JP6844275B2 - Optical filters and their uses - Google Patents

Description

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

In recent years, the development of ambient light sensors has been promoted for use in information terminal devices such as smartphones and tablet terminals. The ambient light sensor in the information terminal device is an illuminance sensor that detects the illuminance of the environment in which the information terminal device is placed to adjust the brightness of the display, and a display that detects the color tone of the environment in which the information terminal device is placed. It is used as a color sensor that adjusts the color tone of the light.

In order to naturally match the human luminosity factor with the brightness and color tone of the display, it is important that only visible light reaches the ambient light sensor. For example, the ambient light sensor can bring the spectral sensitivity characteristics closer to the luminosity factor by installing an optical filter such as a near-infrared cut filter.

On the other hand, in order to emphasize the design of the information terminal device, it is required to reduce the transmittance of the transmitting window that allows light to enter the ambient light sensor (make it look blackish), and the amount of visible light incident on infrared light. There is a problem that the number of light is reduced, it becomes difficult to detect accurate illuminance and color tone, and malfunction occurs. 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. Therefore, 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 the light that reaches the ambient light sensor (especially near infrared rays) even for the incident light at a high incident angle. It is required that the strength) does not change.

As a means for matching the spectral characteristics of the ambient light sensor with the human visual sensitivity, an apparatus provided with an infrared cut filter having a metal multilayer film formed on a glass plate is disclosed (see, for example, Patent Document 1). When glass is used as a base material, the base material itself has heat resistance, so that it can be applied to a process having a so-called solder reflow process, and as a result, the optical parts and devices can be downsized and the manufacturing process can be simplified. It becomes possible to change. Further, an optical filter having a dielectric multilayer film in which metal oxides having different refractive indexes are alternately laminated on a glass base material by using a vacuum vapor deposition method, a sputtering method, a CVD method, or the like replaces the base material with thin glass. It is also possible to reduce the wall thickness to, for example, 0.1 mm. However, the near-infrared cut filter having the metal multilayer thin film 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, in a so-called colored glass filter that cuts near-infrared light by light absorption, the difference in optical characteristics between vertically incident light and obliquely incident light is small and the viewing angle is excellent, but the density of predetermined optical characteristics is obtained. Therefore, the thickness of the substrate becomes thick, and it is difficult to reduce the size of the optical component (Non-Patent Document 1).

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

As a method for solving the problem of heat resistance, a method for manufacturing 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 or the like is formed on both sides of a transparent substrate of a thermoplastic resin having a specific glass transition point by a vacuum vapor deposition method under specific temperature conditions. ..

However, even in the near-infrared cut filter described in Patent Document 3, its heat resistance is lower than the glass transition temperature of the base material, which is not 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 is also excellent in heat resistance characteristics, curls and cracks are less likely to occur in the solder reflow process of filter parts, and even after being incorporated into a product, the temperature is high. It has been desired to develop an optical filter useful for applications such as a near-infrared cut filter, which is less likely to cause optical distortion due to curling or the like.

Japanese Unexamined Patent Publication No. 2011-060788 Japanese Unexamined Patent Publication No. 2012-008532 Japanese Unexamined Patent Publication No. 2010-044278

Sigma Kouki Co., Ltd. General Catalog Near Infrared Absorption Filter CCF-50S-500C

INDUSTRIAL APPLICABILITY The present invention can achieve both excellent visible light transmittance and near-infrared ray cut performance even when the incident angle becomes large due to the reduction in height of a device provided with a solid-state image sensor or an ambient light sensor, and further heat resistance. One of the problems is to provide an optical filter having excellent characteristics (solder flow resistance) and improved crack resistance.

The present invention relates to, for example, the following aspects [1] to [17].
[1] It has a base material containing 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 base material. An optical filter characterized by satisfying the following requirements (a) to (d):
(A) when the spectral transmittance of the preceding optical filter to store 1000 hours 85 ° C. 85% RH environment measured from the vertical direction of the optical filter, the average value T _a transmittance in the wavelength range of 400~650nm _-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) The average value T b-0} of the transmittance 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 is 7% or less;}
; (D) before storage when measured from the vertical direction the spectral transmittance of the optical filter of the optical filter, the average value of the transmittance at a wavelength 580~650nm and T _Ra, the average transmittance at a wavelength of 500~580nm When the value is T _Ga and the average value of the transmittance at a wavelength of 420 to 500 nm is T _Ba , both T _Ga / T _Ra and T _Ba / T _Ra are 0.9 to 1.6.

[2] The optical filter according to Item [1], wherein cracks do not occur 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 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, Ta _-30 . And, when the transmittance of the optical filter before storage is measured from an oblique direction of 60 degrees with respect to the vertical direction of the optical filter, the average value Ta _{-60 of the transmittance in the wavelength range of 400 to 650 nm is eventually obtained.} 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) The shortest wavelength value (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.
Absolute difference from 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 the transmittance at a wavelength of 420 to 500 nm is T _Bb , both T _Gb / T _Rb and T _Bb / T _R b are 0.9 to 1.6.

[6] The optical filter according to item [5], wherein the optical filter further satisfies the following requirement (h):
Is 0.95 to 1.05 both the value of _{(h) (T Gb / T} Rb) / value of (T _Ga / T _Ra) and _{(T Bb / T Rb) /} (T Ba / T Ra) ..

[7] The item according to any one of Items [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, and the like. Polysulfone resin, polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioki Sun-based UV curable resin, maleimide-based resin, alicyclic epoxy thermo-curable resin, polyether ether ketone-based resin, polyarylate-based resin, allyl ester-based curable resin, acrylic-based UV-curable resin, vinyl-based UV-curable resin The item according to any one of Items [1] to [7], wherein the resin is at least one selected from the group consisting of a resin and a resin containing silica as a main component formed by the solgel method. Optical filter.

[9] The optical filter according to any one of Items [1] to [8], wherein dielectric multilayer films are provided on both sides of the base material.
[10] The optical filter according to any one of Items [1] to [9], wherein the base material 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-based glass or a phosphate-based glass containing a copper component.

[12] The optical filter according to any one of Items [1] to [11], which is for a solid-state image sensor.
[13] A solid-state image sensor 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 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 device comprising the ambient light sensor according to item [16].

According to the present invention, it has high visible light transmittance and near-infrared ray cutting performance for both incident light from the vertical direction and incident light from the oblique direction, has high heat resistance, and has improved crack resistance. It is possible to provide an optical filter having resistance to solder reflow.

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 is suitable for assembly or use at high temperatures. In particular, it can be suitably used for correcting the visual sensitivity of a solid-state image sensor such as a CCD or CMOS image sensor.

Further, the optical filter of the present invention can also be suitably used for an ambient light sensor application. An ambient light sensor using such an optical filter has little dependence on the incident angle 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 the electronic device provided with the ambient light sensor which concerns on one Embodiment of this invention. It is a figure explaining the mode of measuring a transmission spectrum from (A) a vertical direction, (B) an angle of 30 degrees obliquely, and (C) an angle of 60 degrees obliquely. 6 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. 6 is a graph showing the spectral transmittance of the optical filter obtained in Example 1 measured in a vertical direction before and after storage in an environment of 85 ° C. and 85% RH for 1000 hours. 3 is a graph showing the spectral transmittance of the optical filter obtained in Example 2 measured in a vertical direction before and after storage in an environment of 85 ° C. and 85% RH for 1000 hours. 3 is a graph showing the spectral transmittance of the optical filter obtained in Example 3 measured from the vertical direction before and after storage in an environment of 85 ° C. and 85% RH for 1000 hours. 6 is a graph showing the spectral transmittance of the optical filter obtained in Example 4 measured in the vertical direction before and after storage in an environment of 85 ° C. and 85% RH for 1000 hours. 6 is a graph showing the spectral transmittance of the optical filter obtained in Example 5 measured in a vertical direction before and after storage in an environment of 85 ° C. and 85% RH for 1000 hours. 3 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 2 measured from the vertical direction before and after storage in an environment of 85 ° C. and 85% RH for 1000 hours. 3 is a graph showing the spectral transmittance of the optical filter obtained in Comparative Example 3 measured from the vertical direction before and after storage in an environment of 85 ° C. and 85% RH for 1000 hours.

Hereinafter, embodiments of the present invention will be described with reference to drawings and the like. However, the present invention can be implemented in many different modes and is not construed as being limited to the description of the embodiments illustrated below. In order to clarify the description, the drawings may schematically represent the width, thickness, shape, etc. of each part as compared with the actual embodiment, but this is merely an example and limits the interpretation of the present invention. It's not a thing. Further, in the present specification and each figure, the same elements as those described above with respect to the above-mentioned figures are designated by the same reference numerals or similar reference numerals (signatures in which a, b, etc. are simply added after the numbers). The detailed description may be omitted as appropriate.

[Optical filter]
The optical filter of the present invention includes a base material containing 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 is characterized by having a multilayer film.

The optical filter of the present invention has high visible light transmittance and near-infrared ray cutting performance for both incident light from a vertical direction and incident light from an oblique direction (particularly, incident light having a high incident angle). In the present specification, the light vertically incident on the base material constituting the optical filter is regarded as the vertically incident light, and the light incident from the oblique direction is referred to as the vertically incident light as a reference (incident angle 0 degree). Diagonally incident light.

The optical filter of the present invention satisfies the following requirements (a) to (d).
Requirement (a): Average value of transmittance in the wavelength range of 400 to 650 nm when the spectral transmittance of the optical filter before storage 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 image sensor application, and excellent sensor sensitivity is achieved when used as an ambient light sensor application. Can be done.

_{Requirement (b): The average value OD a-0} of the optical density in the wavelength range of 800 to 1200 nm when the optical density (OD value) of the optical filter before storage is measured from the vertical direction of the optical filter is 1. It is 0 or more, preferably 1.7 or more, and 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 is extremely high, the transmittance in the visible region tends to decrease, and there is no significant difference in practical characteristics. Therefore, when used as an ambient light sensor, the upper limit of the optical density should be within the above range. It is preferable to do so.

By satisfying the requirement (b), the near-infrared cut characteristic becomes good, and when the optical filter of the present invention is used for a solid-state image sensor, a good image can be obtained, and the optical filter of the present invention can be used as an ambient light sensor. When used as an application, it can prevent malfunction of the sensor.

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

Average value of optical density in a certain wavelength range = -Log10 (Average transmittance (%) / 100 in a certain wavelength range) ... Equation (1)
_{Requirement (c): The average value T b-0} of the transmittance 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 value _Ta-0 of the transmittance is 7% or less, preferably 5% or less, and more preferably 3% or less.

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

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

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

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

By satisfying the requirement (e), if the average transmittance is in 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 image sensor application. When used as an ambient light sensor application, excellent sensor sensitivity can be achieved.

Requirement (f): The shortest wavelength value (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 from 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, and more preferably 8 nm or less.

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

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 the average value of T _Gb is T Gb and the average value of the transmittance at a wavelength of 420 to 500 nm is T _Bb , both T _Gb / T _Rb and T _Bb / T _R b are 0.9 to 1.6, preferably 0. It is .95 to 1.55.

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

Requirements _{(h) :( T Gb / T} Rb) / (T Ga / T Ra) values and _{(T Bb / T Rb) /} ( either the value of T _Ba / T _Ra) is 0.95 to 1.05 , Preferably 0.96 to 1.04, more preferably 0.97 to 1.03.

The closer the value in the requirement (h) is to 1.00, the less the characteristic change before and after storage, and the optical filter of the present invention can be used as a solid-state image sensor even after assembly at high temperature and when used at high temperature. When this is done, a good image can be obtained, and when used as an ambient light sensor application, excellent sensor sensitivity can be achieved.

In the optical filter of the present invention as described above, cracks do not occur in the dielectric multilayer film after the storage.
1 (A) to 1 (C) show an optical filter according to an embodiment of the present invention. The optical filter 100a shown in FIG. 1A has a dielectric multilayer film 104 on at least one surface of the base material 102. The dielectric multilayer film 104 has a property of reflecting near infrared rays. Further, FIG. 1B shows an optical filter 100b provided with a first dielectric multilayer film 104a on one surface of the base material 102 and a second dielectric multilayer film 104b provided on the other surface. As described above, the dielectric multilayer film that reflects near infrared rays may be provided on one side of the base material or on both sides. When it is provided on one side, it is excellent in manufacturing cost and ease of manufacture, and when it is provided on both sides, it is possible to obtain an optical filter which has high strength and is less likely to warp or twist. When the optical filter is applied to an ambient light sensor application, it is preferable that the optical filter has a small warp or twist. Therefore, it is preferable to provide a dielectric multilayer film on both sides of the base material.

The dielectric multilayer film 104 preferably transmits light having a wavelength corresponding to visible light and then has reflection characteristics over the entire wavelength range of 800 to 1150 nm with respect to light incident from the vertical direction, and more preferably. It preferably has reflective properties 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 sides of the base material 102, it has 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 the base material). When 1 dielectric multilayer film 104a is provided on one side of the base material 102 and measured from an angle of 5 degrees with respect to the vertical direction of the optical filter (or the base material) on the other side of the base material 102, it is around 1000 nm to 1250 nm. A form having a second dielectric multilayer film 104b mainly having a reflection characteristic can be mentioned.

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

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

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

[Base material]
2 (A) to 2 (C) show the structure of the base material 102. The base material 102 includes a resin layer containing the compound (A) and a glass substrate. Further, the base material 102 preferably has a layer containing one or more kinds of near-infrared absorbing fine particles.

Hereinafter, a layer containing at least one compound (A) and a transparent resin is also referred to as a "transparent resin layer", and other resin layers are also simply referred to as a "resin layer".
FIG. 2 shows the base material 102, which has 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. The layer corresponding to the transparent resin layer 112 may be provided on both sides of the glass substrate 110.

The average transmittance of the base material 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 a base material having such transmission characteristics is used, an optical filter having high light transmission characteristics in a wavelength band required for a solid-state image sensor application or an ambient light sensor can be obtained, and when used for a solid-state image sensor 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 of the base material at a wavelength of 800 to 1200 nm is preferably 20% or less, more preferably 18% or less, and particularly preferably 15% or less. When a base material having such absorption characteristics is used, an optical filter having excellent near-infrared cut characteristics can be obtained regardless of the incident angle by combining with a dielectric multilayer film having specific reflection characteristics, and solid-state imaging can be obtained. It can be suitably used as an optical filter for an apparatus or an 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 appropriately select the base material so as to achieve both the required strength of the base material and the thinning, preferably 10 to 200 μm. , More preferably 15 to 180 μm, still more preferably 20 to 150 μm, and particularly preferably 25 to 120 μm.

When the thickness of the base material is within the above range, the optical filter using the base material can be made thinner and lighter, and is suitable for various applications such as a solid-state image sensor mounted on an information terminal and an ambient light sensor. 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 it can improve the near-infrared cut characteristic and reduce the dependence on the angle of incidence. Examples include glass.

<Transparent resin>
The transparent resin layer to be laminated on the glass substrate can be formed by using the transparent resin. As the transparent resin used for the base material, one type may be used alone, or two or more types may be used.

The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, it is dielectric by high-temperature vapor deposition performed at a vapor deposition temperature of 100 ° C. or higher while ensuring thermal stability and moldability on a film. Examples thereof include resins having a glass transition temperature (Tg) of preferably 110 to 380 ° C., more preferably 110 to 370 ° C., and even more preferably 120 to 360 ° C. in order to use the base material on which the body multilayer film can be formed. Further, when the glass transition temperature of the resin is 140 ° C. or higher, a film capable of forming a dielectric multilayer film by vapor deposition at a higher temperature can be obtained, which is particularly preferable.

As the transparent resin, when a resin plate having a thickness of 0.1 mm made of the resin is formed, the total light transmittance (JISK7105) of the resin plate is preferably 75 to 95%, more preferably 78 to 95%. , Particularly preferably 80 to 95% of the resin can be used. If a resin having a total light transmittance in such a range is used, the obtained substrate exhibits good transparency as an optical film.

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

Examples of the transparent resin include cyclic polyolefin resin, aromatic polyether resin, polyimide resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamide resin, aramid resin, polysulfone resin, and poly. Ethersulfon-based resin, polyparaphenylene-based resin, polyamideimide-based resin, polyethylene naphthalate (PEN) -based resin, fluorinated aromatic polymer-based resin, (modified) acrylic-based resin, epoxy-based resin, silsesquioxane-based UV curable resin, maleimide resin, alicyclic epoxy thermocurable resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic UV curable resin, vinyl UV curable resin, And a resin containing silica as a main component formed by the solgel method can be mentioned.

≪Cyclic polyolefin resin≫
The cyclic polyolefin resin is 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). And a resin obtained by hydrogenating the resin is preferable.

Wherein (2), R ^x1 ~R ^x4 each independently represents an atom or a group selected from the following (i ') ~ (ix' ), k x, m x and p ^x are each independently 0 or Represents a positive integer.
(I') Hydrogen atom (ii') Halogen atom (iii') Trialkylsilyl group (iv') Substituent or unsubstituted carbon number 1 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 hydrocarbon group (vi') polar group having 1 to 30 carbon atoms (excluding (iv'))
(Vii') Alkylidene groups formed by mutual bonding of ^{R x1} and R ^x2 or R ^x3 and R ^{x4 (however, R x1 to} R ^{x4 that} are not involved in the bond are independently described in (i'). ) ~ (Vi') represents an atom or group selected.)
(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 heterocycle (however, R ^{x1 to} R not involved in the bond). ^x4 represents an atom or group independently 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 (however, R x1} and R ^x4 not involved in the bond are independently described in (i). Represents an atom or group selected from') to (vi').)

In the 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 formed by being 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 resin preferably has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (4) and the structural unit represented by the following formula (5).

In the formula (4), R ^{1 to} R ⁴ independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d independently represent an integer of 0 to 4.

In the formula (5), R ^{1 to} R ⁴ and a to d are independently ^{synonymous with R 1 to} R ⁴ and a to d in the formula (4), and Y is a single bond, −SO ₂ -Or> C = O, R ⁷ and R ⁸ independently represent a halogen atom, a monovalent organic group or a nitro group having 1 to 12 carbon atoms, and g and h independently represent 0 to 4, respectively. Indicates an integer of, and m indicates 0 or 1. However, when m is 0, R ⁷ is not a cyano group.

Further, the aromatic polyether resin further has at least one structural unit selected from the group consisting of the structural unit represented by the following formula (6) and the structural unit represented by the following formula (7). Is preferable.

In the formula (6), R ⁵ and R ⁶ each independently represents a monovalent organic group having 1 to 12 carbon atoms, Z is 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 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 independently ^{synonymous with R 7} , R ⁸ , Y, m, g and h in formula (5), respectively, and R ⁵ , R ⁶ , Z, n, e and f are independently ^{synonymous with R 5} , R ⁶ , Z, n, e and f in the above formula (6).

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

≪Fluorene Polycarbonate Resin≫
The fluorene polycarbonate-based resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized by, for example, the 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, and is synthesized by the methods described in, for example, JP-A-2010-285505 and JP-A-2011-197450. Can be done.

≪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 and an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond and an ester bond. It is preferably a polymer containing 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 groups or methacrylic groups in the molecule and a compound that is decomposed by ultraviolet rays to generate active radicals. What is done can be mentioned.

≪Epoxy resin≫
The epoxy resin is not particularly limited, but can be roughly classified into an ultraviolet curable 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 the 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 compound having one or more epoxy groups in the molecule and a composition containing an acid anhydride. it can.

≪Commercial product≫
Examples of commercially available transparent resins include the following commercially available products. Examples of commercially available cyclic polyolefin resins include Arton manufactured by JSR Corporation, Zeonoa manufactured by Zeon Corporation, APEL manufactured by Mitsui Chemicals Co., Ltd., and TOPAS manufactured by Polyplastics Corporation. Examples of commercially available products of the polyether sulfone-based resin include Sumitomo Bakelite Co., Ltd. Sumitomo, Sumitomo Chemical Co., Ltd. Sumika Excel PES, and the like. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate-based resins include Pure Ace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate-based resins include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available fluorene polyester-based resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include Acryviewer manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available products of the silsesquioxane-based ultraviolet curable resin include Silplus manufactured by Nippon Steel Chemical Co., Ltd. Examples of commercially available polyetheretherketone resins include EXPEEK manufactured by Kurabo Industries Ltd. Examples of commercially available polyarylate resins include Unitika Ltd.'s Unifier. Examples of other commercially available products include HD films manufactured by Gunze Corporation.

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

≪Squarylium compound≫
The squarylium-based compound is not particularly limited, but is at least one selected from the group consisting of the squarylium-based compound represented by the following formula (I) and the squarylium-based compound represented by the following formula (II). Compound is 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):
Each plurality of R ^a is 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, a -L ¹ or -NR ^e R ^f group;
Each of the plurality of R ^bs independently represents a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L ¹ or -NR ^g R ^h group;
Each of the multiple Yas 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 ;
Are each R ^e and R ^f independently represent a hydrogen ^{atom, -L a, -L b, -L} c, a -L ^d or -L ^e;
R ^g and R ^h are independently hydrogen atoms, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C (O) R ⁱ group (R ⁱ is -L ^a , Represents -L ^b , -L ^c , -L ^d or -L ^e );
R ^j and R ^k independently represent the 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 halogen-substituted alkyl group having 1 to 12 carbon atoms 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 an alkoxy group having 1 to 9 carbon atoms 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 phosphoric acid group and an amino group.

Condition (β):
At least one of the two R ^a on one benzene ring, but bonded to each other and Y on the same benzene ring, form a heterocyclic ring-constituting atom number of 5 or 6 comprising at least one nitrogen atom;
The heterocycle may have a substituent, and R ^{b and R a} not involved in the formation of the heterocycle are independently synonymous with ^{R b} and R ^a of the condition (α), respectively.

Wherein L ^a ~L ^h, the total number of carbon atoms including the substituent is preferably respectively 50 or less, still more preferably a few 40 or less carbon atoms, and particularly preferably 30 or less carbon atoms. If the number of carbon atoms is more than this range, it may be difficult to synthesize the compound, 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 group of: vinyl group, 1-propenyl group, 2-propenyl group, butenyl group, 1,3-butadienyl group, 2-methyl-1-propenyl group, 2-pentenyl group, hexenyl group, octenyl group and other alkenyl groups. In addition, alkynyl groups such as ethynyl group, propynyl group, butynyl group, 2-methyl-1-propynyl group, hexynyl group and octynyl group can be mentioned.

Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms in L ^b and L include a trichloromethyl group, a trifluoromethyl group, a 1,1-dichloroethyl group, a pentachloroethyl group, a pentafluoroethyl group and a heptachloro. Propyl groups and heptafluoropropyl groups can be mentioned.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms in L ^c and L include a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; a norbornan group and an adamantan group. And other polycyclic alicyclic groups can be mentioned.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms in L ^d and L include a phenyl group, a tolyl group, a xsilyl group, a mesityl group, a cumenyl group, a 1-naphthyl group, a 2-naphthyl group and an anthracenyl group. Examples thereof include a phenanthryl group, an acenaphthyl group, a phenalenyl group, a tetrahydronaphthyl group, an indanyl group and a biphenylyl group.

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, acrydin, morpholine, phenazine and other heterocyclic groups.

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 a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a hexyloxycarbonyl group and an octyl. 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 The group is 2-cyclohexylethyl, more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.

The L ^b is preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, and more preferably a trichloro group. It is a methyl group, a pentachloroethyl group, a trifluoromethyl group, and a pentafluoroethyl group.

The 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. Is.

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

The ^Le is preferably a group composed of furan, thiophene, pyrrole, indole, indoline, indoline, benzofuran, benzothiophene and morpholin, and more preferably a group composed of furan, thiophene, pyrrole and morpholin.

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

The 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, and more preferably. It is a methoxycarbonyl group and an ethoxycarbonyl group.

Wherein L ^a ~L ^h further, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, have at least one atom or group selected from the group consisting of a phosphate group and an amino group You may. Examples of such are 4-sulfobutyl group, 4-cyanobutyl group, 5-carboxypentyl group, 5-aminopentyl group, 3-hydroxypropyl group, 2-phosphorylethyl group, 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 and 4-cyanobutoxycarbonyl group can be mentioned.

The R ^a in the condition (alpha), preferably a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, n- propyl group, an 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. ..

^{The R b under the} condition (α) 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. , Cyclohexyl group, phenyl group, hydroxyl group, amino group, dimethylamino group, cyano group, nitro group, acetylamino group, propionylamino group, N-methylacetylamino group, trifluoromethanoylamino group, pentafluoroetanoylamino 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, pentafluoroetanoylamino group, t-butanoylamino group, cyclohexinoylamino group.

The Ya is preferably an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-t-butylamino group, and 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 , Di-t-butylamino group.

At least one nitrogen atom formed by interconnecting at least one of two ^Ra on one benzene ring with Y on the same benzene ring under the condition (β) of the formula (I). Examples of the heterocycle having 5 or 6 constituent atoms include pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine, pyrazine and the like. Among these heterocycles, a heterocycle which constitutes the heterocycle and in which one atom next 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 represents a group, R ^d adjacent may form a ring which may have a substituent ^{linked; L a ~L e, L 1} , R e and R ^f, wherein the same meanings as defined ^{L a ~L e, L 1,} R e and R ^f in formula (I).

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

^{The R d} in the formula (II) is preferably hydrogen atom, chlorine atom, fluorine atom, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and 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, pentafluoroethyl group.

The 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. Is.
In the above formula (II), adjacent R ^ds may be connected to each other to form a ring. Examples of such a ring include a benzoindrenin ring, an α-naphthoimidazole ring, a β-naphthoimidazole ring, an α-naphthoxazole ring, a β-naphthoxazole ring, an α-naphthiazole ring, and a β-naphthiazole ring. , Α-Naft Serenasol Ring, β-Naft Serenasol Ring.

Compound (I) and compound (II) have the following formulas (I-2) and the following formula (II-2) in addition to the description methods such as the following formula (I-1) and the following formula (II-1). The structure can also be expressed by a description method that takes a resonance structure as described above. 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 method of describing the structure. Represents the same compound. Unless otherwise specified in the present invention, the structure of the squarylium-based compound shall be represented by the description methods such as the following formula (I-1) and the following formula (II-1).

Further, 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 it is easy to synthesize.

Specific examples of the compounds (I) and (II) include the compounds (a-1) shown in Tables 1 to 3 below, which have a basic skeleton represented by the following formulas (IA) to (IH). )-(A-36) can be mentioned.

The compounds (I) and (II) may be synthesized by a generally known method, and are described in, for example, Japanese Patent Application Laid-Open No. 1-2289960, Japanese Patent Application Laid-Open No. 2001-40234, Japanese Patent No. 3196383, and the like. It can be synthesized by referring to the described method and the like.

<< 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 two hydrogen atoms, two monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom, and there are a plurality of R's. _a , R _b , R _c and R _d are independently 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 a combination of at least one 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 the groups represented by the following formulas (A) to (H) to which is bonded. _{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 above formula (I).
L ¹ is synonymous with ^{L 1} defined in the above 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 represent carbon atoms, and a plurality of _{RA to RL} independently represent a hydrogen atom, a halogen atom, a hydroxyl group, a nitro group, an amino group, an amide group, and the like. Represents 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 , and the amino group, amide group, and imide. The group and the silyl group may have the substituent L defined in the above formula (I), and L ^{1 to} L ⁴ are synonymous with ^{L 1 to} L ⁴ defined in the above formula (III).

In the above _{Ra to} R _d and _{RA to RL} , the amino group which may have a substituent L includes an amino group, an ethylamino group, a dimethylamino group, a methylethylamino group, a dibutylamino group and a diisopropylamino. The group and the like can be mentioned.

In the above _{Ra to} R _d and _{RA to RL} , examples of the amide group which may have a substituent L include an amide group, a methylamide group, a dimethylamide group, a diethylamide group, a dipropylamide group and 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.

Wherein in R _a to R _d and R _A to R _L, as good imido group which may have a substituent L, an imido group, methylimide group, Echiruimido group, diethyl imido group, dipropyl imido group, diisopropyl imido group, Examples thereof include a dibutylimide group.

Examples of the _{silyl group which may have a substituent L} in R _{a to R d} and _{RA to} RL include a trimethylsilyl group, a tert-butyldimethylsilyl group, a triphenylsilyl group, a triethylsilyl group and the like. ..

In R _{a to} R _d and _{RA to RL} , -S-L ² includes a thiol group, a methyl sulfide group, an ethyl sulfide group, a propyl sulfide group, a butyl sulfide group, an isobutyl sulfide group and a sec-butyl sulfide group. , Tert-butyl sulfide group, phenyl sulfide group, 2,6-di-tert-butyl phenyl sulfide group, 2,6-diphenyl phenyl sulfide group, 4-cumyl phenyl sulfide group and the like.

In R _{a to} R _d and _{RA to RL} , -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-butyl phenyl disulfide group, 2,6-diphenyl phenyl disulfide group, 4-cumyl phenyl disulfide group and the like.

In R _{a to} R _d and _{RA to RL} , _{examples of -SO 2-} L ³ include a sulfo group, a mesyl group, an ethyl sulfonyl group, an n-butyl sulfonyl group, and a p-toluene sulfonyl group.

In the R _a to R _d and R _A to R _L, as the -N = N-L ^4, Mechiruazo group, phenylazo group, p- methylphenyl azo group, p- dimethyl aminophenyl azo group.

In the above M, examples of the monovalent metal atom include Li, Na, K, Rb, Cs and the like.
In the above 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, Examples include Pb.

In the above M, examples of the substituted metal atom containing a trivalent metal atom include Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga-I, and 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 the above M, examples of the substituted metal atom containing a tetravalent metal atom include 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 can be mentioned.

The M is a divalent transition metal belonging to the 4th to 5th periods of the Periodic Table Group 5 to 11, a trivalent or tetravalent metal halide, or a tetravalent metal oxide. Of these, Cu, Ni, Co and VO are particularly preferable because high visible light transmission and stability can be achieved.

A method for synthesizing the phthalocyanine compound by a cyclization reaction of a phthalonitrile derivative as shown in the following formula (V) is generally known, and the obtained phthalocyanine compounds are described in the following formulas (VI-1) to (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 exemplified for one phthalocyanine compound, but the other three isomers can be used in the same manner. Although these isomers can be separated and used as needed, the present invention deals with isomer mixtures collectively.

Specific examples of the compound (III) include (b-1) to (b-56) shown in Tables 4 to 7 below, which have a basic skeleton represented by the following formulas (III-A) to (III-J). ) And so on.

Compound (III) may be synthesized by a generally known method, for example, the method described in Japanese Patent No. 4081149 and "Parthalocyanine-Chemistry and Function-" (IPC, 1997). It can be referenced and synthesized.

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

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 independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, respectively. Iimide group, cyano group, silyl group, -L ¹ , -S-L 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 _{at least one combination of R h} and R _i is represented by the above formulas (A) to (H). Representing at least one group selected from the group consisting of groups, the amino group, amide group, imide group and silyl group may have the substituent L defined in the above formula (I).
L ¹ is synonymous with ^{L 1} defined in the above 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 independently hydrogen atom, halogen atom, hydroxyl group, carboxy group, nitro group, amino group, amide group, imide group, cyano group, silyl group, -L ¹ , -. S-L ² , -SS-L ² , -SO _2- L ³ , -N = N-L ⁴ (L ^{1 to} L ⁴ are synonymous with L ^{1 to} L ⁴ _{in R a to} R _i. ) Or an aromatic hydrocarbon group having 6 to 14 carbon atoms, which is formed by bonding Zs or Ys selected from two adjacent twos to each other; 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 heteroaromatic hydrocarbon group having 3 to 14 carbon atoms and containing at least one nitrogen atom, oxygen atom or sulfur atom. These aromatic hydrocarbon groups, alicyclic hydrocarbon groups and heteroaromatic hydrocarbon groups 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 to each other or Y to each other in Z _{a to} Z _c and Y _{a to Y d include the substituent L.} Examples thereof include compounds exemplified by aromatic hydrocarbon groups.

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

Examples of the heteroaromatic hydrocarbon group having 3 to 14 carbon atoms formed by bonding Z to each other or Y to each other in Z _{a to} Z _c and Y _{a to Y d include the substituent L.} Examples of the compound exemplified as the heterocyclic group in (excluding an alicyclic hydrocarbon group containing at least one nitrogen atom, oxygen atom or sulfur atom) can be mentioned.

In the above formulas (IV-1) to (IV-3), even if it has -S-L ² , -SS-L ² , -SO _2- L ³ , -N = N-L ⁴ , and the substituent L. Examples of a good amino group, amide group, imide group, and silyl group include groups similar to the group exemplified by the above formula (III).

X _a ^- is not particularly limited as long as it is a monovalent ^{anion, I -, Br -, PF} 6 -, N (SO 2 CF 3) 2 -, B (C 6 F 5) 4 -, nickel dithio alert Examples thereof include a system complex and a copper dithiolate system 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, and can be synthesized, for example, by the method described in JP-A-2009-108267.

The amount of the compound (A) added is appropriately selected according to the desired properties, but is preferably 0.01 to 20.0 parts by weight, more preferably 0, with respect to 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 base material 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 (antimon-doped tin oxide), and GZO (gallium-doped zinc oxide), and the first defined below. The first fine particles and the second fine particles are particularly preferable from the viewpoint of absorption-permeation characteristics.

First fine particles: General formula A _{1 / n} CuPO ₄ (However, in the formula, A is at least one selected from the group consisting of _{alkali metals, alkaline earth metals and NH 4, and n is A which is alkaline.} An oxide represented by 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, and if there are multiple Ms, they may be separate atoms, W is tungsten, O is oxygen, 0.001≤x / y≤1, 2.2. A metal oxide represented by ≦ 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. For the particle diameter of the near-infrared absorbing fine particles, a suspension in which the near-infrared absorbing fine particles are dispersed (hereinafter, also simply referred to as “dispersion liquid”) is a dynamic light scattering photometer (manufactured by Otsuka Electronics Co., Ltd., model number DLS-8000HL / HH). ) Was measured by a dynamic light scattering method (using a He-Ne laser, a cell chamber temperature of 25 ° C.). If the average value of the particle diameters 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 is reduced 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 is reduced. Therefore, if the particle diameter is in the above range, scattered light is very small and good visible light transmittance can be achieved, which is preferable. From the viewpoint of scattered light, it is preferable that the particle diameter is small, but considering the ease of industrial production and the production cost, 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, and 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 absorbing characteristics may not be obtained. The value tends to increase easily.

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

If necessary, a dispersant can be added to the dispersion medium of the near-infrared absorbing fine particles in order to improve the dispersed state of the near-infrared absorbing fine particles. Dispersants include those that have a modifying effect on the surface of near-infrared absorbing fine particles, such as surfactants, silane compounds, silicone resins, titanate-based coupling agents, aluminum-based coupling agents, and zirco-aluminate-based cups. Ring agents and the like are used.

Surfactants include anionic surfactants (special polycarboxylic acid type polymer surfactants, alkyl phosphate esters, etc.) and nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl phenol ether, polyoxy). Examples include ethylene carboxylic acid ester, sorbitan higher carboxylic acid ester, etc.), cationic surfactant (polyoxyethylene alkylamine carboxylic acid ester, alkylamine, alkylammonium salt, etc.), and amphoteric surfactant (higher alkylbetaine, etc.). ..

Examples of the silane compound include a silane coupling agent, chlorosilane, alkoxysilane, silazane and the like. 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 methyl phenyl silicone resin.
Examples of the titanate-based coupling agent include those having an asyloxy group, a phosphoroxy group, a pyrophosphoxy group, a sulfoxide group, an allyloxy group and the like.

Examples of the aluminum-based coupling agent include acetalkoxyaluminum diisopropyrate.
Examples of the zircoaluminate-based 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 depends on the type of the dispersant, but is preferably 0.5 to 10 parts by weight with respect to 100 parts by weight of the dispersion. When the amount of the dispersant is within the range, the dispersibility of the near-infrared absorbing fine particles is good, the transparency is not impaired, and the precipitation of the near-infrared absorbing fine particles over time is suppressed.

Commercially available near-infrared absorbing fine particles include P-2 (ITO) manufactured by Mitsubishi Materials Co., Ltd., Pastran (ITO) manufactured by Mitsui Kinzoku Co., Ltd., T-1 (ATO) manufactured by Mitsubishi Materials Co., Ltd., and Ishihara Sangyo ( SN-100P (ATO) manufactured by HakusuiTech Co., Ltd., Pazette GK (GZO) manufactured by HakusuiTech Co., Ltd., YMF-02A (second fine particle) 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 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, the "crystallite" means a unit crystal that can be regarded as a single crystal, and the "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 It means that it is identified by X-ray diffraction, and "substantially composed of A _{1 / n} CuPO ₄ crystallites" means that the crystallites sufficiently form 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). The X-ray diffraction is measured using an X-ray diffractometer on the powdered near-infrared absorbing fine particles.

The reasons for adopting alkali metals (Li, Na, K, Rb, Cs), alkaline earth metals (Ca, Sr, Ba), or NH ₄ as A in the formula (1) are as follows (i) to (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 ion (Li ⁺ : 0.090 nm, Na ⁺ : 0.116 nm, K ⁺ : 0.152 nm, Rb ⁺ : 0.166 nm, Cs ⁺ : 0.181 nm), alkaline earth metal. ions ^{(Ca 2+: 0.114nm, Sr 2+} : 0.132nm, Ba 2+: 0.149nm) and NH ₄ ⁺ to match the ionic radius of (0.166nm), can be maintained sufficiently crystalline structure ..

(Ii) an alkali metal ion, a metal ion and NH ₄ ⁺ is an alkaline earth, because it exists stably as monovalent or divalent cations in solution, in the process of manufacturing the near-infrared-absorbing particles, the precursor is produced At that time, cations are easily incorporated into the crystal structure.

(Iii) A _{cation having a strong coordination bond with PO 4} ^3- (for example, a transition metal ion) 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 incorporated into the skeleton composed of _{PO 4} ^3- and Cu ^{2+ and has a thermodynamically stable structure.}
The near-infrared absorbing fine particles can exhibit sufficient near-infrared absorbing 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 application.

Therefore, in the micro-IR spectrum, the near-infrared absorbing fine particles have ^{a peak absorption intensity of about 1000 cm -1} assigned to the phosphate group as a reference (100%), and ^{are attached to water of about 1600 cm -1} . The absorption intensity of the peak is preferably 8% or less, and ^{the absorption intensity of the peak around 3750 cm -1} attributed to the hydroxyl group is preferably 26% or less, and the absorption intensity of the peak around ^{1600 cm -1} attributed to water is preferably 26% or less. Is 5% or less, and ^{the absorption intensity of the peak around 3750 cm -1} attributable to the hydroxyl group is more preferably 15% or less. The micro IR spectrum is measured by using a Fourier transform infrared spectrophotometer for powdered near-infrared absorbing fine particles. Specifically, for example, using a Fourier transform infrared spectrophotometer Magna760 manufactured by Thermo Fisher Scientific, a piece of the first fine particles is placed on the diamond plate, flattened with a roller, and microscopic FT-IR method is performed. Measured by.

≪Second fine particle≫
By reducing the ratio of oxygen to tungsten in tungsten trioxide (WO ₃ ) to a specific composition range, free electrons are generated in the tungsten oxide, and good properties can be achieved as a near-infrared absorbing material. 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, and further, when the tungsten oxide is _{described as W y} O _z , 2.2 ≦ z / y ≦ 2.999. Is preferable. When this z / y value is 2.2 or more, it is possible to prevent the appearance of a crystal phase of _{WO 2 other than the intended one in the tungsten oxide, and to improve the chemical stability of the material.} Since it can be obtained, 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 are generated in the tungsten oxide, and the material becomes an efficient near-infrared absorbing material.

Further, in the tungsten oxide fine particles obtained by atomizing the tungsten oxide, the so-called "magnelli phase" having a composition ratio represented by 2.45 ≦ z / y ≦ 2.999 when _{the general formula W y} O _{z is used.} Is chemically stable and has good absorption characteristics in the near-infrared region, and is therefore preferable as a near-infrared absorbing material.

Further, 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 the absorption characteristics derived from the free electrons are exhibited in the near infrared region. It is preferable because it is effective as a near-infrared absorbing material having a wavelength of around 1000 nm. That is, the preferable composition of the second fine particles is the general formula MxWyOz (M is one or more of the above 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 the element M added will be described. If the value of x / y is larger than 0.001, a sufficient amount of free electrons are generated and the desired infrared shielding effect can be obtained. Then, as the amount of the element M added increases, the amount of free electrons supplied increases and the infrared shielding efficiency also increases, but the effect is saturated when the value of x / y is about 1. Further, when the value of x / y is smaller than 1, it is preferable because it is possible to avoid the formation of an impurity phase 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 is preferably one or more selected from. 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, It is more preferable that it is one or more kinds of elements selected from Ti, Nb, V, Mo, Ta, and Re, and from the viewpoint of improving the optical properties and weather resistance as a near-infrared absorbing material, the above-mentioned More preferably, the element M belongs to an alkali metal, an alkaline earth metal element, a transition metal element, a group 4 element, or a group 5 element.

Next, the value of z / y indicating the control of the amount of oxygen will be described. Regarding the value of z / y, the near-infrared absorbing material represented by _{M x} W _y O _z also has the same mechanism as the near-infrared absorbing material represented by _{W y} O _{z described above, and z / y.} Even when y = 3.0, 2.2 ≦ z / y ≦ 3.0 is preferable because free electrons are supplied depending on the amount of the element M added as described above.

<Other ingredients>
In addition to the above-mentioned components, the base material further contains additives such as near-ultraviolet absorbers, antioxidants, surfactants, fluorescent quenchers, and metal complex compounds, as long as the effects of the present invention are not impaired. May be good. These other components may be used alone or in combination of two or more.

Examples of the near-ultraviolet absorber include azomethine-based compounds, indole-based compounds, benzotriazole-based compounds, and triazine-based compounds.
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] Methyl, tris (2,6-di-t-butylphenyl) phosphite and the like can be mentioned.

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

The copolymer (S) copolymerizes an alkyl fluorinated group-containing monomer (M1), a polyoxyethylene chain-containing monomer (M2), and an ethylenically unsaturated monomer (M3) having a silicone chain. If necessary, a monomer other than the above (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-ester M-40G, M-90G, AM-90G manufactured by Shin Nakamura Chemical Industry Co., Ltd., and Blemmer PME-200 and PME manufactured by NOF CORPORATION. -400 and 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 the formula (M3'), R ⁴ represents an alkyl group or a phenyl group having 1 to 20 carbon atoms, and R ⁵ and R ⁶ independently represent an alkyl group, a phenyl group, or a phenyl group having 1 to 20 carbon atoms. , Represents the general formula (2), and m represents an integer from 0 to 200. In the formula (2), R ⁷ , R ⁸ and R ⁹ independently represent an alkyl group or a phenyl group having 1 to 20 carbon atoms, and n represents an integer of 0 to 200.

Further, as a specific example of the ethylenically unsaturated monomer (M3) having a silicone chain, a monomer represented by the following formula M-3-1 to 3 can be mentioned.

In formulas M-3-1 to 3, Me and Ph represent methyl and phenyl groups, respectively, and r, s and t independently represent integers from 0 to 200, respectively.
The method for producing the copolymer (S) is not limited, and is based on a known method, that is, a polymerization mechanism such as a radical polymerization method, a cationic polymerization method, or an anion polymerization method, and is based on a solution polymerization method, a massive polymerization method, and an emulsion. It can be produced by a polymerization method or the like, but the radical polymerization method is particularly simple and industrially preferable. In the radical polymerization method, a polymerization initiator such as a radical initiator can be used.

When the copolymer (S) is produced, the blending ratios of the monomers (M1), (M2) and (M3) with respect to the total 100% by mass of the monomers used as the raw materials of 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, 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 even more preferably 15,000 to 25,000.

Examples of the surfactant other than the above-mentioned 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 at at least one of the terminal, main chain and side chain is preferable.
Commercially available products of fluorine-based surfactants include, for example, BM-1000, BM-1100 (all manufactured by BMCHEMIE); Megafuck F142D, F172, F173, F183, F178, F191, F471, F476 (manufactured by Dainippon Ink and Chemicals Co., Ltd.); Florard FC-170C, -171, 430, -431 (manufactured by Sumitomo 3M Ltd.); Surflon S-112, same- 113, -131, -141, -145, -382, Surflon SC-101, -102, -103, -104, -105, -106 (all manufactured by Asahi Glass Co., Ltd.) ); Ftop E F301, 303, 352 (all manufactured by Shin-Akita Kasei Co., Ltd.); Futergent FT-100, -110, -140A, -150, -250, -251, Examples thereof include -300, -310, -400S, Futergent FTX-218, and -251 (all manufactured by Neos Co., Ltd.).

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 (all manufactured by Toray Dow Corning Silicone Co., Ltd.); TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 ( As mentioned above, GE Toshiba Silicone Co., Ltd.); Organosiloxane Polymer KP341 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.) can be mentioned.

When the resin layer is produced by the 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 a resin or the like when the resin layer is formed, or may be added when the resin is synthesized. The amount to be added is appropriately selected according to the desired characteristics, 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. It is a department.

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

≪Melting molding≫
Specific examples of the melt molding include a method of melt-molding pellets obtained by melt-kneading a resin and a compound (A), and melt-molding a resin composition containing a resin and the compound (A). Examples thereof include a method or a method of melt-molding pellets obtained by removing a solvent from a resin composition containing compound (A), a resin and a solvent. Examples of the melt molding method include injection molding, melt extrusion molding, blow molding and the like.

≪Cast molding≫
Cast molding includes a method of casting a resin composition containing a compound (A), a resin and a solvent on a glass substrate to remove the solvent, or a method of using the compound (A), a photocurable resin and / or a thermosetting resin. The curable composition containing the above can also be produced by casting on a glass substrate to remove the solvent and then curing by an appropriate method such as ultraviolet irradiation or heating.

≪Curing layer≫
Since the resin layer and the glass substrate have different chemical compositions and coefficient of linear thermal expansion, it is preferable to provide a cured layer between the resin layer and the glass substrate to ensure sufficient adhesion between them. The cured layer used in the present invention is not particularly limited as long as it is made of a material capable of ensuring adhesion between the resin layer and the glass substrate, and for example, (a) a structural unit derived from a (meth) acryloyl group-containing compound, ( It is preferable to have a structural unit derived from b) a carboxylic acid group-containing compound and (c) a structural unit derived from an epoxy group-containing compound because the adhesion between the resin layer and the glass substrate is high.

(A) Structural unit derived from the (meth) acryloyl group-containing compound The structural unit (a) is not particularly limited as long as it is a structural unit derived from the (meth) acryloyl group-containing compound. As the (meth) acryloyl group-containing compound, for example, a monofunctional, bifunctional or trifunctional or higher (meth) acrylic acid ester is preferable from the viewpoint of good polymerizable property. In the present invention, "(meth) acrylic" means "acrylic" 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, and (2-acryloyloxyethyl) (2-hydroxypropyl). Phthalates, (2-methacryloyloxyethyl) (2-hydroxypropyl) phthalates and ω-carboxypolycaprolactone monoacrylates can be mentioned.

Examples of these commercially available products include Aronix M-101, M-111, M-114, and M-5300 (all manufactured by Toagosei Co., Ltd.); Nippon Kayaku Co., Ltd.); Viscort 158, 2 311 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.) can be mentioned.

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, and 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 Diol dimethacrylate can be mentioned.

These commercially available products include, for example, Aronix M-210, M-240, and M-6200 (all manufactured by Toagosei Co., Ltd.); Above, Nippon Kayaku Co., Ltd.); Viscort 260, 312, 335HP (all manufactured by 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 trimethylolpropantriacrylate, trimethylolpropanetrimethacrylate, 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) Phosphate, tri (2-methacryloyloxyethyl) phosphate, as well as compounds having a linear alkylene group and an alicyclic structure and having two or more isocyanate groups, and one or more in the molecule. Examples thereof include a polyfunctional urethane acrylate-based compound obtained by reacting with a compound having a hydroxyl group and having 3, 4, or 5 (meth) acryloyloxy groups.

Commercially available products of trifunctional or higher functional (meth) acrylic acid esters include, for example, Aronix M-309, M-315, M-400, M-405, M-450, M-7100, and M-. 8030, M-8060, TO-1450 (all manufactured by Toagosei Co., Ltd.); KAYARADTMPTA, DPHA, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DPEA- 12 (above, manufactured by Nippon Kayaku Co., Ltd.); Viscort 295, 300, 360, GPT, 3PA, 400 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), and polyfunctional urethane acrylate compounds. Examples of commercially available products containing the above include New Frontier R-1150 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.); KAYARADDPHA-40H (manufactured by Nippon Kayaku Co., Ltd.).

These (meth) acryloyl group-containing compounds (a) can be used alone or in combination 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, anhydrides of dicarboxylic acids, and polymers having a carboxylic acid group.

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. Phthalic acid can be mentioned.

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

Further, the polymer having a carboxylic acid group is a compound containing a carboxylic acid group, for example, from one or more polymerizable compounds 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 preferably used.

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

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

Examples of the (meth) acrylic acid oxylanyl (cyclo) alkyl ester include (meth) acrylate glycidyl, (meth) acrylate 2-methylglycidyl, 4-hydroxybutyl (meth) acrylate glycidyl ether, and (meth) acrylate 3,4. -Epoxybutyl, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate and 3,4-epoxycyclohexylmethyl (meth) acrylate can be mentioned.

Examples of α-alkylacrylic acid oxylanyl (cyclo) alkyl esters include α-ethylacrylic acid glycidyl, α-n-propylacrylic acid glycidyl, α-n-butylacrylic acid glycidyl, and α-ethylacrylic acid 6,7-epoxyheptyl. And α-ethylacrylic acid 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 Methyloxetane and 3-ethyl-3- (meth) acryloyloxymethyloxetane can be mentioned.

Of these, glycidyl methacrylate, 2-methylglycidyl methacrylate, 3,4-epoxycyclohexyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3-methylloyloxymethyl-3-ethyloxetane, 3-methyl- 3-Methacrylicoxymethyloxetane or 3-ethyl-3-methyloxetane is preferable from the viewpoint of polymerizable property.

(Arbitrary ingredient)
Optional components such as an acid generator, an adhesion aid, 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. The amount of these additions is appropriately selected according to the desired properties, but is usually used with respect to a total of 100 parts by weight of the (meth) acryloyl group-containing compound, the carboxylic acid group-containing compound, and the epoxy group-containing compound. It is preferably 0.01 to 15.0 parts by weight, preferably 0.05 to 10.0 parts by weight.

The polymerization initiator is a component that produces an active species capable of initiating polymerization of a monomer component 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 of these include ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl] -1- (O-acetyloxime), 1- [9-ethyl-. 6-Benzoyl-9. H. -Carbazole-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazole-3-yl] -ethane-1-one oxime-O-benzoate, ethane-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], etanone-1- [9- Ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), Etanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl) } -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one, 2-dimethylamino-2- (4) -Methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -butane-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 1 -Phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- Examples thereof include (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylbenzophenone, and 1-hydroxycyclohexylphenyl ketone. These polymerization initiators can be used alone or in admixture of two or more.

The cured layer is a pellet obtained by melt-kneading the composition (I) containing, for example, 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 the pellets obtained by removing the solvent from the liquid composition containing the composition (I) and the solvent, or a method of casting (casting) the above-mentioned liquid composition. Can be manufactured by Examples of the melt molding method and the cast molding method include the same methods as described above.

The blending 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), and the blending of the carboxylic acid group-containing compound. The amount is preferably 5 to 30 parts by weight, more preferably 10 to 25 parts by weight, and the blending 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 to be blended 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. It is 0 parts by weight.

The thickness of the cured layer is not particularly limited as long as the effect of the present invention is not impaired, but is preferably 0. It is 1 to 5.0 μm, more preferably 0.2 to 3.0 μm.
[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 laminated. 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 1.7 to 2.5 is usually selected. Examples of such a material include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide and the like as main components, and titanium oxide, tin oxide and /. Alternatively, those containing a small amount of cerium oxide or the like (for example, 0 to 10% by weight based on the main component) can be 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 1.2 to 1.6 is usually selected. Examples of such materials include silica, alumina, lanthanum fluoride, magnesium fluoride and sodium hexafluoride.

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 laminated directly on a base material by a CVD method, a sputtering method, a vacuum vapor deposition method, an ion-assisted vapor deposition method, an ion plating method, or the like. A multilayer film can be formed.

The vapor deposition is usually carried out in a vapor deposition temperature range of 100 ° C. or higher and 10 ° C. or higher lower than the Tg of the transparent resin layer, preferably 100 ° C. or higher and 20 ° C. or higher lower than the Tg of the transparent resin layer. .. It is preferable to perform thin-film deposition under such temperature conditions because a dielectric multilayer film having excellent adhesion can be formed without excessive heating of the base material.

In the present invention, by using a glass substrate as a base material, a dielectric multilayer film can be formed by thin-film 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 even more preferably 200 ° C. or higher. When a dielectric multilayer film is formed by thin-film deposition at such a high temperature, the adhesion of the dielectric multilayer film is improved and the strength of the dielectric multilayer film, which is a vapor-deposited film, is increased. The heat resistance and scratch resistance of the laminated body used are also improved.

The thickness of each of the high refractive index material layer and the low refractive index material layer is 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 in this range, the optical film thickness calculated by λ / 4 as the product (n × d) of the refractive index (n) and the film thickness (d), the high refractive index material layer, and the low refraction The thickness of each layer of the index material layer becomes almost the same value, and there is a tendency that the blocking / transmitting of a specific wavelength can be easily controlled due to the relationship between the optical characteristics of reflection / refraction.

The total number of layers of the high-refractive index material layer and the low-refractive index material layer in the dielectric multilayer film is preferably 16 to 70 layers as a whole, and more preferably 20 to 60 layers. When 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 warpage of the optical filter and cracks of the dielectric multilayer film are reduced. can do.

In one embodiment of the present invention, the thickness of each layer of the high refractive index material layer and the low refractive index material layer, the high refractive index material layer and the low refractive index material layer constituting the high refractive index material layer and the low refractive index material layer according to the absorption characteristics of the compound (A). By appropriately 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 near-infrared from an oblique direction. It is possible to reduce the refractive index when the light is incident.

Here, in order to optimize the conditions, for example, when measured from the vertical direction of the optical filter (or the base material) using optical thin film design software (for example, Essential Macleod, manufactured by ThinFilmCenter), 30 with respect to the vertical direction. The parameters may be set so that the visible light transmittance and the light ray cutting effect in the near infrared region can be compatible with each other when measured from an angle of degrees and when measured from an angle of 60 degrees with respect to the vertical direction. In particular, in order to be suitably used 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, and in order to achieve such characteristics. When designing a dielectric multilayer film, it is preferable to change the incident angle for optimizing 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 optimizes the optical characteristics at an incident angle of 0 degrees).

In the case of the above software, for example, when designing a dielectric multilayer film formed on only one side of a base material, the target transmittance when measured from an angle of 30 degrees with respect to the vertical direction having a wavelength of 400 to 750 nm is 100%. The target transmittance was measured from a vertical direction of wavelength 755 to 790 nm, the target transmittance was 100%, the value of target transmittance was 0.8, and the target transmittance was measured from an angle of 30 degrees with respect to the vertical direction of wavelength 800 to 1000 nm. The target transmittance in the case is 0%, the target transmittance value is 0.5, the target transmittance when measured from an angle of 0 degrees with respect to the vertical direction of a wavelength of 1005 to 1300 nm is 0%, and the target transmittance value is 0.7. There is a parameter setting method such as. For these parameters, the wavelength range can be further divided according to various characteristics of the base material (i) to optimize the design, and the value of the light incident angle and the target distance can be changed. In particular, if the design of at least a part of the wavelength region in the wavelength region of 400 to 700 nm is optimized for light rays from an oblique direction, the visible transmittance due to ripples or the like can be obtained even when the incident angle is very large such as 60 degrees. It is preferable because the decrease can be reduced.

[Other functional membranes]
The optical filter according to the embodiment of the present invention has a surface between the base material and the dielectric multilayer film on the side opposite to the surface on which the dielectric multilayer film is provided, as long as the effect of the present invention is not impaired. Or, on the surface of the dielectric multilayer film opposite to the surface on which the substrate is provided, for the purpose of improving the surface hardness of the substrate or the dielectric multilayer film, improving chemical resistance, preventing static electricity, and erasing scratches. A functional film such as an antireflection film, a hard coat film or an antistatic film can be appropriately provided.

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

The 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 thereof include a method of molding or cast molding.

It can also be produced by applying a curable composition containing a coating agent or the like on a base material or a dielectric multilayer film with a bar coater or the like, and then curing the composition by irradiating with ultraviolet rays or the like.

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

In addition, the curable composition may contain a polymerization initiator. As the polymerization initiator, a known photopolymerization initiator or thermal polymerization initiator can be used, and the photopolymerization initiator and the thermal polymerization initiator may be used in combination. The polymerization initiator may be used alone or in combination of two or more.

The proportion of the polymerization initiator in the curable composition is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, and further, when the total amount of the curable composition is 100% by weight. It is preferably 1 to 5% by 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 antireflection film, a hard coat film or an antistatic film which has excellent curing characteristics and handleability of the curable composition and has a desired hardness. it can.

Further, an organic solvent may be added to the curable composition as a solvent, and known organic solvents can be used. Specific examples of the organic solvent 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 and 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 thereof 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, for the purpose of improving 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, a corona is formed on 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 the embodiment of the present invention has excellent visible transmittance and near-infrared ray cutting ability even when the incident angle is large, and is also excellent in heat resistance, so that it can be applied to a soldering reflow process. Therefore, it is useful for a solid-state image sensor and various ambient light sensors such as an illuminance sensor and a color correction sensor. In particular, it is useful for correcting the luminous efficiency of solid-state image sensors such as CCD and CMOS image sensors such as digital still cameras and mobile phone cameras, and is used for applications that require high-temperature adhesion when incorporating products and use in high-temperature regions. Can also be preferably used. It is also useful for ambient light sensors installed in digital still cameras, smartphones, tablet terminals, mobile phones, wearable devices, automobiles, televisions, game consoles, and the like. Further, it is also useful as a heat ray cut filter or the like attached to a window glass plate or the like of an automobile or a building.

[Ambient light sensor]
An optical filter according to an 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 that can detect the ambient brightness and color tone (such as strong red color in the evening time zone) such as an illuminance sensor and a color correction sensor. For example, information detected by the ambient light sensor. It is possible to control the illuminance and color tone of the display mounted on the device.

FIG. 3 shows an example of an ambient light sensor 200a that detects the brightness of the surroundings. The ambient light sensor 200a includes an optical filter 100 and a photoelectric conversion element 202. When light is incident on the light receiving portion, the photoelectric conversion element 202 generates a current or a voltage due to the photovoltaic effect. The optical filter 100 is provided on the light receiving surface side of the photoelectric conversion element 202. By the optical filter 100, the light incident on the light receiving surface of the photoelectric conversion element 202 becomes the light in the visible light band, and the 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 translucent layer may be interposed between the optical filter 100 and the photoelectric conversion element 202. For example, a translucent resin layer may be provided as a sealing material between the optical filter 100 and the photoelectric conversion element 202.

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

In addition to the silicon semiconductor, the photoelectric conversion layer 208 may use a germanium semiconductor or a silicon-germanium 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, when the photoelectric conversion layer 208 is formed of a silicon semiconductor, the band gap energy of the silicon semiconductor is 1.12 eV, so that it can absorb light having a wavelength of 700 to 1100 nm, which is near infrared light in principle. 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 region. The photoelectric conversion element 202 is preferably surrounded by a light-shielding housing 204 so that the light transmitted through the optical filter 100 is selectively irradiated. By including the optical filter 100, the ambient light sensor 200a can block near-infrared light and detect ambient light. As a result, it is possible to solve the problem that the ambient light sensor 200a malfunctions in response to near-infrared light.

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

The photoelectric conversion elements 202a to 202c have sensitivity over a wide range from the visible light wavelength region to the near infrared wavelength region. Therefore, by providing 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 the near-infrared light and prevents the sensor from malfunctioning. , Light corresponding to each color can be detected. The ambient light sensor 200b is provided with an optical filter 100 that blocks light in the near infrared region and color filters 212a to 212c, so that not only can ambient light be separated into light in a plurality of wavelength bands and detected, but also ambient light can be detected. It can be applied even in a dark environment where conventional color sensors cannot detect accurately due to the influence of near infrared rays.

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

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

Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The "part" means a "part by weight" unless otherwise specified. The method for measuring each physical property value and the method for evaluating 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 and the like.

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

(B) Using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: THF), the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of standard polystyrene were measured.

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

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

Here, in the transmittance measured from the vertical direction of the optical filter, as shown in FIG. 6A, the light 1 transmitted perpendicularly to the optical filter 2 is measured by the spectrophotometer 3, and the optical filter is vertical. As for the transmittance when measured from an angle of 30 degrees with respect to the direction, as shown in FIG. 6B, the light 1'transmitted at an angle of 30 degrees with respect to the vertical direction of the optical filter 2 is transmitted by the spectrophotometer 3. When measured and measured from an angle of 60 degrees with respect to the vertical direction of the optical filter, the transmittance of the light 1 transmitted at an angle of 60 degrees with respect to the vertical direction of the optical filter 2 as shown in FIG. 6 (C). '' Was measured with a spectrophotometer 3.

<Crack evaluation>
Visually, those without cracks in the dielectric multilayer film layer (deposited layer) were evaluated as "○", and those with cracks in the dielectric multilayer film layer (deposited layer) were evaluated as "x".

<Reflow resistance evaluation>
The optical filter is fixed on a glass epoxy substrate SL-EP (manufactured by Nitto Shinko Co., Ltd.) with a thickness of 1 mm 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 to reach the maximum temperature of about 270 ° C was defined as the reflow resistance. The case where no cracks occurred was evaluated as "○", and the case where cracks occurred and it was difficult to actually use the product was evaluated as "x".

The near-infrared absorbing dye used in the following examples was synthesized by a generally known method. As a general synthesis method, for example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Application Laid-Open No. 60-228448, Japanese Patent Application Laid-Open No. 1-146846, Japanese Patent Application Laid-Open No. 1-2289960, Japanese Patent No. 4081149, Japanese Patent Application Laid-Open No. 63-124054, "Futarusinin-Chemistry and Function" (IPC, 1997), Japanese Patent Application Laid-Open No. 2007-169315, Japanese Patent Application Laid-Open No. Examples thereof include the methods described in Japanese Patent Application Laid-Open No. -108267, Japanese Patent Application Laid-Open No. 2010-241873, Japanese Patent No. 3699464, and Japanese Patent No. 4740631.

<Plastic synthesis example 1>
35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene, and 41.46 g of potassium carbonate in a 3 L four-necked flask. 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. Then, after nitrogen substitution in the flask, the obtained solution was reacted at 140 ° C. for 3 hours, and the water produced was removed from the Dean-Stark apparatus at any time. When the formation of water was no longer observed, the temperature was gradually raised to 160 ° C., and the reaction was carried out at the same 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 filter medium 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>
8-Methyl-8-methoxycarbonyltetracyclo [4.4.0.12,5.17,10] dodeca-3-ene (hereinafter, also referred to as "DNM") 100 parts represented by the following formula (8). , 18 parts of 1-hexene (molecular weight modifier) and 300 parts of toluene (solvent for ring-opening polymerization reaction) were placed in a reaction vessel substituted with nitrogen, and this solution was heated to 80 ° C. Next, 0.2 parts of a toluene solution of triethylaluminum (0.6 mol / liter) and a toluene solution of methanol-modified tungsten hexachloride (concentration 0.025 mol / liter) were added to the solution in the reaction vessel as a polymerization catalyst. Nine parts were added, and the 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 parts of _{RuHCl (CO) [P (C 6} H ₅ ) ₃ ] _{3 was added to the ring-opening polymer solution.} Then, under the conditions of a hydrogen gas pressure of 100 kg / cm ² and a reaction temperature of 165 ° C., the hydrogenation reaction was carried out by heating and stirring for 3 hours. After cooling the obtained reaction solution (hydrogenated polymer solution), hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the coagulated product, which was 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 substrate containing a transparent glass substrate was produced under the following procedure and conditions.

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

<Preparation of curable composition solution (1)>
Isocyanurate ethylene oxide-modified triacrylate (trade name: Aronix M-315, manufactured by Toa Synthetic Chemical Co., Ltd.) 30 parts by weight, 1,9-nonanediol diacrylate 20 parts by weight, methacrylic acid 20 parts by weight, glycidyl methacrylate 30 By weight, 3-glycidoxypropyltrimethoxysilane, 5 parts by weight, 1-hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by Ciba Specialty Chemical Co., Ltd.), 5 parts by weight, and Sun Aid SI-110 main agent (Sanshin Kagaku) 1 part by weight of Kogyo Co., Ltd. is mixed, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 50 wt%, filtered with a millipore filter having a pore size of 0.2 μm, and a curable composition solution (made by Kogyo Co., Ltd.). 1) was prepared.

<Preparation of base material>
Subsequently, the curable composition solution (1) was applied to one side of a transparent glass substrate "OA-10G" manufactured by Nippon Electric Glass Co., Ltd., which was cut into a size of 60 mm in length and 60 mm in width, by spin coating, and then hot. The solvent was volatilized and removed by heating on a plate at 80 ° C. for 2 minutes to form a cured layer. At this time, the coating conditions of the spin coater were adjusted so that the film thickness of the cured layer was about 0.8 μm. Next, a resin solution (D-1) was applied onto the cured layer using a spin coater under conditions such that the long wavelength side half value was 646 nm, and the solvent was heated on a hot plate at 80 ° C. for 5 minutes. It was volatilized and removed to form a transparent resin layer. Next, exposure was performed from the glass surface side 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 substrate having a length of 60 mm and a width of 60 mm. ..

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

_{The dielectric multilayer film (I) is formed by alternately laminating silica (SiO 2} ) layers and titanium (TiO ₂ ) layers at a vapor deposition temperature of 200 ° C. (26 layers in total). _{The dielectric multilayer film (II) is formed by alternately laminating silica (SiO 2} ) layers and titanium (TiO ₂ ) layers at a vapor deposition temperature of 200 ° C. (20 layers in total). In both the dielectric multilayer films (I) and (II), the silica layer and the titania layer are formed in the order of the titania layer, the silica layer, the titania layer, ..., the silica layer, the titania layer, and the silica layer from the substrate side. The layers were alternately laminated, and 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 number of layers of each layer, the wavelength-dependent characteristics of the refractive index of the substrate and the absorption characteristics of the applied compound (A) so as to achieve the antireflection effect in the visible region and the selective transmission / reflection performance in the near infrared region. Optimization was performed using optical thin film design software (Essential Macleod, manufactured by Thin Film Center). When optimizing, in this embodiment, the input parameters (Target values) to the software are as shown in Table 9 below.

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

The spectral transmittance was measured from angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the obtained optical filter, and the optical characteristics in each wavelength region were evaluated. The results are shown in FIG. 7 and 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, and the sample was allowed to stand in an atmosphere of 25 ° C. and 55% RH for 2 days. 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 FIGS. 8 and 13.

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

An optical filter having a thickness of 0.160 mm was obtained under the same procedure and conditions as in Example 1 except that the obtained base material was used. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material. The spectral transmittance was measured from angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the obtained optical filter, and the 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, and the sample was allowed 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 FIGS. 9 and 13.

[Example 3]
In Example 2, the compound (D-3) was prepared under 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 under the same procedure and conditions as in Example 1 except that the obtained base material was used. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material. The spectral transmittance was measured from angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the obtained optical filter, and the 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, then a sample was taken out, 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 FIGS. 10 and 13.

[Example 4]
In Example 2, except that the 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 compound (A) was obtained under the same procedure and conditions as in Example 2.

Subsequently, an optical filter having a thickness of 0.220 mm was obtained under the same procedure and conditions as in Example 1 except that the obtained base material was used. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material. The spectral transmittance was measured from angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the obtained optical filter, and the 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, then a sample was taken out, 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 FIGS. 11 and 13.

[Example 5]
<Preparation of 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), isocyanurate ethylene oxide-modified triacrylate (trade name: Aronix M-315, Toa Synthetic) (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- A mixture of 5 parts by weight of hydroxycyclohexylbenzophenone (trade name: IRGACURE184, manufactured by Ciba Specialty Chemical Co., Ltd.) and 1 part by weight of Sun Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) has a solid content concentration of 50 wt. A curable composition solution (2) containing near-infrared absorbing fine particles was prepared by dissolving in propylene glycol monomethyl ether acetate so as to be%.

<Manufacturing of base material and optical filter>
Except that 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 substrate 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 under the same procedure and conditions as in Example 1 except that the obtained base material was used. The design of the dielectric multilayer film was carried out using the same design parameters as in Example 1 in consideration of the wavelength dependence of the refractive index of the base material. The spectral transmittance was measured from angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the obtained optical filter, and the 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, then a sample was taken out, 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 FIGS. 12 and 13.

[Comparative Example 1]
A solution having a resin concentration of 20% by weight was prepared by adding 100 parts by weight of the resin B obtained in Resin Synthesis Example 2, 0.04 parts of the above compound (a-1) as compound (A), and dichloromethane to a container. 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 under reduced pressure at 100 ° C. for 8 hours to obtain a substrate made 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 under 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 base material and an optical filter were produced in the same manner as in Example 1 except that the vapor deposition temperatures of the dielectric multilayer films (I) and (II) were changed to 120 ° C. in Example 1. The spectral transmittance was measured from angles of 30 ° and 60 ° with respect to the vertical direction and the vertical direction of the obtained optical filter, and the 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, and the sample was allowed to stand in an atmosphere of 25 ° C. and 55% RH for 2 days. 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 FIGS. 13 and 13. The optical filter obtained in Comparative Example 2 cracked after the storage and did not show reflow resistance.

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

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

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

The optical characteristics of the obtained optical filter are shown in FIGS. 14 and 13. The average value of the optical densities of the optical filters obtained in Comparative Example 3 at wavelengths of 800 to 1200 nm was 0.6, which did not show good near-infrared light cut characteristics.

The composition of the base material, various compounds, etc. applied in Examples and Comparative Examples are as follows.
<Form of base material>
Form (1): A curable composition layer and a transparent resin layer containing the compound (A) are provided on one side of a transparent glass substrate. Form (2): A curable composition layer on one side of a near-infrared absorbing glass substrate. And a form having a transparent resin layer containing the compound (A) (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 (3). 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 pigment>
≪Compound (A) ≫
Compound (a-1): The above compound (a-1) (absorption maximum wavelength in dichloromethane, 698 nm).
Compound (a-2): The above compound (a-2) (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): A solution consisting of 100 parts by weight of resin A, 1.0 part by weight of compound (a-1) and dichloromethane (resin concentration 10% by weight).
Resin solution (D-2): A 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): A 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 Industry Co., Ltd.)

<Curable composition solution>
Curable composition solution (1): Isocyanic acid ethylene oxide-modified triacrylate (trade name: Aronix M-315, manufactured by Toa Synthetic Chemical Co., Ltd.) 30 parts by weight, 1,9-nonanediol diacrylate 20 parts by weight, methacrylic acid 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: IRGACURE184, manufactured by Ciba Specialty Chemical Co., Ltd.) and 1 part by weight of Sun Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) is mixed, dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 50 wt%, and then with a millipore filter having 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), isocyanurate ethylene oxide-modified triacrylate (commodity) Name: Aronix M-315, manufactured by Toa Synthetic 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 Chemical Co., Ltd.) and 1 part by weight of Sun Aid SI-110 main agent (manufactured by Sanshin Chemical Industry Co., Ltd.) It is a solution that is mixed and dissolved in propylene glycol monomethyl ether acetate so that the solid content concentration becomes 50 wt%.

1,1', 1'' ... Light 2 ... Optical filter 3 ... Spectral photometric meter 100 ... Optical filter 102 ... Base material 104 ... Dielectric multilayer film 106 ... Reflection Preventive 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 separation insulating layer 216 ・ ・ ・ Passivity film 300 ・ ・ ・ Electronic device 302 ・ ・ ・ Housing 304 ・ ・ ・ Display panel 306 ・ ・ ・ Microphone 308 ・ ・ ・ Speaker unit 310 ・ ・ ・ Surface panel

Claims (11)

It has a base material containing 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 base material. , A method for manufacturing an optical filter that satisfies the following requirements (a), (b) and (d).
The glass transition temperature of the resin constituting the resin layer is 140 to 380 ° C.
A method for manufacturing an optical filter, which comprises a step of forming the dielectric multilayer film by vapor deposition at a temperature of 180 ° C. or higher.
(A) When the spectral transmittance of the optical filter is measured from the vertical direction of the optical filter, the average value Ta _-0 of the transmittance in the wavelength range of 400 to 650 nm is 45% or more and 90% or less;
(B) When the optical density (OD value) of the optical filter 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;
(D) the spectral transmittance of the optical filter when measured from the vertical direction of the optical filter, the average value of the transmittance at a wavelength 580~650nm and T _Ra, the average value of the transmittance at a wavelength 500 to 580 nm T _Ga When the average value of the transmittance at a wavelength of 420 to 500 nm is T _Ba , both T _Ga / T _Ra and T _Ba / T _Ra are 0.9 to 1.6. The method for manufacturing an optical filter according to claim 1, wherein the optical filter further satisfies the following requirement (e).
_{(E) The average value of the transmittance Ta-30} in the wavelength range of 400 to 650 nm when the spectral transmittance of the optical filter is measured from an oblique direction of 30 degrees with respect to the vertical direction of the optical filter, and the optical filter. When the transmittance of the optical filter is measured from an oblique direction of 60 degrees with respect to the vertical direction of the optical filter, the average value Ta _-60 of the transmittance in the wavelength range of 400 to 650 nm is 45% or more and 90% or less. is there. The method for producing an optical filter according to any one of claims 1 to 2, wherein the compound (A) is at least one compound selected from the group consisting of a squarylium-based compound and a phthalocyanine-based compound. .. 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, or a polysulphon resin. , Polyether sulfone resin, polyparaphenylene resin, polyamideimide resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, silsesquioxane type ultraviolet rays Curable resin, maleimide resin, alicyclic epoxy thermocurable resin, polyether ether ketone resin, polyarylate resin, allyl ester curable resin, acrylic ultraviolet curable resin, vinyl ultraviolet curable resin, and The method for producing an optical filter according to any one of claims 1 to 3, wherein the resin is at least one selected from the group consisting of a resin containing silica as a main component formed by the solgel method. The method for manufacturing an optical filter according to any one of claims 1 to 4, wherein a dielectric multilayer film is provided on both sides of the base material. The method for producing an optical filter according to any one of claims 1 to 5, wherein the base material has a layer containing near-infrared absorbing fine particles. The method for producing an optical filter according to any one of claims 1 to 6, wherein the glass substrate is a fluorophosphate-based glass or a phosphate-based glass containing a copper component. A method for manufacturing a solid-state image sensor, which comprises a step of providing an optical filter obtained by the manufacturing method according to any one of claims 1 to 7. A method for manufacturing a camera module, which comprises a step of providing an optical filter obtained by the manufacturing method according to any one of claims 1 to 7. A method for manufacturing an ambient light sensor, which comprises a step of providing an optical filter obtained by the manufacturing method according to any one of claims 1 to 7. A method for manufacturing an electronic device, which comprises a step of providing an ambient light sensor obtained by the manufacturing method according to claim 10.

Images