JP2014052604A - Light selective transmission filter, base material therefor, and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a light selective transmission filter which has a superior light selective transmission property, is scratch resistant, exhibits no warpage, waving, deformation, or the like, and offers extremely good handleability and superior practicability, and to provide a manufacturing method therefor, a base material used therefor, and a solid-state image sensor having such light selective transmission filter.SOLUTION: A light selective transmission filter comprises a base material and a reflective film formed at least on one surface of the base material, where the base material contains one or more dyes. Surface hardness of the light selective transmission filter shall be between HB and 4H.

Description

The present invention relates to a light selective transmission filter, a base material, and an application thereof. More specifically, in addition to optical members and optical device members, a light selective transmission filter useful for applications such as display device parts, mechanical parts, electrical / electronic parts, and a substrate used therefor, a method for producing a light selective transmission filter, and The present invention relates to a solid-state imaging device having a light selective transmission filter.

A light selective transmission filter is a filter that selectively reduces the transmittance of light of a specific wavelength. Depending on the wavelength of light to be reduced, an infrared (IR) cut filter, an ultraviolet cut filter, an infrared / ultraviolet cut filter, etc. Is mentioned. Such a light selective transmission filter is useful as an optical filter used for display device parts, mechanical parts, electrical / electronic parts, etc., in addition to optical members and optical device members. For example, as one of the representative optical members, there is a solid-state imaging device (also referred to as a camera module) mounted on an optical imaging device such as a mobile phone camera, a digital camera, or a digital video camera. In general, optical noise that hinders image processing or the like is reduced by providing an infrared (IR) cut filter that blocks infrared rays (particularly, near-infrared region having a wavelength> 780 nm) that becomes optical noises.

In recent years, in the field of optical members typified by such solid-state imaging devices, digital camera modules are being mounted on mobile phones, etc., and miniaturization is progressing. The demand for is increasing. The light selective transmission filter mainly uses an inorganic multilayer film formed by depositing metal or the like on a base material, and the refractive index of each wavelength is controlled. Conventionally, a glass plate has been used as the base material. However, in response to the growing demand for thinning, technologies based on resins are being studied.

As a light selective transmission filter using a resin as a base material, for example, Patent Document 1 discloses a light selective transmission filter having functional films such as inorganic films on both surfaces of a reflow resistant resin film. It is extremely useful as a particularly excellent light selective transmission filter. Patent Document 1 also describes that it is preferable to form the functional film at a temperature of less than 120 ° C. because damage to the substrate can be reduced. Patent Document 2 discloses a near-infrared cut filter composed of a transparent base material made of a resin film, an optical multilayer film, and a resin absorption film containing a dye or a pigment. A method of forming an optical multilayer film by alternately depositing titanium dioxide and silicon dioxide on a PET film substrate, and then coating the resin with a dye and binder resin dissolved thereon to form a resin absorption film Is described. Furthermore, Patent Document 3 discloses a near-infrared cut filter having a norbornene-based resin substrate containing a near-infrared absorber and a near-infrared reflective film that is a dielectric multilayer film. In the examples, norbornene-based transparent filters are disclosed. A technique is described in which a multilayer deposited film composed of a silica layer and a titania layer is formed on one surface of a substrate obtained by using a resin and a near infrared absorber at a deposition temperature of 150 ° C.

JP 2009-157273 A JP 2006-304189 A JP 2005-338395 A

As described above, various light selective transmission filters having a reflective film have been studied. In general, a light selective transmission filter having a reflective film is used as a reflection type filter having a function of reflecting light. However, an incident angle dependency (also referred to as a viewing angle dependency) in which a reflection characteristic changes depending on an incident angle of light. Recently, a reflection absorption filter having a function of absorbing light has been proposed as described in Patent Documents 2 and 3 and the like. However, the conventional reflection-absorbing filter has a problem in handleability because the surface hardness is not sufficient. In particular, the surface is easily damaged when mounted on a solid-state imaging device or the like, and has a problem that it cannot withstand practical use.

The present invention has been made in view of the above-described present situation, has excellent light selective transparency, is hardly damaged, has no warping, undulation, deformation, etc., has extremely good handling properties, and has excellent practicality. It is an object of the present invention to provide a selective transmission filter and a manufacturing method thereof, a base material used for the selective light transmission filter, and a solid-state imaging device having the selective light transmission filter.

The inventors of the present invention have studied various light selective transmission filters having a reflective film. If the substrate has a base material containing a pigment and a reflective film, the reflection absorption type having both a light absorption function and a light reflection function. As a filter, attention has been paid to the fact that the dependency on the incident angle is sufficiently reduced and that the filter has sharp transmission and absorption characteristics. The inventors have found that when the surface hardness (pencil hardness) of the light selective transmission filter is within a predetermined range, the light selective transmission filter is not easily damaged, and does not warp, swell, deform, or the like, and is extremely easy to handle. Since such a light selective transmission filter can sufficiently withstand incorporation by a machine such as a pickup, it is excellent in practicality. In addition, the reflection absorption type filter whose surface hardness is in the range specified in the present invention is new and unprecedented.

The present inventors also paid attention to the fact that when obtaining a light selective transmission filter, the temperature at the time of reflection film formation on the substrate containing the dye affects the surface hardness and shape of the obtained light selective transmission filter, In particular, when performing a high temperature vapor deposition process at 160 ° C. or higher, a light selective transmission filter using a base material that has been sufficiently suppressed to generate warpage, undulation, deformation, etc. without impairing the absorption function. Then, it was found that a light selective transmission filter having a high level of surface hardness that could not be achieved could be obtained. Conventionally, such high-temperature vapor deposition has not been performed on a substrate containing a dye. This is because, although it is a base material that does not contain a dye, it has been reported by Patent Document 1 that undulation occurs when the deposition temperature on the base material is 120 ° C. or higher. This is because there were concerns about warping, deformation, and the like. Therefore, it is considered that only low temperature deposition at 150 ° C. or lower has been performed as shown in the example of Patent Document 3. In addition, when a base material containing a dye is used, there is a concern that the absorption function of the base material may be impaired if it is deposited at high temperature due to decomposition, alteration, or precipitation of the dye. One. On the other hand, a glass substrate containing a dye can be deposited at high temperature, but the substrate itself is fragile, and the surface hardness (pencil hardness) that can be measured is as low as B or less, and there is a limit to thinning. .

And the light selective transmission filter obtained by said light selective transmission filter or the said manufacturing method finds that it is a light selective transmission filter very effective for optical uses, such as a solid-state image sensor, or an opto device use, etc., and the said subject. The present inventors have arrived at the present invention by conceiving that it can be solved on a case-by-case basis.

That is, the present invention is a light selective transmission filter having a base material and a reflective film formed on at least one surface thereof, wherein the base material contains one or more kinds of dyes, and the light selective transmission filter This is a light selective transmission filter having a surface hardness of HB to 4H.
The present invention is also a solid-state imaging device having at least the light selective transmission filter, a lens unit portion, and a sensor portion.
The present invention is also a substrate for a light selective transmission filter which is a base material used for the light selective transmission filter.
The present invention is a method for producing the light selective transmission filter, wherein the production method includes a step of depositing a reflective film on at least one surface of the substrate at a temperature of 160 ° C. or higher. It is also a manufacturing method.
The present invention is described in detail below. In addition, what combined two or three or more of the preferable forms of this invention described in a paragraph below is also a preferable form of this invention.

The light selective transmission filter of the present invention includes a base material and a reflective film formed on at least one surface thereof, but may further include other layers as necessary.
In addition, 1 or 2 or more each may be sufficient as a base material, a reflecting film, and the other layer contained as needed.

The light selective transmission filter has a surface hardness of HB to 4H. By having a surface with such a high hardness, it becomes a light selective transmission filter that is not easily damaged, has no warpage, undulation, deformation, etc., and is extremely easy to handle. It can withstand and has excellent practicality. The surface hardness is preferably F or more, more preferably H or more, and further preferably 2H or more.
The surface hardness is preferably the hardness of the reflective film surface.

In this specification, the surface hardness of the light selective transmission filter means pencil hardness, for example, using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho) and conforming to JIS-K5600-5-4 (established in 1999). Then, it can be measured as a load of 1000 g. In addition, it means that surface hardness is so high that it goes to the right in order of 2B <B <HB <F <H <2H <3H <4H.

<Base material>
In the above light selective transmission filter, the substrate may be one containing one or more kinds of pigments, but may contain two or more kinds of pigments. By using such a light-absorbing base material containing a pigment in combination with a reflective film, it is possible to sufficiently reduce the incident angle dependency of the light blocking characteristics. For example, when a multilayer film (optical multilayer film) is used as a reflective film, the number of layers of the multilayer film can be reduced, and stress in the multilayer film can be relieved, thereby preventing cracks and cracks in the multilayer film. can do. Such a light selective transmission filter substrate used in the light selective transmission filter of the present invention is also one aspect of the present invention.

The thickness of the substrate is preferably 1 mm or less. As a result, the light selective transmission filter of the present invention can be sufficiently thinned to meet the demand for lowering the height of optical members and the like. More preferably, it is 500 micrometers or less, More preferably, it is 200 micrometers or less, Especially preferably, it is 100 micrometers or less, Most preferably, it is 80 micrometers or less. Moreover, it is preferable that it is 1 micrometer or more, More preferably, it is 40 micrometers or more.
In addition, when the said base material contains a support body so that it may mention later, it is preferable that the thickness of this support body is 120 micrometers or less.

The base material preferably has an absorption maximum wavelength in a wavelength region of 600 to 800 nm, and among them, it is preferable that at least one of the absorption maximum wavelengths exists in 600 to 710 nm. By having such absorption characteristics, the wavelength range to be cut off can be cut off more sharply, and the light selective transmission property that shows a high transmittance in the wavelength range to be transmitted is excellent. It becomes possible to further reduce the dependency. More preferably, the peak wavelength (that is, the maximum absorption wavelength) having the lowest transmittance among one or two or more absorption maximum wavelengths existing in the wavelength range of 600 to 800 nm is 600 to 710 nm. The transmittance at the maximum absorption wavelength is preferably 60% or less, more preferably 50% or less, and still more preferably 30% or less.
In addition, when the said base material contains the resin layer mentioned later, it is suitable that this resin layer also has the same absorption characteristic.

The absorption maximum wavelength of the substrate (and the resin layer) can be obtained by measuring the absorption spectrum by a normal method, but can also be obtained from these transmittance spectra as an alternative method.
In this specification, the transmittance can be measured using a spectrophotometer (for example, Shimadzu UV-3100, manufactured by Shimadzu Corporation). In this case, the thickness of the base material (and the resin layer) used for transmittance measurement is preferably 1 to 200 μm.

The base material may also be excellent in transparency from the short wavelength region of visible light to the ultraviolet region, but the light selective transmission filter is combined with a base material and a reflective film that reflects the ultraviolet region. In the case of a cut filter, the minimum value of the transmittance of the resin layer in the 350 to 400 nm wavelength region is preferably 20 to 80% from the viewpoint of easily reducing the incident angle dependency due to the reflective film. For the same reason, the minimum value of the transmittance in the 350 to 400 nm wavelength region is also preferably 20 to 80% for the resin layer when the substrate includes a resin layer described later.

The base material further preferably has a haze of 10% or less in the visible light region of the base material. More preferably, it is 5% or less, further preferably 3% or less, and particularly preferably 1% or less. In this embodiment, it is preferable that the transmittance of the base material at 500 nm of visible light is 60% or more. More preferably, it is 70% or more, further preferably 80% or more, and particularly preferably 85% or more.
In addition, when the said base material contains the resin layer mentioned later, it is suitable that this resin layer also has the same characteristic.

-Dye-
The base material contains one or more kinds of pigments.
The term “dye” means a substance that absorbs light having a specific wavelength. When the substrate further contains a resin component as described later, it is preferable to use a dye that can be mixed or kneaded with the resin component. Moreover, what has an absorption maximum in the wavelength range of 600-800 nm is preferable, and it is suitable to use especially the compound in which at least 1 of an absorption maximum wavelength exists in 600-710 nm. By constructing the base material using a compound having such absorption characteristics, it becomes more excellent in light selective transmission, and when the base material containing the dye and the reflective film are combined, the incidence by the reflective film Angular dependence can be further reduced. Thus, a form in which at least one of the dyes is a compound in which at least one of the absorption maximum wavelengths is present at 600 to 710 nm is also a preferred form of the present invention. More preferably, the peak wavelength with the lowest transmittance (that is, the maximum absorption wavelength) of one or two or more absorption maximum wavelengths is 600 to 710 nm.

The absorption maximum wavelength of the dye can be obtained by measuring the absorption spectrum by a usual method, but can also be obtained from the transmittance spectrum of the dye as an alternative method.
The transmittance of the dye is determined by filling a solution obtained by dissolving the dye in a solvent (for example, methanol, dimethylacetamide) into a 1 cm thick transparent quartz cell, and using a spectrophotometer (for example, Shimadzu UV-3100, Shimadzu Corporation). Can be used. Although the density | concentration of the pigment | dye at the time of the transmittance | permeability measurement is not specifically limited, For example, it is preferable to make a pigment | dye 0.000001-0.01 mass% with respect to 100 mass% of total amounts of a solvent and a pigment | dye, More preferably, it is 0.00. It is set to 00001-0.001 mass%.

The dye is preferably a compound in which the conjugated skeleton it has is nonionic, and in particular, the conjugated skeleton it has is nonionic and has an absorption maximum wavelength in the wavelength region of 600 to 800 nm. It is preferable that the compound has at least one absorption maximum wavelength at 600 to 710 nm. By using at least such a compound, the incident angle dependency can be more stably reduced over a long period of time.
Here, the conjugated skeleton that the dye has is nonionic means that all the conjugated skeletons that the dye has are neither anionic, cationic, or zwitterionic, that is, the conjugated skeleton. It means having no ionized moiety (anion, cation or zwitterion) in it. If an ionized moiety is present in the conjugated skeleton, near infrared absorption performance derived from the compound cannot be expressed sufficiently by light or heat, but light resistance and heat resistance can be achieved by not having an ionized moiety in the conjugated skeleton. It becomes possible to further exhibit the near infrared absorption performance over a long period of time.
In addition, having a zwitterion means having both a positive charge and a negative charge in one molecule. Zwitterions are also referred to as inner salts.

Of the above compounds, the portion other than the conjugated skeleton is not limited to nonionic properties. For example, a dye having a structure in which an anionic group is introduced by a sulfonic acid group is also included in the compound whose conjugated skeleton is nonionic. Among these, a part other than the conjugated skeleton is preferably a nonionic compound, and thereby, a decrease in near-infrared absorption performance can be further suppressed. That is, the compound is preferably a nonionic compound, in other words, a compound having no anion, cation, or zwitterion moiety (group).

Thus, the non-ionic property of the conjugated skeleton of the dye can make the near-infrared absorption performance of the substrate excellent in long-term stability, which is presumed to be due to the following mechanism.
Near-infrared absorption is considered to be largely due to electronic transition between conjugated orbitals of the dye used. In this absorption, the absorption characteristics such as the absorption edge wavelength and extinction coefficient can be controlled to some extent by the type and number of substituents (atomic groups) of the dye and, if the dye is a metal complex, the type of metal ion. However, the light absorption performance in the near-infrared region basically depends on the electronic structure of the conjugated electron that the dye has. Therefore, it is considered that the stability of the near infrared absorption performance of the substrate is due to the stability of the conjugated system of the conjugated skeleton in the dye. Therefore, the mechanism of the influence on the stability of the near-infrared absorption performance due to the presence or absence of the ionized structure portion in the conjugated skeleton is not clear, but is considered as follows.

For example, when using a substrate having a resin layer containing a dye and a resin component as described later, there is a substance that is easily dissociated into ions such as water in the resin layer by heating the resin layer containing the dye. If it is mixed with time, water is easily ionized in the ionization part. As a result, the near-infrared absorption performance may not be sufficient because the anion / cation moiety in the dye interacts or reacts strongly electronically and breaks the conjugated system. In addition, when light is applied to a resin layer containing a dye, oxygen molecules are excited by irradiation with light, particularly ultraviolet rays, and a highly reactive state (singlet oxygen) is generated. The ionized moiety easily reacts with singlet oxygen, and if it reacts, the conjugated system is broken, so that the near infrared absorption performance may not be sufficient.
From such points, it is considered effective to use a compound having a non-ionic conjugated skeleton as the dye.

The compound having a non-ionic conjugated skeleton is a compound having a heterocyclic 5-membered ring structure (heterocyclic 5-membered aromatic compound) from the viewpoint of superior heat resistance and light resistance. Is preferred. Among these, a compound in which the heterocyclic 5-membered ring structure is a pyrrole ring is preferable. More preferably, it is a tetrapyrrole compound.
Here, a group of compounds containing four pyrrole rings is called a tetrapyrrole compound, and there are a cyclic group and a linear one, and a cyclic tetrapyrrole compound is more preferable.

The cyclic tetrapyrrole compound means a group of cyclic compounds containing four pyrrole rings, but the compound contains a structure in which adjacent pyrrole rings are connected via carbon atoms or nitrogen atoms. Is preferred. Specifically, for example, a) a compound in which four bonds between adjacent pyrrole rings are bonds through one carbon atom, such as porphyrins and chlorins, and b) a phthalocyanine, for example. A compound in which all four bonds between adjacent pyrrole rings are bonds through one nitrogen atom, and c) three bonds among the four bonds between adjacent pyrrole rings, such as cholines. Preferred examples include a compound composed of a bond through one carbon atom and the remaining one composed of a bond between carbon atoms constituting a pyrrole ring. In a), porphyrins and chlorins are preferable, in b) phthalocyanines are preferable, and in c) choline is preferable. That is, examples of the cyclic tetrapyrrole compound include porphyrins (also referred to as porphyrin dyes), chlorins (also referred to as chlorin dyes), phthalocyanines (also referred to as phthalocyanine dyes) and / or cholines (also referred to as choline dyes). Among these, porphyrins and / or phthalocyanines are preferred because they are easily available industrially. The cyclic tetrapyrrole compound is also preferably a metal complex having a metal ion at the center from the viewpoint of further excellent light resistance.

The dye is also preferably a compound in which the metal serving as the central metal ion is copper from the point that it becomes a substrate that is particularly excellent in light resistance. In particular, divalent copper (Cu (II)) is preferable. Thereby, even if it raises pigment concentration, it becomes a substrate which is still more excellent in light resistance. In addition, it is a central metal ion from the viewpoint that the dye is easily dissolved / dispersed in the state of a single molecule or an associated molecule, can be a resin layer having a particularly high dye concentration, and can sufficiently absorb even a thin film. A compound in which the metal is zinc is preferred. In particular, divalent zinc (Zn (II)) is preferable.
Thus, as the dye, a compound in which the metal serving as the central metal ion is copper or zinc is particularly preferable. As metal complexes having these metals as central metal ions, porphyrins or phthalocyanines are particularly preferred, and phthalocyanines are most preferred.
Porphyrins mean a group of compounds having a porphyrin skeleton, and a hydrogen atom bonded to a carbon atom constituting a pyrrole ring or a bonded carbon atom connecting pyrrole rings is replaced with another atom (group) or group. It is included.

Here, a molecule having excellent planarity such as a phthalocyanine-based compound may have different positions of absorption maximum peaks when present as a single molecule and when present in an associated state (associated molecule). Usually, a peak derived from a single molecule (absorption maximum) appears on the long wavelength side, and a peak derived from an associated molecule (absorption maximum) appears on the short wavelength side.

Among the above dyes, a form in which at least a part is dispersed in the resin layer in a state of showing an absorption peak derived from an associated molecule is preferable from the viewpoint of further improving light resistance. Furthermore, it is preferable that at least one of the absorption maximum peaks derived from the associated molecules of the dye exists in a wavelength region of 600 to 710 nm. In other words, the base material preferably contains a dye having an absorption maximum peak derived from an associated molecule in a wavelength region of 600 to 710 nm. In addition, from the viewpoint of suppressing the incident angle dependency when combined with a reflective film, the maximum wavelength derived from a single molecule among one or more absorption maximum wavelengths in which the dye is present in a wavelength region of 600 to 800 nm. It is preferable that at least one of these is present at 600 to 710 nm.

Specifically, for example, as described above, it is preferable to use one or two or more of a porphyrin pigment, a chlorin pigment, a phthalocyanine pigment, a choline pigment, etc. It is more preferable to use a dye and / or a phthalocyanine dye.

As the phthalocyanine dye, a metal phthalocyanine complex is suitable. For example, a metal element such as copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, and lead is used as a central metal. Metal phthalocyanine complexes. Among these metal elements, those having one or more of copper, vanadium, and zinc as a central metal are preferable because they are more excellent in solubility, visible light transmittance, and light resistance. The central metal is more preferably copper, zinc or indium, still more preferably copper or zinc, and particularly preferably copper. The phthalocyanine-based dye using copper does not deteriorate by light even when dispersed in any resin component (binder resin), and has very excellent light resistance. Moreover, since the phthalocyanine complex (phthalocyanine dye) containing zinc as a metal element is excellent in solubility in a resin component, it has a high light transmittance in a 400 to 600 nm region and a high light absorption property in a 600 to 800 nm region. Is easy to obtain.
Examples of the porphyrin pigment include tetraazaporphyrin.

Among the phthalocyanine dyes, the following general formula (I):

(Wherein R ^{a1 to} R ^d1 , R ^{a2 to} R ^d2 , R ^{a3 to} R ^d3, and R ^{a4 to} R ^d4 are the same or different and are a hydrogen atom (H), a fluorine atom (F), an OR ⁱ group, or Represents an SR ^j group, R ⁱ and R ^j are the same or different and may have an alkyl group having 1 to 4 carbon atoms, an optionally substituted phenyl group, or an optionally substituted group; Represents a naphthyl group, and M represents a copper atom (Cu), a zinc atom (Zn), or an indium atom (In). Thereby, it becomes possible to fully exhibit the effect of this invention. Thus, a form in which at least the compound represented by the general formula (I) is used as the dye in the present invention is also suitable.

In the general formula (I), R ^{a1 to} R ^d1 , R ^{a2 to} R ^d2 , R ^{a3 to} R ^d3, and R ^{a4 to} R ^d4 are the same or different and are a hydrogen atom (H), a fluorine atom (F), Represents an OR ⁱ group or SR ^j group, and R ⁱ and R ^j are the same or different and have an alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, or a substituent. It represents a naphthyl group which may be substituted, but R ⁱ and R ^j are preferably a phenyl group or a phenyl group having a substituent.
In addition, when a phenyl group or a naphthyl group has a substituent, examples of the substituent include an organic group having 1 to 4 carbon atoms (for example, an alkyl group, an alkoxycarbonyl group, etc.), a halogen group (halogen atom), and a cyano group. Etc. are suitable. Among these, a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chloro group (chlorine atom), a methyl group, or a cyano group is particularly preferable.

R ^{a1 to} R ^d1 , R ^{a2 to} R ^d2 , R ^{a3 to} R ^d3 and R ^{a4 to} R ^d4 are preferably such that at least one of them represents an OR ⁱ group. The carbon to which the OR ⁱ group is bonded represents the α-position carbons in the four aromatic rings of the phthalocyanine skeleton (C _α : carbons at positions 1, 4, 8, 11, 15, 18, 22, 25 of the phthalocyanine ring. Or β-position carbon (C _β : represents carbons at positions 2, 3, 9, 10, 16, 17, 23, and 24 of the phthalocyanine ring). Further, the number of OR ⁱ groups to be introduced is not particularly limited, but preferably 1 or 2 for each aromatic ring of the phthalocyanine skeleton. That is, one or two of R ^{a1 to} R ^d1 , one or two of R ^{a2 to} R ^d2 , one or two of R ^{a3 to} R ^d3 , and R ^{a4 to} R It is preferred that one or two of ^d4 are the same or different and are OR ⁱ groups. Among them, has one OR ⁱ groups in C _alpha position, others are form a hydrogen atom; has one OR ⁱ group C _beta position, others are form a fluorine atom; a C _beta position It is particularly preferred that it is in any form of having two identical or different OR ⁱ groups and the others being fluorine atoms. That is, the compound represented by the general formula (I) is particularly preferably a compound represented by the following general formula (I-1), (I-2), or (I-3).

In the general formula (I-3), the OR ⁱ groups may be the same or different. In the general formulas (I-1) to (I-3), the OR ⁱ group is as described above, and is preferably a phenoxy group or a substituted phenoxy group. Examples of the substituent that the substituted phenoxy group has include the above-described substituents, and among them, a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chloro group (chlorine atom), a methyl group, or a cyano group is particularly preferable.

In the general formula (I), M is preferably a copper atom (Cu) or a zinc atom (Zn).

In order to obtain the compound represented by the general formula (I), for example, it is preferable to produce the compound according to the technique described in JP-B-6-31239. Specifically, MXn (wherein M represents a copper atom (Cu), a zinc atom (Zn), or an indium atom (In). X represents a halogen atom or an organic acid group. A metal halide or an organic acid metal represented by the following general formula (II):

(Wherein R ^{a to} R ^d are the same or different and each represents a hydrogen atom (H), a fluorine atom (F), an OR ⁱ group, or an SR ^j group. R ⁱ and R ^j are the same or different; A phthalonitrile derivative represented by an alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent. Or it is suitable to obtain by heating and making it react in presence of an organic solvent.

In the general formula (II), at least one of R ^{a to} R ^d preferably represents an OR ⁱ group. The number of OR ⁱ groups to be introduced is not particularly limited, but is preferably 1 or 2. Among them, a form having one OR ⁱ group and the other being a hydrogen atom; a form having one OR ⁱ group and the other being a fluorine atom; and having two identical or different OR ⁱ groups It is particularly preferable that the other form is a fluorine atom. That is, the phthalonitrile derivative represented by the general formula (II) is particularly preferably a compound represented by the following general formula (II-1), (II-2), or (II-3).

In the general formula (II-3), the OR ⁱ groups may be the same or different. In the general formulas (II-1) to (II-3), the OR ⁱ group is as described above, but is preferably a phenoxy group or a substituted phenoxy group. Examples of the substituent that the substituted phenoxy group has include the above-described substituents, and among them, a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chloro group (chlorine atom), a methyl group, or a cyano group is particularly preferable.

Examples of the metal halide and organic acid salt metal represented by MXn include cuprous iodide, zinc iodide, indium iodide, cuprous chloride, cupric chloride, zinc chloride, indium chloride, odor, and the like. Cuprous bromide, cupric bromide, zinc bromide, indium bromide, cupric fluoride, zinc fluoride or indium fluoride, zinc acetate, copper acetate, copper stearate, zinc stearate, etc. . Among these, cuprous iodide, zinc iodide, indium iodide, cuprous chloride, cupric chloride, indium chloride, copper stearate, and zinc stearate are preferable.

When the reaction between the metal halide or organic acid metal and the phthalonitrile derivative represented by the general formula (II) is performed in an organic solvent, examples of the organic solvent include benzene, toluene, xylene, nitrobenzene, mono Inert solvents such as chlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, ethylene glycol, benzonitrile; aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfone; etc. 1 type (s) or 2 or more types can be used. Of these, chloronaphthalene, N-methyl-2-pyrrolidone, nitrobenzene, ethylene glycol, and benzonitrile are preferable.

With regard to the above reaction, the reaction temperature is not necessarily constant depending on the type of raw material, the type of solvent, and other conditions, but it is usually preferably 100 to 300 ° C. More preferably, it is the range of 120-260 degreeC. Further, the temperature may be raised stepwise to control the exothermic reaction.

As the dye in the light selective transmission filter, a dye other than the preferred form of the dye (referred to as another dye) may be used, or the preferred form of the compound and the other dye may be used in combination. Good. When used in combination, the content of the other pigment is preferably 30% by mass or less with respect to 100% by mass of the total amount of the pigment. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, Most preferably, it does not contain other pigment | dye substantially. In addition, as said other pigment | dye, what has an absorption maximum in the wavelength range of 600-800 nm is suitable. More preferably, it has an absorption maximum in a wavelength region of 650 to 750 nm. Moreover, it is preferable that it does not have an absorption maximum substantially in the wavelength range of 400 nm or more and less than 600 nm.

Specific examples of the other dyes include cyanine dyes, quaterylene dyes, squarylium dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes, and the like, one or two of these. The above can be used.

In the substrate, the concentration (content) of the pigment varies depending on the configuration of the substrate, the thickness of the resin layer, and the like. For example, as described later, the substrate includes a pigment and a resin component. In this case, the total amount of the dye is preferably 0.001% by mass or more with respect to 100% by mass of the total amount of the dye and the resin component. More preferably, it is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, Most preferably, it is 1 mass% or more. However, if the dye concentration is too high, the resin layer is made very thin in order to have sufficient transmittance in the visible light region to be transmitted, and film formation with a more uniform film thickness may be difficult. From such a viewpoint, it is suitable that it is 20 mass% or less. More preferably, it is 15 mass% or less.
In addition, by using at least the preferred form of the dye, a resin layer having more excellent light resistance can be obtained even when the dye concentration is high.

The base material may also contain a compound having an absorption function in a wavelength range of 350 to 400 nm. Thereby, deterioration of the base material (and light selective transmission filter) resulting from light in a wavelength range of 350 to 400 nm (substantially purple light) can be sufficiently suppressed.
Here, as a form containing the compound having an absorptivity in the wavelength range of 350 to 400 nm, the above-described dye may be a form that is a compound further having an absorption function in the wavelength range of 350 to 400 nm, Moreover, the form which uses together the compound which has an absorption function in the wavelength range of 350-400 nm separately may be sufficient. Examples of the latter compound having an absorption function in the wavelength region of 350 to 400 nm include, for example, one kind of ultraviolet absorbing compound such as TINUVIN P, TINUVIN 234, TINUVIN 329, TINUVIN 213, TINUVIN 571, and TINUVIN 326 (manufactured by BASF). Two or more types can be used.

-Resin component-
It is preferable that the base material further contains a resin component. That is, it is preferable that the base material contains a pigment and a resin component. This makes it possible to greatly reduce the thickness of the entire light selective transmission filter as compared with the case where only glass is used as the base material, and also to impart various physical properties such as a high level of surface hardness and heat resistance. it can. Thus, the form in which the substrate further contains a resin component is one of the preferred forms of the present invention.

The substrate containing the dye and the resin component preferably has, for example, a form having a resin layer containing the dye and the resin component, and the configuration (form) of such a substrate is, for example, the resin The structure which consists of a layer, the structure which has this resin layer and a support body, etc. are mentioned. Examples of the latter structure include a structure in which a resin layer is formed on one or both sides of a support, and a form in which a resin layer is sandwiched between supports. Especially, it is suitable that it is a base material which consists of a resin layer containing a pigment | dye and a resin component from viewpoints, such as handleability and heat resistance. Moreover, when a support body is included, it is preferable that this support body is not glass, and it is suitable that it is a resin film so that it may mention later.
The resin layer and the support may each be a single layer or two or more layers.

As described above, the substrate in the present invention preferably has a resin layer containing a pigment and a resin component. In this case, the resin layer is preferably formed by dispersing or dissolving a pigment in the resin layer. That is, it is preferable that the resin layer is formed of a resin composition in which a pigment is dispersed or dissolved in a resin composition containing the pigment and a resin component. By appropriately selecting this resin component, it is possible to achieve both a high transmittance in a wavelength region (for example, visible region) to be transmitted and a high absorptivity in a wavelength region (for example, an infrared region) to be blocked. It becomes possible.
In addition, as a pigment | dye and a resin component, 1 type (s) or 2 or more types can each be used.

As the resin component, it is preferable that the glass transition temperature is 170 ° C. to 360 ° C. As a result, it can sufficiently withstand the formation of a reflective film at higher temperatures (high temperature deposition), so that the surface hardness is sufficiently high and not easily damaged, and the occurrence of warpage, undulation, deformation, etc. is more sufficiently suppressed and handled. It is possible to more effectively provide a light selective transmission filter having extremely good properties and excellent practicality. Thus, the form in which the resin component has a glass transition temperature of 170 ° C. to 360 ° C. is also a preferred form of the present invention. The glass transition temperature is more preferably 180 ° C. or higher, further preferably 190 ° C. or higher, particularly preferably 200 ° C. or higher, and more preferably 300 ° C. from the viewpoint of good adhesion between the reflective film and the resin component. Below, it is 240 degrees C or less more preferably.
The glass transition temperature can be measured using, for example, SSC5200H (manufactured by Seiko Denshi Kogyo Co., Ltd.) at a heating rate of 20 ° C./min.

Specifically, at least one selected from the group consisting of solvent-soluble resins, solvent-soluble resin raw materials, and liquid resin raw materials is preferable as the resin component. Such a resin component has a high dispersibility of the dye, so that it can form a light absorbing film excellent in light selective absorption and can disperse the dye at a high concentration, so that the light selective transmission filter can be made thin. Is possible. Further, when the resin component is used, a resin layer can be formed (film formation) by a solvent casting method described later, so that the pigment can be uniformly dispersed at a high concentration in the resin layer, and the resin layer can be formed at a relatively low temperature. Can be formed.
The resin layer itself may be solvent-soluble or insoluble.

Here, the “solvent-soluble resin” means a resin that is soluble in an organic solvent, and is preferably a resin that can be dissolved by 1 part by mass or more with respect to 100 parts by mass of dimethylacetamide or N-methylpyrrolidone. is there. The “solvent-soluble resin raw material” means a solvent-soluble resin raw material, that is, a resin raw material that is solvent-soluble, for example, 1 part by mass with respect to 100 parts by mass of dimethylacetamide or N-methylpyrrolidone. What melt | dissolves above is suitable. The “liquid resin raw material” means a liquid resin raw material, that is, a resin raw material that is liquid. The term “liquid” means that the viscosity of the product itself is 100 Pa · s or less at room temperature (25 ° C.). The viscosity can be measured with a B-type viscometer.
The “resin raw material” includes a precursor of the resin, a raw material of the precursor, and a monomer (such as a curable monomer) for forming the resin.

As described above, the resin component is preferably at least one selected from the group consisting of a solvent-soluble resin, a solvent-soluble resin raw material, and a liquid resin raw material. Among these, it is preferable to use a solvent-soluble resin. is there. When the solvent-soluble resin is used, the light resistance is excellent as compared with the case where the solvent-soluble resin material or the liquid resin material is used. This is because the solvent-soluble resin is less likely to cause deterioration in the absorption performance of the dispersed dye than the solvent-soluble resin material and the liquid resin material. The reason is that the solvent-soluble resin is prepared from its monomers and precursors to complete the polymerization and reaction. Further purification may be performed. It is considered that the solvent-soluble resin thus obtained has almost no unreacted substances, reactive ends, ionic groups, catalysts, acid / basic groups, etc. that promote the deterioration and decomposition of the dye. On the other hand, solvent soluble resin raw materials and liquid resin raw materials still have many factors that promote the deterioration and decomposition of such pigments. In addition, it is difficult to complete the polymerization and reaction of the solvent-soluble resin raw material and the liquid resin raw material while maintaining the absorption performance and absorption spectrum of the dye in a state where the dye is dispersed (the number of unreacted sites increases and a desired The physical properties cannot be obtained sufficiently.) Therefore, even if the same pigment is dispersed, the light resistance of the resin layer varies depending on the resin component. Therefore, it is preferable to use at least a solvent-soluble resin from the viewpoint of light resistance.

Specific examples of the solvent-soluble resin include fluorinated aromatic polymers, poly (amide) imide resins, polyamide resins, aramid resins, and polycycloolefin resins. Among these, a fluorinated aromatic polymer and / or a poly (amide) imide resin is preferable from the viewpoint of superior light resistance. More preferred is a poly (amide) imide resin, and even more preferred is a polyimide resin.

The solvent-soluble resin also has a reactive group capable of undergoing a crosslinking reaction (curing reaction) (for example, a ring-opening polymerizable group such as an epoxy group, an oxetane ring, an ethylene sulfide group, an acrylic group, a methacryl group, a vinyl group). Or a radical curable group such as an addition curable group).
When a solvent-soluble resin is used as the resin component, the solvent-soluble resin may be used as it is as a resin component constituting the resin layer, or the resin-soluble resin is changed by a crosslinking reaction or the like. It may be a resin component constituting the layer.
The amount of reactive groups that can be cross-linked and the extent of the cross-linking reaction during film formation are not particularly limited, but it is preferable that the solvent solubility of the resin can be maintained.

The fluorinated aromatic polymer includes an aromatic ring having at least one fluorine group and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. Specifically, for example, a polyimide having a fluorine atom, polyether, polyetherimide, polyetherketone, polyethersulfone, polyamide ether, polyamide, polyether A nitrile, polyester, etc. are mentioned. Among these, it is preferable that it is a polymer which has as an essential part the repeating unit containing the aromatic ring which has an at least 1 or more fluorine group, and an ether bond, and the following general formula (1-1) or (1- A polyether ketone having a fluorine atom containing the repeating unit represented by 2) is more preferred. Among these, fluorinated polyether ketone (FPEK) is particularly preferable.
In addition, the repeating unit represented by the general formula (1-1) or (1-2) may be the same or different, and may be in any form such as a block shape or a random shape.

In the general formula (1-1), R ¹ represents a divalent organic chain having an aromatic ring having ¹ to 150 carbon atoms. Z represents a divalent chain or a direct bond. x and y are integers of 0 or more, satisfy x + y = 1 to 8, and are the same or different and represent the number of fluorine atoms bonded to the aromatic ring. n ¹ represents a degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.
In General Formula (1-2), R ² may have a substituent, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or an alkylamino having 1 to 12 carbon atoms. Group, an alkylthio group having 1 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an arylamino group having 6 to 20 carbon atoms, or an arylthio group having 6 to 20 carbon atoms. . R ³ represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. z is the number of fluorine atoms bonded to the aromatic ring and is 1 or 2. n ¹ represents a degree of polymerization, preferably in the range of 2 to 5000, and more preferably in the range of 5 to 500.

In the general formula (1-1), x + y is preferably in the range of 2 to 8, and more preferably in the range of 4 to 8. Further, the position at which the ether structure moiety (—O—R ¹ —O—) is bonded to the aromatic ring is preferably para to Z.

In the general formulas (1-1) and (1-2), R ¹ and R ³ are divalent organic chains. For example, any one represented by the following structural formula group (2): Or it is preferable that it is the organic chain of the combination.

In the structural formula group (2), Y ^{1 to} Y ⁴ are the same or different and each represents a hydrogen group or a substituent, and the substituent is a halogen atom or an alkyl which may have a substituent. A group, an alkoxy group, an alkylamino group, an alkylthio group, an aryl group, an aryloxy group, an arylamino group or an arylthio group;

More preferable specific examples of R ¹ and R ³ include organic chains represented by the following structural formula group (3).

In the general formula (1-1), Z represents a divalent chain or a direct bond. For example, the divalent chain is preferably a chain represented by the following structural formula group (4) (structural formulas (4-1) to (4-13)).

In the structural formula group (4), X is a divalent organic chain having 1 to 50 carbon atoms. Examples thereof include the organic chain represented by the structural formula group (3) described above, and among them, diphenyl ether. A chain, a bisphenol A chain, a bisphenol F chain, and a fluorene chain are preferred.

In R ² in the general formula (1-2), examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, An isopentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, 2-ethylhexyl group and the like are preferable.
Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group. , Dodecyloxy group, furfuryloxy group, allyloxy group and the like are preferable.
As the alkylamino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, propylamino group, n-butylamino group, sec-butylamino group, tert-butylamino group and the like are preferable.
As the alkylthio group, methylthio group, ethylthio group, propylthio group, n-butylthio group, sec-butylthio group, tert-butylthio group, iso-propylthio group and the like are preferable.

As the aryl group, phenyl group, benzyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, A biphenylyl group, a benzhydryl group, a trityl group, a pyrenyl group, and the like are preferable.
Examples of the aryloxy group include groups derived from a phenoxy group, a benzyloxy group, hydroxybenzoic acid and esters thereof (for example, methyl ester, ethyl ester, methoxyethyl ester, ethoxyethyl ester, furfuryl ester, and phenyl ester). A naphthoxy group, o-, m- or p-methylphenoxy group, o-, m- or p-phenylphenoxy group, phenylethynylphenoxy group, a group derived from cresotinic acid and esters thereof, and the like are preferable.
The arylamino group includes an anilino group, o-, m- or p-toluidino group, 1,2- or 1,3-xylidino group, o-, m- or p-methoxyanilino group, anthranilic acid and its Groups derived from esters are preferred.
The arylthio group is preferably a phenylthio group, a phenylmethanethio group, an o-, m- or p-tolylthio group, a group derived from thiosalicylic acid and esters thereof, and the like.

Among these, R ² is preferably an alkoxy group, an aryloxy group, an arylthio group, or an arylamino group, which may have a substituent. However, R ² may or may not contain a double bond or a triple bond.

Examples of the substituent for R ² in the general formula (1-2) include an alkyl group having 1 to 12 carbon atoms as described above; a halogen atom such as fluorine, chlorine, bromine and iodine; a cyano group, a nitro group, and a carboxy group. An ester group or the like is preferred. Moreover, hydrogen of these substituents may or may not be halogenated. Among these, preferably, a halogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, and a carboxy ester, which may or may not be halogenated. It is a group.

The above-mentioned poly (amide) imide resin means a narrowly defined polyimide resin (which includes an imide bond and does not include an amide bond, and the amide bond here can form an imide bond by a dehydration reaction of an amic acid. And a polyamide-imide resin (meaning a resin containing an amide bond and an imide bond that cannot form an imide bond by a dehydration reaction of an amic acid).
The imide bond in the polyimide resin is usually a bond chain having an amide bond and a carboxyl group adjacent thereto (in the present invention, this bond chain is also referred to as an amic acid. Usually, adjacent to the carbon atom to which the amide bond is bonded. The structure is formed by dehydration reaction between an amide bond and a carboxyl group.
When a polyimide resin is produced from a polyamic acid by a dehydration reaction, a slight amount of amic acid can remain in the molecule. Therefore, in the present invention, the term “polyimide resin” includes an imide bond and does not include an amide bond that cannot form an imide bond by a dehydration reaction of an amic acid, but can form an imide bond by a dehydration reaction of an amic acid. It may contain no amide bond or some amount.

As said solvent soluble resin, the polyimide resin whose imide bond content rate (ratio of the number of amide bonds which can be imidized by imidation reaction and the total amount of imide bonds of 100 mol% of imide bonds) in polyimide resin is 80 mol% or more. Resins are preferred. More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more, Most preferably, it is 98 mol% or more.

Here, the polyamide-imide resin includes an amide bond that cannot form an imide bond by an amic acid dehydration reaction and an imide bond, but does not include an amide bond that can form an imide bond by an amic acid dehydration reaction. Some amount may be included. When an amide bond that can form an imide bond by dehydration reaction of amic acid is included, the number of amide bonds (the number of amide bonds that cannot form imide bond by dehydration reaction and the number of amide bonds that can form imide bond by dehydration reaction) The content of the amide bond capable of forming an imide bond by dehydration reaction of the amic acid with respect to 100 mol% of the total amount of the sum and the number of imide bonds is preferably less than 20 mol%. More preferably, it is less than 10 mol%, More preferably, it is less than 5 mol%, Most preferably, it is less than 2 mol%.

The poly (amide) imide resin is a poly (amide) imide resin raw material (poly (amide) imide precursor) obtained by reacting a polyvalent carboxylic acid compound with a polyvalent amine compound and / or a polyvalent isocyanate compound. Can be obtained by imidization reaction.
The poly (amide) imide resin also preferably has transparency. In order to improve transparency, it is preferable that there are few aromatic rings. Among them, it is preferable to have a structure in which the aromatic ring is replaced with an alicyclic ring or a fatty chain. More preferably, the weight of the aromatic ring in the total weight of 100% is 65% or less, more preferably 45% or less, and particularly preferably 30% or less.

Although it will not specifically limit as said poly (amide) imide resin if it is a compound which has an imide bond, For example, following General formula (5):

A compound having a repeating unit represented by (in the formula, R ⁴ are the same or different and each represents an organic group) is preferable.
R ⁴ in the general formula (5) is preferably a divalent organic group, and more preferably a divalent organic group having 2 to 39 carbon atoms. The organic group preferably contains one or more hydrocarbon skeletons. The hydrocarbon skeleton is preferably an aliphatic chain hydrocarbon, an aliphatic cyclic hydrocarbon, or an aromatic hydrocarbon. The organic group may also have a heterocyclic skeleton.

R ⁴ in the general formula (5) also has two or more kinds selected from the above-described hydrocarbon skeleton and / or heterocyclic skeleton, and these are different via a carbon-carbon bond, or Those containing a skeleton bonded via a bonding group different from a carbon-carbon bond are preferred. Examples of the linking group include —O—, —SO ₂ —, —CO—, —Si (CH ₃ ) ₂ —, —C ₂ H ₄ O—, —S—, and the like.
Each R ⁴ in the repeating unit represented by the general formula (5) may be the same or different.

The organic group represented by R ⁴ may be directly bonded to a nitrogen atom, and as a bonding group, —O—, —SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ). _{2 -, - Si (CH 3} ) 2 -, - C 2 H 4 O -, - S- , etc. may be included.
In addition, although part or all of the hydrogen atoms in the cyclohexyl ring in the general formula (5) may be substituted, those which are unsubstituted (a form in which all are hydrogen atoms) are preferable.
The repeating units represented by the general formula (5) may be the same or different, and may be in any form such as block or random.

Preferable specific examples of the poly (amide) imide resin include, for example, Neoprim L-3430 (thickness 50 μm, 100 μm, 200 μm, etc.) manufactured by Mitsubishi Gas Chemical Company. In addition, although this product is a film shape, since it is soluble in an organic solvent, it is preferably used as the solvent-soluble resin.

Examples of the solvent-soluble resin raw material or liquid resin raw material include, for example, an epoxy compound as a raw material for an epoxy resin, a vinyl compound ((meth) acrylic compound, a styrene compound, etc.) as a raw material for a vinyl polymer resin, poly ( Amido) imide precursors and the like. An epoxy compound and a vinyl compound are preferable.

The said epoxy resin is a hardened | cured material of the curable composition containing the compound (epoxy compound) which has an epoxy group. Examples of the form of the cured product include a form obtained by curing the epoxy compound with light and / or heat in the presence of a cationic curing catalyst, a form of a cured product obtained by reacting the epoxy compound with an additional curing agent, and the like. In the latter case, a conventionally known curing accelerator can be used in combination for accelerating the curing reaction. Examples of the additional curing agent include acid anhydrides, polyhydric phenol compounds, polyhydric amines, etc. Among them, acid anhydrides are preferable.

As said epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, a hydrogenated epoxy compound etc. are suitable, For example, Osaka Gas Chemical Co., Ltd. fluorene epoxy (Oncoat EX-1); Bisphenol A epoxy compound (Epicoat 828EL) manufactured by Japan Epoxy Resin; Hydrogenated bisphenol A epoxy compound (Epicoat YX8000) manufactured by Japan Epoxy Resin; Alicyclic liquid epoxy compound (Celoxide 2021) manufactured by Daicel Industries, Ltd. Can be preferably used.
In addition, in this specification, an epoxy group includes an oxirane ring that is a three-membered ether, and includes a glycidyl group (including a glycidyl ether group and a glycidyl ester group) in addition to a narrowly defined epoxy group. Means.

The curable composition containing the epoxy compound preferably contains a component having flexibility (flexible component). By including a flexible component, it is possible to obtain a resin composition having a sense of unity, such as not cracking, not losing shape, being easily peeled off, and having flexibility when being removed from molding or from a substrate or mold.
The flexible component may be a compound different from the epoxy compound, or at least one of the epoxy compounds may be a flexible component.

The vinyl polymer resin is a polymer obtained by (co) polymerizing a vinyl compound as a polymerization raw material, and examples thereof include an acrylic resin, a styrene resin, and an acrylic-styrene resin.
An acrylic resin is a cured product of a curable composition containing a compound having a (meth) acryloyl group (also referred to as a (meth) acryloyl group-containing compound or a (meth) acrylic compound). A styrene resin is a styrene resin. Is a cured product of a curable composition containing a styrene monomer (also referred to as a styrene compound) such as divinylbenzene, and acrylic-styrene resin is a curable composition containing a (meth) acryloyl group-containing compound and a styrene monomer. It is a cured product of the composition. Among the vinyl polymer resins, acrylic resins and acrylic-styrene resins are preferable.

Preferred examples of the (meth) acryloyl group-containing compound include (meth) acrylate monomers, urethane (meth) acrylates, polyester (meth) acrylates, and epoxy (meth) acrylates. A (meth) acrylate (co) polymer (having a (meth) acryloyl group) obtained by (co) polymerizing a (meth) acrylate monomer can also be suitably used. A composition containing a polymerizable oligomer such as urethane (meth) acrylate, polyester (meth) acrylate, and (meth) acrylate (co) polymer, and a (meth) acrylate monomer is an acrylic resin because it can be easily formed into a film. It is preferable to use it as a raw material.
As said acrylic-styrene resin raw material, the composition which used the styrene-type monomer further in the suitable form of the said acrylic resin raw material is preferable.

The poly (amide) imide precursor is a raw material for forming a poly (amide) imide resin, that is, a compound that is subjected to an imidization reaction. For example, a polyamic acid is preferable. Specifically, for example, HPC-7000-30 manufactured by Hitachi Chemical Co., Ltd. is preferably used.

The resin layer is also preferably a layer formed of a resin composition containing the dye and a resin component. The resin composition further contains other components as necessary. There may be. Although it does not specifically limit as another component, When an inorganic component, such as a metal oxide, is included as another component, the content is 50 mass in 100 mass% of resin compositions from a viewpoint which is excellent in transparency with respect to visible light. It is preferable that it is less than%. More preferably, it is less than 20 mass%, More preferably, it is less than 5 mass%, Most preferably, it is less than 1 mass%. Most preferably, the resin composition forming the resin layer is substantially free of inorganic components.

Regarding the film thickness (thickness) of the resin layer, it is possible to reduce the film thickness in the present invention. However, since the film thickness can be reduced, invasion and diffusion of moisture and the like from the thickness direction are easily suppressed. It will be advantageous. The film thickness (thickness) of the resin layer is preferably 10 μm or less. As a result, the light selective transmission filter can be sufficiently thinned to meet the demand for lowering the height of optical members and the like. More preferably, it is 5 μm or less. Moreover, it is preferable that it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more.

-Support-
When the base material further has a support as described above, the support is preferably made of resin. Thereby, compared with the case where a glass substrate is used, the surface hardness of the light selective transmission filter can be made higher, and the film can be made thinner. The support is preferably in the form of a film (support film). A resin film (also referred to as a resin film) is more preferable.

As the support film, a resin having excellent transparency is preferably used. Specifically, for example, (meth) acrylic resin, epoxy resin, polycarbonate resin, polyester resin, fluorinated aromatic polymer, poly (amide) imide resin, polyamide resin, aramid resin, cycloolefin resin and the like can be used. . Among these, fluorinated aromatic polymer, poly (amide) imide resin, polyamide resin, aramid resin, cycloolefin resin, epoxy resin and / or acrylic resin are excellent in heat resistance when the reflective layer is formed by vapor deposition. preferable. More preferably, at least a poly (amide) imide resin is used.

As a suitable combination of the material of the support (preferably the support film) and the resin component contained in the resin layer, for example, poly (amide) imide resin / poly (amide) as the support film / resin component Examples thereof include imide resins, poly (amide) imide resins / acrylic resins, poly (amide) imide resins / fluorinated aromatic polymers, polyamide resins / acrylic resins, aramid resins / acrylic resins, cycloolefin resins / acrylic resins, and the like. Among them, poly (amide) imide resin / poly (amide) imide resin is preferable, polyimide resin / polyimide resin, polyimide resin / polyamideimide resin, or polyamideimide resin / polyamideimide resin is more preferable. , Polyimide resin / polyimide resin.

The method for forming the base material is not particularly limited. For example, the resin composition for forming the resin layer may be the surface of the support (or if the substrate has another layer between the support and the resin layer, the other By applying to the surface of the layer and drying or curing (referred to as coating method or coating method), or by thermocompression bonding a resin film formed from the resin composition to the support In addition to the forming method, a kneading method and the like can also be mentioned. Among these, when obtaining the base material which has a support body and a resin layer, it is preferable to employ | adopt the coating method. That is, the resin layer is preferably a layer formed by a coating method, whereby the adhesion between the resin layer and the support becomes more sufficient. In addition, also when obtaining the base material which does not have a support body, it is preferable to use the apply | coating method, for example, after apply | coating the resin composition which forms a resin layer in a temporary base material, it peels from this base material. It is preferable to obtain the substrate.

Among the coating methods, the solvent casting method is preferable, and the form in which the resin layer is a layer formed by the solvent casting method is also a preferred embodiment of the present invention. When the solvent casting method is used, since the pigment can be dispersed more uniformly, it is possible to form a light-absorbing film excellent in light selective absorption, which is preferable. In addition, since the dye can be dispersed at a high concentration, it is possible to reduce the thickness of the dye, and it is possible to meet the demand for reducing the height of members such as a solid-state imaging device. Furthermore, since the resin layer can be formed at a relatively low temperature, a dye having a relatively low heat resistance can also be used. On the other hand, in the kneading method, since the resin is melted and used at a high temperature (for example, 200 ° C. or more), the dye having low heat resistance is decomposed and there is a possibility that sufficient light absorption cannot be obtained. is there. In addition, the dispersibility of the dye may not be sufficiently high.

In the solvent casting method, a resin layer is formed into a film by forming a solution obtained by dissolving a resin composition for forming a resin layer in a solvent and drying (curing) the solution on a support. Membrane). Moreover, when using a liquid resin raw material as a resin component, a pigment | dye may be directly disperse | distributed to this resin raw material, and after diluting this resin raw material with a solvent, you may disperse | distribute a pigment | dye.

The solvent (organic solvent) is not particularly limited as long as it can dissolve the resin composition for forming the resin layer, and can be appropriately selected according to the type of the resin component. For example, methyl ethyl ketone (2-butanone), ketones such as methyl isobutyl ketone (4-methyl-2-pentanone), cyclohexanone; PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether Glycol derivatives such as ethylene glycol ethyl ether acetate (ether compounds, ester compounds, ether ester compounds, etc.); amides such as N, N-dimethylacetamide; esters such as ethyl acetate, propyl acetate, butyl acetate; N-methyl -Pyrrolidone (more specific Pyrrolidones such as 1-methyl-2-pyrrolidone); aromatic hydrocarbons such as toluene and xylene; aliphatic hydrocarbons such as cyclohexane and heptane; ethers such as diethyl ether and diptyl ether; Is preferred. More preferred are methyl ethyl ketone, ethyl acetate, and N, N-dimethylacetamide.

As the usage-amount of the said solvent, it is preferable that it is 150 mass parts or more with respect to 100 mass parts of total amounts of the said resin composition, and 1900 mass parts or less are preferable. More preferably, it is 200 parts by mass or more and 1400 parts by mass or less. By setting it as the said range, a resin layer with a high pigment | dye density | concentration is easy to be obtained, for example.

<Reflective film>
In addition to the base material, the light selective transmission filter also has a reflective film formed on at least one surface of the base material. The reflection film may be a film having a light reflection function, and may be a single layer or a multilayer of two or more layers, but is preferably a multilayer film. That is, the reflective film is preferably an optical multilayer film. The reflective film is preferably an inorganic film from the viewpoint of excellent heat resistance, and particularly preferably an inorganic multilayer film capable of controlling the refractive index of each wavelength. As an inorganic multilayer film, a low refractive index material and a high refractive index material are alternately laminated on a resin layer, a support, and other functional material layers by vapor deposition (preferably vacuum vapor deposition) or sputtering. It is preferable to be a refractive index control multilayer film. The reflective film is also preferably a transparent conductive film. As the transparent conductive film, a transparent conductive film as a film that reflects infrared rays, such as indium-tin oxide (ITO), is preferable. Among these, an inorganic multilayer film is particularly suitable.

As the inorganic multilayer film, a dielectric multilayer film in which dielectric layers A and dielectric layers B having a refractive index higher than that of the dielectric layer A are alternately stacked is preferable.
As the material constituting the dielectric layer A, a material having a refractive index of 1.6 or less can be generally used, and a material having a refractive index range of 1.2 to 1.6 is preferably selected. As such a material, for example, silica, alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoride sodium and the like are suitable.

As the material constituting the dielectric layer B, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is preferably selected. Examples of such materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide as the main component, titanium oxide, tin oxide, cerium oxide, and the like. Those containing a small amount of are suitable.

In general, the thickness of each of the dielectric layer A and the dielectric layer B is preferably 0.1λ to 0.5λ when the wavelength of light to be blocked is λ (nm). When the thickness is outside this range, the product (n × d) of the refractive index (n) and the film thickness (d) is significantly different from the optical film thickness calculated by λ / 4, and the optical characteristics of reflection / refraction May be lost, and control for blocking / transmitting a specific wavelength may not be possible.

The method of laminating the dielectric layer A and the dielectric layer B is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a CVD method, a sputtering method, a vapor deposition method ( A dielectric multilayer film can be formed by alternately laminating the dielectric layer A and the dielectric layer B, preferably by vacuum vapor deposition.

The reflective film such as the inorganic multilayer film can be suitably formed by the above-described method and the like, and among these, it is preferable to form by a vapor deposition method.
In this case, it is preferable to use the following method in order to further reduce the possibility of the light selective transmission filter being deformed and curled or cracked by vapor deposition. Specifically, a reflective film transfer method of forming a reflective film by forming a vapor deposition layer on a temporary base material such as glass that has been subjected to a release treatment, and transferring the vapor deposition layer to the base material of the light selective transmission filter Is preferred. In this case, it is preferable to form an adhesive layer on the substrate.
When the substrate is formed of an organic material, specifically a resin composition, a dielectric layer or the like is deposited on the uncured or semi-cured resin composition, and then the resin composition is cured. The method is preferred. When such a method is used, the base material becomes fluid at the time of cooling after multi-layer deposition, and becomes a liquid state, so the difference in thermal expansion coefficient between the resin composition and the dielectric layer does not become a problem, Deformation (curl) of the light selective transmission filter can be more sufficiently suppressed.

As described above, it is preferable to use a vapor deposition method for forming a reflective film (preferably an optical multilayer film, more preferably an inorganic multilayer film) on the substrate, but the vapor deposition temperature should be 160 ° C. or higher. Is preferred. When vapor deposition is performed at such a high temperature, the inorganic film (inorganic film constituting the inorganic multilayer film) becomes dense and hard, and there are advantages such as improving various resistances and improving the yield. In particular, the surface hardness of the obtained light selective transmission filter can be remarkably improved, and the occurrence of warpage, undulation, deformation, and the like can be sufficiently suppressed, which is preferable. Thus, the form in which the reflective film is formed by vapor deposition at a temperature of 160 ° C. or higher on at least one surface of the substrate is one of the preferred forms of the present invention. More preferably, it is 180 degreeC or more as vapor deposition temperature, More preferably, it is 200 degreeC or more.

Moreover, the light selective transmission filter of the present invention can be suitably obtained by performing the high-temperature vapor deposition step as described above. That is, the method for producing a light selective transmission filter is also a method for producing a light selective transmission filter including a step of depositing a reflective film on at least one surface of a substrate at a temperature of 160 ° C. or higher. It is. Thereby, it is possible to suitably obtain a light selective transmission filter having a surface hardness in the above-described range. More preferably, it is 180 degreeC or more as vapor deposition temperature, More preferably, it is 200 degreeC or more.

Here, since the reflective film of the light selective transmission filter of the present invention is preferably formed by high-temperature vapor deposition as described above, it is particularly preferable to use a substrate that can withstand such vapor deposition temperature. is there. As such a substrate, it is preferable to use a resin component or a pigment having the above-mentioned preferred forms, and it is particularly preferable to use a resin component having a glass transition temperature in the above-described range. It is also preferable to use a resin component or a support film having a low linear expansion coefficient. Thereby, the inorganic layer crack by the difference of an inorganic and organic linear expansion coefficient can be suppressed further. In addition, if a resin component or support film having a low linear expansion coefficient is used, not only can it be deposited at a high temperature, but even if it is deposited at a low temperature, the difference in the linear expansion coefficient from the reflective film (such as an inorganic film) is small. Inorganic layer cracks due to differences in inorganic and organic linear expansion coefficients even in heating and harsh usage environments such as the reflow process used when manufacturing solid-state imaging devices with selective transmission filters It can be suppressed more.

The resin component or support film having a low linear expansion coefficient is preferably one having a linear expansion coefficient of 60 ppm or less. More preferably, it is 50 ppm or less, More preferably, it is 30 ppm or less, Most preferably, it is 10 ppm or less.
Specifically, as the resin component or the support film having a low linear expansion coefficient, for example, a poly (amide) imide resin, an aramid resin, a polyamide resin, an epoxy resin, a polyester resin, an organic-inorganic hybrid resin, and the like are preferable. A form in which the resin component or the support film is formed of at least one selected from the group consisting of these is one of the preferred forms of the present invention. The linear expansion coefficient can also be reduced by stretching the resin; dispersing inorganic fine particles; using glass cloth; increasing the crosslinking density; compositing; crystallizing;

Moreover, although the said reflecting film may be formed only in one surface of the said base material, and may be formed in both surfaces, it is preferable to be formed in both surfaces. By having a reflective film on both surfaces of the substrate, warpage of the light selective transmission filter of the present invention and cracking of the reflective film can be further suppressed. In addition, when the said base material consists of a resin layer and a support body, it is suitable for a reflecting film to be formed in the surface of a resin layer. Particularly preferred is a form in which a reflective film made of an inorganic multilayer film is formed on both surfaces of a substrate, and the surface of the resin layer is in close contact with the reflective film made of a support or an inorganic multilayer film. The light selective transmission filter having such a form is particularly excellent in light resistance and heat resistance.

As another preferred mode, a mode in which a reflective film is formed on at least one surface of a resin film different from the base material and the base material is further formed on the surface of the reflective film can be mentioned. That is, it is a form in which the reflective film and the base material are laminated in this order on the surface of the resin film. The reflective film is preferably provided on both surfaces of the resin film. In this case, the base material may be laminated on the surface of one reflective film or may be laminated on the surfaces of two reflective films. In this case, the resin film can use the same thing as the support film mentioned above, and it is the same as that of the support film also about a suitable form.

Further, as described above, the reflective film is preferably an optical multilayer film, but the number of laminated layers is preferably in the range of 10 to 80 layers when the optical multilayer film is provided only on one surface of the substrate. More preferably, it is the range of 25-50 layers. On the other hand, when it has an optical multilayer film on both surfaces of the said base material, the range of 10-80 layers is preferable as the total number of lamination | stacking of an optical multilayer film on both surfaces of a base material. More preferably, it is the range of 25-50 layers.
The thickness of the reflective film is preferably 0.5 to 10 μm. More preferably, it is 2-8 micrometers. In the form in which the reflective film is formed on both surfaces of the base material, the total thickness of the reflective films on both surfaces is preferably within the above range.

<Other layers>
The light selective transmission filter of the present invention may have various other functions other than the function of selectively reducing desired light transmittance. For example, in the case of an infrared cut filter which is one of the preferred forms as a light selective transmission filter, the form having various functions other than the infrared cut such as the function of shielding ultraviolet rays, and the infrared cut filter such as toughness and strength The form which has the function to improve the physical property of can be mentioned.
Thus, in the form in which the light selective transmission filter of the present invention has other functions, a functional material layer for forming a reflective film on one surface of the substrate and imparting other functions to the other surface Is preferably formed. The functional material layer is formed directly on the base material by a CVD method, a sputtering method, a vapor deposition method (preferably a vacuum vapor deposition method), or is formed on a temporary base material that has been subjected to a release treatment. The functional material layer can be obtained by pasting the functional material layer onto the base material with an adhesive. It can also be obtained by applying a liquid composition containing a raw material to the substrate, drying it, and forming a film.

The light selective transmission filter of the present invention preferably has a thickness (total thickness of the base material and other layers such as a reflective film) of 1 mm or less. The thickness of the light selective transmission filter refers to the maximum thickness of the light selective transmission filter. More preferably, it is 200 μm or less, more preferably 150 μm or less, and particularly preferably 120 μm or less in that it can meet the demand for thin film formation. Moreover, it is preferable that it is 1 micrometer or more from the point which is excellent in reflow resistance, especially the heat resistance in the temperature of 260 degreeC, More preferably, it is 10 micrometers or more, More preferably, it is 30 micrometers or more. Moreover, it is preferable that the range of the thickness of a light selective transmission filter is 1-150 micrometers, More preferably, it is 10-120 micrometers, More preferably, it is 30-120 micrometers.

By setting the thickness of the light selective transmission filter to 1 mm or less, the light selective transmission filter can be further reduced in size and weight, and can be suitably used for various applications. In particular, it can be suitably used in optical applications such as optical members. In optical applications, as with other optical members, the light selective transmission filter is strongly required to be small and light. Since the light selective transmission filter of the present invention can be made 1 mm or less in thickness, it can achieve a thinner film, especially when used in a lens unit such as an imaging lens. can do. In other words, when a thin light selective transmission filter of 1 mm or less is used as the optical member, the optical path can be shortened and the optical member can be made small. Specifically, the camera module includes a lens, a light selective transmission filter, and a sea moss sensor.

1 and 2 schematically show an example of a camera module. Note that these figures refer to materials from the Electronic Journal 81st Technical Seminar (Electronic Journal 81st Technical Seminar).
As shown in FIG. 1, the light selective transmission filter has a role of cutting light of a desired wavelength (in the camera module, for example, light having a wavelength of 700 nm or more) to prevent malfunction of the sea moss sensor. When a light selective transmission filter is inserted into the camera module, the focal length is extended, so that the back focus is extended and the module is enlarged. When the thickness of the light selective transmission filter is t and the refractive index n is about 1.5, as shown in FIG. 2, the back focus is extended by about t / 3 and the module becomes large, but the light selective transmission filter is thinned. Thus, the focal length can be shortened and the module can be made smaller. Thereby, for example, the optical path length of an optical size of 1/10 inch is preferably 120% or less when there is no light selective transmission filter. More preferably, it is 110% or less, More preferably, it is 105% or less.

The light selective transmission filter of the present invention selectively reduces the light transmittance. The light to be reduced may be between 10 nm and 100 μm, and can be selected depending on the application to be used. Depending on the wavelength of the light to be reduced, it can be an infrared cut filter, an ultraviolet cut filter, an infrared / ultraviolet cut filter, etc. Among them, the infrared light of 650 nm to 10 μm and the ultraviolet light of 200 nm to 350 nm are reduced. It is preferable that other light is transmitted. That is, the light selective transmission filter is preferably an infrared / ultraviolet cut filter.

The infrared cut filter may be a filter having a function of selectively reducing light of any wavelength (range) among light having a wavelength of 650 nm to 10 μm that is an infrared region. The wavelength range to be selectively reduced is preferably 650 nm to 2.5 μm, 650 nm to 1 μm, or 800 nm to 1 μm. A filter that selectively reduces at least one of wavelengths in these ranges is also included in the infrared cut filter. The range of the wavelength to be selectively reduced is more preferably 650 nm to 1 μm in the near infrared region.
The ultraviolet cut filter is a filter having a function of blocking ultraviolet rays. The wavelength range to be selectively reduced is preferably 200 to 350 nm.
The infrared / ultraviolet cut filter is a filter having a function of blocking both ultraviolet rays and infrared rays. The wavelength range to be selectively reduced is preferably the same as described above.

In the embodiment in which the light selective transmission filter of the present invention is an infrared cut filter, it is preferable to selectively reduce the infrared transmittance of 800 to 1000 nm to 5% or less. The transmittance in other wavelength regions is preferably 75% or more, but only the transmittance in a specific wavelength region may be high depending on the use of the filter. For example, when the infrared cut filter is used as a camera module, it is preferable that the transmittance of infrared light is 5% or less and the transmittance of visible light (480 to 550 nm) is 80% or more. More preferably, it is 85% or more. Moreover, it is preferable that the transmittance | permeability of the light of the wavelength range of 500 nm is 85% or more among visible light, and it is more preferable that it is 90% or more. In the infrared cut filter, the transmittance of other wavelengths (other than the infrared region) is more preferably 85% or more, and still more preferably 90% or more. That is, the light selective transmission filter is preferably an infrared cut filter having a light transmittance of 80% or more at a wavelength of 480 to 550 nm and a transmittance of 5% or less at 800 to 1000 nm.
The transmittance can be measured using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation).

In the embodiment in which the light selective transmission filter of the present invention is an ultraviolet cut filter, it is preferable to selectively reduce the transmittance of ultraviolet light of 200 to 350 nm to 5% or less. The transmittance in other wavelength regions is preferably 75% or more.

In the embodiment in which the light selective transmission filter of the present invention is an infrared / ultraviolet cut filter, a filter that selectively reduces infrared light of 650 nm to 10 μm and ultraviolet light of 200 to 350 nm to 5% or less is preferable. The transmittance in the wavelength region is preferably 75% or more.

The light selective transmission filter has a configuration (form) in which a reflective film is formed on at least one surface of a base material containing a dye. This configuration sufficiently reduces the incident angle dependency of light blocking characteristics. can do.
Here, the incident angle dependency of the light blocking characteristic is determined by using, for example, a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation) and the transmittance (for example, 0 °, 20 °, 25 °) with the incident angle changed. , 30 °, etc. The transmittance at an incident angle of 0 ° is a transmittance measured as light enters from the thickness direction of the light selective transmission filter, and the transmittance at an incident angle of 20 ° is a light selection. It is a transmittance measured as light enters from a direction inclined by 20 ° with respect to the thickness direction of the transmission filter.
In addition, the incident angle dependence of the light blocking characteristic needs to be sufficiently reduced by absorption of the absorption layer, and the transmittance spectrum does not change with respect to the change in the incident angle, or the degree of the change is small. It is preferable. Specifically, even if the incident angle is changed from 0 ° to 20 ° (more preferably to 25 °), it is preferable that the transmittance spectrum does not change in the region where the transmittance is 80% or more, more preferably. Is that the transmittance spectrum does not change in a region where the transmittance is 70% or more, and more preferably, the transmittance spectrum does not change in a region where the transmittance is 60% or more. Most preferably, the spectrum does not change in any transmittance region.

As described above, the light selective transmission filter of the present invention has excellent light selective transmission, is not easily damaged, has no warping, undulation, deformation, etc., and is extremely easy to handle, and has an incident angle of light blocking characteristics. Dependence can be sufficiently reduced and sufficient thinning is possible, so it is not only useful as a heat ray cut filter attached to glass in automobiles and buildings, but also as a camera module (solid imaging It is also useful as a filter for blocking optical noise in applications and correcting visibility. Among these, the light selective transmission filter of the present invention is useful as a filter for use in camera modules such as digital still cameras and mobile phone cameras that are becoming thinner and lighter. That is, the light selective transmission filter is preferably a light selective transmission filter for a solid-state imaging device (camera module).

A solid-state imaging device usually includes a lens unit (imaging lens) unit, a light selective transmission filter, and a sensor unit such as a CCD or a CMOS. However, a camera module using the light selective transmission filter of the present invention is usually a lens. It is disposed between a unit (imaging lens) unit and a sensor unit such as a CCD or CMOS. Thus, the solid-state imaging device having at least the light selective transmission filter, the lens unit portion, and the sensor portion of the present invention is also one aspect of the present invention. Normally, in a solid-state imaging device using a reflective light selective transmission filter, a lens unit using a large number of lenses is used to suppress the influence caused by the incident angle dependency (such as the occurrence of color unevenness due to the incident angle). However, in the solid-state imaging device of the present invention, the use of the above-described light selective transmission filter sufficiently eliminates the influence due to the incident angle dependency, so that the number of lenses constituting the lens unit portion Thus, a reduction in thickness and weight can be realized.
In addition, about a lens unit part, the form as described in an international publication 2008/081892 pamphlet can be employ | adopted preferably.

Specific examples of the solid-state imaging device include a mobile phone, a digital camera, a vehicle-mounted camera, a surveillance camera, a display device (LED, etc.), and the like. Thus, a mobile phone camera, a digital camera, an in-vehicle camera, a surveillance camera, and a display device using the light selective transmission filter of the present invention are also included in the preferred embodiments of the present invention.

The light selective transmission filter of the present invention has the above-described configuration, has excellent light selective transmission, is not easily damaged, has no warping, undulation, deformation, etc., has extremely good handling properties, and has excellent practicality. It is. Further, the solid-state imaging device (camera module) using the light selective transmission filter of the present invention captures an image in which the occurrence of color unevenness due to the incident angle, which is a problem by using the reflective light selective transmission filter, is suppressed. be able to. Furthermore, since sufficient thinning is possible, it can be used particularly suitably in applications that require reduction in thickness and weight. Specifically, it can be suitably used for various applications such as optical device applications, display device applications, mechanical parts, electrical / electronic parts, etc., and is particularly useful as a light selective transmission filter for lenses such as imaging lenses, Among them, it is particularly useful as an IR cut filter for camera modules.

It is a cross-sectional schematic diagram which shows the structure of a camera module. It is a schematic diagram which shows the expansion | extension of a back focus by the presence or absence of a light selective transmission filter. It is a conceptual diagram which shows the transmittance | permeability measuring method.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “% by mass”. In addition, the glass transition temperature (Tg) and number average molecular weight of each resin component, and the surface hardness of the obtained light selective transmission filter were measured as follows.

<Glass transition temperature>
It measured using SSC5200H (made by Seiko Denshi Kogyo Co., Ltd.) at a heating rate of 20 ° C./min.
<Number average molecular weight>
It measured by GPC (gel permeation chromatography) by styrene conversion.
Model: HLC-8120GPC manufactured by Tosoh Corporation
Column: G-5000HXL + GMHXL-L
Developing solvent: THF
Flow rate: 1 mL / min
Standard: Standard polystyrene used <Surface hardness measurement>
Using a pencil scratch hardness tester (manufactured by Yasuda Seiki Seisakusho), the surface hardness of the multilayer film was measured according to JIS-K5600-5-4 (established in 1999). The load was 1000 g. It means that the surface hardness is higher toward the right in the order of 2B <B <HB <F <H <2H <3H <4H.

<Synthesis of FPEK (fluorinated polyether ketone)>
Synthesis example 1
In a reactor equipped with a thermometer, a cooling pipe, a gas introduction pipe, and a stirrer, 16.74 parts of BPDE (4,4′-bis (2,3,4,5,6-pentafluorobenzoyl) diphenyl ether), 10.5 parts of HF (9,9-bis (4-hydroxyphenyl) fluorene), 4.34 parts of potassium carbonate, and 90 parts of DMAc (dimethylacetamide) were charged. The mixture was warmed to 80 ° C. and reacted for 8 hours. After completion of the reaction, the reaction solution was poured into a 1% aqueous acetic acid solution with vigorous stirring with a blender. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated polyether ketone polymer (FPEK-HF) corresponding to the fluorinated aromatic polymer.
The polymer had a glass transition temperature (Tg) of 242 ° C. and a number average molecular weight (Mn) of 70770.

Synthesis example 2
The same as Synthesis Example 1 except that 10.1 part of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane (6FBA) was used instead of HF. Thus, a fluorinated polyether ketone polymer (FPEK-6FBA) corresponding to the fluorinated aromatic polymer was obtained.
The polymer had a glass transition temperature (Tg) of 193 ° C. and a number average molecular weight (Mn) of 52420.

Synthesis example 3
It corresponds to the fluorinated aromatic polymer in the same manner as in Synthesis Example 1 except that 6.8 parts of 4,4 ′-(propane-2,2-diyl) diphenol (BA) is used instead of HF. A fluorinated polyether ketone polymer (FPEK-BA) was obtained.
The glass transition temperature (Tg) of the polymer was 180 ° C., and the number average molecular weight (Mn) was 67400.

<Preparation of dye>
Preparation Example 1 (3PhOPcZn)
[Cα, Cα, Cα, 1-tetrakis (phenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (phthalocyanine) System dye, central metal: Zn, absorption maximum wavelength 700 nm, hereinafter abbreviated as “3PhOPcZn”). This 3PhOPcZn is a dye having a structure represented by the formula (6b) obtained by using a phthalonitrile derivative represented by the following formula (6a) (wherein X represents a phenoxy group).

Preparation Example 2 (HBFB)
As a cyanine dye, 1H-Benzindolinium, 3-butyl-2- [5- (3-butyl-1,3-dihydro-1,1-dimethyl-2H-benzindol-2-ylidene) -1,3-pentadiene- 1-yl] -1,1-dimethyl-tetrafluoroborate (1-) (absorption maximum wavelength 680 nm, hereinafter abbreviated as “HBFB”) was prepared.
The structure of HBFB is shown below. As shown below, HBFB has a cation in the conjugated skeleton.

Preparation Example 3 (s2084)
As a squarylium dye, 2- (8-Hydroxy-1,1,7,7-tetramethyl-1,2,3,5,6,7-hexahydropyrido [3,2,1-ij] quinolin-9-yl) -4- (8-hydroxy-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H-pyrido [3,2,1-ij] quinolinium-9 (5H) -ylidene)- 3-oxocyclobut-1-enolate (absorption maximum wavelength 668 nm, hereinafter abbreviated as “S2084”) was prepared.
Note that the structure of S2084 is shown below. As shown below, s2084 has a zwitterion in the conjugated skeleton.

Test example 1
To 5 g of FPEK-HF obtained in Synthesis Example 1, 20 g of toluene and 0.00325 g of 3PhOPcZn were added and dissolved. The solution was poured onto a glass plate, applied with a 500 μm applicator, and then dried at 100 ° C. for 2 hours, 120 ° C. for 2 hours, and 150 ° C. for 2 hours to obtain a 100 μm film. This film is cut into a square of 60 mm square, and a multilayer film [a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on both sides of the film, is deposited on both sides by 25 layers on one side. A total of 50 layers] were deposited. Deposition temperatures were 65 ° C, 90 ° C, 160 ° C, and 180 ° C. The results are summarized in Table 1.

Test example 2
A film was produced in the same manner as in Test Example 1 except that FPEK-6FBA obtained in Synthesis Example 2 was used instead of FPEK-HF, and multilayer film deposition was performed. The results are summarized in Table 1.

Test example 3
A film was produced in the same manner as in Test Example 1 except that FPEK-BA obtained in Synthesis Example 3 was used instead of FPEK-HF, and multilayer film deposition was performed. The results are summarized in Table 1.

Test example 4
To 5 g of FPEK-HF obtained in Synthesis Example 1, 20 g of toluene and 0.00108 g of HBFB were added and dissolved. The solution was poured onto a glass plate, applied with a 500 μm applicator, and then dried at 100 ° C. for 2 hours, 120 ° C. for 2 hours, and 150 ° C. for 2 hours to obtain a 100 μm film. This film is cut into a square of 60 mm square, and a multilayer film [a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on both sides of the film, is deposited on both sides by 25 layers on one side. A total of 50 layers] were deposited. Deposition temperatures were 65 ° C, 90 ° C, 160 ° C, and 180 ° C. The results are summarized in Table 1.

Test Example 5
To 5 g of FPEK-HF obtained in Synthesis Example 1, 20 g of toluene and 0.00108 g of s2084 were added and dissolved. The solution was poured onto a glass plate, applied with a 500 μm applicator, and then dried at 100 ° C. for 2 hours, 120 ° C. for 2 hours, and 150 ° C. for 2 hours to obtain a 100 μm film. This film is cut into a square of 60 mm square, and a multilayer film [a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on both sides of the film, is deposited on both sides by 25 layers on one side. A total of 50 layers] were deposited. Deposition temperatures were 65 ° C, 90 ° C, 160 ° C, and 180 ° C. The results are summarized in Table 1.

Test Example 6
45 g of DMAc and 0.08 g of 3PhOPcZn were added to 5 g of Neoprim L-3430 film (100 μm thickness, Tg: 303 ° C.) manufactured by Mitsubishi Gas Chemical Co., and stirred and dissolved at 120 ° C. for 1 hour. This solution is poured onto a neoprime L-3430 film (100 μm thickness, Tg: 303 ° C.) manufactured by Mitsubishi Gas Chemical Company, and applied with a 10 μm applicator, then at 100 ° C. for 1 hour, 120 ° C. for 1 hour, and 150 ° C. Dry for 1 hour. Furthermore, a 104 μm film was obtained by applying this solution to the back surface in the same manner. This film is cut into a square of 60 mm square, and a multilayer film [a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on both sides of the film, is deposited on both sides by 25 layers on one side. A total of 50 layers] were deposited. Deposition temperatures were 65 ° C, 90 ° C, 160 ° C, and 180 ° C. The results are summarized in Table 1.

Test Example 7
20 g of methylene chloride and 0.00325 g of 3PhOPcZn were added to and dissolved in 5 g of Arton F5023 resin (Tg: 165 ° C.) manufactured by JSR. The solution was poured onto a glass plate, applied with a 500 μm applicator, and then dried at 50 ° C. for 2 hours, 100 ° C. for 2 hours, and 120 ° C. for 2 hours to obtain a 100 μm film. This film is cut into a square of 60 mm square, and a multilayer film [a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on both sides of the film, is deposited on both sides by 25 layers on one side. A total of 50 layers] were deposited. Deposition temperatures were 65 ° C, 90 ° C, 160 ° C, and 180 ° C. The results are summarized in Table 1.

Test Example 8
20 g of methylene chloride and 0.00325 g of 3PhOPcZn were added and dissolved in 5 g of Iupilon E-2000 resin (Tg: 145 ° C.) manufactured by Mitsubishi Engineering Plastics. The solution was poured onto a glass plate, applied with a 500 μm applicator, and then dried at 50 ° C. for 2 hours, 100 ° C. for 2 hours, and 120 ° C. for 2 hours to obtain a 100 μm film. This film is cut into a square of 60 mm square, and a multilayer film [a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on both sides of the film, is deposited on both sides by 25 layers on one side. A total of 50 layers] were deposited. Deposition temperatures were 65 ° C, 90 ° C, 160 ° C, and 180 ° C. The results are summarized in Table 1.

Reference example 1
A multilayer film [a silica (SiO ₂ ) layer and a titania (TiO ₂ ) layer are alternately laminated on both sides of a 50 mm square HOYA blue glass S-C500S (absorption: 600 to 700 nm, thickness 1 mm), A total of 50 layers were deposited on each side by 25 layers. The deposition temperature was 250 ° C. When the surface hardness measurement was performed, the pencil hardness B was not scratched, but the pencil hardness HB was measured together with the substrate glass.

Reference example 2
Multilayer film [Silica (SiO ₂ ) layer and titania (TiO ₂ ) layer alternately laminated on both sides of 50 mm square SCHOTT quartz glass D263 (no absorption, thickness 0.55 mm), 25 layers on one side A total of 50 layers] were deposited on each side. The deposition temperature was 250 ° C. When the surface hardness was measured, the pencil hardness was 4H.

Table 1 summarizes the evaluation results of the light selective transmission filters obtained in the test examples described above. Specifically, the appearance of the surface of the obtained light selective transmission filter (whether it is smooth or warped) is visually evaluated, and the surface of the obtained light selective transmission filter (reflection film) For the surface), the surface hardness (pencil hardness) was measured by the method described above.

From Table 1, the light selective transmission filters of Test Examples 1 to 8 deposited at 65 ° C. and 90 ° C. were smooth without warping or undulation, but both had low surface hardness and were easily scratched. There was a problem in handling. On the other hand, the light selective transmission filters of Test Examples 1 to 6 deposited at 160 ° C. were smooth and had high surface hardness and excellent handleability. Furthermore, the absorption characteristics were not impaired even at such a deposition temperature. Such a reflection absorption filter having a surface hardness of HB or higher (preferably F or higher, more preferably H or higher) is novel. Further, in Test Examples 7 and 8 deposited at 160 ° C., the substrate was warped, swelled and deformed during the deposition, and a practical light selective transmission filter could not be obtained.

<Evaluation of incident angle dependency>
Incident angle dependence was evaluated about the light selective transmission filter obtained by vapor-depositing at 160 degreeC among Test Examples 1-6.
The transmittance at 200 to 1100 nm was measured using Shimadzu UV-3100 (manufactured by Shimadzu Corporation). As shown in FIG. 3, when the light selective transmission filter is installed so as to be perpendicular to the incident light as shown in FIG. 3 (the transmittance spectrum measured in this way is also referred to as 0 ° spectrum. Light selective transmission). Measured when light enters from the thickness direction of the filter) and when the 25 ° light selective transmission filter is tilted with respect to the incident light (the transmittance spectrum thus measured is 25 °). It is also referred to as a spectrum, which is measured in such a manner that light enters from a direction inclined by 25 ° with respect to the thickness direction of the light selective transmission filter.

As a result, although the spectrum was not shown, it was confirmed that there was no change in the spectrum of 0 ° and 25 ° in the region where the transmittance was 60% or more, and the incident angle dependency of the light blocking characteristic was reduced. Therefore, it was also found that the light selective transmission filter of the present invention has a performance to reduce the incident angle dependency of the light blocking characteristic.

1: Lens 2: Light selective transmission filter 3: Sensor 4: Light source 5: Light selective transmission filter 6: Light receiving portion

Claims (5)

A light selective transmission filter having a base material and a reflective film formed on at least one surface thereof,
The substrate includes one or more dyes,
The light selective transmission filter, wherein the surface hardness of the light selective transmission filter is HB to 4H. The light selective transmission filter according to claim 1, wherein the base material further includes a resin component. A solid-state imaging device comprising at least the light selective transmission filter according to claim 1, a lens unit portion, and a sensor portion. A base material for a selective light transmission filter, which is a base material used for the selective light transmission filter according to claim 1. A method for producing a light selective transmission filter according to claim 1 or 2,
The manufacturing method includes a step of depositing a reflective film at a temperature of 160 ° C. or higher on at least one surface of a base material.

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