as above, a coating solution containing a coupling agent was prepared, and then an evaluation substrate 1 having a coating film was prepared. The cross-cut test was carried out in the same manner as above. The results are shown in Table 2.

[0132] Example 9 In Example 3, titanium (IV) n-butoxide (Ti(OC4H9)4) was replaced with Same as Example 3 except that aluminum n-butoxide (Al(OC4H9)3) was used. After preparing a coating solution containing a coupling agent, an evaluation substrate 1 having a coating film was prepared. A cross-cut test was also carried out in the same manner. The results are shown in Table 3.

[0133] (Examples 10 to 12) 1. Preparation of coating solution containing coupling agent (1) Put 0.3 mL of 0.5N (mol / L) HCl solution and 2-methoxyethanol into a container. 2.2 mL of the solution was weighed out and mixed in a sealed container. (2) Add tetraethyl orthosilicate (Si(OC2H5)4) to the container and seal it. The mixture was mixed at 40° C. for 30 minutes to cause the reaction represented by the following reaction formula. Si(OC2H5)4+H2O → HO-Si(OC2H5)3+C2H5OH The above reaction consumes all water and produces hydroxyl groups, so the alumina of Ti, which has a high hydrolysis rate, It was expected that the addition of hydroxide would not result in precipitation of hydroxide and the solution would become homogeneous. (3) In the above container, tetra-n-butoxy titanium polymer (Ti4O3(OC4H9 ) 10 ) were added in the proportions shown in Table 4, and mixed in a sealed container for 30 minutes. In this case, the reaction in the container was as shown in the following reaction formula: It is believed that a reaction occurred that could cause 10OH-Si(OC2H5)3+Ti4O3(OC4H9) 10 →Ti4O3(O- Si(OC2H5)3) 10 +10C4H9OH Ti4O3(OC4H9) 10 Instead of (Example 10), Ti7O6(OC4H9)1 6 (Example 11) and Ti 10 O9(OC4H9) 22 Similarly, using (Example 12) Coating solutions were prepared. Table 4 shows the composition of silicon compounds and titanium compounds in each coating solution. The content ratios in Table 4 are for HO-Si(OC2H5)3 and the formula Ti k O k-1 (OC4H9) 2k+2 The total of each titanium compound represented by the formula (I) is 100 mol %. This means the mixing ratio of HO-Si(OC2H5)3 and titanium compound when .

[0134] 2. Formation of coating film The coupling agent-containing coating solution was further mixed with 0.5N aqueous HCl solution. Weigh out 1.2 mL of the liquid, 4.7 mL of water, and 8.1 mL of 2-methoxyethanol, and place them in a sealed container. The mixture was mixed for 30 minutes at RT to prepare a coating film forming solution. For example, Ti4O3(OC4H9) 10 When using the following reaction formula, It is believed that a reaction occurred. Ti4O3{O-Si(OC2H5)3} 10 +30H2O→Ti4O3{(O-Si (OH)3} 10 +30C2H5OH HO-Si(OC2H5)3+3H2O→Si(OH)4+3C2H5OH The obtained coating film forming solution was applied to an absorbent material made of fluorophosphate glass using a spin coater. On a glass substrate (HOYA Corporation CD700, thickness 0.59 mm), 0.03 mL / c m 2 The coating was applied so that the result was as follows. The absorbent glass substrate on which the coating film forming solution was applied was placed on a hot plate heated to 250°C. The absorbent material is placed on the substrate and heated for 30 minutes to dehydrate and condense, forming a hardened film (bonding layer) on the surface. A glass substrate (evaluation substrate 1) was prepared.

[0135] 3. Formation of resin film The following is applied to the absorbent glass substrate having a cured film (bonding layer) on the surface thereof obtained by the above process. A resin film was further formed by the procedure of (a). (1) Weigh out 0.2 g of polyvinyl butyral resin and 1.8 g of cyclopentanone into a container. The mixture was mixed under closed conditions. (2) Add 0.09 g of toluene diisocyanate to the container and mix in a sealed container to make a resin. A membrane forming solution was prepared. (3) The resin film forming solution obtained is applied to the surface obtained by the above process using a spin coater. The solution was applied at a rate of 0.03 mL / cm2 onto an absorbent glass substrate having a cured film (bonding layer). It was distributed. (4) The absorbent glass substrate on which the resin film-forming solution was applied was heated to 160° C. as a hot plate. The glass substrate was placed on the plate and heated for 20 minutes to harden it, forming a resin film on the surface (evaluation Substrate 2) was prepared.

[0136] In the above Examples 10 to 12, the evaluation substrate 1 on which only the cured film (bonding layer) was formed and the bonding layer Regarding the evaluation substrate 2 on which a resin film was further formed, (1) untreated and and (2) boiling treatment was carried out in the same manner as in Examples 1 to 9.

[0137] The above (1) untreated evaluation board and (2) boiled evaluation board were The surface of the evaluation substrate 1 on which the hardened film (bonding layer) was applied in accordance with the provisions of IS 5600-5-6 Alternatively, a cross-cut adhesion test is performed on the surface of the evaluation substrate 2 on which the resin film is provided. The evaluation was performed based on the evaluation criteria of 0 to 5 in the same manner as in Examples 1 to 9. The results are shown in Table 4.

[0138] In addition, the evaluation substrate 2 obtained in Example 11 was subjected to STEM-EDX measurement to obtain the ST EM-EDX line (EDX line detection in the depth direction of each element that composes the optical filter The strength line of the bonded layer was obtained by dividing the total number of Si atoms and Ti atoms by the number of Ti atoms. The atomic percentage α (atomic%) and the percentage of Si atoms in the total number of Si atoms and Ti atoms The atomic percentage of each of the atoms was calculated using the following formula.

[0139]

number

[0140]

number

[0141] (Note: X Si is the integrated EDX intensity of Si atoms in the region that constitutes the bonding layer, and X Ti teeth The EDX line integrated intensity of Ti atoms in the region that constitutes the bonding layer, K Si is the k-phase of the Si atom. ctor (correction factor), K Ti is the k factor (correction coefficient) of Ti atom, M Si is a Si atom The atomic weight of M Ti means the atomic weight of Ti atom.) The results are shown in Table 5.

[0142] [Table 1]

[0143] [Table 2]

[0144] [Table 3]

[0145] [Table 4]

[0146] [Table 5]

[0147] As shown in Tables 1 to 3, in Examples 1 to 9, the cured film formed on the absorbing glass substrate The membrane has the general formula M{OSi(OR 7 )(OR 8 ) (OR9 )} n A specific coupling represented by Since the hardened film (bonding layer) contains hydrolysis and dehydration condensation products of the adhesive, it is suitable for absorbing glass substrates. It can be seen that the film has high adhesion. In addition, from Tables 4 and 5, in Examples 10 to 12, the film was formed on an absorbing glass substrate. The cured film (bonding layer) or resin film is a compound represented by the general formula (Ti k O k-1 ){OSi(OR 10 ) (OR 11 ) (OR 12 )} 2k+2 Hydrolysis, dehydration and condensation of a specific coupling agent represented by the formula: The cured film (bonding layer) contains the compound, or a resin film formed on the cured film (bonding layer). This shows that the film has high adhesion to the absorbing glass substrate. In Example 12, even if the blending ratio (mol%) of the titanium compound constituting the cured film is low, Adhesion is improved in comparison with Examples 1 to 3, which have the same blend ratio (mol%) of titanium compound. For this reason, it is better to use a polymer rather than a monomer as the titanium compound. It is clear that excellent adhesion can be achieved at a lower content.

[0148] On the other hand, as shown in Table 1, in Comparative Example 1, the cured film (bonding layer) formed on the absorbing glass substrate ) does not contain hydrolysis or dehydration condensation products of specific coupling agents, so it is suitable for use in the presence of water. It can be seen that the adhesion to the absorbing glass substrate is poor below this level. [Industrial Applicability]

[0149] According to the invention, an absorbing glass substrate made of phosphate-based glass or fluorophosphate glass is provided. The present invention provides an infrared cut filter having a resin film having high adhesion to the It is possible to provide an imaging device having an infrared cut filter. [Explanation of symbols]

[0150] 1 Optical filter (infrared cut filter (IRCF)) 2 Reflective film (UVIR film) 3. Glass substrate 3' Absorbing glass substrate 4 Anti-reflection film (AR film) 5. Absorption Resin Film L Lens CG cover glass IC Image Sensor

Claims

1. A silicon atom is formed on an absorbing glass substrate made of phosphate glass or fluorophosphate glass. A single layer structure containing at least one selected from Ti atoms, Zr atoms and Al atoms together with the SiO2 atoms.

13. An optical filter comprising: a resin film provided via a bonding layer having a thickness of 100 nm and a thickness of 100 nm.

2. In the bonding layer, the ratio of the number of Si atoms, Ti atoms, Zr atoms, and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms, and Al atoms is The ratio of the total number of Ti atoms, Zr atoms and Al atoms is more than 0 atomic % and less than 33 atomic %.

2. The optical filter according to claim 1, wherein the content of the fluorine-containing gas is 3 atomic % or less.

3. For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, General formula (I) M(OSiR １ R ２ R ３ ) n (I) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R １ , R ２ and R ３ is acid A linear or branched hydrocarbon having 1 to 10 carbon atoms, which may contain hydrogen or nitrogen atoms. groups, which may be the same or different, and n is a group in which M is a Ti atom or a Zr atom. When M is an Al atom, the number is 4, and when M is an Al atom, the number is 3; １ R ２ R ３ The groups may be the same or different. and a compound represented by the following general formula (II): (Ti ｋ O ｋ－１ )(OSiR ４ R ５ R ６ ) ２ｋ＋２ (II) (However, R ４ , R ５ and R ６ is a group having 1 to 2 carbon atoms which may contain an oxygen atom or a nitrogen atom. 10 linear or branched hydrocarbon groups, which may be the same or different from each other k is a real number between 2 and 15, and a plurality of -OSiR ４ R ５ R ６ The groups are the same They may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: Through the bonding layer A resin film is provided The optical filter according to claim 1 or 2.

4. For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, General formula (III) M{OSi(OR ７ ) (OR ８ ) (OR ９ )} n (III) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R ７ , R ８ and R ９ Charcoal A linear or branched hydrocarbon group having a prime number of 1 to 10, which may be the same or different. n may be 4 when M is a Ti atom or a Zr atom, and n may be 4 when M is an Al atom. is 3, and multiple -OSi(OR ７ ) (OR ８ ) (OR ９ ) groups are identical to each other. may be the same or different.) and a compound represented by the following general formula (IV): (Ti ｋ O ｋ－１ ){OSi(OR １０ ) (OR １１ ) (OR １２ )} ２ｋ＋２ (IV) (However, R １０ , R １１ and R １２ is a linear or branched carbon atom having 1 to 10 carbon atoms. k is a hydrogen atom, which may be the same or different, and k is 2 or more and 15 or less. is a real number, and multiple -OSi(OR １０ ) (OR １１ ) (OR １２ ) groups are identical to each other may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: Through the bonding layer A resin film is provided The optical filter according to any one of claims 1 to 3.

5. The coupling agent represented by the general formula (III) is represented by the following general formula (V): Si(OR ７ )(OR ８ ) (OR ９ )OH (V) (However, R ７ , R ８ and R ９ is a straight-chain or branched-chain hydrocarbon having 1 to 10 carbon atoms groups, which may be the same or different. and a silicon compound represented by the following general formula (VI): Ti(OR １３ )(OR １４ )(OR １５ )(OR １６ ) (VI) (However, R １３ , R １４ , R １５ and R １６ is a linear or branched alkyl group having 1 to 10 carbon atoms. They are chain-like hydrocarbon groups, which may be the same or different from each other, and have the following general formula: (VII) Zr(OR １７ )(OR １８ )(OR １９ )(OR ２０ ) (VII) (However, R １７ , R １８ , R １９ and R ２０ is a linear or branched alkyl group having 1 to 10 carbon atoms. It is a chain-like hydrocarbon group, which may be the same or different from each other. General formula (VIII) Al(OR ２１ )(OR ２２ )(OR ２３ ) (VIII) (However, R ２１ , R ２２ and R ２３ is a linear or branched carbon atom having 1 to 10 carbon atoms. are hydrogen atoms, which may be the same or different. One or more metal alkoxides represented by the formula:

5. The optical filter according to claim 4, which comprises a reaction product of

6. The adhesive layer according to any one of claims 1 to 5, further comprising a dehydration condensate of silanol. Optical filters included

7. For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, General formula (V) Si(OR ７ )(OR ８ ) (OR ９ )OH (V) (However, R ７ , R ８ and R ９ is a straight-chain or branched-chain hydrocarbon having 1 to 10 carbon atoms groups, which may be the same or different. and 50 mol % or more and less than 100 mol % of a silicon compound represented by the following general formula (VI): Ti(OR １３ )(OR １４ )(OR １５ )(OR １６ ) (VI) (However, R １３ , R １４ , R １５ and R １６ is a linear or branched alkyl group having 1 to 10 carbon atoms. They are chain-like hydrocarbon groups, which may be the same or different from each other, and have the following general formula: (VII) Zr(OR １７ )(OR １８ )(OR １９ )(OR ２０ ) (VII) (However, R １７ , R １８ , R １９ and R ２０ is a linear or branched alkyl group having 1 to 10 carbon atoms. It is a chain-like hydrocarbon group, which may be the same or different from each other. General formula (VIII) Al(OR ２１ )(OR ２２ )(OR ２３ ) (VIII) (However, R ２１ , R ２２ and R ２３ is a linear or branched carbon atom having 1 to 10 carbon atoms. are hydrogen atoms, which may be the same or different. A reaction product of more than 0 mol % and 50 mol % or less of a metal alkoxide selected from the group consisting of Through a bonding layer containing a hydrolysis and dehydration condensation product of a coupling agent composition containing 7. The optical filter according to claim 1, further comprising a resin film.

8. The coupling agent composition contains more than 80 mol % of a silicon compound represented by the general formula (V). Less than 100 mol % and one or more metals selected from the general formulae (VI) to (VIII) The optical filter according to claim 7, which is a reaction product of more than 0 mol % and less than 20 mol % of an alkoxide. Tha.

9. The coupling agent composition contains 85 to 94 molar equivalents of the silicon compound represented by the general formula (V). % and one or more metal alkoxides selected from the general formulae (VI) to (VIII).

8. The optical filter according to claim 7, which comprises a reaction product with 6 to 15 mol %.

10. A silicon atom is formed on an absorbing glass substrate made of phosphate glass or fluorophosphate glass. A resin film containing at least one selected from Ti atoms, Zr atoms and Al atoms together with the silicon atoms. An optical filter comprising:

11. In the resin film, the ratio of the number of Si atoms, Ti atoms, Zr atoms, and Al atoms to the total number of Si atoms, Ti atoms, Zr atoms, and Al atoms is The ratio of the total number of Ti atoms, Zr atoms and Al atoms is more than 0 atomic % and less than 33 atomic %.

11. The optical filter according to claim 10, wherein the content is 3 atomic % or less.

12. For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, General formula (I) M(OSiR １ R ２ R ３ ) n (I) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R １ , R ２ and R ３ is acid A linear or branched hydrocarbon having 1 to 10 carbon atoms, which may contain hydrogen or nitrogen atoms. groups, which may be the same or different, and n is a group in which M is a Ti atom or a Zr atom. When M is an Al atom, the number is 4, and when M is an Al atom, the number is 3; １ R ２ R ３ The groups may be the same or different. and a compound represented by the following general formula (II): (Ti ｋ O ｋ－１ )(OSiR ４ R ５ R ６ ) ２ｋ＋２ (II) (However, R ４ , R ５ and R ６ is a group having 1 to 2 carbon atoms which may contain an oxygen atom or a nitrogen atom. 10 linear or branched hydrocarbon groups, which may be the same or different from each other k is a real number between 2 and 15, and a plurality of -OSiR ４ R ５ R ６ The groups may be the same or different. The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: A resin film is provided The optical filter according to claim 10 or 11.

13. For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, General formula (III) M{OSi(OR ７ ) (OR ８ ) (OR ９ )} n (III) (wherein M is a Ti atom, a Zr atom, or an Al atom, and R ７ , R ８ and R ９ Charcoal A linear or branched hydrocarbon group having a prime number of 1 to 10, which may be the same or different. n may be 4 when M is a Ti atom or a Zr atom, and n may be 4 when M is an Al atom. is 3, and multiple -OSi(OR ７ ) (OR ８ ) (OR ９ ) groups are identical to each other. may be the same or different.) and a compound represented by the following general formula (IV): (Ti ｋ O ｋ－１ ){OSi(OR １０ ) (OR １１ ) (OR １２ )} ２ｋ＋２ (IV) (However, R １０ , R １１ and R １２ is a linear or branched carbon atom having 1 to 10 carbon atoms. k is a hydrogen atom, which may be the same or different, and k is 2 or more and 15 or less. is a real number, and multiple -OSi(OR １０ ) (OR １１ ) (OR １２ ) groups are identical to each other may be the same or different.) The compound includes a hydrolysis and dehydration condensation product of one or more coupling agents selected from the compounds represented by the formula: A resin film is provided The optical filter according to any one of claims 10 to 12.

14. The coupling agent represented by the general formula (III) is represented by the following general formula (V): Si(OR ７ )(OR ８ ) (OR ９ )OH (V) (However, R ７ , R ８ and R ９ is a straight-chain or branched-chain hydrocarbon having 1 to 10 carbon atoms groups, which may be the same or different. and a silicon compound represented by the following general formula (VI): Ti(OR １３ )(OR １４ )(OR １５ )(OR １６ ) (VI) (However, R １３ , R １４ , R １５ and R １６ is a linear or branched alkyl group having 1 to 10 carbon atoms. They are chain-like hydrocarbon groups, which may be the same or different from each other, and have the following general formula: (VII) Zr(OR １７ )(OR １８ )(OR １９ )(OR ２０ ) (VII) (However, R １７ , R １８ , R １９ and R ２０ is a linear or branched alkyl group having 1 to 10 carbon atoms. It is a chain-like hydrocarbon group, which may be the same or different from each other. General formula (VIII) Al(OR ２１ )(OR ２２ )(OR ２３ ) (VIII) (However, R ２１ , R ２２ and R ２３ is a linear or branched carbon atom having 1 to 10 carbon atoms. are hydrogen atoms, which may be the same or different. One or more metal alkoxides represented by the formula:

14. The optical filter of claim 13, comprising a reaction product of

15. Any one of claims 10 to 14, wherein the resin film further contains a dehydration condensate of silanol.

2. The optical filter according to claim 1 .

16. For an absorbing glass substrate made of phosphate glass or fluorophosphate glass, the following general Formula (V) Si(OR ７ )(OR ８ ) (OR ９ )OH (V) (However, R ７ , R ８ and R ９ is a straight-chain or branched-chain hydrocarbon having 1 to 10 carbon atoms groups, which may be the same or different. and 50 mol % or more and less than 100 mol % of a silicon compound represented by the following general formula (VI): Ti(OR １３ )(OR １４ )(OR １５ )(OR １６ ) (VI) (However, R １３ , R １４ , R １５ and R １６ is a linear or branched alkyl group having 1 to 10 carbon atoms. They are chain-like hydrocarbon groups, which may be the same or different from each other, and have the following general formula: (VII) Zr(OR １７ )(OR １８ )(OR １９ )(OR ２０ ) (VII) (However, R １７ , R １８ , R １９ and R ２０ is a linear or branched alkyl group having 1 to 10 carbon atoms. It is a chain-like hydrocarbon group, which may be the same or different from each other. General formula (VIII) Al(OR ２１ )(OR ２２ )(OR ２３ ) (VIII) (However, R ２１ , R ２２ and R ２３ is a linear or branched carbon atom having 1 to 10 carbon atoms. are hydrogen atoms, which may be the same or different. Reaction with more than 0 mol % and not more than 50 mol % of a metal alkoxide selected from the group consisting of A coupling agent composition containing a hydrolysis and dehydration condensation product The optical filter according to any one of claims 10 to 15, further comprising a resin film.

17. The coupling agent composition contains more than 80 mol % of a silicon compound represented by the general formula (V). % or less and one or more metal aryl groups represented by the general formulas (VI) to (VIII) 17. The optical filter of claim 16, which comprises a reaction product of more than 0 mole % and less than 20 mole % of alkoxide. Tha.

18. The coupling agent composition contains 85 to 94 molar equivalents of the silicon compound represented by the general formula (V). % and one or more metal alkoxides represented by the general formulas (VI) to (VIII).

17. The optical filter according to claim 16, which comprises a reaction product with up to 15 mol %.

19. A solid-state imaging element, an imaging lens, and the optical filter according to any one of claims 1 to 18. An imaging device comprising:

Images