JP2014067019A - Resin composition for forming light selective transmission filter and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition capable of forming a light selective transmission filter which has excellent light selective transmission, whose incident angle dependency is sufficiently reduced, and which can sufficiently cope with a film thinning request, and to provide the light selective transmission filter using the resin composition, a resin sheet used for the light selective transmission filter, and a solid-state imaging device having the light selective transmission filter.SOLUTION: The resin composition for forming the light selective transmission filter is the resin composition containing two or more kinds of dyes and a resin component and used for forming the light selective transmission filter. The two or more kinds of dyes include at least a dye A and a dye B which have different absorption characteristics.

Description

The present invention relates to a resin composition for forming a light selective transmission filter and its use. More specifically, in addition to optical members and opto-device members, resin compositions used for the formation of light selective transmission filters useful for applications such as display device parts, mechanical parts, and electrical / electronic parts, and light selective transmission using the same The present invention relates to a solid-state imaging device having a filter, a resin sheet, and 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. In recent years, application to applications that can be used outdoors, such as mobile phones, digital cameras, in-vehicle cameras, surveillance cameras, display elements (LEDs, etc.), has also been studied. Thus, resistance to the external environment such as high light resistance is required.

As the light selective transmission filter using resin as a base material, there are mainly a reflection type filter having a function of reflecting light and an absorption type filter having a function of absorbing light. Although it is excellent in performance, it has an incident angle dependency (also referred to as a viewing angle dependency) in which the reflection characteristic changes depending on the incident angle of light, and reduction thereof has been a problem. On the other hand, although the absorption filter is not dependent on the incident angle, a considerable thickness is required to realize sufficient absorption characteristics, and there is room for improvement from the viewpoint of thinning.

Therefore, a filter using both a reflection function and an absorption function has been proposed. For example, Patent Document 1 discloses a light absorption obtained by applying and drying a pigment ink containing a near-infrared absorber on a glass substrate. A light absorption filter is disclosed in which a film and a film having a higher refractive index than the light absorption film are alternately laminated. This light absorption filter is intended to realize thinning while reducing the angle dependency. Patent Document 2 discloses a resin containing a specific squarylium compound for the purpose of obtaining a near-infrared cut filter having a wide viewing angle, excellent near-infrared cutting ability, low hygroscopicity, and having no foreign matter or warping. A near-infrared cut filter having a substrate is disclosed. Furthermore, Patent Document 3 is transparent for the purpose of providing a near-infrared cut filter that can be reduced in thickness, has high transparency in the visible light region, and has excellent stopping power in the near-infrared region. A near-infrared cut filter comprising a base material 1, optical multilayer films 2 and 3 formed on one or both surfaces of the base material 1, and at least one resin absorption film 4 formed on at least one surface of the base material 1. It is disclosed. In Patent Document 3, the optical multilayer films 2 and 3 are formed by alternately laminating two or more kinds of thin films having different refractive indexes, and exhibit high transmission characteristics in the visible light region and low transmission characteristics in the near infrared region. The resin absorbing film 4 is a film formed by coating a resin material to which a dye or pigment is added, and the dye or pigment is described as a film having absorption in the near infrared region.

JP 2006-106570 A JP 2012-008532 A JP 2006-301894A

As described above, various light selective transmission filters have been studied, which can sharply block the wavelength range (for example, the infrared region) to be blocked and have high transmittance in the wavelength range (for example, the visible region) to be transmitted. There is a demand for a light selective transmission filter that is excellent in light selective transmission as shown, and that can further reduce the incidence angle dependency of the blocking performance and reduce the film thickness. However, none of the conventional resin compositions can sufficiently satisfy all of these requirements. For example, in the light selective transmission filters described in Patent Documents 1 to 3, there is room for contrivance for further reducing the incident angle dependency and exhibiting sharper light selective transmission.

The present invention has been made in view of the above-mentioned present situation, and has an excellent light selective transmission property, a light selective transmission filter that has a sufficiently reduced incident angle dependency and can fully meet the demand for thinning. It is an object of the present invention to provide a resin composition capable of forming a light-sensitive material, a light selective transmission filter using the same, a resin sheet used for the light selective transmission filter, and a solid-state imaging device having the light selective transmission filter.

The inventors of the present invention have studied various resin compositions useful for the formation of a light selective transmission filter. In order to obtain a light selective transmission filter applicable to various applications, a phthalocyanine dye is used from the viewpoint of light resistance. It was noted that the resin composition was useful. Then, in the resin composition containing the dye and the resin component, when a phthalocyanine dye is used as the dye, attention is paid to the fact that two absorption maxima are observed in the wavelength region of 600 to 800 nm. Has a maximum absorption wavelength (λ _A2 ), and when a phthalocyanine dye (Dye A) in which the ratio of absorbance at two absorption maximum wavelengths is within a specific range, sharp transmission absorption characteristics are exhibited at the long wavelength side. And when it combined with the reflective film, it discovered that incident angle dependence could be fully reduced. On the other hand, since the absorption band width is narrow, even when it is desired to block light having a large incident angle, it has been found that there is a problem that a part of the light is transmitted and cannot be sufficiently blocked. Therefore, when another dye B is used in combination with a dye having a maximum absorption wavelength λ _B on the shorter wavelength side than the maximum absorption wavelength (λ _A2 ) of the dye A, a sufficient absorption band width can be secured and sharp transmission absorption can be achieved. It has been found that a light selective transmission filter which exhibits characteristics and can sufficiently reduce the incident angle dependency when combined with a reflective film can be obtained.

Such unique optical characteristics of the resin composition are particularly effective when applied to a light selective transmission filter, particularly when applied to a light selective transmission filter for lenses such as an imaging lens. Further, when a resin sheet including a resin layer formed of such a resin composition is used as a resin sheet included in the light selective transmission filter, the incident angle dependency is increased when a reflection film (reflection layer) is further included. It has also been found that the light selective transmission filter can be stably reduced over a long period of time, and that the entire light selective transmission filter can be made much thinner compared to the case where glass is used as the substrate. Then, it is found that such a light selective transmission filter is a light selective transmission filter that is extremely effective for optical applications such as solid-state imaging devices and optical device applications, especially for lens applications, and to solve the above-mentioned problems brilliantly. The present invention was reached.

That is, the present invention is a resin composition that includes two or more dyes and a resin component, and is used for forming a light selective transmission filter, and the two or more dyes include dye A and dye B having different absorption characteristics. The dye A includes at least a phthalocyanine dye having two absorption maximum wavelengths (λ _A1 , λ _A2 ) in a wavelength range of 650 to 800 nm, and has a maximum absorption wavelength λ _A2 on the long wavelength side thereof, said maximum absorption wavelength lambda _A2, rather than the maximum absorption wavelength lambda _B of the dye B is in the long wavelength side, the two absorption maximum wavelength (λ _A1, λ _A2) absorbance ratio at _(a A2 _/ a _A1) is The light selective transmission filter-forming resin composition satisfying 2 or more when the absorbance of a composition comprising the dye A and a resin component and the content ratio of the dye A being 3% by mass is measured.

The present invention is also a light selective transmission filter including a resin sheet, and the resin sheet is a light selective transmission filter including a resin layer formed from the resin composition for forming a light selective transmission filter.
The present invention is also a resin sheet used for the light selective transmission filter.
The present invention is also a solid-state imaging device having at least the light selective transmission filter, the lens unit section, and the sensor section described above.
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.

In this specification, “absorption maximum” means that the relationship between wavelength and absorbance is represented by a two-dimensional graph of the X axis and Y axis (where the X axis is the wavelength and the Y axis is the absorbance) It means the peak at which the absorbance changes from increasing to decreasing, and the wavelength at this peak is called the “absorption maximum wavelength”. Further, among absorption maximum wavelengths (also referred to as absorption peak wavelengths), those having the maximum absorbance are referred to as maximum absorption wavelengths (also referred to as “maximum absorption peak wavelengths”).

[Resin composition for forming light selective transmission filter]
The resin composition for forming a light selective transmission filter of the present invention (hereinafter also simply referred to as a resin composition) is a resin composition used for forming a light selective transmission filter and contains a dye and a resin component. It is preferable that the pigment is dispersed or dissolved in a resin composition containing a resin component.
In addition, although it is suitable to use 2 or more types of pigment | dyes, the resin component can use 1 type, or 2 or more types, Moreover, the said resin composition is 1 type of other components further as needed. Or it may contain 2 or more types.

-Dye-
The said pigment | dye contains the pigment | dye A and the pigment | dye B from which an absorption characteristic differs at least.
The dye A is a phthalocyanine dye that satisfies the following absorption characteristics (1) to (3). By using such a dye A in combination with another dye B, a sufficient absorption band width can be secured. In addition, a light selective transmission filter having excellent light selective transmission can be provided, and the obtained light selective transmission filter has excellent durability.
(1) It has two absorption maximum wavelengths (λ _A1 , λ _A2 ) in a wavelength range of 650 to 800 nm, and has a maximum absorption wavelength λ _A2 on the long wavelength side.
(2) The maximum absorption wavelength λ _A2 of the dye A (that is, the wavelength of the peak having the lowest transmittance) λ _A2 is on the longer wavelength side than the maximum absorption wavelength λ _B of the dye B.
(3) The absorbance ratio (A _A2 / A _A1 ) at the two absorption maximum wavelengths (λ _A1 , λ _A2 ) is composed of the dye A and the resin component, and the content ratio of the dye A is 3% by mass. When the absorbance of the composition is measured, it satisfies 2 or more.

The two absorption maximum wavelengths (λ _A1 , λ _A2 ) may be in the wavelength range of 650 to 800 nm, and at least one of them is preferably in the wavelength range of 650 to 730 nm. That is, it is preferable that there are two absorption maximum wavelengths in the wavelength range of 650 to 800 nm, and at least one of them exists in the range of 650 to 730 nm. By having such absorption characteristics, the wavelength range desired to be cut off can be cut off more sharply, and the light selective transparency that shows high transmittance in the wavelength range desired to be transmitted is further improved. When combining a resin sheet using a reflective film with a reflective film, it becomes possible to significantly reduce the incident angle dependency of the reflective film.

Of the above two absorption maximum wavelengths, if the wavelength on the short wavelength side is λ _A1 and the wavelength on the long wavelength side is λ _A2 , the wavelength of the peak with the highest absorption (that is, the wavelength of the peak with the lowest transmittance). ) Is on the long wavelength side, that is, λ _A2 . This makes it possible to show a sharp transmission / absorption characteristic on the short wavelength side close to 600 nm, so that the incident angle dependency can be sufficiently reduced. Further, it is preferable that the maximum absorption wavelength λ _A2 exists in a wavelength range of 650 to 730 nm. More preferably, the maximum absorption wavelength λ _A2 exists in a wavelength region of 680 to 720 nm. The transmittance at the maximum absorption wavelength λ _A2 is preferably 60% or less, more preferably 50% or less, still more preferably 30% or less, and particularly preferably 20% or less.

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.
In any case, it is preferable to use a solvent dispersion method. In the solvent dispersion method, a solution obtained by dissolving a dye in a solvent (for example, chloroform or dimethylacetamide) is filled in a 1 cm thick transparent quartz cell, and a spectrophotometer (for example, Shimadzu UV-3100, Shimadzu Corporation) is used. Can be used. If the measurement mode is absorbance, the dye absorption spectrum is obtained, and if the measurement mode is transmittance, the dye transmittance spectrum is obtained. Although the density | concentration of the pigment | dye at the time of a 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 0.00001- 0.001% by mass.

The dye A also has a peak wavelength (that is, transmittance) of the two absorption maximum wavelengths (λ _A1 , λ _A2 ) when the absorbance characteristics are evaluated by the resin film evaluation method. The wavelength of the lowest peak is preferably λ _A2 . This makes it possible to exhibit a sharp transmission / absorption characteristic on the short wavelength side close to 600 nm, and thus further improves the light selective transparency. Furthermore, the larger the ratio (A _A2 / A _A1 ) of the absorbance at the two absorption maximum wavelengths (λ _A1 , λ _A2 ), the better the visible light transmittance at 650 nm or less, and the longer the wavelength than 650 nm. It becomes possible to show sharp transmission and absorption characteristics on the side. The absorbance ratio (A _A2 / A _A1 ) is preferably 2.0 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. Moreover, although an upper limit is not specifically limited, A thing of 10 or less is easy to obtain industrially and preferable.

The absorbance (A _A1 , A _A2 ) is a value obtained by measuring the absorbance of a composition comprising the dye A and a resin component and the content ratio of the dye A being 3% by mass. The absorbance can be measured using, for example, Shimadzu Corporation UV-1800 (measuring machine).
In addition, it is suitable to use a polyimide resin for the resin component at the time of measuring the said light absorbency ( _AA1 , _AA2 ).

The “resin film evaluation method” is a method for evaluating the absorbance characteristics in the state of a film dispersed or dissolved in a resin component.
The “film dispersed or dissolved in the resin component” is a film made of a specific dye and a resin component, and is a condition (λ _A1 ) capable of evaluating the absorbance at two absorption maximum wavelengths (λ _A1 , λ _A2 ). In this case, the content of the specific dye and the thickness of the film may be selected so that the absorbance at λ _A2 satisfies the conditions under which the absorbance can be measured without exceeding the measurement limit of the spectrophotometer.
In the resin film evaluation method, the film for evaluation is preferably selected from a range in which the content ratio of the specific dye is 0.01 to 15% by mass and a thickness of the film is in the range of 0.1 to 10 μm. More preferably, the pigment content is 3% by mass and the film thickness is 3 μm.
The film for evaluation contains a specific dye and a resin component (may contain a solvent if necessary), and is formed (applied, dried if necessary) on a transparent substrate (glass, transparent resin film). Can be obtained. By measuring the absorbance of the substrate with film thus obtained, the absorbance A _A1 , A _A2 , A _A2 / A _A1 of the dye can be obtained.

Here, depending on the combination of specific dye and the resin component, even if changing the thickness of the content and film in particular dyes, sometimes the absorption maximum at the position of the lambda _A2 is not observed. In such a case, in a film in which the absorbance at λ _A1 is not saturated and the absorbance can be measured, the absorbance at λ _A1 (maximum value) A _A1 and the absorbance at a wavelength corresponding to λ _A2 confirmed by the solvent dispersion method are expressed as A _A2 And the ratio (A _A2 / A _A1 ) may be obtained.
In addition, although it does not specifically limit as a resin component for evaluation, In the film | membrane using at least 1 sort (s) of the resin component which can be used as a resin component of this invention mentioned later, the above-mentioned (A _A2 / A _A1 ) ratio is satisfied. Any specific dye can be suitably used for the resin composition of the present invention. The resin component for evaluation is preferably a solvent-soluble resin described later. A resin component preferable as a resin component for evaluation is also preferably one selected from the group consisting of a fluorinated aromatic polymer, a poly (amide) imide resin, a polyamide resin, an aramid resin, and a polycycloolefin resin. Among these, a fluorinated aromatic polymer or a poly (amide) imide resin is more preferable, a poly (amide) imide resin is more preferable, and a polyimide resin is particularly preferable.
The absorbance can be measured using, for example, Shimadzu Corporation UV-1800 (measuring machine).

The dye A may be a phthalocyanine dye that satisfies the absorption characteristics (1) to (3) described above. Specifically, for example, one of the compounds represented by the following general formula (I) or Two or more are preferably used.

Wherein, M ¹ is represents a metal atom, a metal oxide or a metal halide. R ^{a1 to} R ^a4 , R ^{b1 to} R ^b4 , R ^{c1 to} R ^c4 and R ^{d1 to} R ^d4 may be the same or different and may have a hydrogen atom (H), a fluorine atom (F) or a substituent. Represents a good OR ⁱ group. The OR ⁱ group represents an alkoxy group, a phenoxy group or a naphthoxy group. However, all of R ^{a1 to} R ^a4 and R ^{d1 to} R ^d4 do not represent a hydrogen atom (H) or a fluorine atom (F).

In the general formula (I), R ⁱ constituting the OR ⁱ group is an alkyl group, a phenyl group, or a naphthyl group, and may have a substituent. As the alkyl group, for example, an alkyl group having 1 to 20 carbon atoms is preferable, more preferably an alkyl group having 1 to 8 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably carbon. It is a C 1-4 alkyl group.

Examples of the substituent that the OR ⁱ group may have include electrons such as an alkoxycarbonyl group (—COOR), a halogen group (halogen atom), a cyano group (—CN), and a nitro group (—NO ₂ ). An attractive group; an electron donating group such as an alkyl group (—R); and the like, and may include one or more of these. The electron withdrawing group is preferably an alkoxycarbonyl group, a chloro group (chlorine atom) or a cyano group, and more preferably a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chloro group or a cyano group.
Note that R constituting the alkoxycarbonyl group (—COOR) and the alkyl group (—R) is preferably an alkyl group having 1 to 4 carbon atoms. The alkoxycarbonyl group is preferably a methoxycarbonyl group or a methoxyethoxycarbonyl group, and the alkyl group is preferably a methyl group or a dimethyl group.

When the OR ⁱ group has a substituent, the number of substituents is not particularly limited, but is preferably 1 to 4, for example. More preferably, it is 1 or 2.
When one OR ⁱ group has two or more substituents, the substituents may be the same or different. Further, the position of the substituent in the OR ⁱ group is not particularly limited.

R ^{a1 to} R ^a4 , R ^{b1 to} R ^b4 , R ^{c1 to} R ^c4 and R ^{d1 to} R ^d4 are preferably such that at least one of them represents an OR ⁱ group. Thereby, it will become more excellent in light resistance.
Here, the carbon to which the OR ⁱ group is bonded is the α-position carbon in the four aromatic rings of the phthalocyanine skeleton (C _α : the carbon at the 1,4,8,11,15,18,22,25-position of the phthalocyanine ring. Or β-position carbon (C _β : represents the 2,3,9,10,16,17,23,24-position carbon of the phthalocyanine ring), but at least the α-position carbon. Is preferred. Among them, form OR ⁱ group is attached to an average of 2 or more carbons of the alpha-position carbon (C _alpha), and more preferably, OR ⁱ to one or more alpha-position carbon (C _alpha) on each aromatic ring This is a form in which groups are bonded. Moreover, it is also preferable that a hydrogen atom or a fluorine atom is bonded to an average of 4 or more carbons in the β-position carbon (C _β ). More preferably, a hydrogen atom or a fluorine atom is bonded to an average of 6 or more carbons among β-position carbon (C _β ), and still more preferably, hydrogen atoms are bonded to all carbons of β-position carbon (C _β ). Or it is the form which the fluorine atom couple | bonded. By setting it as such a form, since it becomes a phthalocyanine type pigment | dye which fully satisfy | fills the absorption characteristics (1)-(3) mentioned above, it becomes possible to fully exhibit the effect of this invention.

In the general formula (I), M ¹ represents a metal atom, a metal oxide or a metal halide. The metal atom and the metal atom constituting the metal oxide or metal halide are not particularly limited. For example, copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, Lead etc. are mentioned, These 1 type (s) or 2 or more types can be used. Especially, since solubility, visible-light transmittance, and light resistance are more excellent, what uses any one or more of copper, vanadium, and zinc as a central metal is preferable. More preferably, it is copper or zinc, More preferably, it is copper. The phthalocyanine dye having copper as a central metal is not deteriorated by light even when dispersed in any resin component (binder resin), and has very excellent light resistance. On the other hand, a phthalocyanine complex (phthalocyanine dye) having zinc as a central metal has excellent solubility in a resin component, high light transmittance in a wavelength region of 400 to 600 nm, and high light absorption in a wavelength region of 600 to 800 nm. Since it is easy to obtain a light selective transmission filter having properties, it is particularly preferable.

The halogen atom which comprises the said metal halide is not specifically limited, For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned.

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, a metal halide represented by M ¹ Xn (wherein M ¹ represents a metal atom, X represents a halogen atom or an organic acid group, and n is a valence) or An organic acid metal or a metal compound such as a metal or metal oxide (that is, a metal compound selected from the group consisting of metal, metal oxide, metal carbonyl, metal halide and organic acid metal) and Formula (i):

(Wherein R ^{a to} R ^d are the same or different and represent a hydrogen atom (H), a fluorine atom (F), or an OR ⁱ group which may have a substituent. The OR ⁱ group is an alkoxy group) And a phthalonitrile derivative represented by phenoxy group or naphthoxy group) is preferably obtained by heating and reacting in the presence of no solvent or an organic solvent. Especially, it is preferable to make it react in an organic solvent. The cyclization reaction of the phthalonitrile derivative is not particularly limited, and is conventionally described in JP-B-631239, JP37212298, JP32226504, JP2010-77408, and the like. Known methods can be applied singly or appropriately modified. Specific forms of the substituent and the OR ⁱ group are as described above for the general formula (I).

In the general formula (i), R ^{a to} R ^d are preferably such that at least one of these represents an OR ⁱ group. Among them, it is preferable that R ^a and / or R ^d (α position) is an OR ⁱ group. In addition, R ^b and / or R ^c (β position) is preferably a hydrogen atom or a fluorine atom, and more preferably, both R ^b and R ^c are a hydrogen atom or a fluorine atom.

In the above reaction, two or more compounds different from each other in R ^{a to} R ^d may be used in combination as the phthalonitrile derivative represented by the general formula (i).

The metal compound is not particularly limited as long as it reacts with the phthalonitrile derivative to give the compound represented by the general formula (I). For example, metals such as iron, copper, zinc, vanadium, titanium, indium and tin; metal halides such as chloride, bromide and iodide of the metal; vanadium oxide, titanyl oxide and copper oxide of the metal Metal oxide; organic acid metal such as acetate of the metal; complex compound of the metal such as acetylacetonate; metal carbonyl such as carbonyl iron; and the like.

Among these metal compounds, examples of the metal halide and organic acid salt metal represented by M ¹ Xn include cuprous iodide, zinc iodide, indium iodide, cuprous chloride, and cupric chloride. , Zinc chloride, indium chloride, cuprous bromide, cupric bromide, zinc bromide, indium bromide, cupric fluoride, zinc fluoride or indium fluoride, zinc acetate, copper acetate, copper stearate And zinc stearate. Among these, cuprous iodide, zinc iodide, indium iodide, cuprous chloride, cupric chloride, indium chloride, copper stearate, and zinc stearate are preferable.

When the reaction of the metal compound such as the metal halide or organic acid metal and the phthalonitrile derivative represented by the general formula (i) is performed in an organic solvent, examples of the organic solvent include benzene, toluene, and xylene. , Inert solvents such as nitrobenzene, monochlorobenzene, dichlorobenzene, trichlorobenzene, chloronaphthalene, methylnaphthalene, ethylene glycol and benzonitrile; aprotic such as dimethylsulfoxide, dimethylformamide, N-methyl-2-pyrrolidone and dimethylsulfone 1 type, or 2 or more types, such as polar solvent; Of these, chloronaphthalene, N-methyl-2-pyrrolidone, nitrobenzene, ethylene glycol, and benzonitrile are preferable.

When a solvent is used in the above reaction, the amount of the organic solvent used is preferably such that the concentration of the phthalonitrile compound represented by the general formula (i) is 1 to 50% by mass. More preferably, the amount is 10 to 40% by mass.

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. Although there is no restriction | limiting in particular also for reaction time, Usually, it is preferable to set it as 2 to 24 hours, More preferably, it is 5 to 20 hours.
The above reaction may also be performed in an air atmosphere, but depending on the type of metal compound, an inert gas or oxygen-containing gas atmosphere (for example, nitrogen gas, helium gas, argon gas, oxygen / nitrogen mixed gas, etc.) It is preferable to be carried out under the distribution of
After the cyclization reaction, crystallization, filtration, washing, and / or drying may be performed according to a conventionally known method.

As the dye A, one or more compounds represented by the following general formula (II) are also preferably used.

Wherein, M ² represents a metal atom, a metal oxide or a metal halide. Z ² , Z ³ , Z ⁶ , Z ⁷ , Z ¹⁰ , Z ¹¹ , Z ¹⁴ and Z ¹⁵ are the same or different, and the substituent (a) represented by the following formula (ii-a) or the following The substituent (b) represented by Formula (ii-b) is represented. Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ are the same or different and are a fluorine atom or a substituent represented by the following formula (ii-b ′) ( b ′). Here, when Z ¹ and Z ⁴ are unit 1; Z ⁵ and Z ⁸ are unit 2; Z ⁹ and Z ¹² are unit 3; Z ¹³ and Z ¹⁶ are unit 4; 1 to 3 of the two groups (atoms) constituting the unit each represent a fluorine atom, and the remaining units are each a substituent (b ′) of the two groups (atoms) constituting the unit. Or one of two groups (atoms) constituting the unit represents a substituent (b ′) and the other represents a fluorine atom.

In formula (ii-a), R ¹ is the same or different and represents a chlorine atom, a bromine atom, a nitro group or a cyano group. m ¹ is an integer of 1 to 5. R ² may be the same or different and may have a substituent, an alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, —COOR ³ , Represents a fluorine atom. R ³ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. m ^{1 ′} is an integer of 0 to 4.
In formula (ii-b), R ^{4 s} are the same or different and may have a substituent, an alkyl group having 1 to 20 carbon atoms, and an optionally substituted substituent having 1 to 20 carbon atoms. an alkoxy group, -COOR ^5, or represents a fluorine atom. R ⁵ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. n ¹ is an integer from 0 to 5.
In formula (ii-b ′), R ^{4 ′} is the same or different and may have a substituent, an alkyl group having 1 to 20 carbon atoms, or an optionally substituted carbon atom having 1 to 1 carbon atoms. 20 represents an alkoxy group, —COOR ^{5 ′} , an optionally substituted aryl group having 6 to 30 carbon atoms, or a halogen atom. R ^{5 ′} represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. n ¹ ′ is an integer of 0 to 5.

In the general formula (II), M ² represents a metal atom, a metal oxide, or a metal halide. Preferred forms of the metal atom and the metal atom constituting the metal oxide or metal halide are as follows: during the above-mentioned formula (I), it is similar to the metal atom represented by M ^1.

As the dye A, one or more compounds represented by the following general formula (III) are also preferably used.

Wherein, M ³ represents a metal-free, metal atom, a metal oxide or a metal halide. Z ^{17 to} Z ³² are the same or different and are represented by a fluorine atom, a chlorine atom, a bromine atom, a substituent (iii-a) represented by the following formula (iii-a), and a formula (iii-b) below. Substituent (iii-b), substituent (iii-c) represented by the following formula (iii-c), substituent (iii-d) represented by the following formula (iii-d), the substituent (iii-e) represented by iii-e), the substituent (iii-f) represented by the following formula (iii-f), and the substituent (iii) represented by the following formula (iii-g) -G), the group (iii-h) derived from 7-hydroxycoumarin, or the group (iii-i) derived from 2,3-dihydroxyquinoxaline. Here, 6 to 12 of Z ^{17 to} Z ³² are the substituents (iii-a), (iii-c), (iii-d), (iii-e), (iii-f), (iii) -G), any one of (iii-h) and (iii-i), or 9-12 of these are substituents (iii-b), and the rest are fluorine atoms, base atoms Or represents a bromine atom.

In formulas (iii-a) and (iii-b), R ⁵ represents an alkoxy group having 1 to 8 carbon atoms or a halogen atom. R ⁶ represents an alkylene group having 1 to 3 carbon atoms. R ⁷ represents an alkyl group having 1 to 8 carbon atoms. p is an integer of 0-4. n ² is an integer of 1 to 3. m ² is an integer of 1 to 4.
In formulas (iii-c) and (iii-d), R ⁸ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or a group represented by — (R ⁶ O) _m2 R ⁷ . R ⁵ , p, R ⁶ , m ² and R ⁷ have the same definitions as the respective symbols in the above formulas (iii-a) and (iii-b).
In the formulas (iii-e), (iii-f), and (iii-g), X ¹ represents an oxygen atom or a sulfur atom. Ar represents a phenyl group or a naphthyl group which may be substituted with one or more R ⁹ . R ⁹ is the same or different and represents a cyano group, a nitro group, COOY ¹ , OY ¹ , a halogen atom, an aryl group, or an alkyl group having 1 to 8 carbon atoms which may be substituted with a halogen atom. Y ¹ represents an alkyl group having 1 to 12 carbon atoms. R ¹⁰ represents a halogen atom or an alkyl group having 1 to 8 carbon atoms which may be substituted with an alkoxy group having 1 to 8 carbon atoms. R ¹¹ represents an alkylene group having 1 to 5 carbon atoms. R ¹² is the same or different and represents an alkoxy group having 1 to 8 carbon atoms or an alkyl group having 1 to 8 carbon atoms.

The dye B is not particularly limited as long as it has the maximum absorption wavelength λ _B on the shorter wavelength side than the maximum absorption wavelength λ _A2 of the dye A described above. For example, phthalocyanine dyes other than the dye A described above, porphyrin dyes, chlorin dyes, choline dyes, cyanine dyes, quaterylene dyes, squarylium dyes, naphthalocyanine dyes, nickel complex dyes, copper ion dyes, etc. These can be used, and one or more of these can be used. Among these, it is preferable to use a phthalocyanine dye other than the dye A.

The phthalocyanine dye other than the dye A preferably has two absorption maximum wavelengths in the wavelength range of 600 to 800 nm, and at least one absorption maximum wavelength exists in the range of 600 to 730 nm. That is, it is preferable that there are two absorption maximum wavelengths in the wavelength range of 600 to 800 nm, and at least one of them exists in the range of 600 to 730 nm. By having such absorption characteristics, the wavelength range desired to be cut off can be cut off more sharply, and the light selective transparency that shows high transmittance in the wavelength range desired to be transmitted is further improved. When an absorption sheet (resin sheet) using a light source is combined with a reflective film, the incident angle dependency due to the reflective film can be greatly reduced.

Of the above two absorption maximum wavelength, the wavelength on the short wavelength side lambda _B1, and the wavelength on the long wavelength side and lambda _B2, lambda _B1 is more preferably be present in a wavelength region 730 nm, more preferably Is in the wavelength region of 700 nm or less. Particularly preferably, it exists in a wavelength region of 680 nm or less. The lower limit of the absorption maximum wavelength λ _B1 is more preferably 650 nm or more. It is preferable to use a dye having a transmittance of 90% or more at a wavelength of 500 nm and a transmittance of 60% or less at the maximum absorption wavelength λ _B1 . The transmittance at the maximum absorption wavelength λ _B1 is more preferably 50% or less, still more preferably 30% or less, and particularly preferably 20% or less.

The ratio of absorbance (A _B2 / A _B1 ) at the absorption maximum wavelength (λ _B1 , λ _B2 ) of the dye B can be evaluated by the same method as that for the dye A. Of the two absorption maximum wavelengths (λ _B1 , λ _B2 ), it is preferable that the peak wavelength having the highest absorption rate (that is, the peak wavelength having the lowest transmittance) is λ _B1 . This makes it possible to exhibit a sharp transmission / absorption characteristic on the short wavelength side close to 600 nm, and thus further improves the light selective transparency. Also, the smaller the absorbance ratio (A _B2 / A _B1 ) at the above two absorption maximum wavelengths (λ _B1 , λ _B2 ), the more preferable the absorption waveform on the shorter wavelength side than λ _B1 becomes sharper. is there. Specifically, it is suitable that it is 0.75 or less. When (A _B2 / A _B1 ) is larger than 0.75, there is a possibility that the rising of the absorption on the shorter wavelength side than the maximum absorption wavelength becomes gentle. The absorbance ratio (A _B2 / A _B1 ) is preferably 0.75 or less, and more preferably 0.5 or less. The lower limit of (A _B2 / A _B1 ) is preferably 0 or more.

In addition, in this invention, although the pigment | dye which does not correspond to any of the said pigment | dye A and the pigment | dye B may be included as needed, content of such another pigment | dye is the effect by the said pigment | dye A and the pigment | dye B. Is preferably 30% by mass or less with respect to 100% by mass of the total amount of the pigments. 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.

The resin composition may also contain a compound having an absorptivity in the wavelength range of 350 to 400 nm. Thereby, deterioration of the light selective transmission filter (and the resin sheet) due to light in the wavelength range of 350 to 400 nm (substantially purple light) can be sufficiently suppressed.
Here, the form containing the compound having the absorption ability in the wavelength range of 350 to 400 nm is a form in which the dye A and / or dye B is a compound having an absorption ability in the wavelength range of 350 to 400 nm. Alternatively, it may be separately used in combination with a compound having an absorptivity in the wavelength range of 350 to 400 nm. Examples of the latter compound having an absorptivity in the wavelength range 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-
In the resin composition, the resin component is preferably a resin component that can sufficiently dissolve or disperse the pigment. That is, it is preferable that the pigment is uniformly dispersed or dissolved in the resin composition. By appropriately selecting such a resin component, both high transmittance in the wavelength range (for example, visible region) to be transmitted and high absorbency in the wavelength region (for example, infrared region) to be blocked are compatible. Is possible.

As the resin component, for example, at least one selected from the group consisting of a solvent-soluble resin, a solvent-soluble resin material, and a liquid resin material is suitable. 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. In addition, when the resin component is used, a resin layer in the light selective transmission filter 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, The resin layer can be formed at a relatively low temperature.
In addition, the resin layer itself formed of the resin composition included in the light selective transmission filter 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 ¹³ 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 ³ represents the 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 (1-2), R ¹⁴ 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 ¹⁵ 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 ³ represents the 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 ¹³ —O—) is bonded to the aromatic ring is preferably para to Z.

In the general formulas (1-1) and (1-2), R ¹³ and R ¹⁵ 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 preferred specific examples of R ¹³ and R ¹⁵ 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 ¹⁴ in the general formula (1-2), examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, 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 ¹⁴ 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 ¹⁴ 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. In this structure, a carboxyl group is bonded to a carbon atom, which is formed by a 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 ¹⁶ are the same or different and each represents an organic group) is preferable.
The ^{R 16} in the general formula (5), the divalent organic group is preferable, and is 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 ¹⁶ 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.
In addition, each R ¹⁶ in the repeating unit represented by the general formula (5) may be the same or different.

The organic group represented by R ¹⁶ 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.

-Other ingredients-
Although the said resin composition contains a pigment | dye and a resin component as mentioned above, it may contain another component further as needed. Examples of the other components include the other pigments described above. When the inorganic component such as a metal oxide is included as the other component, the content is a resin composition from the viewpoint of excellent transparency to visible light. It is preferable that it is less than 50 mass% in 100 mass% of things. 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.

-Manufacturing method of resin composition-
The resin composition essentially includes the phthalocyanine dye and the resin component described above, and may contain other components as necessary, but the preparation method is not particularly limited. These components can be obtained by mixing in a usual manner. For example, it can be obtained by adding a resin component and, if necessary, a solvent component to the pigment, mixing and dissolving.

[Light selective transmission filter]
The present invention is also a light selective transmission filter including a resin sheet, and the resin sheet is also a light selective transmission filter including a resin layer formed from the above-described resin composition for forming a light selective transmission filter of the present invention. .
In addition, the resin sheet and the resin layer may each contain 1 or 2 or more.

-Resin sheet-
The resin sheet in the light selective transmission filter is a resin sheet (including a film shape) having a resin layer formed from the resin composition for forming a light selective transmission filter. Such a resin sheet has a sharp transmission / absorption characteristic. For example, when combined with a reflective film, the resin sheet can provide a light selective transmission filter whose viewing angle dependency (also referred to as incident angle dependency) is sufficiently reduced. Besides being excellent in light resistance and heat resistance. Further, when the resin sheet is combined with a suitable optical multilayer film as a reflective film, the number of layers of the optical multilayer film can be reduced, and stress in the multilayer film can be relieved, so that cracks and cracks in the multilayer film are sufficiently prevented. You can also. Such a resin sheet used for the light selective transmission filter of the present invention is also one aspect of the present invention.

The configuration (form) of the resin sheet is not particularly limited as long as it includes a resin layer, and may further include other layers as necessary. Among these, it is preferable to further have a support. Even if the resin sheet is configured to include a support and a resin layer (absorption layer), even if the support is difficult to disperse the pigment, the resin layer is coated on the surface of the resin sheet as the resin sheet of the present invention. The effect of can be provided. In addition, the absorption characteristics can be further controlled by changing the thickness of the resin layer, and the thickness of the resin sheet is hardly changed from the thickness of the support by coating the resin layer. This effect can be imparted, and the resin layer can be used for adjusting the thickness of the support.

The form of the resin sheet is more preferably a form in which a resin layer is formed on one or both sides of the support, and more preferably a form in which a resin layer is formed on both sides of the support. Moreover, it is good also as a resin sheet which pinched | interposed the resin layer with the support body film.
In addition, the resin layer which comprises a resin sheet, and other layers, such as a support body, may each be a single layer or two or more layers.

The thickness of the resin sheet 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 300 micrometers or less, Most preferably, it is 200 micrometers or less, Most preferably, it is 150 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 resin sheet contains a support body, it is preferable that the thickness of this support body is 120 micrometers or less.

In the resin sheet, the resin layer is formed from the above-described resin composition for forming a light selective transmission filter of the present invention, and a resin composition in which a pigment is dispersed or dissolved in the resin composition. Thus, it is preferable that a resin layer is formed. Thereby, a resin layer in which the pigment is more uniformly dispersed or dissolved in the resin layer can be obtained.

Regarding the film thickness (thickness) of the resin layer, in the present invention, it is possible to reduce the film thickness by using the above-described resin composition for selective light transmission filter formation. It is advantageous in terms of light resistance that the film can be made thin from the viewpoint that penetration and diffusion of moisture and the like from the thickness direction are easily suppressed. The film thickness (thickness) of the resin layer is preferably 5 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 3 μm or less. Moreover, it is preferable that it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more.

The resin layer may be excellent in transparency from the short wavelength region of visible light in the ultraviolet region, but in the case of an ultraviolet cut filter that combines a resin sheet and a reflective film that reflects the ultraviolet region, It is preferable that the minimum value of the transmittance of the resin layer in the wavelength range of 350 to 400 nm is 20 to 80% from the viewpoint of easily reducing the dependency on the incident angle due to the reflective film. For the same reason, the minimum value of the transmittance in the 350 to 400 nm wavelength region in the resin sheet is preferably 20 to 80%.

The resin layer preferably has two absorption maximum wavelengths in a wavelength region of 600 to 800 nm, and at least one absorption maximum wavelength preferably exists in 600 to 730 nm. That is, it is preferable that there are two absorption maximum wavelengths in the wavelength range of 600 to 800 nm, and at least one of them exists in the range of 600 to 730 nm. By having such absorption characteristics, the light selective transparency is further improved, and when the resin sheet including such a resin layer is combined with the reflective film, the incident angle dependency by the reflective film is greatly increased. It becomes possible to reduce it. 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 region of 600 to 800 nm is 600 to 730 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.
These absorption maximum wavelengths can be obtained by measuring an absorption spectrum by a normal method, but can also be obtained from a transmittance spectrum as an alternative method.

As the absorption and transmission characteristics of the resin layer, it is particularly preferable that the transmittance (T630) at a wavelength of 630 nm is 50% or more and the transmittance (T700) at a wavelength of 700 nm is 50% or less. As a result, a sharper cut-off characteristic can be exhibited, which is preferable. T630 is more preferably 55% or more, still more preferably 60% or more, and T700 is more preferably 45% or less, still more preferably 40% or less. The resin composition forming the resin layer, the resin sheet including the resin layer, and / or the light selective transmission filter including the resin sheet also have the same absorption and transmission characteristics (absorption) as the resin layer as described above. It is preferable to show the maximum wavelength and the transmittance at each wavelength.

The resin layer preferably has a haze of 10% or less in the visible light region of the resin layer. More preferably, it is 5% or less, further preferably 3% or less, and particularly preferably 1% or less. In this embodiment, the transmittance of the resin layer at 500 nm of visible light is preferably 60% or more. More preferably, it is 70% or more, further preferably 80% or more, and particularly preferably 85% or more.
In addition, also about the said resin sheet and light selective transmission filter, it is preferable that the haze in visible region and the transmittance | permeability in visible light 500nm are in the range mentioned above, respectively.
The transmittance can be measured using a spectrophotometer (for example, Shimadzu UV-3100, manufactured by Shimadzu Corporation). The thickness of the resin layer and the resin sheet used for the transmittance measurement is preferably 1 to 200 μm.

As described above, it is preferable that the resin sheet further has a support, but the support is preferably a film (support film).
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 resin sheet is not particularly limited. For example, the resin composition for forming the resin layer may be the surface of the support (or the other layer in the case where another layer is provided between the support and the resin layer. 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 resin sheet which has a support body and a resin layer, it is preferable to employ | adopt the application | 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 resin sheet 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 to a temporary base material, it peels from this base material. Thus, the resin sheet can be obtained.

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 form 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.

Examples of the apparatus for performing the solvent casting method include a die coater, a gravure coater, a knife coater, a blade coater, a rod coater, an air doctor coater, a curtain coater, a fountain coater, a kiss coater, a spin coater, a spray coater, and a dip coater. Is mentioned. Among them, a die coater and a gravure coater are preferable because they can be applied by a roll-to-roll method, so that productivity is high and application accuracy is also high.

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. Two or more kinds of the above-mentioned solvents can be mixed and used. By mixing, the adjustment range of concentration and viscosity is widened, and the coating amount can be easily controlled. Moreover, a drying temperature can be lowered | hung by mixing a low-boiling solvent with low solubility in a high-boiling solvent with high solubility.

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-
The light selective transmission filter preferably includes a reflective film (also referred to as a reflective layer). As a result, it is possible to provide a light selective transmission filter that is more excellent in light selective transmission, has a sufficiently reduced incidence angle dependency of light blocking characteristics, and can realize a sufficient thinning. Thus, the form in which the light selective transmission filter further includes a reflective film is also a preferred form of the present invention.

The reflective film is preferably a multilayer film. That is, the reflective film is preferably an optical multilayer film. In addition, as the optical multilayer film, an inorganic multilayer film or the like that can control the refractive index of each wavelength is preferable in terms of excellent heat resistance. As an inorganic multilayer film, a refractive index control multilayer in which 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 a vacuum deposition method or a sputtering method. A membrane is preferred. 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 preferable.

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 for 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, CVD, sputtering, vacuum deposition A dielectric multilayer film can be formed by alternately laminating the dielectric layers A and B by, for example.

The reflective film such as the inorganic multilayer film can be suitably formed by the above method or the like, but in order to further reduce the possibility of the light selective transmission filter being deformed and curled or cracked by vapor deposition. The following method can be used. That is, specifically, a reflective film in which a vapor deposition layer is formed on a temporary substrate such as glass that has been subjected to mold release treatment, and the vapor deposition layer is transferred to a resin sheet that serves as a base material for a light selective transmission filter. This transfer method is preferred. In this case, it is preferable to form an adhesive layer on the resin sheet.

When the resin sheet is formed of an organic material, specifically, a resin composition, a dielectric layer or the like is vapor-deposited on an uncured or semi-cured resin sheet (resin composition). A curing 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 that the difference in thermal expansion coefficient between the resin composition and the dielectric layer does not matter, 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 resin sheet, but the vapor deposition temperature should be 100 ° C. or higher. Is preferred. More preferably, it is 120 degreeC or more, More preferably, it is 150 degreeC or more. 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. Therefore, it is very meaningful to use a resin sheet or pigment that can withstand such a deposition temperature. In addition, for such high temperature vapor deposition, it is preferable to use a resin layer or support film having a low linear expansion coefficient as the resin layer or support film constituting the resin sheet. Thereby, the inorganic layer crack by the difference of an inorganic and organic linear expansion coefficient can be suppressed more. In addition, when a resin layer or a support film having a low linear expansion coefficient is used, not only can vapor deposition be performed at a high temperature, but even if vapor deposition is performed at a low temperature, the difference in linear expansion coefficient from the inorganic film is small. An inorganic layer crack due to a difference in inorganic and organic linear expansion coefficient does not occur even in a heating environment or a severe use environment in a manufacturing process such as a reflow process adopted when manufacturing a solid-state imaging device.

As the resin layer or support film having a low linear expansion coefficient, those having a linear expansion coefficient of 60 ppm or less are preferable. 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 layer 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. The form in which the resin layer 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;

The reflective film is preferably formed on at least one surface of the resin sheet. The reflective film may be formed only on one surface of the resin sheet or may be formed on both surfaces, but is preferably formed on both surfaces. Thereby, the curvature of the light selective transmission filter concerning the present invention and the crack of a reflective film can fully be reduced. In addition, when the said resin sheet 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. In particular, it is preferable that a reflective film made of an inorganic multilayer film is formed on both surfaces of the resin sheet, and the surface of the resin layer is in close contact with the support or the reflective film made of the inorganic multilayer film. The light selective transmission filter having such a form is particularly excellent in light resistance and heat resistance.

As another preferred embodiment, there may be mentioned a form in which a reflective film is formed on at least one surface of a resin film different from the resin sheet, and the resin sheet is further formed on the surface of the reflective film. That is, it is a form in which the reflective film and the resin sheet 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 that case, the said resin sheet may be laminated | stacked on the surface of one reflective film, or may be laminated | stacked on the surface 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.

As described above, the reflective film is preferably an optical multilayer film, but the number of layers is preferably in the range of 10 to 80 layers when the optical multilayer film is provided only on one surface of the resin sheet. More preferably, it is the range of 25-50 layers. On the other hand, in the case where the optical multilayer film is provided on both surfaces of the resin sheet, the number of laminated optical multilayer films is preferably in the range of 10 to 80 layers, more preferably 25 to 25, as the total number of laminated sheets on both surfaces of the resin sheet. The range is 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 resin sheet, the total thickness of the reflective films on both surfaces is preferably within the above range.

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 physical properties of the infrared cut filter such as toughness and strength. The form which has the function to improve 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 resin sheet and imparting other functions to the other surface Is preferably formed. For example, the functional material layer is formed directly on the resin sheet by the CVD method, the sputtering method, or the vacuum evaporation method, or the functional material layer formed on the temporary base material that has been subjected to the release treatment. It can be obtained by pasting the resin sheet with an adhesive. Moreover, it can obtain also by apply | coating the liquid composition containing a raw material to the said resin sheet, drying, and forming into a film.

The light selective transmission filter preferably has a thickness (total thickness of the resin sheet 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, particularly preferably 120 μm or less, and most preferably 60 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. The range of the thickness of the light selective transmission filter is preferably 1 to 150 μm, more preferably 10 to 120 μm, still more preferably 30 to 120 μm, and particularly preferably 30 to 60 μm.

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 light to be reduced, it can be an infrared cut filter, an ultraviolet cut filter, an infrared / ultraviolet cut filter, etc. Among them, it reduces infrared light of 650 nm to 10 μm and ultraviolet light of 200 to 350 nm. 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 650 to 1000 nm to 5% or less. The transmittance in other wavelength regions is preferably 70% or more, and more preferably 75% or more, but only the transmittance in a specific wavelength region is high depending on the use of the filter. Good. 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 (450 to 600 nm) is 70% or more. . More preferably, it is 80% or more. Moreover, it is preferable that the transmittance | permeability of the light of the wavelength range of 480-550 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 70% or more, and more 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 70% or more, and more preferably 75% or more.

Preferably, the light selective transmission filter has a configuration in which a reflection film is formed on at least one surface of a resin sheet having a resin layer containing the dye and the resin component. Angular dependence can be reduced more sufficiently.

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 is particularly excellent in light resistance and light selective transmission, can sufficiently reduce the incident angle dependence of the light blocking characteristic, and can be sufficiently thinned. Therefore, it is not only useful as a heat ray cut filter mounted on the glass of automobiles and buildings, but also as a filter for blocking light noise and correcting visibility in camera module (also called solid-state image sensor) applications. Is also useful. 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).

[Solid-state image sensor]
The 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, but the solid-state imaging device using the light selective transmission filter of the present invention is usually It is arranged between a lens 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 is a light selective transmission filter having the above-described configuration, which can effectively block light of a desired wavelength, and has a sufficiently reduced incident angle dependency of light blocking characteristics. is there. Therefore, the solid-state imaging device (camera module) using the light selective transmission filter of the present invention can capture an image in which the occurrence of color unevenness due to the incident angle, which has been a problem, is suppressed by using the reflective filter. In addition, since it can be sufficiently thinned, it can be particularly suitably used 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. Moreover, since it can show a high level of light resistance, it is preferably used for applications that require severe light resistance, such as applications that may be exposed to direct sunlight.

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 “%” and “wt%” mean “mass%”.

Synthesis example 1
Synthesis of 3- (2-methoxycarbonylphenoxy) phthalonitrile In a 200 ml four-necked separable flask, 6.9 g (0.040 mol) of 3-nitrophthalonitrile, 6.8 g (0.044 mol) of methyl salicylate, potassium carbonate 11 0.06 g (0.080 mol) and 27.8 g of acetonitrile were charged and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 10.3 g (yield 92.8%) of 3- (2-methoxycarbonylphenoxy) phthalonitrile.

Synthesis example 2
Synthesis of 3- (4-methoxyethylcarbonylphenoxy) phthalonitrile In a 200 ml four-necked separable flask, 13.85 g (0.080 mol) of 3-nitrophthalonitrile, 16.65 g of methoxyethyl 4-hydroxybenzoate (0. 084 mol), 13.27 g (0.096 mol) of potassium carbonate, and 55.4 g of acetonitrile were charged and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 19.55 g (yield 75.8%) of 3- (4-methoxyethylcarbonylphenoxy) phthalonitrile.

Synthesis example 3
Synthesis of 3- (2-chlorophenoxy) phthalonitrile In a 500 ml four-necked separable flask, 17.3 g (0.10 mol) of 3-nitrophthalonitrile, 13.6 g (0.105 mol) of 2-chlorophenol, potassium carbonate 16.6 g (0.12 mol) and 69.3 g of acetonitrile were charged and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 27.8 g (yield 91.7%) of 3- (2-chlorophenoxy) phthalonitrile.

Synthesis example 4
Synthesis of 3- (2,6-dichlorophenoxy) phthalonitrile In a 500 ml four-necked separable flask, 15.0 g (0.087 mol) of 3-nitrophthalonitrile and 15.7 g (0.095 mol) of 2,6-dichlorophenol were added. ), 23.9 g (0.17 mol) of potassium carbonate, and 60.0 g of acetonitrile, and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 17.5 g (yield 69.9%) of 3- (2,6-dichlorophenoxy) phthalonitrile.

Synthesis example 5
Synthesis of 3- (2,6-dimethylphenoxy) phthalonitrile In a 500 ml four-necked separable flask, 15.0 g (0.087 mol) of 3-nitrophthalonitrile and 11.2 g of 2,6-dimethylphenol (0.091 mol) ), 23.9 g (0.17 mol) of potassium carbonate, and 60.0 g of acetonitrile, and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 17.5 g (yield 69.9%) of 3- (2,6-dimethylphenoxy) phthalonitrile.

Synthesis Example 6
Synthesis of 3- (4-cyanophenoxy) phthalonitrile In a 200 ml four-necked separable flask, 13.8 g (0.08 mol) of 3-nitrophthalonitrile, 10.1 g (0.084 mol) of 4-cyanophenol, potassium carbonate 13.3 g (0.096 mol) and 55.4 g of acetonitrile were charged and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 19.3 g (yield 98.2%) of 3- (4-cyanophenoxy) phthalonitrile.

Synthesis example 7
Synthesis of 4- (2,6-dichlorophenoxy) phthalonitrile In a 500 ml four-necked separable flask, 15.0 g (0.087 mol) of 4-nitrophthalonitrile and 15.7 g (0.095 mol) of 2,6-dichlorophenol ), 23.9 g (0.17 mol) of potassium carbonate, and 60.0 g of acetonitrile, and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 22.8 g (yield 91.1%) of 4- (2,6-dichlorophenoxy) phthalonitrile.

Synthesis example 8
Synthesis of 3- (2-methylphenoxy) phthalonitrile In a 500 ml four-necked separable flask, 15.0 g (0.087 mol) of 3-nitrophthalonitrile, 9.98 g (0.091 mol) of 2-methylphenol, potassium carbonate 23.9 g (0.17 mol) and 60.0 g of acetonitrile were charged and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 18.6 g (yield 91.6%) of 3- (2-methylphenoxy) phthalonitrile.

Synthesis Example 9
Synthesis of 4- (2-chlorophenoxy) phthalonitrile Into a 500 ml four-necked separable flask, 17.3 g (0.10 mol) of 4-nitrophthalonitrile, 13.6 g (0.105 mol) of 2-chlorophenol, potassium carbonate 16.6 g (0.12 mol) and 69.3 g of acetonitrile were charged and stirred at 60 ° C. overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 21.5 g (yield 84.4%) of 4- (2-chlorophenoxy) phthalonitrile.

Synthesis Example 10
Synthesis of 4,5-bis (3-chlorophenoxy) -3,6-difluorophthalonitrile Into a 500 ml four-necked separable flask, 10.0 g (0.050 mol) of tetrafluorophthalonitrile and 6.97 g of potassium fluoride ( 0.12 mol) and 30 g of acetone were charged, and further 13.04 g (0.101 mol) of 3-chlorophenol and 13.04 g of acetone were charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 3-chlorophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 9.64 g (yield 46.2%) of 4,5-bis (3-chlorophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 11
Synthesis of 4,5-bis (4-chlorophenoxy) -3,6-difluorophthalonitrile Into a 500 ml four-necked separable flask, 30.0 g (0.15 mol) of tetrafluorophthalonitrile and 20.9 g of potassium fluoride ( 0.36 mol) and 90 g of acetone were charged, and 39.7 g (0.31 mol) of 4-chlorophenol and 66.2 g of acetone were further charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 4-chlorophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 39.60 g (yield 63.3%) of 4,5-bis (4-chlorophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 12
Synthesis of 4,5-bis (2,3-dichlorophenoxy) -3,6-difluorophthalonitrile 30 g (0.150 mol) tetrafluorophthalonitrile, 20.91 g potassium fluoride in a 500 ml four-necked separable flask ( 0.36 mol) and 90 g of acetone were added, and 49.62 g (0.303 mol) of 2,3-dichlorophenol and 49.62 g of acetone were further added to the dropping funnel. While stirring at -1 ° C, an acetone solution of 2,3-dichlorophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 53.07 g (yield 72.8%) of 4,5-bis (2,3-dichlorophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 13
Synthesis of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile Into a 500 ml four-necked separable flask, 50 g (0.25 mol) of tetrafluorophthalonitrile and 34.8 g of potassium fluoride ( 0.60 mol) and 50 g of acetone were charged, and further, 82.3 g (0.50 mol) of 2,5-dichlorophenol and 82.3 g of acetone were charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 2,5-dichlorophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 88.8 g (yield 72.7%) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 14
Synthesis of 4,5-bis (3-cyanophenoxy) -3,6-difluorophthalonitrile In a 500 ml four-necked separable flask, 12.0 g (0.050 mol) of tetrafluorophthalonitrile, 8.37 g of potassium fluoride ( 0.144 mol) and 30 g of acetone were charged, and 14.5 g (0.122 mol) of 3-cyanophenol and 14.5 g of acetone were further charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 4-cyanophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 18.81 g (yield 78.7%) of 4,5-bis (3-cyanophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 15
Synthesis of 4,5-bis (4-cyanophenoxy) -3,6-difluorophthalonitrile Into a 500 ml four-necked separable flask, 100.0 g (0.50 mol) of tetrafluorophthalonitrile and 58.7 g of potassium fluoride ( 1.0 mol) and 100.0 g of acetone were charged, and 120.3 g (1.0 mol) of 4-cyanophenol and 120.3 g of acetone were further charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 4-cyanophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 145.7 g (yield: 73.2%) of 4,5-bis (4-cyanophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 16
Synthesis of 4,5-bis (3-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile 10.0 g (0.050 mol) of tetrafluorophthalonitrile and 6.97 g of potassium fluoride were placed in a 200 ml four-necked separable flask. (0.120 mol) and 30 g of acetone were charged, and further 15.66 g (0.103 mol) of methyl 3-hydroxybenzoate and 15.66 g of acetone were charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of methyl 3-hydroxybenzoate was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum dried to obtain 15.56 g (yield 67.0%) of 4,5-bis (3-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 17
Synthesis of 4,5-bis (4-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile In a 500 ml four-necked separable flask, 30.0 g (0.150 mol) of tetrafluorophthalonitrile, 19.2 g of potassium fluoride (0.33 mol) and 50.0 g of acetone were charged, and 46.53 g (0.31 mol) of methyl 4-hydroxybenzoate and 74.5 g of acetone were further charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of methyl 4-hydroxybenzoate was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 30.7 g (yield 42.8%) of 4,5-bis (4-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 18
Synthesis of 4,5-bis (4-nitrophenoxy) -3,6-difluorophthalonitrile In a 500 ml four-necked separable flask, 15.72 g (0.078 mol) of tetrafluorophthalonitrile, 10.94 g of potassium fluoride ( 0.188 mol) and 45.0 g of acetone were charged, and further, 22.16 g (0.159 mol) of 4-nitrophenol and 30.0 g of acetone were charged in a dropping funnel. While stirring at -1 ° C, an acetone solution of 4-nitrophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 28.28 g (yield 82.2%) of 4,5-bis (4-nitrophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 19
Synthesis of 4,5-bis (4-bromophenoxy) -3,6-difluorophthalonitrile In a 500 ml four-necked separable flask, 17.00 g (0.03 mol) of tetrafluorophthalonitrile, 4.92 g of potassium fluoride ( 0.08 mol) and 60.0 g of acetone were charged, and 12.23 g (0.07 mol) of 4-bromophenol and 30.0 g of acetone were further charged into the dropping funnel. While stirring at −1 ° C., an acetone solution of 4-bromophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 9.56 g (yield 54.0%) of 4,5-bis (4-bromophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 20
Synthesis of 4,5-bis (4-fluorophenoxy) -3,6-difluorophthalonitrile In a 500 ml four-necked separable flask, 112.80 g (0.06 mol) of tetrafluorophthalonitrile and 8.99 g of potassium fluoride ( 0.15 mol) and 60.0 g of acetone were charged, and further, 22.16 g (0.159 mol) of 4-fluorophenol and 30.0 g of acetone were charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 4-fluorophenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 15.71 g (yield 63.9%) of 4,5-bis (4-fluorophenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 21
Synthesis of 4,5-bis (3-trifluoromethylphenoxy) -3,6-difluorophthalonitrile 30.0 g (0.150 mol) of tetrafluorophthalonitrile, potassium fluoride 20. 91 g (0.360 mol) and 45.0 g of acetone were charged, and 49.34 g (0.304 mol) of 3-trifluoromethylphenol and 30.0 g of acetone were further charged in the dropping funnel. While stirring at -1 ° C, an acetone solution of 3-trifluoromethylphenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 38.50 g (yield 58.6%) of 4,5-bis (3-trifluoromethylphenoxy) -3,6-difluorophthalonitrile.

Synthesis Example 22
Synthesis of 4- (2-methylphenoxy) -3,5,6-trifluorophthalonitrile Into a 500 ml four-necked separable flask, 50 g (0.25 mol) of tetrafluorophthalonitrile and 14.8 g of potassium fluoride (0. 255 mol) and 150 g of acetone were charged, and 27.3 g (0.25 mol) of 2-methylphenol and 63.7 g of acetone were further charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 2-methylphenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 48.5 g (yield 67.1%) of 4- (2-methylphenoxy) -3,5,6-trifluorophthalonitrile.

Synthesis Example 23
Synthesis of 4- (2-methylphenoxy) -5- (4-methoxycarbonylphenoxy) -3,6-diolophthalonitrile 4- (2-Methylphenoxy) was obtained in Synthesis Example 22 in a 500 ml four-necked separable flask. Methylphenoxy) -3,5,6-trifluorophthalonitrile (36.0 g, 0.0.125 mol), potassium fluoride (10.87 g, 0.187 mol), and acetone (70.2 g) were charged. -16.3 g (0.132 mol) of methyl hydroxybenzoate and 30 g of acetone were charged. While stirring at -1 ° C, an acetone solution of methyl 4-hydroxybenzoate was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 28.5 g (yield 58.2%) of 4- (2-methylphenoxy) -5- (4-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile. Obtained.

Synthesis Example 24
Synthesis of 4- (2-chlorophenoxy) -3,5,6-trifluorophthalonitrile
A 500 ml four-necked separable flask was charged with 50 g (0.250 mol) of tetrafluorophthalonitrile, 17.4 g (0.30 mol) of potassium fluoride, and 50 g of acetone. Further, 33.2 g of 2-chlorophenol ( 0.257 mol) and 33.2 g of acetone were charged. While stirring at -1 ° C, an acetone solution of 2-chlorophenol was added dropwise from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 50.1 g (yield 65.0%) of 4- (2-chlorophenoxy) -3,5,6-trifluorophthalonitrile.

Synthesis Example 25
Synthesis of 4- (2-chlorophenoxy) -5- (4-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile 4- (2-chloro) obtained in Synthesis Example 24 in a 200 ml four-necked separable flask Phenoxy) -3,5,6-trifluorophthalonitrile 36.0 g (0.0.125 mol), potassium fluoride 10.87 g (0.187 mol), and acetone 70.2 g were charged. 16.3 g (0.132 mol) of methyl hydroxybenzoate and 30 g of acetone were charged. While stirring at -1 ° C, an acetone solution of methyl 4-hydroxybenzoate was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and dried under vacuum to obtain 28.5 g (yield 58.2%) of 4- (2-chlorophenoxy) -5- (4-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile. Obtained.

Synthesis Example 26
Synthesis of 4- (4-methoxycarbonylphenoxy) -3,5,6-trifluorophthalonitrile Into a 500 ml four-necked separable flask, 50 g (0.25 mol) of tetrafluorophthalonitrile and 15.9 g of potassium fluoride (0 275 mol) and 150 g of acetone, and 39.9 g (0.26 mol) of methyl 4-hydroxybenzoate and 40 g of acetone were further charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of methyl 4-hydroxybenzoate was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 30.0 g (yield 35.8%) of 4- (4-methoxycarbonylphenoxy) -3,5,6-trifluorophthalonitrile.

Synthesis Example 27
Synthesis of 4,5-bis (4-methoxyphenoxy) -3,6-difluorophthalonitrile In a 500 ml four-necked separable flask, 30.0 g (0.15 mol) of tetrafluorophthalonitrile and 18.3 g of potassium fluoride ( 0.315 mol) and 70.0 g of acetone were charged, and 37.6 g (0.30 mol) of 4-methoxyphenol and 37.6 g of acetone were further charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 4-methoxyphenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to give 39.15 g (yield 63.9%) of 4,5-bis (4-methoxyphenoxy) -3,6-difluorophthalonitrile.
Got.

Synthesis Example 28
Synthesis of 4- (2,6-dimethylphenoxy) -3,5,6-trifluorophthalonitrile Into a 200 ml four-necked separable flask, 30 g (0.150 mol) of tetrafluorophthalonitrile and 9.58 g of potassium fluoride ( 0.165 mol) and 90 g of acetone were charged, and further, 19.24 g (0.157 mol) of 2,6-dimethylphenol and 20.0 g of acetone were charged into the dropping funnel. While stirring at -1 ° C, an acetone solution of 2,6-dimethylphenol was dropped from the dropping funnel over about 2 hours, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 34.4 g (yield 75.9%) of 4- (2,6-dimethylphenoxy) -3,5,6-trifluorophthalonitrile.

<Synthesis of Dye A>
Test Example 1-1
(1) of [C, C, C, 1-tetrakis (2-methoxycarbonylphenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as A-Pc1) Synthesis In a 200 ml four-necked flask, 4.17 g (0.0150 mol) of 3- (2-methoxycarbonylphenoxy) phthalonitrile obtained in Synthesis Example 1 and 1.32 g (0.0041 mol) of zinc (II) iodide. , 16.70 g of benzonitrile was charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the reaction solution was dropped into methanol (89 g) corresponding to 20 times the theoretical yield of the phthalocyanine compound to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was again stirred and washed with methanol (45 g) corresponding to 10 times the theoretical yield of the phthalocyanine compound, and suction filtered. The obtained cake was dried at 100 ° C. for 24 hours using a vacuum dryer to obtain 2.00 g of the desired product (A-Pc1) (yield 45.0%).
With respect to the phthalocyanine compound (A-Pc1) thus obtained, the spectral characteristics in the polyimide were measured by the following method, and the results are shown in Table 1.

(2) Preparation of resin composition, production and evaluation of resin sheet 100 parts of dimethylacetamide was added to 8 parts of Neoprim L-3430 (Mitsubishi Gas Chemical Co., Ltd., 50 μm thickness), and stirred at 120 ° C. for 1 hour to dissolve. . To 6.063 g of this solution, 15 mg of the phthalocyanine compound (A-Pc1) obtained above was added, mixed and dissolved to prepare a resin coating solution. The obtained resin coating liquid is applied onto a glass plate with a spin coater and dried at 120 ° C. for 20 minutes (the thickness of the resin film after drying: 3 μm), whereby a sample (a coated glass having a resin layer formed on the glass plate) ) The absorption spectrum of the obtained sample, that is, a resin sheet (also referred to as an absorption sheet) was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-1800). The results are summarized in Table 1 below.

Test Example 1-2
Synthesis of [C, C, C, 1-tetrakis (2-methoxycarbonylphenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] copper (referred to as A-Pc2) In a four-necked flask, 4.00 g (0.0144 mol) of 3- (2-methoxycarbonylphenoxy) phthalonitrile obtained in Synthesis Example 1, 0.39 g (0.0040 mol) of copper (I) chloride, diethylene glycol monomethyl ether 9 .33 g was charged and reacted at 180 ° C. with stirring for 10 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 2.94 g of the target product (A-Pc2) (yield 69.5%).
For the phthalocyanine compound (A-Pc2) thus obtained, a resin composition was prepared and an absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-3
Synthesis of [C, C, C, 1-tetrakis (4-methoxyethylcarbonylphenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as A-Pc3) 200 ml In a four-necked flask, 8.38 g (0.026 mol) of 3- (4-methoxyethylcarbonylphenoxy) phthalonitrile obtained in Synthesis Example 2, 2.28 g (0.0072 mol) of zinc (II) iodide, 19.55 g of nitrile was charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 4.11 g of the target product (A-Pc3) (yield 46.7%).
For the phthalocyanine compound (A-Pc3) thus obtained, a resin composition was prepared and an absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-4
Synthesis of [C, C, C, 1-tetrakis (2-chlorophenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as A-Pc4) 200 ml of four In a one-necked flask, 10.19 g (0.040 mol) of 3- (2-chlorophenoxy) phthalonitrile obtained in Synthesis Example 3, 3.51 g (0.011 mol) of zinc (II) iodide, and 23.8 g of benzonitrile. Was allowed to react for 24 hours with stirring at 160 ° C. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 2.74 g of the target product (A-Pc4) (yield 25.3%).
For the phthalocyanine compound (A-Pc4) thus obtained, a resin composition was prepared and an absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-5
Synthesis of [C, C, C, 1-tetrakis (2,6-dichlorophenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as A-Pc5) 200 ml In a four-necked flask, 2.3 g (0.0080 mol) of 3- (2,6-dichlorophenoxy) phthalonitrile obtained in Synthesis Example 4; 0.70 g (0.0022 mol) of zinc (II) iodide; Nitrile (13.1 g) was charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 0.80 g of the target product (A-Pc5) (yield 32.8%).
For the phthalocyanine compound (A-Pc5) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-6
Synthesis of [C, C, C, 1-tetrakis (2,6-dichlorophenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] copper (referred to as A-Pc6) 200 ml 3- (2,6-dichlorophenoxy) phthalonitrile 4.00 g (0.0144 mol), copper chloride (I) 0.38 g (0.0038 mol), diethylene glycol monomethyl obtained in Synthesis Example 4 9.33 g of ether was charged and reacted at 180 ° C. with stirring for 10 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 3.22 g of the target product (A-Pc6) (yield 76.3%).
For the phthalocyanine compound (A-Pc6) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-7
Synthesis of [C, C, C, 1-tetrakis (2,6-dimethylphenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as A-Pc7) 200 ml 3- (2,6-dimethylphenoxy) phthalonitrile 3.72 g (0.015 mol), zinc iodide (II) 1.32 g (0.0041 mol) obtained in Synthesis Example 5 14.90 g of nitrile was charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 2.59 g of the target product (A-Pc7) (yield 65.4%).
For the phthalocyanine compound (A-Pc7) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-8
Synthesis of [C, C, C, 1-tetrakis (2,6-methylphenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] copper (referred to as A-Pc8) 200 ml 3- (2,6-dimethylphenoxy) phthalonitrile 4.00 g (0.0161 mol), copper (I) chloride 0.44 g (0.0044 mol), diethylene glycol monomethyl obtained in Synthesis Example 5 9.33 g of ether was charged and reacted at 180 ° C. with stirring for 10 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 2.87 g of the target product (A-Pc8) (yield 67.44%).
For the phthalocyanine compound (A-Pc8) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-9
Synthesis of [C, C, C, 1-tetrakis (4-cyanophenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as A-Pc9) 200 ml of four In a one-necked flask, 8.0 g (0.0326 mol) of 3- (4-cyanophenoxy) phthalonitrile obtained in Synthesis Example 6; 2.86 g (0.0090 mol) of zinc (II) iodide; 18.6 g of benzonitrile. Was allowed to react for 24 hours with stirring at 160 ° C. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 3.6 g of the target product (A-Pc9) (yield 47.3%).
For the phthalocyanine compound (A-Pc9) thus obtained, a resin composition was prepared and an absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-10
Synthesis of [ZnPc- {α- (2,6-Cl ₂ PhO) ₂ H ₆ } {β- (2,6-Cl ₂ PhO) ₂ H ₆ }] Zinc (referred to as A-Pc10) In a neck flask, 2.5 g (0.0086 mol) of 3- (2,6-dichlorophenoxy) phthalonitrile obtained in Synthesis Example 4 and 4- (2,6-dichlorophenoxy) phthalonitrile obtained in Synthesis Example 7 2.5 g (0.0086 mol), zinc iodide (II) 1.1 g (0.0048 mol), and benzonitrile 7.5 g were charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 4.2 g of the target product (A-Pc10) (3- (2,6-dichlorophenoxy) phthalonitrile and 4- (2,6 -Yield 79.2% based on dichlorophenoxy) phthalonitrile).
For the phthalocyanine compound (A-Pc10) thus obtained, a resin composition was prepared and an absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

Test Example 1-11
Synthesis of [ZnPc- {α- (2-CH ₃ PhO) ₂ H ₆ } {β- (2-Cl ₂ PhO) ₂ H ₆ }] zinc (referred to as A-Pc11) Synthesis into a 200 ml four-necked flask 2.34 g (0.010 mol) of 3- (2-methylphenoxy) phthalonitrile obtained in Example 8 and 2.55 g (0.010 mol) of 4- (2-chlorophenoxy) phthalonitrile obtained in Synthesis Example 9 Then, 1.76 g (0.0055 mol) of zinc (II) iodide and 7.5 g of benzonitrile were charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 4.24 g of the target product (A-Pc11) (3- (2-methylphenoxy) phthalonitrile and 4- (2-chlorophenoxy) (Yield 81.5% based on phthalonitrile).
For the phthalocyanine compound (A-Pc11) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 1. Summarized.

In Table 1, A-Pc1 to A-Pc11 are phthalocyanine dyes having a structure represented by Formula (6) in Table 1.
M, X, Y and R ^α in the formula (6) are as shown in Table 1 for each dye. For example, for Pc1, R ^α is “4-methoxycarbonylphenoxy, 4 hydrogens”, and X and Y are “8 hydrogens”. R ^α in formula (6) (8 in total) Of these, 4 are 2-methoxycarbonylphenoxy groups, the remaining R ^α is a hydrogen atom, and all of X and Y (a total of 8) are hydrogen atoms.

In Table 1 and Table 2 described later, Q1, Q2, λQ1, λQ2, and Abs (Q2) / Abs (Q1) mean the following.
Q1: Absorption on the short wavelength side of phthalocyanine Q2: Absorption on the long wavelength side of phthalocyanine λQ1: Absorption maximum wavelength on absorption on the short wavelength side of phthalocyanine λQ2: Absorption maximum wavelength on absorption on the long wavelength side of phthalocyanine Abs (Q1): λQ1 Absorbance Abs (Q2) at (Max value): Absorbance Abs (Q2) / Abs (Q1) at λQ2 (Max value): Ratio of Abs (Q1) to Abs (Q2) Mean a substituent bonded to carbon at positions 1, 4, 8, 11, 15, 18, 22, 25 of the phthalocyanine ring, and the β-position substituent means 2, 3, 9, 10, 16 of the phthalocyanine ring. , 17, 23, and 24, and substituents bonded to carbons.

In the absorbent sheet of this test example, only λQ1 may be observed and λQ2 may not be observed. In such a case, Abs (Q2) / Abs (Q1) was calculated by measuring the absorbance at the absorption maximum wavelength indicated if the dye contained was in an unassociated state, and using the absorbance as Abs (Q2). . As described above, when only the absorption maximum is observed at λQ1, the column λQ2 in Tables 1 and 2 is marked with *.

<Synthesis of Dye B>
Test Example 2-1
[2,3,9,10,16,17,23,24-octakis (3-chlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc1) 4,5-bis (3-chlorophenoxy)-obtained in Synthesis Example 10 in a 200 ml four-necked flask 3.17 g (0.010 mol) of 3,6-difluorophthalonitrile, 0.88 g (0.0028 mol) of zinc (II) iodide and 9.73 g of benzonitrile were charged and reacted at 160 ° C. with stirring for 24 hours. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 4.12 g of the target product (B-Pc1) (yield 95.1%).
For the phthalocyanine compound (B-Pc1) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-2
[2,3,9,10,16,17,23,24-octakis (4-chlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc2) 4,5-bis (4-chlorophenoxy)-obtained in Synthesis Example 11 in a 200 ml four-necked flask Charged 8.34 g (0.020 mol) of 3,6-difluorophthalonitrile, 1.76 g (0.0055 mol) of zinc (II) iodide and 19.46 g of benzonitrile, and reacted at 160 ° C. with stirring for 24 hours. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 8.09 g of the target product (B-Pc2) (yield 93.4%).
For the phthalocyanine compound (B-Pc2) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-3
[2,3,9,10,16,17,23,24-octakis (2,3-dichlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H- Synthesis of phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as B-Pc3) 4,5-bis (2,3-bis) obtained in Synthesis Example 12 in a 200 ml four-necked flask Dichlorophenoxy) -3,6-difluorophthalonitrile 4.86 g (0.0100 mol), zinc iodide (II) 0.88 g (0.0028 mol) and benzonitrile 11.34 g were charged and stirred at 160 ° C. for 24 hours. Reacted for hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 4.75 g of the target product (B-Pc3) (yield 94.6%).
For the phthalocyanine compound (B-Pc3) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-4
[2,3,9,10,16,17,23,24-octakis (2,5-dichlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H- Synthesis of Phthalocyaninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc4) 4,5-bis (2,5- Dichlorophenoxy) -3,6-difluorophthalonitrile 8.26 g (0.0170 mol), zinc iodide (II) 1.42 g (0.0045 mol), and benzonitrile 33.05 g were charged and stirred at 160 ° C. for 24 hours. Reacted for hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 7.17 g of the target product (B-Pc4) (yield 84.0%).
For the phthalocyanine compound (B-Pc4) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-5
[2,3,9,10,16,17,23,24-octakis (2,5-dichlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H- Synthesis of phthalocyaninato (2-)-N29, N30, N31, N32] vanadium oxide (referred to as B-Pc5) 4,5-bis (2,5) obtained in Synthesis Example 13 in a 100 ml four-necked flask -Dichlorophenoxy) -3,6-difluorophthalonitrile 15.00 g (0.0309 mol), vanadium (III) chloride 1.58 g (0.010 mol), 1,2,4-trimethylbenzene 21.99 g and benzonitrile 2.40 g was charged and reacted at 170 ° C. for 18 hours with stirring while blowing M gas (mixed gas of nitrogen and oxygen, oxygen concentration 7% by volume) into the liquid phase part. It was. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 13.61 g (yield: 87.7%) of the target product (B-Pc5).
For the phthalocyanine compound (B-Pc5) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-6
[2,3,9,10,16,17,23,24-octakis (3-cyanophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc6) 4,5-bis (3-cyanophenoxy)-obtained in Synthesis Example 14 in a 200 ml four-necked flask 3.98 g (0.010 mol) of 3,6-difluorophthalonitrile, 0.88 g (0.0028 mol) of zinc (II) iodide, and 9.29 g of benzonitrile were charged and reacted at 160 ° C. with stirring for 24 hours. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 3.47 g of the target product (B-Pc6) (yield 83.7%).
For the phthalocyanine compound (B-Pc6) thus obtained, a resin composition was prepared and an absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-7
[2,3,9,10,16,17,23,24-octakis (4-cyanophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc7) 4,5-bis (4-cyanophenoxy)-obtained in Synthesis Example 15 in a 200 ml four-necked flask 3.17 g (0.0205 mol) of 3,6-difluorophthalonitrile, 1.72 g (0.0054 mol) of zinc (II) iodide and 32.66 g of benzonitrile were charged and reacted at 160 ° C. for 24 hours with stirring. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 7.04 g of the target product (B-Pc7) (yield 82.9%).
For the phthalocyanine compound (B-Pc7) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-8
[2,3,9,10,16,17,23,24-octakis (3-methoxycarbonylphenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalate Synthesis of Russian Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc8) 4,5-bis (3-methoxycarbonylphenoxy) obtained in Synthesis Example 16 in a 200 ml four-necked flask ) -3,6-difluorophthalonitrile 9.29 (0.020 mol), zinc iodide (II) 1.76 g (0.0055 mol) and benzonitrile 21.67 g were charged and reacted at 160 ° C. for 24 hours with stirring. I let you. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 7.50 g of the desired product (B-Pc8) (yield 78.1%).
For the phthalocyanine compound (B-Pc8) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-9
[2,3,9,10,16,17,23,24-octakis (4-methoxycarbonylphenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalate Synthesis of Russian Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc9) 4,5-bis (4-methoxycarbonylphenoxy) obtained in Synthesis Example 17 in a 200 ml four-necked flask ) -3,6-difluorophthalonitrile 9.29 (0.0200 mol), zinc iodide (II) 1.76 g (0.0055 mol) and benzonitrile 21.67 g were charged and reacted at 160 ° C. with stirring for 24 hours. I let you. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 8.82 g of the target product (B-Pc9) (yield 91.8%).
For the phthalocyanine compound (B-Pc9) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-10
[2,3,9,10,16,17,23,24-octakis (4-nitrophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc10) 4,5-bis (4-nitrophenoxy)-obtained in Synthesis Example 18 in a 200 ml four-necked flask 3.38 g (0.0100 mol) of 3,6-difluorophthalonitrile, 0.88 g (0.0028 mol) of zinc (II) iodide and 10.23 g of benzonitrile were charged and reacted at 160 ° C. with stirring for 24 hours. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 4.39 g of the target product (B-Pc10) (yield 96.6%).
For the phthalocyanine compound (B-Pc10) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-11
[2,3,9,10,16,17,23,24-octakis (4-bromophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc11) 4,5-bis (4-bromophenoxy)-obtained in Synthesis Example 19 in a 200 ml four-necked flask 9.45 g (0.008 mol) of 3,6-difluorophthalonitrile, 0.70 g (0.0022 mol) of zinc (II) iodide and 12.65 g of benzonitrile were charged and reacted at 160 ° C. with stirring for 24 hours. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 3.81 g of the target product (B-Pc11) (yield 91.2%).
For the phthalocyanine compound (B-Pc11) thus obtained, the resin composition was prepared and the absorbent sheet was produced in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-12
[2,3,9,10,16,17,23,24-octakis (4-fluorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc12) 4,5-bis (4-fluorophenoxy)-obtained in Synthesis Example 20 in a 200 ml four-necked flask 3.84 g (0.0100 mol) of 3,6-difluorophthalonitrile, 0.88 g (0.0028 mol) of zinc (II) iodide, and 9.60 g of benzonitrile were charged and reacted at 160 ° C. with stirring for 24 hours. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 3.52 g of the target product (B-Pc12) (yield 88.0%).
For the phthalocyanine compound (B-Pc12) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-13
[2,3,9,10,16,17,23,24-octakis (3-trifluoromethylphenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H- Synthesis of phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as B-Pc13) 4,5-bis (3-trifluoro) obtained in Synthesis Example 21 in a 200 ml four-necked flask Methylphenoxy) -3,6-difluorophthalonitrile (3.84 g, 0.0100 mol), zinc iodide (II), 0.88 g (0.0028 mol), and benzonitrile, 8.97 g, were charged and stirred at 160 ° C. for 24 hours. Reacted for hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 3.52 g of the target product (B-Pc13) (yield 88.0%).
For the phthalocyanine compound (B-Pc13) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-14
[C, C, C, 2-tetrakis (2-methylphenoxy) -C, C, C, 3-tetrakis (4-methoxycarbonylphenoxy) -1,4,8,11,15,18,22,25- Synthesis of Octafluoro-29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as B-Pc14) 4- (4) obtained in Synthesis Example 23 in a 200 ml four-neck flask 2-methylphenoxy) -5- (4-methoxycarbonylphenoxy) 3,6-difluorophthalonitrile 8.41 g (0.0200 mol), zinc iodide (II) 1.76 g (0.0055 mol), benzonitrile 12 .61 g was charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 7.43 g (yield: 85.2%) of the target product (B-Pc14).
For the phthalocyanine compound (B-Pc14) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-15
[C, C, C, 2-tetrakis (2-chlorophenoxy) -C, C, C, 3-tetrakis (4-methoxycarbonylphenoxy) -1,4,8,11,15,18,22,25- Synthesis of Octafluoro-29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as B-Pc15) Obtained in Synthesis Example 25 obtained above in a 200 ml four-necked flask 4- (2-chlorophenoxy) -5- (4-methoxycarbonylphenoxy) -3,6-difluorophthalonitrile (8.82 g, 0.0200 mol), zinc iodide (II) 1.76 g (0.0055 mol) ) And 20.57 g of benzonitrile were charged and reacted at 160 ° C. with stirring for 24 hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 8.54 g (yield 93.5%) of the target product (B-Pc15).
For the phthalocyanine compound (B-Pc15) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-16
[C, C, C, 2-tetrakis (2-chlorophenoxy) -C, C, C, 3-tetrakis (4-methoxycarbonylphenoxy) -1,4,8,11,15,18,22,25- Synthesis of Octafluoro-29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] vanadium oxide (referred to as B-Pc16) 4 obtained in Synthesis Example 25 in a 100 ml four-necked flask -(2-chlorophenoxy) -5- (4-methoxycarbonylphenoxy) -3,6-difluororophthalonitrile 12.00 g (0.0272 mol), vanadium (III) chloride 1.39 g (0.009 mol), First, 17.59 g of 1,2,4-trimethylbenzene and 1.92 g of benzonitrile were charged, and M gas (a mixed gas of nitrogen and oxygen, While blowing oxygen concentration of 7% by volume) in the liquid phase, stirring 18 hours to be reacted. After completion of the reaction, after completion of the reaction, exactly the same operation as in Test Example 1-1 was performed to obtain 11.14 g (yield: 89.4%) of the desired product (B-Pc16).
For the phthalocyanine compound (B-Pc16) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-17
[C, C, C, 2-tetrakis (4-methoxycarbonylphenoxy) -C, C, C, 1,3,4,8,11,15,18,22,25-dodecafluoro-29H, 31H-phthalate Synthesis of Russian Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc17) 4- (4-methoxycarbonylphenoxy) -3 obtained in Synthesis Example 26 in a 200 ml four-necked flask , 5,6-trifluorophthalonitrile 3.32 g (0.010 mol), zinc iodide (II) 0.88 g (0.0028 mol) and benzonitrile 7.75 g were charged and reacted at 160 ° C. for 24 hours with stirring. I let you. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 2.67 g of the target product (B-Pc17) (yield 76.7%).
For the phthalocyanine compound (B-Pc17) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-18
[C, C, C, 2-tetrakis (2-chlorophenoxy) -C, C, C, 1,3,4,8,11,15,18,22,25-dodecafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc18) 4- (2-chlorophenoxy) -3,5 obtained in Synthesis Example 24 in a 200 ml four-necked flask , 6-trifluorophthalonitrile 3.09 g (0.010 mol), zinc iodide (II) 0.88 g (0.0028 mol), and benzonitrile 7.20 g were charged and reacted at 160 ° C. with stirring for 24 hours. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 3.01 g of the target product (B-Pc18) (yield 92.7%).
For the phthalocyanine compound (B-Pc18) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-19
[2,3,9,10,16,17,23,24-octakis (4-methoxyphenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Vanadium Oxide (referred to as B-Pc19) 4,5-bis (4-methoxyphenoxy) obtained in Synthesis Example 27 in a 100 ml four-necked flask -3,6-difluorophthalonitrile 12.00 g (0.0294 mol), vanadium (III) chloride 1.50 g (0.010 mol), 1,2,4-trimethylbenzene 17.59 g and benzonitrile 1.92 g The reaction was carried out for 18 hours with stirring while blowing M gas (mixed gas of nitrogen and oxygen, oxygen concentration: 7% by volume) at 170 ° C. into the liquid phase part. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 11.54 g (yield 92.4%) of the target product (B-Pc19).
For the phthalocyanine compound (B-Pc19) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-20
[C, C, C, 2-tetrakis (2-methylphenoxy) -C, C, C, 1,3,4,8,11,15,18,22,25-dodecafluoro-29H, 31H-phthalocyan Synthesis of Ninato (2-)-N29, N30, N31, N32] Zinc (referred to as B-Pc20) 4- (2-methylphenoxy) -3,5 obtained in Synthesis Example 22 in a 200 ml four-necked flask , 6-trifluorophthalonitrile 5.76 g (0.020 mol), zinc iodide (II) 1.76 g (0.0055 mol) and benzonitrile 8.64 g were charged and reacted at 160 ° C. with stirring for 24 hours. . After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 7.94 g of the target product (B-Pc20) (yield 90.9%).
For the phthalocyanine compound (B-Pc20) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

Test Example 2-21
[C, C, C, 2-tetrakis (2,6-dimethylphenoxy) -C, C, C, 1,3,4,8,11,15,18,22,25-dodecafluoro-29H, 31H- Synthesis of phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as B-Pc21) 4- (2,6-dimethylphenoxy) obtained in Synthesis Example 28 in a 200 ml four-necked flask −3,5,6-trifluorophthalonitrile (3.02 g, 0.010 mol), zinc iodide (II), 0.88 g (0.0028 mol), and benzonitrile, 7.05 g, were charged and stirred at 160 ° C. while stirring. Reacted for hours. After completion of the reaction, the completely same operation as in Test Example 1-1 was performed to obtain 2.83 g of the target product (B-Pc21) (yield 88.9%).
For the phthalocyanine compound (B-Pc21) thus obtained, the resin composition was prepared and the absorbent sheet was prepared in the same manner as described in Test Example 1-1, and the evaluation results are shown in Table 2. Summarized.

B-Pc1 to B-Pc21 are phthalocyanine dyes having a structure represented by Formula (7) in Table 2. M, X and Y in the formula (7) are as shown in Table 2 for each dye. For example, for Pc1, X and Y being “eight of 3-chlorophenoxy” mean that all of X and Y in formula (7) (eight in total) are 3-chlorophenoxy groups. , Pc14, X is “4-methylphenoxy 4” and Y is “4-methoxycarbonylphenoxy 4”. All of X in formula (7) (4 in total) are 2-methylphenoxy. And all Y's (four in total) are 4-methoxycarbonylphenoxy groups.

<Evaluation of dye>
Test Example 2-22
100 parts of dimethylacetamide was added to 8 parts of Neoprim L-3430 (Mitsubishi Gas Chemical Co., Ltd., 50 μm thickness) and stirred at 120 ° C. for 1 hour to dissolve. To 6.063 g of this solution, cyanine dye {1H-Benzindolinium, 3-butyl-2- [5- (3-butyl-1,3-dihydro-1,1-dimethyl-2H-benzindol-2-ylidene) -1 , 3-pentadien-1-yl] -1,1-dimethyl-tetrafluoroborate (1-)} (referred to as Cy-1) was added, mixed and dissolved to prepare a resin coating solution. The obtained resin coating liquid is applied onto a glass plate with a spin coater and dried at 120 ° C. for 20 minutes (the thickness of the resin film after drying: 3 μm), whereby a sample (a coated glass having a resin layer formed on the glass plate) ) The absorption spectrum of the obtained sample was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-1800), and the results are summarized in Table 3.

Test Example 2-23
100 parts of dimethylacetamide was added to 8 parts of Neoprim L-3430 (Mitsubishi Gas Chemical Co., Ltd., 50 μm thickness) and stirred at 120 ° C. for 1 hour to dissolve. To 6.063 g of this solution, 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} (referred to as Sc-1) was added, mixed and dissolved to prepare a resin coating liquid. The obtained resin coating liquid is applied onto a glass plate with a spin coater and dried at 120 ° C. for 20 minutes (the thickness of the resin film after drying: 3 μm), whereby a sample (a coated glass having a resin layer formed on the glass plate) ) The absorption spectrum of the obtained sample was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-1800), and the results are summarized in Table 3.

Examples 1 to 17 (spectral characteristic measurement in polyimide by mixing two kinds of dyes)
100 parts of dimethylacetamide was added to 8 parts of Neoprim L-3430 (Mitsubishi Gas Chemical Co., Ltd., 50 μm thickness) and stirred at 120 ° C. for 1 hour to dissolve. In this solution 6.063 g, a dye mixture obtained by weighing the dye (A) and the dye (B) shown in Table 4 so that the total amount becomes 15 mg in the weight ratio shown in Table 4 was mixed and dissolved to obtain a resin. A coating liquid (resin composition) was prepared. The obtained resin coating liquid was applied onto a glass substrate with a spin coater and dried at 120 ° C. for 20 minutes to produce an absorbent sheet having a resin layer formed on the glass substrate surface. The absorption spectrum of the obtained absorption sheet was measured with a spectrophotometer (manufactured by Shimadzu Corporation: UV-1800). The results are summarized in Table 4 below.
In each example, a resin coating liquid (resin composition) was used in the same manner as in each example, except that 15 mg of only the dye (A) used in each example was used instead of the dye (A) and the dye (B). Table 4 shows the results of preparing and evaluating an absorbent sheet in the same manner as in each Example.

When the absorption characteristics of the absorption sheets obtained in Examples 1 to 17 were compared with the absorption characteristics of the absorption sheets obtained by using the dye (A) alone, the dye (A) was used alone. , The transmittance at 630 nm is lowered, sharp transmission / absorption characteristics are not obtained on the shorter wavelength side than λmax, and the light selective permeability is lowered. When the resin layer further contains the dye B in addition to the dye A, the transmittance at a maximum absorption of 630 nm is increased, a sharp transmission / absorption characteristic is obtained at a wavelength shorter than λmax, and the light selective permeability is improved. That is, it can be seen from Table 4 that the absorption width in the 600 to 800 nm wavelength region is increased.
In Table 4, “λmax” means the maximum absorption wavelength.
Note that “λmax” and “% T” listed in Table 4 are derived from the absorbent sheet to be evaluated.

Here, the absorption width is a wavelength width at an arbitrary transmission intensity.
When the resin sheet of the present invention and a reflective film (for example, an optical multilayer film) are combined, a light selective transmission filter having sharp transmission / absorption characteristics can be provided. At this time, since the reflection film has an incident angle dependency, when the incident angle is large, the transmittance spectrum changes (shifts to the short wavelength side) compared to the incident angle of 0 degree, but the resin sheet depends on the incident angle. Therefore, sharp transmission / absorption characteristics can be maintained. In addition, when the absorption width (absorption band width) is wide (large), the design conditions of the reflection film are widened, and manufacture of IRCF (infrared cut filter) becomes easy.

<Evaluation of incident angle dependency>
Example 18
The resin coating liquid obtained in Example 1 was applied in a thickness of 40 μm onto Neoprim L-3430 (Mitsubishi Gas Chemical Co., Ltd., 50 μm thickness) as a support film, dried at 150 ° C. for 60 minutes, and a resin sheet ( 1) was obtained. The obtained absorbent sheet was 53 μm.
After cutting this resin sheet (1) into a rectangle having a width of 60 mm and a length of 100 mm, a multilayer film {silica (SiO ₂ : film thickness 120 to 190 nm) layer reflecting infrared rays at a deposition substrate temperature of 150 ° C. on both sides And titania (TiO ₂ : film thickness: 70 to 120 nm) layers are alternately laminated. The number of layers is 20 layers on one side, vapor deposition on both sides: a total of 40 layers} by vapor deposition, and a light selective transmission filter (optical Filter) (1) was produced.

Comparative Example 1
The resin coating liquid obtained in Test Example 2-9 was applied to Neoprim L-3430 (Mitsubishi Gas Chemical Co., Ltd., 50 μm thickness) as a support film in a thickness of 40 μm, dried at 150 ° C. for 60 minutes, and absorbed. A sheet (C1) was obtained. The obtained absorbent sheet was 53 μm.
After cutting this absorption sheet (C1) into a rectangle having a width of 60 mm and a length of 100 mm, a multilayer film {silica (SiO ₂ : film thickness 120 to 190 nm) layer reflecting infrared rays at a deposition substrate temperature of 150 ° C. on both surfaces And titania (TiO ₂ : film thickness: 70 to 120 nm) layers are alternately stacked. The number of layers is 20 layers on one side, vapor deposition: 40 layers in total} is formed by vapor deposition, and a light selective transmission filter (optical) Filter) (C1) was produced.

The incident angle dependency of the light selective transmission filter (1, C1) thus obtained was evaluated.
Specifically, 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 is not shown, in the light selective transmission filter (1) having the resin layer containing two kinds of dyes of the present invention, 0 ° and 25 ° in the region where the transmittance is 60% or more and 40% or more. It was confirmed that the dependence of the light blocking characteristic on the incident angle was reduced.
On the other hand, in the light selective transmission filter (C1), the incident angle dependency was expressed even in the region of the transmittance of 75%. When the thickness and number of layers of the multilayer film were changed and light was cut off in the absorption maximum wavelength (λQ2) region on the long wavelength side, the incident angle dependency was slightly improved, but small absorption in the region where light should be transmitted A peak (λQ1) appeared, and the waveform was not suitable for a light selective transmission filter.
Therefore, it was found that the light selective transmission filter of the present invention can 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 resin composition containing two or more dyes and a resin component, and used for forming a light selective transmission filter,
The two or more dyes include at least a dye A and a dye B having different absorption characteristics,
The dye A is a phthalocyanine-based dye having two absorption maximum wavelengths (λ _A1 , λ _A2 ) in a wavelength region of 650 to 800 nm, and has a maximum absorption wavelength λ _A2 on the long wavelength side thereof,
The maximum absorption wavelength λ _A2 is longer than the maximum absorption wavelength λ _B of the dye B,
The ratio of absorbance (A _A2 / A _A1 ) at the two absorption maximum wavelengths (λ _A1 , λ _A2 ) is composed of Dye A and a resin component, and the content ratio of Dye A is 3% by mass. A resin composition for forming a light selective transmission filter characterized by satisfying 2 or more when the absorbance of an object is measured. A light selective transmission filter including a resin sheet,
The light selective transmission filter, wherein the resin sheet includes a resin layer formed from the resin composition for forming a light selective transmission filter according to claim 1. The light selective transmission filter according to claim 2, wherein the light selective transmission filter further includes a reflective film. A resin sheet used in the light selective transmission filter according to claim 2. A solid-state imaging device comprising at least the light selective transmission filter according to claim 2, a lens unit portion, and a sensor portion.

Images