JP2018120097A - Optical filter and use therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an optical filter that ensures compatibility between excellent visible-light transmittance and near-infrared cut performance, even when an incident angle increases, with reduced height of a device and the like including a solid imaging device or an environmental light sensor, and also has excellent heat resistant properties (solder reflow resistance) and improved crack resistance.SOLUTION: An optical filter 100a has a base material 102 that contains a glass substrate and a resin layer containing a compound (A) having an absorption maximum at wavelengths of 600-800 nm, and a dielectric multilayer 104 formed on at least one side of the base material 102, and satisfies specific requirements.SELECTED DRAWING: Figure 1

Description

  The present invention relates to an optical filter and its use. More specifically, the present invention relates to an optical filter including a dye compound having absorption in a specific wavelength region, a solid-state imaging device including the optical filter, a camera module and an ambient light sensor, and an electronic apparatus having the ambient light sensor.

  In recent years, environmental light sensors have been developed for use in information terminal devices such as smartphones and tablet terminals. The ambient light sensor in the information terminal device senses the illuminance of the environment where the information terminal device is placed and controls the brightness of the display, and the ambient light sensor senses the color tone of the environment where the information terminal device is placed. It is used as a color sensor that adjusts the color tone of the image.

  In order to match the human visibility with the brightness and color tone of the display in a natural way, it is important that only visible light reaches the ambient light sensor. For example, the ambient light sensor can have a spectral sensitivity characteristic close to visual sensitivity by installing an optical filter such as a near infrared cut filter.

  On the other hand, due to the demand for design of information terminal devices, it is required to reduce the transmittance of the transmissive window through which light is incident on the ambient light sensor (to make the appearance black), and the amount of visible light incident on infrared light Decreases, making it difficult to accurately detect illuminance and color tone, resulting in malfunctions. In addition, the height of the information terminal device is reduced, and the distance from the light incident window to the ambient light sensor is shortened. For this reason, for example, the proportion of incident light from a high incident angle such as an incident angle of 60 ° increases, and the spectral characteristics of light reaching the ambient light sensor (particularly near infrared rays) even for incident light with a high incident angle. (Strength) is required not to change.

  An apparatus provided with an infrared cut filter in which a metal multilayer film is formed on a glass plate is disclosed as means for matching the spectral characteristics of an ambient light sensor with human visibility (see, for example, Patent Document 1). When glass is used as a base material, the base material itself has heat resistance, so it can be applied to a process having a so-called solder reflow process. As a result, downsizing of optical components and devices and simplification of the manufacturing process are possible. Can be realized. In addition, an optical filter having a dielectric multilayer film in which metal oxides having different refractive indexes are alternately laminated on a glass substrate by using a vacuum deposition method, a sputtering method, a CVD method, or the like replaces the substrate with thin glass. For example, the thickness can be reduced to 0.1 mm. However, the near-infrared cut filter in which the metal multilayer thin film is formed on the glass plate has a problem that the detection accuracy of the ambient light sensor is lowered because the optical characteristics greatly change depending on the incident angle of the incident light.

  On the other hand, a so-called colored glass filter that cuts near-infrared light by light absorption has a small difference in optical characteristics with respect to normal incident light and oblique incident light and is excellent in viewing angle, but obtains a predetermined optical characteristic density. Therefore, the thickness of the substrate is increased, and it is difficult to reduce the size of the optical component (Non-Patent Document 1).

  As a solution to such a problem, there has been proposed a near-infrared cut filter that combines a thin resin and excellent viewing angle characteristics by combining a dye-containing resin substrate and a dielectric multilayer film (for example, Patent Document 2). . However, since the optical filter described in Patent Document 2 is a resin substrate, the heat resistance is far from that of a glass substrate.

  As a method for solving the problem of heat resistance, a method for producing a near-infrared cut filter having a transparent resin substrate and a near-infrared reflective film has been proposed (see, for example, Patent Document 3). In the method of Patent Document 3, a near-infrared reflective film made of a dielectric multilayer film is formed on both surfaces of a thermoplastic resin transparent substrate having a specific glass transition point by a vacuum deposition method under a specific temperature condition. .

  However, even in the near-infrared cut filter described in Patent Document 3, the heat resistance is lower than the glass transition temperature of the substrate, which is never sufficient for the solder reflow process, and cannot be used in many solder reflow processes. There was a problem.

  Therefore, in addition to characteristics such as sufficient viewing angle performance and thin wall performance, it also has excellent heat resistance characteristics, is less likely to cause curling and cracking in the solder reflow process of filter parts, and is high temperature even after incorporation into the product. The appearance of an optical filter useful for applications such as a near-infrared cut filter, which hardly causes optical distortion due to curling or the like underneath, has been desired.

JP 2011-060788 A JP 2012-008532 A JP 2010-044278 A

Sigma Kogyo general catalog near infrared absorption filter CCF-50S-500C

  The present invention is capable of achieving both excellent visible light transmittance and near-infrared cut performance even when the incident angle is increased due to the reduction in height of a device provided with a solid-state imaging device or an ambient light sensor. An object is to provide an optical filter having excellent characteristics (solder reflow resistance) and improved crack resistance.

The present invention relates to the following aspects [1] to [17], for example.
[1] A substrate including a glass substrate and a resin layer containing a compound (A) having an absorption maximum at a wavelength of 600 to 800 nm, and a dielectric multilayer film formed on at least one surface of the substrate. And satisfying the following requirements (a) to (d):
(A) The average value T _a of the transmittance in the wavelength range of 400 to 650 nm when the spectral transmittance of the optical filter before being stored in an environment of 85 ° C. and 85% RH for 1000 hours is measured from the vertical direction of the optical filter. _-0 is 45% or more and 90% or less;
(B) When the optical density (OD value) of the optical filter before storage is measured from the vertical direction of the optical filter, the average value OD _a-0 of the optical density in the wavelength range of 800 to 1200 nm is 1.0 or more. Is
(C) When the spectral transmittance of the optical filter after storage is measured from the vertical direction of the optical filter, the average value T _b-0 of the transmittance in the wavelength range of 400 to 650 nm and the requirement (a) The absolute value of the difference from the stated transmittance average value _Ta-0 is 7% or less;
(D) When the spectral transmittance of the optical filter before storage is measured from the vertical direction of the optical filter, the average value of the transmittance at a wavelength of 580 to 650 nm is defined as T _Ra, and the average of the transmittance at a wavelength of 500 to 580 nm T _Ga / T _Ra and T _Ba / T _Ra are both 0.9 to 1.6 when the value is T _Ga and the average value of transmittance at a wavelength of 420 to 500 nm is T _Ba .

[2] The optical filter according to item [1], wherein no cracks are generated in the dielectric multilayer film of the optical filter after storage.
[3] The optical filter according to item [1] or [2], wherein the optical filter further satisfies the following requirement (e):
(E) The average value T _a-30 of the transmittance in the wavelength range of 400 to 650 nm when the spectral transmittance of the optical filter before storage is measured from an oblique direction of 30 degrees with respect to the vertical direction of the optical filter. and, wherein when the transmittance before the optical filter storage was measured from 60 ° oblique direction with respect to the vertical direction of the optical filter, the average value T _a-60 of the transmittance in the wavelength range of 400~650nm is, one Is 45% or more and 90% or less.

[4] The optical filter according to any one of items [1] to [3], wherein the optical filter further satisfies the following requirement (f):
(F) When the spectral transmittance of the optical filter before storage is measured from the vertical direction of the optical filter, the shortest wavelength value (Xa) at which the transmittance is 50% in the wavelength range of 350 to 500 nm;
Absolute difference between the shortest wavelength value (Xb) at which the transmittance is 50% in the wavelength range of 350 to 500 nm when the spectral transmittance of the optical filter after storage is measured from the vertical direction of the optical filter The value is 12 nm or less.

[5] The optical filter according to any one of items [1] to [4], wherein the optical filter further satisfies the following requirement (g):
(G) said when the spectral transmittance of the optical filter after storage was determined from the vertical direction of the optical filter, the average value of the transmittance at a wavelength 580~650nm and T _Rb, the average transmittance at a wavelength of 500~580nm When the value is T _Gb and the average value of transmittance at a wavelength of 420 to 500 nm is T _Bb , T _Gb / T _Rb and T _Bb / T _Rb are both 0.9 to 1.6.

[6] The optical filter according to item [5], wherein the optical filter further satisfies the following requirement (h):
(H) The values of (T _Gb / T _Rb ) / (T _Ga / T _Ra ) and (T _Bb / T _Rb ) / (T _Ba / T _Ra ) are both 0.95 to 1.05. .

  [7] The item [1] to [6], wherein the compound (A) is at least one compound selected from the group consisting of a squarylium compound and a phthalocyanine compound. Optical filter.

  [8] The resin constituting the resin layer is a cyclic polyolefin resin, an aromatic polyether resin, a polyimide resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, a polyamide resin, an aramid resin, Polysulfone resin, polyethersulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioki Sun UV curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin Resin and sol-gel method The optical filter according to any one of claim [1] to [7], wherein the at least one resin of the formed silica selected from the group consisting of a resin whose main component Ri.

[9] The optical filter according to any one of items [1] to [8], wherein a dielectric multilayer film is provided on both surfaces of the substrate.
[10] The optical filter according to any one of items [1] to [9], wherein the substrate has a layer containing near-infrared absorbing fine particles.

  [11] The optical filter according to any one of items [1] to [10], wherein the glass substrate is a fluorophosphate glass or a phosphate glass containing a copper component.

[12] The optical filter according to any one of items [1] to [11], which is for a solid-state imaging device.
[13] A solid-state imaging device comprising the optical filter according to any one of items [1] to [12].

[14] A camera module comprising the optical filter according to any one of items [1] to [12].
[15] The optical filter according to any one of items [1] to [11], which is used for an ambient light sensor.

[16] An ambient light sensor comprising the optical filter according to any one of items [1] to [11] and [15].
[17] An electronic apparatus comprising the ambient light sensor according to item [16].

  According to the present invention, both visible light from the vertical direction and incident light from the oblique direction have high visible light transmittance and near infrared cut performance, high heat resistance, and improved crack resistance. An optical filter having solder reflow resistance can be provided.

  When the optical filter of the present invention is a near-infrared cut filter, it has excellent near-infrared cut ability, low hygroscopicity, less foreign matter and warpage, excellent heat resistance, and suitable for assembly or use at high temperatures, In particular, it can be suitably used for visual sensitivity correction of a solid-state imaging device such as a CCD or a CMOS image sensor.

  In addition, the optical filter of the present invention can be suitably used for ambient light sensor applications. An ambient light sensor using such an optical filter has a small incident angle dependency of incident light, and can measure illuminance and color temperature with high accuracy.

It is a figure explaining the structure of the optical filter which concerns on one Embodiment of this invention. It is a figure explaining the structure of the optical filter which concerns on one Embodiment of this invention. It is a figure explaining the structure of the ambient light sensor which concerns on one Embodiment of this invention. It is a figure explaining the structure of the ambient light sensor which concerns on one Embodiment of this invention. It is a figure explaining an example of an electronic device provided with the ambient light sensor concerning one embodiment of the present invention. It is a figure explaining the aspect which measures a transmission spectrum from (A) perpendicular direction, (B) from a 30-degree angle, and (C) from a 60-degree angle. 4 is a graph showing the spectral transmittance measured from angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the optical filter obtained in Example 1. FIG. It is a graph which shows the spectral transmission factor which measured the optical filter obtained in Example 1 in the environment of 85 degreeC85% RH from the perpendicular direction before 1000 hours storage and after storage. It is a graph which shows the spectral transmission factor which measured the optical filter obtained in Example 2 in the environment of 85 degreeC85% RH from the perpendicular direction before 1000 hours storage and after storage. It is a graph which shows the spectral transmittance which measured the optical filter obtained in Example 3 in the environment of 85 degreeC85% RH from the perpendicular direction before 1000 hours storage and after storage. It is a graph which shows the spectral transmission factor which measured the optical filter obtained in Example 4 in the environment of 85 degreeC85% RH from the perpendicular direction before 1000 hours storage and after storage. It is a graph which shows the spectral transmittance which measured the optical filter obtained in Example 5 in the environment of 85 degreeC85% RH from the perpendicular direction before 1000 hours storage and after storage. It is a graph which shows the spectral transmission factor which measured the optical filter obtained by the comparative example 2 in the environment of 85 degreeC85% RH from the perpendicular direction before 1000 hours storage and after storage. It is a graph which shows the spectral transmission factor which measured the optical filter obtained by the comparative example 3 in the environment of 85 degreeC85% RH from the perpendicular direction before 1000 hours storage and after storage.

  Embodiments of the present invention will be described below with reference to the drawings. However, the present invention can be implemented in many different modes and should not be construed as being limited to the description of the embodiments exemplified below. In order to clarify the description, the drawings may be schematically represented with respect to the width, thickness, shape, and the like of each part as compared to actual aspects, but are merely examples and limit the interpretation of the present invention. It is not a thing. In addition, in this specification and each figure, the same elements as those described above with reference to the previous figures are denoted by the same reference numerals or similar signs (numbers a, b, etc. are added after the numerals). The detailed description may be omitted as appropriate.

[Optical filter]
The optical filter of the present invention includes a base material comprising a glass substrate and a resin layer containing a compound (A) having an absorption maximum at a wavelength of 600 to 800 nm, and a dielectric formed on at least one surface of the base material It has a multilayer film.

  The optical filter of the present invention has high visible light transmittance and near-infrared cut performance for both incident light from the vertical direction and incident light from an oblique direction (particularly, incident light having a high incident angle). In this specification, light that is incident on the base material constituting the optical filter is defined as vertical incident light, and the light incident from an oblique direction with the vertical incident light as a reference (incident angle of 0 degrees). Assume obliquely incident light.

The optical filter of the present invention satisfies the following requirements (a) to (d).
Requirement (a): Average transmittance in a wavelength range of 400 to 650 nm when spectral transmittance of an optical filter before being stored in an environment of 85 ° C. and 85% RH for 1000 hours is measured from the vertical direction of the optical filter. Ta _-0 is 45% or more and 90% or less, preferably 48%, more preferably 52%, and particularly preferably 55% or more.

  By satisfying the requirement (a), a good image can be obtained when the optical filter of the present invention is used as a solid-state imaging device, and an excellent sensor sensitivity is achieved when it is used as an ambient light sensor. Can do.

Requirement (b): When the optical density (OD value) of the optical filter before storage is measured from the vertical direction of the optical filter, the average value OD _a-0 of the optical density in the wavelength range of 800 to 1200 nm is 1. It is 0 or more, preferably 1.7 or more, more preferably 1.8 or more.

  The upper limit is not particularly limited, but is preferably 6.0 or less, and particularly preferably 5.5 or less. When the optical density becomes extremely high, the transmittance in the visible range tends to decrease, and a remarkable difference in practical characteristics will not be seen. It is preferable to do.

  By satisfying the requirement (b), the near-infrared cut characteristics are improved, and when the optical filter of the present invention is used for a solid-state imaging device, a good image can be obtained. When used as an application, sensor malfunction can be prevented.

  The optical density (OD value) is a common logarithm of transmittance, and can be calculated by the following formula (1). When the average value of the optical density in the specified wavelength range is high, it indicates that the optical filter has high light cut characteristics in the wavelength region.

Average value of optical density in a certain wavelength region = −Log 10 (average transmittance (%) in a certain wavelength region / 100) Equation (1)
Requirement (c): The average transmittance T _b-0 in the wavelength range of 400 to 650 nm when the spectral transmittance of the optical filter after storage is measured from the vertical direction of the optical filter, and the requirement (a The absolute value of the difference from the average transmittance _Ta-0 described in (1) is 7% or less, preferably 5% or less, more preferably 3% or less.

  When the absolute value in the requirement (c) is smaller, the property change before and after storage is less, and when the optical filter of the present invention is used as a solid-state imaging device even after assembly under high temperature and when used under high temperature, A good image can be obtained, and when used as an ambient light sensor, excellent sensor sensitivity can be achieved.

Requirement (d): When the spectral transmittance of the optical filter before storage is measured from the vertical direction of the optical filter, the average value of the transmittance at a wavelength of 580 to 650 nm is T _Ra and the transmittance at a wavelength of 500 to 580 nm. T _Ga / T _Ra and T _Ba / T _Ra are both 0.9 to 1.6, preferably 0, when the average value of T _Ga is T _Ga and the average value of transmittance at a wavelength of 420 to 500 nm is T _Ba. .95 to 1.55.

  By satisfying the requirement (d), the RGB balance is good, and when the optical filter of the present invention is used as a solid-state imaging device, a good image can be obtained. When used as an ambient light sensor, an excellent sensor Sensitivity can be achieved.

The optical filter of the present invention preferably further satisfies the following requirements (e), (f), (g) and / or (h).
Requirement (e): The average value T _a− of the transmittance in the wavelength range of 400 to 650 nm when the spectral transmittance of the optical filter before storage is measured from an oblique direction of 30 ° with respect to the vertical direction of the optical filter. ₃₀ and an average value T _a-60 of transmittance in a wavelength range of 400 to 650 nm when the transmittance of the optical filter before storage is measured from an oblique direction of 60 ° with respect to the vertical direction of the optical filter. , Both are 45% or more and 90% or less, preferably 48% or more, and more preferably 55% or more.

  By satisfying the requirement (e), when the average transmittance is within this range at any incident angle in this wavelength range, a good image can be obtained when the optical filter of the present invention is used as a solid-state imaging device. When used as an ambient light sensor, excellent sensor sensitivity can be achieved.

Requirement (f): Value of the shortest wavelength (Xa) at which the transmittance is 50% in the wavelength range of 350 to 500 nm when the spectral transmittance of the optical filter before storage is measured from the vertical direction of the optical filter. When,
Absolute difference between the shortest wavelength value (Xb) at which the transmittance is 50% in the wavelength range of 350 to 500 nm when the spectral transmittance of the optical filter after storage is measured from the vertical direction of the optical filter The value is 12 nm or less, preferably 10 nm or less, more preferably 8 nm or less.

  When the absolute value in requirement (f) is smaller, the characteristic change before and after storage is less, and when the optical filter of the present invention is used as a solid-state imaging device application after assembly under high temperature and when used under high temperature, A good image can be obtained, and when used as an ambient light sensor, excellent sensor sensitivity can be achieved.

Requirements (g): when the spectral transmittance of the optical filter after the storage was measured in the vertical direction of the optical filter, the average value of the transmittance at a wavelength 580~650nm and T _Rb, transmittance at a wavelength of 500~580nm When T _Gb is an average value of T _Gb and T _Bb is an average value of transmittance at a wavelength of 420 to 500 nm, T _Gb / T _Rb and T _Bb / T _Rb are both 0.9 to 1.6, preferably 0 .95 to 1.55.

  By satisfying the requirement (g), the RGB balance is good, and when the optical filter of the present invention is used as a solid-state imaging device, a good image can be obtained. When used as an ambient light sensor, an excellent sensor Sensitivity can be achieved.

Requirement (h): (T _Gb / T _Rb ) / (T _Ga / T _Ra ) and (T _Bb / T _Rb ) / (T _Ba / T _Ra ) are both 0.95 to 1.05 , Preferably 0.96 to 1.04, more preferably 0.97 to 1.03.

  The closer the value in Requirement (h) is to 1.00, the less the characteristic change before and after storage, and the use of the optical filter of the present invention as a solid-state imaging device after assembly under high temperature and during use under high temperature. In this case, a good image can be obtained, and when used as an ambient light sensor, excellent sensor sensitivity can be achieved.

The optical filter of the present invention as described above does not generate cracks in the dielectric multilayer film after the storage.
1A to 1C show an optical filter according to an embodiment of the present invention. An optical filter 100 a shown in FIG. 1A has a dielectric multilayer film 104 on at least one surface of a base material 102. The dielectric multilayer film 104 has a characteristic of reflecting near infrared rays. FIG. 1B shows an optical filter 100b in which a first dielectric multilayer film 104a is provided on one surface of the substrate 102 and a second dielectric multilayer film 104b is provided on the other surface. As described above, the dielectric multilayer film that reflects near-infrared rays may be provided on one side or both sides of the substrate. When it is provided on one side, it is possible to obtain an optical filter that is excellent in production cost and manufacturability and has high strength and is less likely to warp or twist when provided on both sides. When the optical filter is applied to an ambient light sensor, it is preferable to provide a dielectric multilayer film on both surfaces of the base material because it is preferable that the optical filter is less warped or twisted.

  The dielectric multilayer film 104 preferably transmits light having a wavelength corresponding to visible light and has reflection characteristics over the entire range of wavelengths from 800 to 1150 nm with respect to light incident from the vertical direction, and more preferably It is preferable to have reflection characteristics over the entire wavelength range of 800 to 1200 nm, particularly preferably 800 to 1250 nm. As a form having a dielectric multilayer film on both surfaces of the base material 102, a reflection characteristic mainly in the vicinity of a wavelength of 800 to 1000 nm when measured from an angle of 5 degrees with respect to the vertical direction of the optical filter (or base material). 1 dielectric multilayer film 104a is provided on one side of the base material 102, and when measured from an angle of 5 degrees with respect to the vertical direction of the optical filter (or base material) on the other side of the base material 102, around 1000 nm to 1250 nm In particular, there may be mentioned a form having the second dielectric multilayer film 104b mainly having reflection characteristics.

  As another form, the optical filter 100c shown in FIG. 1C has a dielectric multilayer film 104 mainly having reflection characteristics in the vicinity of a wavelength of 800 to 1250 nm when measured from an angle of 5 degrees with respect to the vertical direction. May be provided on one surface of the base material 102, and the antireflection film 106 having anti-reflection characteristics in the visible region may be provided on the other surface of the base material 102. By combining the dielectric multilayer film and the antireflection film with respect to the substrate, it is possible to reflect near infrared rays while increasing the transmittance of light in the visible range.

  The haze value required for the optical filter according to one embodiment of the present invention varies depending on the application. For example, when used as an optical filter for an ambient light sensor, the haze value is preferably 8% or less, more preferably 5 % Or less, particularly preferably 3% or less. When the haze value is larger than 8%, the sensor sensitivity may be lowered.

The thickness of the optical filter may be appropriately selected according to the desired application, but it is preferable that the thickness of the optical filter is thin in consideration of the recent trend toward thinner and lighter information terminals.
The thickness of the optical filter according to an embodiment of the present invention is preferably 210 μm or less, more preferably 190 μm or less, still more preferably 160 μm or less, particularly preferably 130 μm or less, and the lower limit is not particularly limited. Considering the strength of the filter and ease of handling, for example, 20 μm is desirable.

[Base material]
2A to 2C show the configuration of the base material 102. FIG. The base material 102 includes a resin layer containing the compound (A) and a glass substrate. Moreover, it is preferable that the base material 102 has a layer containing one or more near-infrared absorbing fine particles.

Hereinafter, a layer containing at least one compound (A) and a transparent resin is also referred to as “transparent resin layer”, and the other resin layers are also simply referred to as “resin layers”.
FIG. 2 shows a base material 102 having a structure in which a transparent resin layer 112 such as an overcoat layer made of a curable resin or a thermoplastic resin containing the compound (A) is laminated on a glass substrate 110. Note that layers corresponding to the transparent resin layer 112 may be provided on both surfaces of the glass substrate 110.

  The average transmittance of the substrate at a wavelength of 400 to 650 nm is preferably 55% or more, more preferably 60% or more, and particularly preferably 65% or more. When using a substrate having such transmission characteristics, it is possible to obtain an optical filter having high light transmission characteristics in a wavelength band necessary as a solid-state imaging device application or an ambient light sensor, and when used as a solid-state imaging device application, A good image can be obtained, and when used as an ambient light sensor, a highly sensitive sensor function can be achieved.

  The average transmittance at a wavelength of 800 to 1200 nm of the substrate is preferably 20% or less, more preferably 18% or less, and particularly preferably 15% or less. When a substrate having such absorption characteristics is used, an optical filter having excellent near-infrared cut characteristics regardless of the incident angle can be obtained by combining with a dielectric multilayer film having specific reflection characteristics, and solid-state imaging It can be suitably used as a device optical filter or ambient light sensor.

  The thickness of the base material can be appropriately selected according to the desired application, and is not particularly limited, but it is desirable to select it appropriately so that the required base material strength and thinning can be achieved, and preferably 10 to 200 μm. More preferably, it is 15-180 micrometers, More preferably, it is 20-150 micrometers, Most preferably, it is 25-120 micrometers.

  When the thickness of the substrate is in the above range, the optical filter using the substrate can be made thinner and lighter, and is suitable for various uses such as a solid-state imaging device and an ambient light sensor mounted on an information terminal. Can be used.

<Glass substrate>
The glass substrate is not particularly limited, and examples thereof include borosilicate glass, silicate glass, soda lime glass, and near infrared absorbing glass. The near-infrared absorbing glass is preferable in that the near-infrared cut characteristics can be improved and the incident angle dependency can be reduced. Specific examples thereof include a fluorophosphate glass and a phosphate system containing a copper component. Glass etc. are mentioned.

<Transparent resin>
The transparent resin layer laminated on the glass substrate can be formed using a transparent resin. As transparent resin used for a base material, 1 type may be individual, and 2 or more types may be sufficient.

  The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, it ensures thermal stability and moldability to a film, and dielectrics are formed by high-temperature deposition performed at a deposition temperature of 100 ° C. or higher. In order to use as a base material which can form a body multilayer film, the resin whose glass transition temperature (Tg) becomes like this. Preferably it is 110-380 degreeC, More preferably, it is 110-370 degreeC, More preferably, it is 120-360 degreeC. Further, it is particularly preferable that the glass transition temperature of the resin is 140 ° C. or higher because a film capable of depositing a dielectric multilayer film at a higher temperature can be obtained.

  As the transparent resin, when a resin plate made of the resin having a thickness of 0.1 mm is formed, the total light transmittance (JIS K7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95%. Particularly preferably, a resin with 80 to 95% can be used. If a resin having a total light transmittance in such a range is used, the resulting substrate exhibits good transparency as an optical film.

  The weight average molecular weight (Mw) in terms of polystyrene measured by a gel permeation chromatography (GPC) method of the transparent resin is usually 15,000 to 350,000, preferably 30,000 to 250,000. The average molecular weight (Mn) is usually 10,000 to 150,000, preferably 20,000 to 100,000.

  Transparent resins include, for example, cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide resins, aramid resins, polysulfone resins, poly Ether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate (PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane resin UV curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin, And sol-gel method Silica formed Ri may be mentioned a resin as a main component.

≪Cyclic polyolefin resin≫
As the cyclic polyolefin-based resin, a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula (2) and a monomer represented by the following formula (3), A resin obtained by hydrogenating the resin is preferred.

In formula (2), R ^{x1 to} R ^x4 each independently represents an atom or group selected from the following (i ′) to (ix ′), and k ^x , ^mx and p ^x are each independently 0 or Represents a positive integer.
(I ′) a hydrogen atom (ii ′) a halogen atom (iii ′) a trialkylsilyl group (iv ′) a substituted or unsubstituted carbon atom having a linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom -30 hydrocarbon group (v ') substituted or unsubstituted C1-C30 hydrocarbon group (vi') polar group (excluding (iv '))
(Vii ′) an alkylidene group formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^x4 to each other (provided that R ^{x1 to} R ^x4 not involved in the bonding are independently the above (i ′ ) To (vi ′) represents an atom or group selected from.
(Viii ′) R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form a monocyclic or polycyclic hydrocarbon ring or heterocyclic ring (provided that R ^{x1 to} R which are not involved in the bond) ^x4 each independently represents an atom or group selected from the above (i ′) to (vi ′).
(Ix ′) A monocyclic hydrocarbon ring or heterocycle formed by bonding R ^x2 and R ^x3 to each other (provided that R ^x1 and R ^x4 not involved in the bonding are independently the above (i Represents an atom or group selected from ') to (vi').

In formula (3), R ^y1 and R ^y2 each independently represent an atom or group selected from the above (i ′) to (vi ′), or R ^y1 and R ^y2 are bonded to each other. is monocyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or heterocyclic, k ^y and p ^y are each independently, represent 0 or a positive integer.

≪Aromatic polyether resin≫
The aromatic polyether-based resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (4) and a structural unit represented by the following formula (5).

In formula (4), R < ¹ > -R < ⁴ > shows a C1-C12 monovalent organic group each independently, and ad shows the integer of 0-4 each independently.

In the formula (5), the R ¹ to R ⁴ and a~d independently, the formula (4) have the same meanings as R ¹ to R ⁴ and a~d of, Y represents a single bond, -SO ₂ -Or> C = O, R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, and g and h each independently represent 0 to 4 And m represents 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

  The aromatic polyether-based resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (6) and a structural unit represented by the following formula (7). Is preferred.

In formula (6), R ⁵ and R ⁶ each independently represents a monovalent organic group having 1 to 12 carbon atoms, Z represents a single bond, —O—, —S—, —SO ₂ —,> C═O, —CONH—, —COO— or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1.

In formula (7), R ⁷ , R ⁸ , Y, m, g and h are each independently synonymous with R ⁷ , R ⁸ , Y, m, g and h in formula (5), and R ⁵ , R ⁶ , Z, n, e, and f are each independently synonymous with R ⁵ , R ⁶ , Z, n, e, and f in the formula (6).

≪Polyimide resin≫
The polyimide resin is not particularly limited as long as it is a high molecular compound containing an imide bond in a repeating unit. For example, the method described in JP-A-2006-199945 and JP-A-2008-163107 is used. Can be synthesized.

≪Fluorene polycarbonate resin≫
The fluorene polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety. For example, the fluorene polycarbonate resin can be synthesized by a method described in JP-A-2008-163194.

≪Fluorene polyester resin≫
The fluorene polyester resin is not particularly limited as long as it is a polyester resin containing a fluorene moiety. For example, the fluorene polyester resin is synthesized by a method described in JP 2010-285505 A or JP 2011-197450 A. Can do.

≪Fluorinated aromatic polymer resin≫
The fluorinated aromatic polymer resin is not particularly limited, but is selected from the group consisting of an aromatic ring having at least one fluorine atom, an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. The polymer preferably contains a repeating unit containing at least one bond, and can be synthesized, for example, by the method described in JP-A-2008-181121.

≪Acrylic UV curable resin≫
The acrylic ultraviolet curable resin is not particularly limited, but is synthesized from a resin composition containing a compound having one or more acrylic or methacrylic groups in the molecule and a compound that decomposes by ultraviolet rays to generate active radicals. Can be mentioned.

≪Epoxy resin≫
Although it does not restrict | limit especially as an epoxy-type resin, it can divide roughly into an ultraviolet curing type and a thermosetting type. The ultraviolet curable epoxy resin is synthesized from, for example, a composition containing a compound having one or more epoxy groups in a molecule and a compound that generates an acid by ultraviolet rays (hereinafter also referred to as a photoacid generator). Examples of the thermosetting epoxy resin include those synthesized from a composition containing one or more epoxy groups in the molecule and an acid anhydride. it can.

≪Commercial product≫
The following commercial products etc. can be mentioned as a commercial item of transparent resin. Examples of commercially available cyclic polyolefin resins include Arton manufactured by JSR Corporation, ZEONOR manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available polyethersulfone resins include Sumitite manufactured by Sumitomo Bakelite Co., Ltd., Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd., and the like. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available polycarbonate resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd. Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include NIPPON CATALYST ACRYVIEWER. Examples of commercially available silsesquioxane-based ultraviolet curable resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd. Examples of commercially available polyether ether ketone resins include EXPEEK manufactured by Kurabo Industries. As a commercial product of polyarylate-based resin, a unitizer manufactured by Unitika Ltd. can be exemplified. Other commercially available products include HD films manufactured by Gunze Co., Ltd.

<Compound (A)>
The compound (A) is not particularly limited as long as it has an absorption maximum in a wavelength region of 600 to 800 nm, but is selected from the group consisting of squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, croconium compounds, and cyanine compounds. At least one compound is preferable, and squarylium compounds and phthalocyanine compounds are particularly preferable.

≪Squaryllium compound≫
The squarylium compound is not particularly limited, but is at least one selected from the group consisting of a squarylium compound represented by the following formula (I) and a squarylium compound represented by the following formula (II). Are preferred. Hereinafter, they are also referred to as “compound (I)” and “compound (II)”, respectively.

In formula (I), R ^a , R ^b and Ya satisfy the following condition (α) or (β).
Condition (α):
A plurality of R ^a each independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L ¹ or —NR ^e R ^f group;
A plurality of R ^{b s} independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, —L ¹ or —NR ^g R ^h group;
A plurality of Yas each independently represents a —NR ^j R ^k group;
L ¹ represents ^{L a, L b, L c} , L d, L e, L f, L g or L ^h;
R ^e and R ^f each independently represents a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d, or -L ^e ;
R ^g and R ^h are each independently a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C (O) R ⁱ group (R ⁱ is -L ^a , . which -L ^b, -L ^c, represents a -L ^d or -L ^e) represents;
R ^j and R ^k each independently represents a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d, or -L ^e ;
L ^a represents an aliphatic hydrocarbon group of good 1 to 12 carbon atoms have a substituent L;
L ^b represents a C1-C12 halogen-substituted alkyl group which may have a substituent L;
L ^c represents an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L;
L ^d represents an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L;
L ^e represents a heterocyclic group having carbon atoms of 3 to 14 which may have a substituent group L;
L ^f represents a C 1-9 alkoxy group which may have a substituent L;
L ^g represents an acyl group having 1 to 9 carbon atoms which may have a substituent L;
L ^h represents an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L;
L is an aliphatic hydrocarbon group having 1 to 12 carbon atoms, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and an aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents at least one substituent selected from the group consisting of a heterocyclic group having 3 to 14 carbon atoms, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group and an amino group.

Condition (β):
At least one of two R ^a on one benzene ring is bonded to Y on the same benzene ring to form a heterocycle having 5 or 6 member atoms containing at least one nitrogen atom;
The heterocyclic ring may have a substituent, and R ^b and R ^{a that} is not involved in the formation of the heterocyclic ring are independently synonymous with R ^b and R ^{a in} the condition (α).

The total number of carbon atoms including the substituents for L ^{a to} L ^h is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the number of carbon atoms exceeds this range, the synthesis of the compound may be difficult, and the light absorption intensity per unit weight tends to be small.

The aliphatic hydrocarbon group having 1 to 12 carbon atoms in the L ^a and L, for example, a methyl group (Me), ethyl (Et), n-propyl group (n-Pr), isopropyl (i-Pr ), N-butyl group (n-Bu), sec-butyl group (s-Bu), tert-butyl group (t-Bu), pentyl group, hexyl group, octyl group, nonyl group, decyl group, dodecyl group, etc. Alkyl groups such as vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group and octenyl group And alkynyl groups such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group and octynyl group.

Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms in L ^b and L include, for example, trichloromethyl group, trifluoromethyl group, 1,1-dichloroethyl group, pentachloroethyl group, pentafluoroethyl group, heptachloro Mention may be made of propyl and heptafluoropropyl groups.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in L ^c and L include cycloalkyl groups such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a norbornane group and an adamantane group And polycyclic alicyclic groups such as

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L ^d and L include, for example, phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 1-naphthyl group, 2-naphthyl group, anthracenyl group, Mention may be made of phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl and biphenylyl groups.

Wherein L Examples of the heterocyclic group having 3 to 14 carbon atoms in the ^e and L, for example, furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, indole, indoline, indolenine, benzofuran Benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, acridine, morpholine and phenazine.

Examples of the alkoxy group having 1 to 12 carbon atoms in L ^f include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, and an octyloxy group. it can.

Examples of the acyl group having 1 to 9 carbon atoms in L ^g include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, and a benzoyl group.

Examples of the alkoxycarbonyl group having 1 to 9 carbon atoms in L ^h include, for example, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group, and an octyl group. An oxycarbonyl group can be mentioned.

As the L ^a, preferably a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- butyl group, a pentyl group, a hexyl group, an octyl group, 4-phenylbutyl Group, 2-cyclohexylethyl, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

L ^b is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, or a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, and more preferably a trichloromethyl group. A methyl group, a pentachloroethyl group, a trifluoromethyl group, and a pentafluoroethyl group;

L ^c is preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group, or a 4-phenylcycloheptyl group, and more preferably a cyclopentyl group, a cyclohexyl group, or a 4-ethylcyclohexyl group. It is.

The L ^d is preferably a phenyl group, 1-naphthyl group, 2-naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 3,5-di-tert-butylphenyl group, 4-cyclopentylphenyl group. 2,3,6-triphenylphenyl group, 2,3,4,5,6-pentaphenylphenyl group, more preferably phenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, 2,3 , 4,5,6-pentaphenylphenyl group.

As the L ^e, preferably furan, thiophene, pyrrole, indole, indoline, indolenine, benzofuran, benzothiophene, consisting morpholine group, more preferably furan, thiophene, pyrrole, consisting morpholine group.

The L ^f is preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, methoxymethyl group, methoxyethyl group, 2-phenylethoxy group, 3-cyclohexylpropoxy group, pentyloxy group, hexyloxy Group, octyloxy group, more preferably methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group.

L ^g is preferably an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, a 4-propylbenzoyl group, or a trifluoromethylcarbonyl group, and more preferably an acetyl group, a propionyl group, or a benzoyl group. .

The L ^h is preferably a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group, more preferably A methoxycarbonyl group and an ethoxycarbonyl group;

The L ^{a to} L ^h further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, and an amino group. May be. Examples include 4-sulfobutyl, 4-cyanobutyl, 5-carboxypentyl, 5-aminopentyl, 3-hydroxypropyl, 2-phosphorylethyl, 6-amino-2,2-dichloro. Hexyl group, 2-chloro-4-hydroxybutyl group, 2-cyanocyclobutyl group, 3-hydroxycyclopentyl group, 3-carboxycyclopentyl group, 4-aminocyclohexyl group, 4-hydroxycyclohexyl group, 4-hydroxyphenyl group, Pentafluorophenyl group, 2-hydroxynaphthyl group, 4-aminophenyl group, 4-nitrophenyl group, group consisting of 3-methylpyrrole, 2-hydroxyethoxy group, 3-cyanopropoxy group, 4-fluorobenzoyl group, 2 -Hydroxyethoxycarbonyl group, 4-cyanobutoxy It can be mentioned carbonyl group.

R ^a in the condition (α) is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group. Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, nitro group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group. .

R ^b in the condition (α) is preferably a hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group. Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroethanoylamino group , T-butanoylamino group, cyclohexinoylamino group, more preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, hydroxyl group, dimethylamino group, nitro group Acetylamino group, propionylamino group, trifluoromethanoylamino group, These are an ntafluoroethanoylamino group, a t-butanoylamino group, and a cyclohexinoylamino group.

  The Ya is preferably an amino group, methylamino group, dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group, di-t-butylamino group, N -Ethyl-N-methylamino group, N-cyclohexyl-N-methylamino group, more preferably dimethylamino group, diethylamino group, di-n-propylamino group, diisopropylamino group, di-n-butylamino group , A di-t-butylamino group.

In the condition (β) of the formula (I), at least one of two R ^a on one benzene ring is bonded to Y on the same benzene ring, and at least 1 nitrogen atom is formed. Examples of the heterocyclic ring containing 5 or 6 atoms include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine. Among these heterocyclic rings, a heterocyclic ring that constitutes the heterocyclic ring and in which one atom adjacent to the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

Wherein (II), X is independently, O, S, Se, represents N-R ^c or C (R ^d R ^d); in each plurality of R ^c independently represents a hydrogen atom, L ^a, L ^b, L ^c, represents L ^d or L ^e; each independently plurality of R ^d, a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L ¹ or -NR ^e R ^f group, and adjacent R ^d groups may be linked to form an optionally substituted ring; L ^{a to} L ^e , L ¹ , R ^e and R ^f are the same meanings as defined ^{L a ~L e, L 1,} R e and R ^f in formula (I).

R ^c in the formula (II) is preferably a hydrogen atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, n-pentyl group. N-hexyl group, cyclohexyl group, phenyl group, trifluoromethyl group and pentafluoroethyl group, more preferably a hydrogen atom, methyl group, ethyl group, n-propyl group and isopropyl group.

R ^d in the formula (II) is preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl. Group, n-pentyl group, n-hexyl group, cyclohexyl group, phenyl group, methoxy group, trifluoromethyl group, pentafluoroethyl group, 4-aminocyclohexyl group, more preferably hydrogen atom, chlorine atom, fluorine atom Methyl group, ethyl group, n-propyl group, isopropyl group, trifluoromethyl group, and pentafluoroethyl group.

X is preferably O, S, Se, N-Me, N-Et, CH ₂ , C-Me ₂ , C-Et ₂ , and more preferably S, C-Me ₂ , C-Et _2. It is.
In the formula (II), adjacent R ^ds may be linked to form a ring. Examples of such rings include benzoindolenin ring, α-naphthimidazole ring, β-naphthimidazole ring, α-naphthoxazole ring, β-naphthoxazole ring, α-naphthothiazole ring, β-naphthothiazole ring. , Α-naphthoselenazole ring and β-naphthoselenazole ring.

  Compound (I) and Compound (II) are represented by the following formulas (I-2) and (II-2) in addition to the following formulas (I-1) and (II-1). Thus, the structure can also be expressed by a description method that takes a resonance structure. That is, the difference between the following formula (I-1) and the following formula (I-2), and the difference between the following formula (II-1) and the following formula (II-2) is only the structure description method. Represents the same compound. In the present invention, unless otherwise specified, the structure of the squarylium compound is represented by a description method such as the following formula (I-1) and the following formula (II-1).

  Furthermore, for example, the compound represented by the following formula (I-3) and the compound represented by the following formula (I-4) can be regarded as the same compound.

  The structures of the compounds (I) and (II) are not particularly limited as long as they satisfy the requirements of the formulas (I) and (II), respectively. For example, when the structure is represented as in the formulas (I-1) and (II-1), the left and right substituents bonded to the central four-membered ring may be the same or different, It is preferable that they are the same because synthesis is easy.

  Specific examples of the compounds (I) and (II) include compounds (a-1) described in Tables 1 to 3 having basic skeletons represented by the following formulas (IA) to (IH): ) To (a-36).

  The compounds (I) and (II) may be synthesized by a generally known method. For example, JP-A-1-228960, JP-A-2001-40234, JP-A-3196383, etc. It can be synthesized with reference to the method described.

≪Phthalocyanine compounds≫
The phthalocyanine compound is not particularly limited, but is preferably a compound represented by the following formula (III) (hereinafter also referred to as “compound (III)”).

In formula (III), M represents a substituted metal atom including two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a trivalent or tetravalent metal atom, and a plurality of R _a , R _b , R _c and R _d are each independently a hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -S ^{-L 2, -SS-L 2,} -SO 2 -L 3, -N = N-L 4 , or at least one combination of R _a and R _b, R _b and R _c and R _c and R _d Represents at least one group selected from the group consisting of groups represented by the following formulas (A) to (H). However, at least one of R _a , R _b , R _c and R _d bonded to the same aromatic ring is not a hydrogen atom.

The amino group, amide group, imide group and silyl group may have the substituent L defined in the formula (I),
L ¹ has the same meaning as L ¹ defined in Formula (I),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydroxyl group or the L ^a ~L ^e,
L ⁴ represents represents any of the L ^a ~L ^e.

In formulas (A) to (H), R _x and R _y each represent a carbon atom, and a plurality of R _{A to} R _L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, Represents an imide group, a cyano group, a silyl group, -L ¹ , -SL ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , and the amino group, amide group, imide The group and the silyl group may have the substituent L defined in the formula (I), and L ^{1 to} L ⁴ have the same meanings as L ^{1 to} L ⁴ defined in the formula (III).

In R _{a to} R _d and R _{A to} R _L , the amino group which may have a substituent L is an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group, diisopropylamino. Group and the like.

In R _{a to} R _d and R _{A to} R _L , as an amide group which may have a substituent L, an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group, a diisopropylamide group, Examples thereof include a dibutylamide group, an α-lactam group, a β-lactam group, a γ-lactam group, and a δ-lactam group.

In R _{a to} R _d and R _{A to} R _L , the imide group that may have a substituent L is an imide group, a methylimide group, an ethylimide group, a diethylimide group, a dipropylimide group, a diisopropylimide group, A dibutylimide group etc. are mentioned.

In R _{a to} R _d and R _{A to} R _L , examples of the silyl group which may have a substituent L include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, and a triethylsilyl group. .

In the above R _{a to} R _d and R _{A to} R _L , -SL ² includes thiol group, methyl sulfide group, ethyl sulfide group, propyl sulfide group, butyl sulfide group, isobutyl sulfide group, sec-butyl sulfide group Tert-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butylphenyl sulfide group, 2,6-diphenylphenyl sulfide group, 4-cumylphenyl sulfide group, and the like.

In R _{a to} R _d and R _{A to} R _L , -SS-L ² includes a disulfide group, a methyl disulfide group, an ethyl disulfide group, a propyl disulfide group, a butyl disulfide group, an isobutyl disulfide group, and a sec-butyl disulfide group. Tert-butyl disulfide group, phenyl disulfide group, 2,6-di-tert-butylphenyl disulfide group, 2,6-diphenylphenyl disulfide group, 4-cumylphenyl disulfide group and the like.

In R _{a to} R _d and R _{A to} R _L , examples of —SO ₂ —L ³ include a sulfo group, a mesyl group, an ethylsulfonyl group, an n-butylsulfonyl group, and a p-toluenesulfonyl group.

In the above R _{a to} R _d and R _{A to} R _L , examples of —N═N—L ⁴ include a methylazo group, a phenylazo group, a p-methylphenylazo group, and a p-dimethylaminophenylazo group.

In M, examples of the monovalent metal atom include Li, Na, K, Rb, and Cs.
In M, the divalent metal atoms include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, Hg, Sn, Pb etc. are mentioned.

  In M, the substituted metal atom containing a trivalent metal atom includes Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga-I, In -F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH and the like can be mentioned.

In M, the substituted metal atom containing a tetravalent metal atom includes TiF ₂ , TiCl ₂ , TiBr ₂ , TiI ₂ , ZrCl ₂ , HfCl ₂ , CrCl ₂ , SiF ₂ , SiCl ₂ , SiBr ₂ , SiI ₂ , GeF ₂ , GeCl ₂ , GeBr ₂ , GeI ₂ , SnF ₂ , SnCl ₂ , SnBr ₂ , SnI ₂ , Zr (OH) ₂ , Hf (OH) ₂ , Mn (OH) ₂ , Si (OH) ₂ , Ge ( OH) ₂ , Sn (OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , GeR ₂ , SnR ₂ , Ti (OR) ₂ , Cr (OR) ₂ , Si (OR) ₂ , Ge (OR) ₂ , Sn (OR) ₂ (R represents an aliphatic group or an aromatic group), TiO, VO, MnO and the like.

  The M is a divalent transition metal, trivalent or tetravalent metal halide or tetravalent metal oxide belonging to Groups 5 to 11 of the periodic table and belonging to the 4th to 5th periods. Among them, Cu, Ni, Co, and VO are particularly preferable because high visible light transmittance and stability can be achieved.

  A method of synthesizing the phthalocyanine compound by a cyclization reaction of a phthalonitrile derivative such as the following formula (V) is generally known, but the obtained phthalocyanine compounds are represented by the following formulas (VI-1) to ( It is a mixture of four isomers such as VI-4). In the present invention, unless otherwise specified, only one isomer is illustrated for one phthalocyanine compound, but the other three isomers can be used similarly. These isomers can be separated and used as necessary, but in the present invention, the isomer mixture is collectively handled.

  Specific examples of the compound (III) include the basic skeletons represented by the following formulas (III-A) to (III-J), and (b-1) to (b-56) described in Tables 4 to 7 below. ) And the like.

  Compound (III) may be synthesized by a generally known method. For example, the method described in Japanese Patent No. 4081149 or “phthalocyanine-chemistry and function” (IPC, 1997) is used. It can be synthesized by reference.

≪Cyanine compounds≫
The cyanine compound is not particularly limited, but is a compound represented by any one of the following formulas (IV-1) to (IV-3) (hereinafter referred to as “compounds (IV-1) to (IV-3)”. ) ").) Is preferred.

Wherein (IV-1) ~ (IV -3), X a - represents a monovalent anion, a plurality of D are independently represents a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom, are a plurality of R _a , R _b , R _c , R _d , R _e , R _f , R _g , R _h and R _i are each independently a hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, Imido group, cyano group, silyl group, -L ¹ , -SL ² , -SS-L ³ , -SO ₂ -L ³ , -N = N-L ⁴ , or R _b and R _c , R _d And R _e , R _e and R _f , R _f and R _g , R _g and R _h, and R _h and R _i are represented by the above formulas (A) to (H). Represents at least one group selected from the group consisting of groups, wherein the amino group, amide group, imide group and silyl group are the substituents defined in the formula (I) It may have the L,
L ¹ has the same meaning as L ¹ defined in Formula (I),
L ² represents one of L ^a ~L ^e defined in the hydrogen atom or the formula (I), the
L ³ represents either a hydrogen atom or the L ^a ~L ^e,
L ⁴ are, represents any of the L ^a ~L ^e,
Z _{a to} Z _c and Y _{a to} Y _d are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L ¹ ,- ^{S-L 2, -SS-L} 2, -SO 2 -L 3, -N = N-L 4 (L 1 ~L 4 has the same meaning as L ¹ ~L ⁴ in the R _a to R _i. ), Or an aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z or Y selected from adjacent two of these; a nitrogen atom, an oxygen atom or a sulfur atom. A 5- to 6-membered alicyclic hydrocarbon group which may contain at least one; or a C3-C14 heteroaromatic hydrocarbon group containing at least one nitrogen atom, oxygen atom or sulfur atom, These aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic carbons The hydrogenation group may have an aliphatic hydrocarbon group having 1 to 9 carbon atoms or a halogen atom.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms formed by bonding Z or Y in Z _{a to} Z _c and Y _{a to} Y _d include, for example, the substituent L The compound illustrated by the aromatic hydrocarbon group is mentioned.

A 5- to 6-membered ring which may contain at least one nitrogen atom, oxygen atom or sulfur atom, formed by bonding Z or Y to each other in Z _{a to} Z _c and Y _{a to} Y _d Examples of the alicyclic hydrocarbon group include compounds exemplified by the alicyclic hydrocarbon group and the heterocyclic ring in the substituent L (excluding the heteroaromatic hydrocarbon group).

Examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding Z or Y to each other in Z _{a to} Z _c and Y _{a to} Y _d include, for example, the substituent L And the compounds exemplified as the heterocyclic group (excluding alicyclic hydrocarbon groups containing at least one nitrogen atom, oxygen atom or sulfur atom).

In the formulas (IV-1) to (IV-3), -S-L ² , -SS-L ² , -SO ₂ -L ³ , -N = N-L ⁴ , and a substituent L may be present. Examples of the good amino group, amide group, imide group and silyl group include the same groups as those exemplified in the formula (III).

X _a ⁻ is not particularly limited as long as it is a monovalent anion, but I ⁻ , Br ⁻ , PF ₆ ⁻ , N (SO ₂ CF ₃ ) ₂ ⁻ , B (C ₆ F ₅ ) ₄ ⁻ , nickel dithiolate. And the like, and copper dithiolate complex.

  Specific examples of the compounds (IV-1) to (IV-3) include (c-1) to (c-24) shown in Table 8 below.

  The compounds (IV-1) to (IV-3) may be synthesized by a generally known method, for example, by a method described in JP-A-2009-108267.

  The addition amount of the compound (A) is appropriately selected according to the desired properties, but is preferably 0.01 to 20.0 parts by weight, more preferably 0.8 parts per 100 parts by weight of the transparent resin. 03 to 10.0 parts by weight.

<Near-infrared absorbing fine particles>
The near-infrared absorbing fine particles that may be contained in the substrate are not particularly limited as long as they have absorption in the near-infrared wavelength region, but those having absorption at a wavelength of 800 to 1200 nm are preferable. Examples of such near-infrared absorbing fine particles include transparent conductive oxides such as ITO (tin-doped indium oxide), ATO (antimony-doped tin oxide), and GZO (gallium-doped zinc oxide), and the first defined below. In particular, the first fine particles and the second fine particles are preferable from the viewpoint of absorption and transmission characteristics.

First fine particles: general formula A _{1 / n} CuPO ₄ (wherein A is at least one selected from the group consisting of alkali metals, alkaline earth metals, and NH ₄ , and n is an alkali of A 1 in the case of metal or NH _{4 and 2 in} the case of A being an alkaline earth metal).

  Second fine particles: General formula MxWyOz (where M is H, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo , Ta, Re, Be, Hf, Os, Bi, I. When there are a plurality of M, they may be different atoms, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / y ≦ 3.0).

  In the present invention, the alkali metal refers to Li, Na, K, Rb, Cs, the alkaline earth metal refers to Ca, Sr, Ba, and the rare earth element refers to Sc, Y, La, Ce, It refers to Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Lu.

  The average particle diameter of the near-infrared absorbing fine particles is preferably 1 to 200 nm, that is, 200 nm or less, more preferably 150 nm or less, and particularly preferably 100 nm or less. The diameter of the near-infrared absorbing fine particles is a dynamic light scattering photometer (model number DLS-8000HL / HH, manufactured by Otsuka Electronics Co., Ltd.), which is a suspension in which the near-infrared absorbing fine particles are dispersed (hereinafter simply referred to as “dispersion liquid”). ) Using a dynamic light scattering method (using a He—Ne laser, a cell chamber temperature of 25 ° C.). If the average value of the particle diameter of the near-infrared absorbing fine particles is within this range, geometric scattering and Mie scattering that cause a decrease in visible light transmittance can be reduced, and a Rayleigh scattering region is obtained. In the Rayleigh scattering region, the scattered light decreases in inverse proportion to the sixth power of the particle diameter, so that the scattering is reduced and the visible light transmittance is improved as the particle diameter decreases. For this reason, it is preferable if the particle diameter is in the above-mentioned range since the scattered light is extremely reduced and a good visible light transmittance can be achieved. From the viewpoint of scattered light, it is preferable that the particle diameter is small, but considering the ease of industrial production, production cost, etc., the lower limit of the average value of the particle diameter is preferably 1 nm or more, particularly preferably 2 nm or more. .

  The content of the near infrared absorbing fine particles is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the resin component constituting the layer containing the near infrared absorbing fine particles. The upper limit of the content is more preferably 55 parts by weight, particularly preferably 50 parts by weight. The lower limit of the content is more preferably 10 parts by weight, and particularly preferably 15 parts by weight. If the content of the near-infrared absorbing fine particles is less than 5 parts by weight, sufficient near-infrared absorption characteristics may not be obtained. If the content is more than 60 parts by weight, the visible transmittance decreases and the haze due to aggregation of the near-infrared absorbing fine particles The value tends to increase.

  Examples of the dispersion medium for the near-infrared absorbing fine particles include water, alcohol, ketone, ether, ester, aldehyde, amine, aliphatic hydrocarbon, alicyclic hydrocarbon, and aromatic hydrocarbon. A dispersion medium may be used individually by 1 type, and 2 or more types may be mixed and used for it. The amount of the dispersion medium is preferably 50 to 95 parts by weight with respect to 100 parts by weight of the dispersion from the viewpoint of maintaining the dispersibility of the near-infrared absorbing fine particles.

  In the dispersion medium of the near-infrared absorbing fine particles, a dispersant can be blended as needed to improve the dispersion state of the near-infrared absorbing fine particles. Dispersing agents that have a modifying effect on the surface of near-infrared absorbing fine particles, such as surfactants, silane compounds, silicone resins, titanate coupling agents, aluminum coupling agents, zircoaluminate cups A ring agent or the like is used.

  Surfactants include anionic surfactants (special polycarboxylic acid type polymer surfactants, alkyl phosphate esters, etc.), nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkylphenol ether, polyoxy Ethylene carboxylic acid esters, sorbitan higher carboxylic acid esters, etc.), cationic surfactants (polyoxyethylene alkylamine carboxylic acid esters, alkylamines, alkylammonium salts, etc.), and amphoteric surfactants (higher alkylbetaines, etc.). .

  Examples of the silane compound include a silane coupling agent, chlorosilane, alkoxysilane, and silazane. Examples of the silane coupling agent include alkoxysilanes having a functional group (glycidoxy group, vinyl group, amino group, alkenyl group, epoxy group, mercapto group, chloro group, ammonium group, acryloxy group, methacryloxy group, etc.).

Examples of the silicone resin include methyl silicone resin and methylphenyl silicone resin.
Examples of titanate coupling agents include those having an acyloxy group, phosphoxy group, pyrophosphoxy group, sulfoxy group, aryloxy group, and the like.

Examples of the aluminum coupling agent include acetoalkoxyaluminum diisopropylate.
Examples of the zircoaluminate coupling agent include those having an amino group, a mercapto group, an alkyl group, an alkenyl group, and the like.

  The amount of the dispersant is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the dispersion, although it depends on the type of the dispersant. If the amount of the dispersant is within the above range, the dispersibility of the near-infrared absorbing fine particles becomes good, the transparency is not impaired, and the sedimentation of the near-infrared absorbing fine particles over time can be suppressed.

  Commercially available products of near-infrared absorbing fine particles include P-2 (ITO) manufactured by Mitsubishi Materials Corporation, Pastoran (ITO) manufactured by Mitsui Metals Co., Ltd., T-1 (ATO) manufactured by Mitsubishi Materials Corporation, Ishihara Sangyo ( SN-100P (ATO) manufactured by Co., Ltd., Passet GK (GZO) manufactured by Hakusuitec Co., Ltd., YMF-02A (second fine particles) manufactured by Sumitomo Metal Mining Co., Ltd. and the like can be mentioned.

≪First fine particle≫
The first fine particles are composed of a compound represented by the following formula (1), and have near infrared absorption characteristics due to the crystal structure (crystallite) of the compound.

A _{1 / n} CuPO ₄ (1)
In the formula (1), A is at least one selected from the group consisting of alkali metals, alkaline earth metals, and NH ₄ , n is 1 when A is an alkali metal or NH ₄ , and A is 2 for alkaline earth metals.

Here, “crystallite” means a unit crystal that can be regarded as a single crystal, and “particle” is composed of a plurality of crystallites. The "consisting crystallites of the compound represented by formula (1)", for example, can confirm the crystal structure of A _{1 / n} CuPO ₄ by X-ray diffraction, the crystallite substantially A _{1 / n} CuPO ₄ made it means that have been identified by X-ray diffraction, the term "consists crystallites substantially a _{1 / n} CuPO _4", crystallite sufficiently the crystal structure of a _{1 / n} CuPO ₄ It means that impurities may be contained within a range that can be maintained (the crystal structure of A _{1 / n} CuPO ₄ can be confirmed by X-ray diffraction). X-ray diffraction is measured using a X-ray diffractometer for near-infrared absorbing fine particles in a powder state.

The reason for employing alkali metal (Li, Na, K, Rb, Cs), alkaline earth metal (Ca, Sr, Ba), or NH ₄ as A in formula (1) is as follows. It is as (iii).

(I) The crystal structure of the crystallites in the near-infrared absorbing fine particles is a network-like three-dimensional skeleton composed of alternating bonds of PO ₄ ³⁻ and Cu ^2+, and has a space inside the skeleton. The size of the space is alkali metal ions (Li ⁺ : 0.090 nm, Na ⁺ : 0.116 nm, K ⁺ : 0.152 nm, Rb ⁺ : 0.166 nm, Cs ⁺ : 0.181 nm), alkaline earth metal Since the ionic radius of ions (Ca ²⁺ : 0.114 nm, Sr ²⁺ : 0.132 nm, Ba ²⁺ : 0.149 nm) and NH ₄ ⁺ (0.166 nm) are compatible, the crystal structure can be sufficiently maintained. .

(Ii) Alkali metal ions, alkaline earth metal ions, and NH ₄ ⁺ can stably exist as monovalent or divalent cations in the solution, so that a precursor is generated in the process of producing near-infrared absorbing fine particles. At this time, cations are easily incorporated into the crystal structure.

(Iii) A cation having strong coordination bond with PO ₄ ^3- (for example, a transition metal ion or the like) may give a crystal structure different from the crystal structure in the present embodiment that exhibits sufficient near-infrared absorption characteristics. is there.

As A, K is particularly preferable because it has the most suitable cation size as an ion taken into the skeleton composed of PO ₄ ^3- and Cu ²⁺ and takes a thermodynamically stable structure.
The near-infrared absorbing fine particles can exhibit sufficient near-infrared absorption characteristics when the crystallites sufficiently maintain the crystal structure of A _{1 / n} CuPO ₄ . Therefore, when water or a hydroxyl group adheres to the surface of the crystallite, the crystal structure of A _{1 / n} CuPO ₄ cannot be maintained, so that the difference in light transmittance between the visible light region and the near infrared wavelength region is reduced. It cannot be suitably used as an optical filter.

Therefore, the near-infrared absorbing fine particles have a wavelength of around 1600 cm ⁻¹ attributed to water when the absorption intensity of the peak near 1000 cm ⁻¹ attributed to the phosphate group is used as a reference (100%) in the microscopic IR spectrum. The peak absorption intensity is preferably 8% or less, and the peak absorption intensity near 3750 cm ⁻¹ attributed to hydroxyl groups is preferably 26% or less. The peak absorption intensity near 1600 cm ⁻¹ attributed to water is preferred. Is 5% or less, and the absorption intensity of a peak near 3750 cm ⁻¹ attributed to a hydroxyl group is more preferably 15% or less. The microscopic IR spectrum is measured using a Fourier transform infrared spectrophotometer for powdered near-infrared absorbing fine particles. Specifically, for example, a Fourier transform infrared spectrophotometer Magna 760 manufactured by Thermo Fisher Scientific is used, and a piece of the first fine particles is placed on the diamond plate, flattened with a roller, and a microscopic FT-IR method. Measure with

≪Second fine particle≫
By reducing the oxygen ratio of tungsten trioxide (WO ₃ ) to tungsten from 3 and setting it to a specific composition range, free electrons are generated in the tungsten oxide, and good characteristics as a near-infrared absorbing material can be achieved. It has been known.

The composition range of the tungsten and oxygen is such that the composition ratio of oxygen to tungsten is 3 or less. Furthermore, when the tungsten oxide is described as W _y O _z , 2.2 ≦ z / y ≦ 2.999. It is preferable that If the value of z / y is 2.2 or more, it is possible to avoid the appearance of a WO ₂ crystal phase other than the target in the tungsten oxide, and to improve the chemical stability as a material. Therefore, it can be applied as an effective near-infrared absorbing material. On the other hand, if the value of z / y is 2.999 or less, the required amount of free electrons is generated in the tungsten oxide, and an efficient near-infrared absorbing material is obtained.

Further, in the tungsten oxide fine particles obtained by making the tungsten oxide into fine particles, a so-called “Magneli phase” having a composition ratio represented by 2.45 ≦ z / y ≦ 2.999 when the general formula is W _y O _z. Is chemically stable and has good absorption characteristics in the near-infrared region, and is therefore preferable as a near-infrared absorbing material.

  Furthermore, by adding the element M to the tungsten oxide to form a composite tungsten oxide, free electrons are generated in the composite tungsten oxide, and free electron-derived absorption characteristics are expressed in the near infrared region, This is preferable because it is effective as a near-infrared absorbing material having a wavelength of around 1000 nm. That is, the preferred composition of the second fine particles is a general formula MxWyOz (where M is one or more elements, W is tungsten, O is oxygen, 0.001 ≦ x / y ≦ 1, 2.2 ≦ z / It is a metal oxide represented by y ≦ 3.0).

  First, the value of x / y indicating the amount of element M added will be described. If the value of x / y is larger than 0.001, a sufficient amount of free electrons is generated and the intended infrared shielding effect can be obtained. As the amount of the element M added increases, the supply amount of free electrons increases and the infrared shielding efficiency also increases. However, when the value of x / y is about 1, the effect is saturated. Moreover, if the value of x / y is smaller than 1, it is preferable since an impurity phase can be prevented from being generated in the infrared shielding material, and more preferably 0.2 or more and 0.5 or less. The element M is H, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf , Os, Bi, I are preferably at least one selected from the group. Here, from the viewpoint of stability in the MxWyOz to which the element M is added, the element M is an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, More preferably, the element is one or more elements selected from Ti, Nb, V, Mo, Ta, and Re. From the viewpoint of improving optical properties and weather resistance as a near-infrared absorbing material, More preferably, the element M belongs to an alkali metal, alkaline earth metal element, transition metal element, group 4 element, or group 5 element.

Next, the value of z / y indicating the control of the oxygen amount will be described. Regarding the value of z / y, in addition to the fact that the same mechanism as that of the near-infrared absorbing material represented by W _y O _z described above works also in the near-infrared absorbing material represented by M _x W _y O _z , z / Even when y = 3.0, 2.2 ≦ z / y ≦ 3.0 is preferable because free electrons are supplied by the amount of the element M described above.

<Other ingredients>
In the range which does not impair the effect of this invention, a base material contains additives, such as a near ultraviolet absorber, antioxidant, surfactant, fluorescence quencher, a metal complex type compound, in addition to the component mentioned above. Also good. These other components may be used alone or in combination of two or more.

Examples of the near ultraviolet absorber include azomethine compounds, indole compounds, benzotriazole compounds, triazine compounds, and the like.
Antioxidants include, for example, 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5'-dimethyldiphenylmethane, and tetrakis [Methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, tris (2,6-di-t-butylphenyl) phosphite and the like.

  As the surfactant, a commercially available product or a copolymer (S) described later obtained by radical polymerization can be used, and these can be used alone or in combination of two or more.

  The copolymer (S) is a copolymer of a fluorinated alkyl group-containing monomer (M1), a polyoxyethylene chain-containing monomer (M2), and an ethylenically unsaturated monomer (M3) having a silicone chain. If necessary, monomers other than (M1) to (M3) may be used.

Examples of the fluorinated alkyl group-containing monomer (M1) include monomers represented by the following formulas (M-1-1) and (M-1-2).
CH ₂ = CHCOOCH ₂ CH ₂ (CF ₂ ) ₇ CF ₃ (M-1-1)
_{CH 2 = C (CH 3)} COOCH 2 CH 2 (CF 2) 7 CF 3 ··· (M-1-2)
Examples of the polyoxyethylene chain-containing monomer (M2) include NK-esters M-40G, M-90G, AM-90G manufactured by Shin-Nakamura Chemical Co., Ltd., Bremer PME-200, PME manufactured by NOF Corporation. -400, PME-550 and the like.

  Examples of the ethylenically unsaturated monomer (M3) having a silicone chain include a monomer containing a structural unit represented by the following general formula (M3 ′).

In formula (M3 ′), R ⁴ represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and R ⁵ and R ⁶ are each independently an alkyl group having 1 to 20 carbon atoms, a phenyl group, or Represents general formula (2), and m represents an integer of 0 to 200. In formula (2), R ⁷ , R ⁸ and R ⁹ each independently represents an alkyl group having 1 to 20 carbon atoms or a phenyl group, and n represents an integer of 0 to 200.

  In addition, specific examples of the ethylenically unsaturated monomer (M3) having a silicone chain include monomers represented by the following formulas M-3-1 to M-3.

In formulas M-3-1 to M-3-1, Me and Ph represent a methyl group and a phenyl group, respectively, and r, s, and t each independently represents an integer of 0-200.
The production method of the copolymer (S) is not particularly limited, and is based on a known method, that is, a polymerization method such as radical polymerization method, cationic polymerization method, anionic polymerization method, solution polymerization method, bulk polymerization method, and emulsion. Although it can be produced by a polymerization method or the like, the radical polymerization method is particularly convenient and industrially preferable. In the radical polymerization method, a polymerization initiator such as a radical initiator can be used.

  In the production of the copolymer (S), the mixing ratio of each of the monomers (M1), (M2) and (M3) with respect to 100% by mass in total of the monomers as raw materials for the copolymer (S) The monomer (M1) is preferably 20 to 50% by mass, more preferably 25 to 40% by mass, and the monomer (M2) is preferably 15 to 40% by mass, more preferably 20 to 35% by mass. The monomer (M3) is preferably 10 to 30% by mass, and more preferably 15 to 25% by mass. The weight average molecular weight of the copolymer (S) is preferably 5,000 to 25,000, more preferably 10,000 to 25,000, and further preferably 15,000 to 25,000.

  Examples of the surfactant other than the above-described copolymer (S) include a fluorine-based surfactant and a silicone-based surfactant, and these can also be used in combination.

As the fluorine-based surfactant, a compound having a fluoroalkyl group and / or a fluoroalkylene group in at least one of the terminal, main chain and side chain is preferable.
Examples of commercially available fluorosurfactants include BM-1000 and BM-1100 (manufactured by BMCHEMIE); MegaFack F142D, F172, F173, F183, F178, F191, F191, F471, F476 (above, Dainippon Ink & Chemicals, Inc.); Florard FC-170C, -171, -430, -431 (above, manufactured by Sumitomo 3M); Surflon S-112,- 113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (above, manufactured by Asahi Glass Co., Ltd.) F Top E F301, 303, 352 (above, manufactured by Shin-Akita Kasei Co., Ltd.); Footent FT-100, -110, -140A, -1 0, the -250, the -251, the -300, the -310, the same -400S, Ftergent FTX-218, the -251 (or more, (Ltd.) Neos) can be mentioned.

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.); TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 ( GE Toshiba Silicone Co., Ltd.); organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.).

When producing a resin layer by a solution casting method, the production of the resin layer can be facilitated by adding a surfactant or an antifoaming agent.
These additives may be mixed with the resin when forming the resin layer, or may be added when the resin is synthesized. The addition amount is appropriately selected according to the desired properties, but is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight, based on 100 parts by weight of the resin. Part.

<Manufacturing method of substrate>
By melt molding or cast molding a resin solution containing the compound (A) on a glass substrate, the solvent is preferably removed by drying after coating by a method such as spin coating, slit coating, or inkjet, and further if necessary. By performing light irradiation or heating, a base material having a transparent resin layer formed on a glass substrate can be produced.

≪Melt molding≫
As melt molding, specifically, a method of melt-molding pellets obtained by melt-kneading a resin and a compound (A), a resin composition containing the resin and the compound (A) is melt-molded. Examples thereof include a method or a method of melt-molding pellets obtained by removing the solvent from the resin composition containing the compound (A), the resin and the solvent. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

≪Cast molding≫
As cast molding, a method of removing a solvent by casting a resin composition containing a compound (A), a resin and a solvent on a glass substrate, or a compound (A), a photocurable resin and / or a thermosetting resin After the curable composition containing is cast on a glass substrate to remove the solvent, it can be produced by a method of curing by an appropriate method such as ultraviolet irradiation or heating.

≪Hardened layer≫
Since the resin layer and the glass substrate have different chemical compositions and thermal expansion coefficients, it is preferable to provide a cured layer between the resin layer and the glass substrate to ensure their sufficient adhesion. Although it will not specifically limit if the hardened layer used for this invention consists of a material which can ensure the adhesiveness between a resin layer and a glass substrate, For example, (a) Structural unit derived from the (meth) acryloyl group containing compound, ( It is preferable to have b) a structural unit derived from a carboxylic acid group-containing compound and (c) a structural unit derived from an epoxy group-containing compound, since the adhesion between the resin layer and the glass substrate is increased.

(A) Structural unit derived from a (meth) acryloyl group-containing compound The structural unit (a) is not particularly limited as long as it is a structural unit derived from a (meth) acryloyl group-containing compound. As the (meth) acryloyl group-containing compound, for example, monofunctional, bifunctional, or trifunctional or higher (meth) acrylic acid esters are preferable from the viewpoint of good polymerizability. In the present invention, “(meth) acryl” means “acryl” or “methacryl”.

  Examples of the monofunctional (meth) acrylic acid ester include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, diethylene glycol monoethyl ether acrylate, diethylene glycol monoethyl ether methacrylate, (2-acryloyloxyethyl) (2-hydroxypropyl). Mention may be made of phthalate, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalate and ω-carboxypolycaprolactone monoacrylate.

  As these commercially available products, for example, Aronix M-101, M-111, M-114, M-5300 (above, manufactured by Toagosei Co., Ltd.); KAYARDTC-110S, TC-120S (above, Nippon Kayaku Co., Ltd.); Viscoat 158, 2311 (above, Osaka Organic Chemical Industries, Ltd.).

  Examples of the bifunctional (meth) acrylic acid ester include ethylene glycol diacrylate, propylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 9 , 9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene, 1,6-hexanediol diacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol diacrylate and 1,9-nonane Mention may be made of diol dimethacrylate.

  As these commercial products, for example, Aronix M-210, M-240, M-6200 (above, manufactured by Toagosei Co., Ltd.); KAYARADHDDA, HX-220, R-604 ( As mentioned above, Nippon Kayaku Co., Ltd.); Viscoat 260, 312, and 3355 HP (above, Osaka Organic Chemical Industry Co., Ltd.); Light acrylate 1,9-NDA (manufactured by Kyoeisha Chemical Co., Ltd.) be able to.

  Examples of the trifunctional or higher functional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, and dipentaerythritol. Pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, ethylene oxide modified dipentaerythritol hexaacrylate, tri (2-acryloyl) Oxyethyl) In addition to phosphate and tri (2-methacryloyloxyethyl) phosphate, a compound having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and having one or more hydroxyl groups in the molecule And polyfunctional urethane acrylate compounds obtained by reacting with compounds having 3, 4 or 5 (meth) acryloyloxy groups.

  Examples of commercially available trifunctional or higher functional (meth) acrylic acid esters include Aronix M-309, M-315, M-400, M-405, M-450, M-7100, and M- 8030, M-8060, TO-1450 (above, manufactured by Toagosei Co., Ltd.); KAYARADTMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA- 12 (Nippon Kayaku Co., Ltd.); Biscote 295, 300, 360, GPT, 3PA, 400 (Osaka Organic Chemical Co., Ltd.) and polyfunctional urethane acrylate compounds New frontier R-1150 (Daiichi Kogyo Seiyaku Co., Ltd.); KAYARADPDPHA-40H (Nippon Kayaku Co., Ltd.) It can gel.

These (meth) acryloyl group-containing compounds (a) can be used alone or in admixture of two or more in the cured layer.
(B) Structural unit derived from a carboxylic acid group-containing compound The structural unit (b) is not particularly limited as long as it is a structural unit derived from a compound containing a carboxylic acid group. Examples of the carboxylic acid group-containing compound include monocarboxylic acids, dicarboxylic acids, dicarboxylic acid anhydrides, and polymers having carboxylic acid groups.

  Examples of the monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl hexahydrophthalic acid and 2-methacryloyloxyethyl hexahydro. Mention may be made of phthalic acid.

Examples of the dicarboxylic acid include maleic acid, fumaric acid, and citraconic acid.
Examples of the dicarboxylic acid anhydride include the dicarboxylic acid anhydride.

  In addition, the polymer having a carboxylic acid group is a compound having a carboxylic acid group, for example, from a compound having at least one polymer selected from acrylic acid, methacrylic acid, maleic acid, maleic anhydride, and the like. Or a copolymer of these compounds and the (meth) acryloyl group-containing compound can be suitably used.

  Among these, acrylic acid, methacrylic acid, 2-acryloyloxyethyl succinic acid, 2-methacryloyloxyethyl succinic acid or maleic anhydride is preferable from the viewpoint of copolymerization reactivity.

(C) Structural unit derived from an epoxy group-containing compound The structural unit (c) is not particularly limited as long as it is a structural unit derived from an epoxy group-containing compound. Examples of the epoxy group (oxiranyl group) -containing compound include oxiranyl groups such as (meth) acrylic acid oxiranyl (cyclo) alkyl ester, α-alkylacrylic acid oxiranyl (cyclo) alkyl ester, and glycidyl ether compound having an unsaturated bond. An unsaturated compound having an oxetanyl group such as a (meth) acrylic acid ester having an oxetanyl group.

  As (meth) acrylic acid oxiranyl (cyclo) alkyl ester, for example, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, (meth) acrylic acid 3,4 -Epoxybutyl, (7) -epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate.

  Examples of the oxiranyl (cyclo) alkyl ester of α-alkyl acrylate include, for example, glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, glycidyl α-n-butyl acrylate, 6,7-epoxyheptyl α-ethyl acrylate And α-ethyl acrylate 3,4-epoxycyclohexyl.

  Examples of the glycidyl ether compound having an unsaturated bond include o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether.

  Examples of the (meth) acrylic acid ester having an oxetanyl group include 3-((meth) acryloyloxymethyl) oxetane, 3-((meth) acryloyloxymethyl) -3-ethyloxetane, and 3-((meth) acryloyloxymethyl. ) -2-methyloxetane, 3-((meth) acryloyloxyethyl) -3-ethyloxetane, 2-ethyl-3-((meth) acryloyloxyethyl) oxetane, 3-methyl-3- (meth) acryloyloxy Mention may be made of methyl oxetane and 3-ethyl-3- (meth) acryloyloxymethyl oxetane.

  Among these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methacryloyloxymethyl-3-ethyloxetane, 3-methyl- 3-Methacryloyloxymethyloxetane or 3-ethyl-3-methyloxetane is preferred from the viewpoint of polymerizability.

(Optional component)
Arbitrary components such as an acid generator, an adhesion assistant, a surfactant, and a polymerization initiator can be added to the cured layer as long as the effects of the present invention are not impaired. These addition amounts are appropriately selected according to the desired properties, and are usually each based on a total of 100 parts by weight of the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound and the epoxy group-containing compound. The content is 0.01 to 15.0 parts by weight, preferably 0.05 to 10.0 parts by weight.

  The polymerization initiator is a component that generates active species capable of initiating polymerization of monomer components in response to light rays such as ultraviolet rays and electron beams. Such a polymerization initiator is not particularly limited, and examples thereof include an O-acyloxime compound, an acetophenone compound, a biimidazole compound, an alkylphenone compound, and a benzophenone compound. Specific examples thereof include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), 1- [9-ethyl- 6-Benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone-1- [9- Ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-dimethylamino-2- (4 -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, -Phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl benzophenone, 1-hydroxycyclohexyl phenyl ketone and the like can be mentioned.These polymerization initiators can be used alone or in admixture of two or more.

  The cured layer is, for example, a pellet obtained by melt-kneading the composition (I) containing the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound, the epoxy group-containing compound and, if necessary, the optional component. , A method of melt-molding pellets obtained by removing the solvent from the liquid composition containing the composition (I) and the solvent, or a method of casting (cast molding) the liquid composition described above Can be manufactured. Examples of the melt molding method and the cast molding method include the same methods as described above.

  The amount of the (meth) acryloyl group-containing compound is preferably 30 to 70 parts by weight, more preferably 40 to 60 parts by weight per 100 parts by weight of the composition (I). The amount is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight per 100 parts by weight of the composition (I), and the amount of the epoxy group-containing compound is 100 parts by weight of the composition (I). It is preferably 15 to 50 parts by weight, more preferably 20 to 40 parts by weight.

  The amount of the optional component is appropriately selected according to the desired properties, but is preferably 0.01 to 15.0 parts by weight, more preferably 0.05 to 100 parts by weight per 100 parts by weight of the composition (I). 10. 0 parts by weight.

The thickness of the hardened layer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0. It is 1-5.0 micrometers, More preferably, it is 0.2-3.0 micrometers.
[Dielectric multilayer film]
Examples of the dielectric multilayer film include those in which high refractive index material layers and low refractive index material layers are alternately stacked. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index of usually 1.7 to 2.5 is selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, or indium oxide as the main components, and titanium oxide, tin oxide, and / or Or what contains a small amount (for example, 0-10 weight% with respect to a main component) of cerium oxide etc. is mentioned.

  As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index of usually 1.2 to 1.6 is selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride, and sodium hexafluoride sodium.

  The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a dielectric in which high-refractive index material layers and low-refractive index material layers are alternately stacked directly on a substrate by CVD, sputtering, vacuum deposition, ion-assisted deposition, or ion plating. A multilayer film can be formed.

  Vapor deposition is usually performed at a deposition temperature range of 100 ° C. or more and 10 ° C. or more lower than the Tg of the transparent resin layer, preferably 100 ° C. or more and 20 ° C. or more lower than the Tg of the transparent resin layer. . It is preferable to perform deposition under such temperature conditions because a dielectric multilayer film having excellent adhesion can be formed without excessive heating of the substrate.

  In the present invention, by using a glass substrate as a base material, it is possible to form a dielectric multilayer film by vapor deposition at a temperature higher than usual. The specific vapor deposition temperature is preferably 180 ° C. or higher, more preferably 190 ° C. or higher, and further preferably 200 ° C. or higher. When the dielectric multilayer film is formed by vapor deposition at such a high temperature, the adhesion of the dielectric multilayer film is improved and the strength of the dielectric multilayer film as the vapor deposition film is increased. The heat resistance and scratch resistance of the laminate used are also improved.

  The thicknesses of the high-refractive index material layer and the low-refractive index material layer are usually preferably 0.1λ to 0.5λ, where λ (nm) is the near infrared wavelength to be blocked. The value of λ (nm) is, for example, 700 to 1400 nm, preferably 750 to 1300 nm. When the thickness is within this range, the optical thickness obtained by multiplying the refractive index (n) by the thickness (d) (n × d) by λ / 4, the high refractive index material layer, and the low refractive index. The thicknesses of the respective layers of the refractive index material layer are almost the same value, and there is a tendency that the blocking / transmission of a specific wavelength can be easily controlled from the relationship between the optical characteristics of reflection / refraction.

  The total number of stacked high refractive index material layers and low refractive index material layers in the dielectric multilayer film is preferably 16 to 70 layers, and more preferably 20 to 60 layers as a whole. If the thickness of each layer, the thickness of the dielectric multilayer film as a whole of the optical filter, and the total number of layers are within the above ranges, a sufficient manufacturing margin can be secured, and the warpage of the optical filter and cracks in the dielectric multilayer film can be reduced. can do.

  In one embodiment of the present invention, the material types constituting the high refractive index material layer and the low refractive index material layer, the thicknesses of the high refractive index material layer and the low refractive index material layer in accordance with the absorption characteristics of the compound (A) By properly selecting the stacking order and the number of stacks, it has sufficient light-cutting characteristics in the near-infrared wavelength region while ensuring sufficient transmittance in the visible region, and from the oblique direction to the near-infrared ray It is possible to reduce the reflectance when the light enters.

  Here, in order to optimize the conditions, for example, when measuring from the vertical direction of the optical filter (or base material) using optical thin film design software (for example, EssentialMacleod, manufactured by ThinFilmCenter), the vertical direction is 30. When measured from an angle of degrees, the parameters may be set so that the visible light transmittance and the light cut effect in the near infrared region can be compatible in any of the cases measured from an angle of 60 degrees with respect to the vertical direction. In particular, in order to use it suitably as an optical filter for an ambient light sensor, it is important that the change in visible light transmittance and near-infrared cut performance is small at each incident angle. When designing a dielectric multilayer film, it is preferable to change the incident angle that optimizes the optical characteristics depending on the wavelength region (for example, the transmittance at a wavelength of 400 to 750 nm optimizes the optical characteristics at an incident angle of 30 degrees, (The transmittance of 800 to 1200 nm is optimized at an incident angle of 0 degrees, etc.).

  In the case of the above software, for example, in designing a dielectric multilayer film formed only on one side of the substrate, the target transmittance when measured from an angle of 30 degrees with respect to the vertical direction of a wavelength of 400 to 750 nm is 100%, Target Tolerance value of 1, measured from the vertical direction of wavelength 755 to 790 nm, the target transmittance was 100%, Target Tolerance value of 0.8, and measured from an angle of 30 degrees with respect to the vertical direction of wavelength 800 to 1000 nm The target transmittance is 0%, the Target Tolerance value is 0.5, the target transmittance is 0% when measured from an angle of 0 degrees with respect to the vertical direction of the wavelength 1005-1300 nm, and the Target Tolerance value is 0.7. Parameter setting methods such as These parameters can change the light incident angle and Target Tolerance values that optimize the design by further finely dividing the wavelength range according to various characteristics of the substrate (i). In particular, when the design of at least a part of the wavelength region in the wavelength range of 400 to 700 nm is optimized with respect to light rays from an oblique direction, the visible transmittance due to ripples or the like can be improved even when the incident angle is very large, such as an incident angle of 60 degrees. It is preferable because the decrease can be reduced.

[Other functional membranes]
The optical filter according to an embodiment of the present invention is a surface on the opposite side of the surface on which the dielectric multilayer film is provided between the substrate and the dielectric multilayer film, as long as the effects of the present invention are not impaired. Or for the purpose of improving the surface hardness of the base material or dielectric multilayer film, improving the chemical resistance, antistatic and scratch-removing on the surface opposite to the surface on which the base material of the dielectric multilayer film is provided. Functional films such as an antireflection film, a hard coat film, and an antistatic film can be provided as appropriate.

  The optical filter according to an embodiment of the present invention may include one layer made of the above-described functional film, or may include two or more layers. When the optical filter according to an embodiment of the present invention includes two or more layers made of such a functional film, it may include two or more similar layers or two or more different layers.

  A method for laminating such a functional film is not particularly limited, but a coating agent such as an antireflection agent, a hard coating agent and / or an antistatic agent is melted on a base material or a dielectric multilayer film in the same manner as described above. Examples of the method include molding or cast molding.

  In addition, the composition can also be produced by applying a curable composition containing a coating agent or the like onto a substrate or a dielectric multilayer film with a bar coater or the like and then curing the composition by ultraviolet irradiation or the like.

  Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resin and thermosetting resin, and specifically, vinyl compounds, urethane-based, urethane acrylate-based, acrylate-based, and epoxy-based resins. And epoxy acrylate resins. Examples of the curable composition containing these coating agents include vinyl, urethane, urethane acrylate, acrylate, epoxy, and epoxy acrylate curable compositions.

  Moreover, the curable composition may contain the polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or a thermal polymerization initiator can be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination. A polymerization initiator may be used individually by 1 type, and may use 2 or more types together.

  In the curable composition, the blending ratio of the polymerization initiator is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, when the total amount of the curable composition is 100% by weight. Preferably it is 1 to 5 weight%. When the blending ratio of the polymerization initiator is within the above range, it is possible to obtain a functional film such as an antireflective film, a hard coat film or an antistatic film having excellent curing characteristics and handleability of the curable composition and having a desired hardness. it can.

  Furthermore, an organic solvent may be added as a solvent to the curable composition, and known organic solvents can be used. Specific examples of organic solvents include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone, propylene Esters such as glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, N- Examples include amides such as methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The thickness of the functional film is preferably 0.1 to 20 μm, more preferably 0.5 to 10 μm, and particularly preferably 0.7 to 5 μm.
Further, in order to improve the adhesion between the base material and the functional film and / or the dielectric multilayer film, and the adhesion between the functional film and the dielectric multilayer film, the corona is applied to the surface of the base material, the functional film or the dielectric multilayer film. Surface treatment such as treatment or plasma treatment may be performed.

[Use of optical filter]
The optical filter according to an embodiment of the present invention is applicable to a solder reflow process because it has excellent visible transmittance and near-infrared cutting ability even when the incident angle is large, and has excellent heat resistance. Therefore, it is useful for solid-state imaging devices and various ambient light sensors such as illuminance sensors and color correction sensors. It is particularly useful for correcting the visibility of solid-state image sensors such as CCD and CMOS image sensors, such as digital still cameras and mobile phone cameras, and for applications that require high-temperature bonding when used in products or use in high-temperature areas. Can also be suitably used. Further, it is useful for an ambient light sensor mounted on a digital still camera, a smartphone, a tablet terminal, a mobile phone, a wearable device, an automobile, a television, a game machine, or the like. Furthermore, it is useful as a heat ray cut filter mounted on a glass plate for windows of automobiles and buildings.

[Ambient light sensor]
The optical filter according to one embodiment of the present invention and a photoelectric conversion element can be combined and used as an ambient light sensor. Here, the ambient light sensor is a sensor capable of detecting ambient brightness and color tone (such as strong red in the evening time zone) such as an illuminance sensor and a color correction sensor. For example, information detected by the ambient light sensor This makes it possible to control the illuminance and hue of the display mounted on the device.

  FIG. 3 shows an example of the ambient light sensor 200a that detects ambient brightness. The ambient light sensor 200a includes an optical filter 100 and a photoelectric conversion element 202. The photoelectric conversion element 202 generates a current and a voltage due to the photovoltaic effect when light enters the light receiving portion. The optical filter 100 is provided on the light receiving surface side of the photoelectric conversion element 202. By the optical filter 100, light incident on the light receiving surface of the photoelectric conversion element 202 becomes light in the visible light band, and light in the near infrared band (800 nm to 2500 nm) is blocked. The ambient light sensor 200a outputs a signal in response to visible light.

  In the ambient light sensor 200a, another light-transmitting layer may be interposed between the optical filter 100 and the photoelectric conversion element 202. For example, a light-transmitting resin layer may be provided as a sealing material between the optical filter 100 and the photoelectric conversion element 202.

  The photoelectric conversion element 202 includes a first electrode 206, a photoelectric conversion layer 208, and a second electrode 210. Further, a passivation film 216 is provided on the light receiving surface side. The photoelectric conversion layer 208 is formed using a semiconductor that exhibits a photoelectric effect. For example, the photoelectric conversion layer 208 is formed using a silicon semiconductor. The photoelectric conversion layer 208 is a diode-type element, and develops a photovoltaic force by a built-in electric field. Note that the photoelectric conversion element 202 is not limited to a diode-type element, and is a photoconductive-type element (also referred to as a photoresistor, a light-dependent resistor, a photoconductor, or a photocell) or a phototransistor-type element. Also good.

The photoelectric conversion layer 208 may be formed of a germanium semiconductor or a silicon / germanium semiconductor in addition to the silicon semiconductor. Further, as the photoelectric conversion layer 208, a compound semiconductor material such as GaP, GaAsP, CdS, CdTe, or CuInSe ₂ may be used. The photoelectric conversion element 202 formed of a semiconductor material has sensitivity to light in the visible light band to the near infrared band. For example, in the case where the photoelectric conversion layer 208 is formed of a silicon semiconductor, the band gap energy of the silicon semiconductor is 1.12 eV, and thus, in principle, light having a wavelength of 700 to 1100 nm, which is near infrared light, can be absorbed. However, by providing the optical filter 100, the ambient light sensor 200a is insensitive to near infrared light and has sensitivity to light in the visible light range. Note that the photoelectric conversion element 202 is preferably surrounded by a light-shielding casing 204 so that light transmitted through the optical filter 100 is selectively irradiated. By providing the optical filter 100, the ambient light sensor 200a can block ambient light and detect ambient light. Thereby, the trouble that the ambient light sensor 200a malfunctions in response to near infrared light can be solved.

  FIG. 4 shows an example of an ambient light sensor 200b that detects color tone in addition to ambient brightness. The ambient light sensor 200b includes the optical filter 100, photoelectric conversion elements 202a to 202c, and color filters 212a to 212c. A color filter 212a that transmits light in the red light band is provided on the light receiving surface of the photoelectric conversion element 202a, and a color filter 212b that transmits light in the green light band is provided on the light receiving surface of the photoelectric conversion element 202b. A color filter 212c that transmits light in the blue light band is provided on the light receiving surface of the photoelectric conversion element 202c. The photoelectric conversion elements 202 a to 202 c have the same configuration as that shown in FIG. 3 except that they are insulated by the element isolation insulating layer 214. With this configuration, the photoelectric conversion elements 202a to 202c can independently detect illuminance. Note that a passivation film 216 may be provided between the color filters 212a to 212c and the photoelectric conversion elements 202a to 202c.

  The photoelectric conversion elements 202a to 202c have sensitivity over a wide range from the visible light wavelength region to the near infrared wavelength region. Therefore, by providing the color filters 212a to 212c corresponding to the photoelectric conversion elements 202a to 202c in addition to the optical filter 100, the ambient light sensor 200b blocks near-infrared light and prevents malfunction of the sensor. The light corresponding to each color can be detected. The ambient light sensor 200b includes the optical filter 100 that blocks light in the near-infrared region and the color filters 212a to 212c, so that it can not only spectroscopically detect ambient light into light of a plurality of wavelength bands, The conventional color sensor can be applied even in a dark environment where accurate detection cannot be performed under the influence of near infrared rays.

[Electronics]
5A to 5C show an example of an electronic apparatus 300 having the ambient light sensor 200 according to an embodiment of the present invention. 5A is a front view, FIG. 5B is a top view, and FIG. 5C is a detailed view illustrating the configuration of a region D surrounded by a dotted line in FIG. 5B. The electronic device 300 includes a housing 302, a display panel 304, a microphone unit 306, a speaker unit 308, and the ambient light sensor 200. The display panel 304 employs a touch panel and has an input function in addition to a display function.

  The ambient light sensor 200 is provided on the back surface of the front panel 310 provided in the housing 302. That is, the ambient light sensor 200 does not appear in the appearance of the electronic device 300, and light enters through the translucent surface panel 310. The front panel 310 blocks light in the near infrared region by the optical filter 100, and light in the visible light region enters the photoelectric conversion element 202. The electronic device 300 can control the illuminance and color of the display panel 304 by the ambient light sensor 200.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to these Examples at all. “Parts” means “parts by weight” unless otherwise specified. Moreover, the measurement method of each physical property value and the evaluation method of the physical property are as follows.

<Molecular weight>
The molecular weight of the resin was measured by the following method (a) or (b) in consideration of the solubility of each resin in a solvent.

  (A) Weight average molecular weight in terms of standard polystyrene using a gel permeation chromatography (GPC) apparatus (150C type, column: H type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene) manufactured by WATERS (Mw) and number average molecular weight (Mn) were measured.

  (B) Standard polystyrene equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) were measured using a GPC apparatus (HLC-8220 type, column: TSKgel α-M, developing solvent: THF) manufactured by Tosoh Corporation.

<Glass transition temperature (Tg)>
Using a differential scanning calorimeter (DSC6200) manufactured by SII Nano Technologies, Inc., the rate of temperature increase was measured at 20 ° C. per minute under a nitrogen stream.

<Spectral transmittance>
The transmittance in each wavelength region of the optical filter was measured using a spectrophotometer (U-4100) manufactured by Hitachi High-Technologies Corporation.

  Here, in the transmittance when measured from the vertical direction of the optical filter, the light 1 transmitted perpendicularly to the optical filter 2 is measured by the spectrophotometer 3 as shown in FIG. In the transmittance when measured from an angle of 30 degrees with respect to the direction, the spectrophotometer 3 transmits light 1 ′ transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. In the transmittance when measured and measured from an angle of 60 degrees with respect to the vertical direction of the optical filter, light 1 transmitted at an angle of 60 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. ″ Was measured with a spectrophotometer 3.

<Crack evaluation>
Visually, a dielectric multilayer film layer (deposited layer) with no crack was evaluated as “◯”, and a dielectric multilayer film layer (deposited layer) with a crack was evaluated as “x”.

<Reflow resistance evaluation>
The optical filter is fixed on a 1 mm thick glass epoxy substrate SL-EP (manufactured by Nitto Shinko) with Kapton tape, and JEDEC standard J-STD- is used with a reflow device (STR-2010N2M-III) manufactured by Senju Metal Industry Co., Ltd. Based on 02D, the presence or absence of cracks after the solder reflow treatment reaching the maximum temperature of about 270 ° C. was defined as reflow resistance. A case where no crack was generated was evaluated as “◯”, and a case where a crack occurred and actual use was difficult was evaluated as “×”.

  The near-infrared absorbing dye used in the following examples was synthesized by a generally known method. Examples of general synthesis methods include, for example, Japanese Patent No. 336697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. 60-228448, Japanese Patent Laid-Open No. 1-146846, JP-A-1-228960, JP-A-4081149, JP-A-63-124054, “Phthalocyanine—Chemistry and Function” (IPC, 1997), JP-A-2007-169315, JP2009. -108267, Unexamined-Japanese-Patent No. 2010-241873, patent 3699464, patent 4740631, etc. can be mentioned.

<Resin synthesis example 1>
In a 3 L four-necked flask, 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, 41.46 g of potassium carbonate ( 0.300 mol), 443 g of N, N-dimethylacetamide (hereinafter also referred to as “DMAc”) and 111 g of toluene were added. Subsequently, a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean Stark tube and a cooling tube were attached to the four-necked flask. Next, after the atmosphere in the flask was replaced with nitrogen, the resulting solution was reacted at 140 ° C. for 3 hours, and water produced was removed from the Dean-Stark tube as needed. When no more water was observed, the temperature was gradually raised to 160 ° C. and reacted at that temperature for 6 hours. After cooling to room temperature (25 ° C.), the produced salt was removed with a filter paper, the filtrate was poured into methanol for reprecipitation, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum dried at 60 ° C. overnight to obtain a white powder (hereinafter also referred to as “resin A”) (yield 95%). The obtained resin A had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

<Resin synthesis example 2>
100 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] dodec-3-ene (hereinafter also referred to as “DNM”) represented by the following formula (8). , 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were charged into a nitrogen-substituted reaction vessel, and this solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) as a polymerization catalyst and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel. 9 parts was added and this solution was heated and stirred at 80 ° C. for 3 hours to cause a ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

1,000 parts of the ring-opening polymer solution thus obtained was charged into an autoclave, and 0.12 part of RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution. Then, the hydrogenation reaction was performed by heating and stirring for 3 hours under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, and dried to obtain a hydrogenated polymer (hereinafter also referred to as “resin B”). The obtained resin B had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 ° C.

[Example 1]
In Example 1, an optical filter having a base material including a transparent glass substrate was produced according to the following procedure and conditions.

<Preparation of resin solution (D-1)>
In a container, 100 parts by weight of resin A obtained in Resin Synthesis Example 1, compound (a-1) represented by the following formula (a-1) as compound (A) (maximum absorption wavelength 698 nm in dichloromethane) 1.0 Part and dichloromethane were added to prepare a solution having a resin concentration of 10% by weight. Then, it filtered with the Millipore filter with a hole diameter of 5 micrometers, and obtained the resin solution (D-1).

<Preparation of curable composition solution (1)>
Isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Co., Ltd.), 30 parts by weight of 1,9-nonanediol diacrylate, 20 parts by weight of methacrylic acid, glycidyl methacrylate 30 Parts by weight, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals) and Sun-Aid SI-110 main agent (Sanshin Chemical) (Made by Kogyo Co., Ltd.) 1 part by weight was mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration was 50 wt%, and then filtered through a Millipore filter having a pore size of 0.2 μm to obtain a curable composition solution ( 1) was prepared.

<Preparation of base material>
Subsequently, after applying the curable composition solution (1) to one side of a transparent glass substrate “OA-10G” manufactured by Nippon Electric Glass Co., Ltd. cut to a size of 60 mm in length and 60 mm in width, The plate was heated at 80 ° C. for 2 minutes to volatilize and remove the solvent, thereby forming a cured layer. At this time, the application conditions of the spin coater were adjusted so that the thickness of the cured layer was about 0.8 μm. Next, a resin solution (D-1) is applied on the cured layer using a spin coater under conditions such that the half-value on the long wavelength side is 646 nm, heated on a hot plate at 80 ° C. for 5 minutes, and the solvent is removed. Volatile removal was performed to form a transparent resin layer. Next, the glass surface was exposed using a conveyor type exposure machine (exposure amount 1 J / cm ² , illuminance 200 mW), and then baked in an oven at 230 ° C. for 20 minutes to obtain a base material having a length of 60 mm and a width of 60 mm. .

<Production of optical filter>
A dielectric multilayer film (I) is formed as a first optical layer on one side of the obtained base material, and a dielectric multilayer film (II) is formed as a second optical layer on the other side of the base material. An optical filter having a thickness of about 0.160 mm was obtained.

The dielectric multilayer film (I) is formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 200 ° C. (26 layers in total). The dielectric multilayer film (II) is formed by alternately laminating silica (SiO ₂ ) layers and titania (TiO ₂ ) layers at a deposition temperature of 200 ° C. (20 layers in total). In both of the dielectric multilayer films (I) and (II), the silica layer and the titania layer are in order of the titania layer, the silica layer, the titania layer,..., The silica layer, the titania layer, and the silica layer from the substrate side. The outermost layer of the optical filter was a silica layer.

The dielectric multilayer films (I) and (II) were designed as follows.
Regarding the thickness and the number of layers, the wavelength-dependent characteristics of the substrate refractive index and the absorption characteristics of the applied compound (A) so as to achieve the visible antireflection effect and the selective transmission / reflection performance in the near infrared range. Was optimized using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When performing optimization, in this example, the input parameters (Target values) to the software are as shown in Table 9 below.

  As a result of the optimization of the film configuration, in Example 1, the dielectric multilayer film (I) was formed by alternately laminating a silica layer having a film thickness of 30 to 153 nm and a titania layer having a film thickness of 10 to 96 nm. The dielectric multilayer film (II) is a multilayer deposited film having 20 layers, in which a silica layer having a thickness of 38 to 187 nm and a titania layer having a thickness of 11 to 111 nm are alternately stacked. It was. An example of the optimized film configuration is shown in Table 10 below.

  Spectral transmittance was measured from the vertical direction of the obtained optical filter and angles of 30 ° and 60 ° with respect to the vertical direction, and optical characteristics in each wavelength region were evaluated. The results are shown in FIG.

  Subsequently, the obtained optical filter was stored in an environment of 85 ° C. and 85% RH for 1000 hours, a sample was taken out, left in an atmosphere of 25 ° C. and 55% RH for 2 days, and then the spectral transmittance from the vertical direction of the optical filter. Were measured to evaluate the optical characteristics and the presence or absence of cracks in each wavelength region. The results after the storage and the changes before and after the storage are shown in FIG.

[Example 2]
In Example 1, 1.0 part of the compound (A-2) (absorption maximum wavelength 703 nm in dichloromethane) represented by the following formula (a-2) as the compound (A) and the following formula (a-3) The same procedure and conditions as in Example 1 except that the resin solution (D-2) prepared using 2.0 parts of the compound (a-3) (absorption maximum wavelength in dichloromethane of 736 nm) is used. The base material which has a transparent resin layer containing a compound (A) was obtained.

  An optical filter having a thickness of 0.160 mm was obtained in the same procedure and conditions as in Example 1 except that the obtained base material was used. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the base material refractive index. Spectral transmittance was measured from the vertical direction of the obtained optical filter and angles of 30 ° and 60 ° with respect to the vertical direction, and optical characteristics in each wavelength region were evaluated. The results are shown in Table 13.

  Subsequently, the obtained optical filter was stored in an environment of 85 ° C. and 85% RH for 1000 hours, and a sample was taken out and left to stand in an atmosphere of 25 ° C. and 55% RH for 2 days, and then from the vertical direction and the vertical direction of the optical filter. The spectral transmittance was measured, and the optical characteristics and the presence or absence of cracks in each wavelength region were evaluated. The results after the storage and the changes before and after the storage are shown in FIG.

[Example 3]
In Example 2, the same procedure and conditions as in Example 2 except that the resin solution (D-3) using 100 parts by weight of the resin B obtained in Resin Synthesis Example 2 was used instead of the resin A. A substrate having a transparent resin layer containing A) was obtained.

  Subsequently, an optical filter having a thickness of 0.160 mm was obtained by the same procedure and conditions as in Example 1 except that the obtained base material was used. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the base material refractive index. Spectral transmittance was measured from the vertical direction of the obtained optical filter and angles of 30 ° and 60 ° with respect to the vertical direction, and optical characteristics in each wavelength region were evaluated. The results are shown in Table 13.

  Subsequently, the obtained optical filter was stored in an environment of 85 ° C. and 85% RH for 1000 hours, and then a sample was taken out and allowed to stand in an atmosphere of 25 ° C. and 55% RH for 2 days, and then spectrally transmitted from the vertical direction of the optical filter. The rate was measured, and the optical characteristics and the presence or absence of cracks in each wavelength region were evaluated. The results after the storage and the changes before and after the storage are shown in FIG.

[Example 4]
In Example 2, a near-infrared absorbing glass substrate “BS-6” (thickness 210 μm) manufactured by Matsunami Glass Industry Co., Ltd. was used instead of the transparent glass substrate “OA-10G” manufactured by Nippon Electric Glass Co., Ltd. A substrate having a transparent resin layer containing the compound (A) was obtained in the same procedure and conditions as in Example 2.

  Subsequently, an optical filter having a thickness of 0.220 mm was obtained by the same procedure and conditions as in Example 1 except that the obtained base material was used. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the base material refractive index. Spectral transmittance was measured from the vertical direction of the obtained optical filter and angles of 30 ° and 60 ° with respect to the vertical direction, and optical characteristics in each wavelength region were evaluated. The results are shown in Table 13.

  Subsequently, the obtained optical filter was stored in an environment of 85 ° C. and 85% RH for 1000 hours, and then a sample was taken out and allowed to stand in an atmosphere of 25 ° C. and 55% RH for 2 days, and then spectrally transmitted from the vertical direction of the optical filter. The rate was measured, and the optical characteristics and the presence or absence of cracks in each wavelength region were evaluated. The results after the storage and the changes before and after the storage are shown in FIG.

[Example 5]
<Preparation of curable composition solution (2)>
117 parts by weight of a near-infrared absorbing fine particle dispersion (YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd.) (about 33 parts by weight in terms of solid content), ethylene oxide-modified triacrylate (trade name: Aronix M-315, Toagosei Co., Ltd.) Chemical Co., Ltd.) 30 parts by weight, 1,9-nonanediol diacrylate 20 parts by weight, methacrylic acid 20 parts by weight, glycidyl methacrylate 30 parts by weight, 3-glycidoxypropyltrimethoxysilane 5 parts by weight, 1- 5 parts by weight of hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 1 part by weight of Sun-Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) are mixed, and the solid content concentration is 50 wt. % Dissolved in propylene glycol monomethyl ether acetate The curable composition solution containing a near infrared absorbent nanoparticle (2) was prepared.

<Preparation of substrate and optical filter>
In Example 2, instead of the curable composition solution (1), a curable composition solution (2) containing near-infrared absorbing fine particles was used to adjust the thickness of the cured layer to 2.0 μm. Obtained a base material having a transparent resin layer containing the compound (A) under the same procedure and conditions as in Example 2.

  Subsequently, an optical filter having a thickness of 0.161 mm was obtained by the same procedure and conditions as in Example 1 except that the obtained base material was used. The dielectric multilayer film was designed using the same design parameters as in Example 1 in consideration of the wavelength dependency of the base material refractive index. Spectral transmittance was measured from the vertical direction of the obtained optical filter and angles of 30 ° and 60 ° with respect to the vertical direction, and optical characteristics in each wavelength region were evaluated. The results are shown in Table 13.

  Subsequently, the obtained optical filter was stored in an environment of 85 ° C. and 85% RH for 1000 hours, and then a sample was taken out and allowed to stand in an atmosphere of 25 ° C. and 55% RH for 2 days, and then spectrally transmitted from the vertical direction of the optical filter. The rate was measured, and the optical characteristics and the presence or absence of cracks in each wavelength region were evaluated. The results after the storage and the changes before and after the storage are shown in FIG.

[Comparative Example 1]
100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 0.04 part of the compound (a-1) as the compound (A), and dichloromethane were added to a container to prepare a solution having a resin concentration of 20% by weight. The obtained solution was cast on a smooth glass plate, dried at 20 ° C. for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C. under reduced pressure for 8 hours to obtain a base material composed of a transparent resin substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm.
Subsequently, an optical filter was produced in the same procedure and conditions as in Example 1 except that the obtained base material was used. The obtained filter was severely warped and distorted and could not be evaluated.

[Comparative Example 2]
A substrate and an optical filter were produced in the same manner as in Example 1 except that the deposition temperature of the dielectric multilayer films (I) and (II) was changed to 120 ° C. in Example 1. Spectral transmittance was measured from the vertical direction of the obtained optical filter and angles of 30 ° and 60 ° with respect to the vertical direction, and optical characteristics in each wavelength region were evaluated. The results are shown in Table 13.

  Subsequently, the obtained optical filter was stored in an environment of 85 ° C. and 85% RH for 1000 hours, a sample was taken out, left in an atmosphere of 25 ° C. and 55% RH for 2 days, and then the spectral transmittance from the vertical direction of the optical filter. Were measured to evaluate the optical characteristics and the presence or absence of cracks in each wavelength region. The results after the storage and the changes before and after the storage are shown in FIG. 13 and Table 13. The optical filter obtained in Comparative Example 2 was cracked after storage and did not exhibit reflow resistance.

[Comparative Example 3]
A substrate was prepared in the same procedure as in Example 1. Subsequently, a dielectric multilayer film (XIII) is formed on one surface of the obtained base material, and a dielectric multilayer film (XIV) is further formed on the other surface of the base material, so that the optical thickness is about 0.110 mm. A filter was obtained.

  The dielectric multilayer film (XIII) and the dielectric multilayer film (XIV) are the same as those in Example 1 except that the input parameters (Target values) to the optical thin film design software (Essential Macintosh, manufactured by ThinFilmCenter) are as shown in Table 11 below. A film was formed on the substrate in the same procedure as described above.

  As a result of the optimization of the film configuration, in Comparative Example 3, the dielectric multilayer film (XIII) was formed by alternately laminating a silica layer having a film thickness of 30 to 153 nm and a titania layer having a film thickness of 10 to 96 nm. The dielectric multi-layer film (XIV) is a multi-layer vapor-deposited film with 18 layers, in which a silica layer with a film thickness of 32 to 156 nm and a titania layer with a film thickness of 9 to 89 nm are alternately stacked. It was. Table 12 shows an example of the optimized film configuration.

  The optical characteristics of the obtained optical filter are shown in FIG. The average value of the optical density at the wavelength of 800 to 1200 nm of the optical filter obtained in Comparative Example 3 was 0.6, and good near infrared light cut characteristics were not exhibited.

The configurations of the base materials and various compounds applied in the examples and comparative examples are as follows.
<Form of substrate>
Form (1): having a curable composition layer and a transparent resin layer containing compound (A) on one side of the transparent glass substrate Form (2): curable composition layer on one side of the near-infrared absorbing glass substrate And a transparent resin layer containing the compound (A) Form (3): a form having a curable composition layer containing near-infrared absorbing fine particles and a transparent resin layer containing the compound (A) on one surface of the transparent glass substrate ( 4): Transparent resin substrate containing the compound (A) (Comparative Example)

<Transparent resin>
Resin A: Aromatic polyether resin (resin synthesis example 1)
Resin B: Cyclic polyolefin resin (resin synthesis example 2)
<Near-infrared absorbing dye>
<< Compound (A) >>
Compound (a-1): The above compound (a-1) (maximum absorption wavelength 698 nm in dichloromethane)
Compound (a-2): Compound (a-2) above (absorption maximum wavelength in dichloromethane: 703 nm)
Compound (a-3): The above compound (a-3) (absorption maximum wavelength in dichloromethane 736 nm)

<Resin solution>
Resin solution (D-1): solution consisting of 100 parts by weight of resin A, 1.0 part of compound (a-1) and dichloromethane (resin concentration: 10% by weight)
Resin solution (D-2): solution consisting of 100 parts by weight of resin A, 1.0 part of compound (a-2), 2.0 parts of compound (a-3) and dichloromethane (resin concentration: 10% by weight)
Resin solution (D-3): solution consisting of 100 parts by weight of resin B, 1.0 part of compound (a-2), 2.0 parts of compound (a-3) and dichloromethane (resin concentration: 10% by weight)
<Glass substrate>
Glass substrate (1): Transparent glass substrate “OA-10G (thickness 150 μm)” (manufactured by Nippon Electric Glass Co., Ltd.)
Glass substrate (2): Near-infrared absorbing glass substrate “BS-11 (thickness 120 μm)” (manufactured by Matsunami Glass Industrial Co., Ltd.)

<Curable composition solution>
Curable composition solution (1): Isocyanuric acid ethylene oxide modified triacrylate (trade name: Aronix M-315, manufactured by Toagosei Chemical Co., Ltd.), 30 parts by weight of 1,9-nonanediol diacrylate, methacryl 20 parts by weight of acid, 30 parts by weight of glycidyl methacrylate, 5 parts by weight of 3-glycidoxypropyltrimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE 184, manufactured by Ciba Specialty Chemicals) After mixing 1 part by weight of Sun-Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) and dissolving in propylene glycol monomethyl ether acetate so that the solid content concentration is 50 wt%, it is filtered with a Millipore filter with a pore size of 0.2 μm. It is a filtered solution.

  Curable composition solution (2): near-infrared absorbing fine particle dispersion (YMF-02A manufactured by Sumitomo Metal Mining Co., Ltd.) 117 parts by weight (about 33 parts by weight in terms of solid content), isocyanuric acid ethylene oxide modified triacrylate (product) Name: Aronix M-315, manufactured by Toa Gosei Chemical Co., Ltd.) 30 parts by weight, 1,9-nonanediol diacrylate 20 parts by weight, methacrylic acid 20 parts by weight, glycidyl methacrylate 30 parts by weight, 3-glycidoxypropyl 5 parts by weight of trimethoxysilane, 5 parts by weight of 1-hydroxycyclohexylbenzophenone (trade name IRGACURE184, manufactured by Ciba Specialty Chemicals) and 1 part by weight of Sun-Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) Propylene glycol monomethyl ether so that the solid concentration is 50 wt%. A solution of the acetate.

1, 1 ', 1''... Light 2 ... Optical filter 3 ... Spectrophotometer 100 ... Optical filter 102 ... Base material 104 ... Dielectric multilayer 106 ... Reflection Prevention film 110 ... Glass substrate 112 ... Transparent resin layer 200 ... Ambient light sensor 202 ... Photoelectric conversion element 204 ... Housing 206 ... First electrode 208 ... Photoelectric conversion layer 210 ... second electrode 212 ... color filter 214 ... element isolation insulating layer 216 ... passivation film 300 ... electronic device 302 ... housing 304 ... display panel 306 ... microphone unit 308 ... Speaker unit 310 ... Front panel

Claims (17)

A substrate including a glass substrate and a resin layer containing a compound (A) having an absorption maximum at a wavelength of 600 to 800 nm, and a dielectric multilayer film formed on at least one surface of the substrate; and An optical filter that satisfies the following requirements (a) to (d):
(A) The average value T _a of the transmittance in the wavelength range of 400 to 650 nm when the spectral transmittance of the optical filter before being stored in an environment of 85 ° C. and 85% RH for 1000 hours is measured from the vertical direction of the optical filter. _-0 is 45% or more and 90% or less;
(B) When the optical density (OD value) of the optical filter before storage is measured from the vertical direction of the optical filter, the average value OD _a-0 of the optical density in the wavelength range of 800 to 1200 nm is 1.0 or more. Is
(C) When the spectral transmittance of the optical filter after storage is measured from the vertical direction of the optical filter, the average value T _b-0 of the transmittance in the wavelength range of 400 to 650 nm and the requirement (a) The absolute value of the difference from the stated transmittance average value _Ta-0 is 7% or less;
(D) When the spectral transmittance of the optical filter before storage is measured from the vertical direction of the optical filter, the average value of the transmittance at a wavelength of 580 to 650 nm is defined as T _Ra, and the average of the transmittance at a wavelength of 500 to 580 nm T _Ga / T _Ra and T _Ba / T _Ra are both 0.9 to 1.6 when the value is T _Ga and the average value of transmittance at a wavelength of 420 to 500 nm is T _Ba .   The optical filter according to claim 1, wherein no crack is generated in the dielectric multilayer film of the optical filter after storage. The optical filter according to claim 1 or 2, wherein the optical filter further satisfies the following requirement (e):
(E) The average value T _a-30 of the transmittance in the wavelength range of 400 to 650 nm when the spectral transmittance of the optical filter before storage is measured from an oblique direction of 30 degrees with respect to the vertical direction of the optical filter. and, wherein when the transmittance before the optical filter storage was measured from 60 ° oblique direction with respect to the vertical direction of the optical filter, the average value T _a-60 of the transmittance in the wavelength range of 400~650nm is, one Is 45% or more and 90% or less. The optical filter according to any one of claims 1 to 3, wherein the optical filter further satisfies the following requirement (f):
(F) When the spectral transmittance of the optical filter before storage is measured from the vertical direction of the optical filter, the shortest wavelength value (Xa) at which the transmittance is 50% in the wavelength range of 350 to 500 nm;
Absolute difference between the shortest wavelength value (Xb) at which the transmittance is 50% in the wavelength range of 350 to 500 nm when the spectral transmittance of the optical filter after storage is measured from the vertical direction of the optical filter The value is 12 nm or less. The optical filter according to claim 1, wherein the optical filter further satisfies the following requirement (g):
(G) said when the spectral transmittance of the optical filter after storage was determined from the vertical direction of the optical filter, the average value of the transmittance at a wavelength 580~650nm and T _Rb, the average transmittance at a wavelength of 500~580nm When the value is T _Gb and the average value of transmittance at a wavelength of 420 to 500 nm is T _Bb , T _Gb / T _Rb and T _Bb / T _Rb are both 0.9 to 1.6. The optical filter according to claim 5, wherein the optical filter further satisfies the following requirement (h):
(H) The values of (T _Gb / T _Rb ) / (T _Ga / T _Ra ) and (T _Bb / T _Rb ) / (T _Ba / T _Ra ) are both 0.95 to 1.05. .   The optical filter according to any one of claims 1 to 6, wherein the compound (A) is at least one compound selected from the group consisting of squarylium compounds and phthalocyanine compounds.   The resin constituting the resin layer is a cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polysulfone resin , Polyethersulfone resins, polyparaphenylene resins, polyamideimide resins, polyethylene naphthalate resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, silsesquioxane ultraviolet rays Curable resin, maleimide resin, alicyclic epoxy thermosetting resin, polyetheretherketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin, and Formed by sol-gel method The optical filter according to claim 1, characterized in that at least one resin were as silica selected from the group consisting of a resin composed mainly of.   The optical filter according to any one of claims 1 to 8, wherein a dielectric multilayer film is provided on both surfaces of the base material.   The optical filter according to claim 1, wherein the substrate has a layer containing near-infrared absorbing fine particles.   The optical filter according to any one of claims 1 to 10, wherein the glass substrate is a fluorophosphate glass or a phosphate glass containing a copper component.   The optical filter according to claim 1, wherein the optical filter is for a solid-state imaging device.   A solid-state imaging device comprising the optical filter according to claim 1.   A camera module comprising the optical filter according to claim 1.   The optical filter according to claim 1, wherein the optical filter is used for an ambient light sensor.   An ambient light sensor comprising the optical filter according to claim 1.   An electronic apparatus comprising the ambient light sensor according to claim 16.

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