KR20130108186A - Light selective transmission filter, resin sheet, and solid-state image sensing device - Google Patents

Abstract

PURPOSE: A light selective transmission filter, a resin sheet and a solid-state image sensing device are provided to improve light selective transmission as enabling light thickness, and to improve light resistance and heat resistance. CONSTITUTION: A light selective transmission filter (2) includes a resin sheet. The resin sheet has a resin layer including pigment and resin component. The pigment has non-ionic conjugated frame, and includes a pigment A which has maximum absorption wavelength in the wavelength area of 600-800 nm and has at least one maximum absorption wavelength existing in 600-730 nm.

Description

LIGHT SELECTIVE TRANSMISSION FILTER, RESIN SHEET, AND SOLID-STATE IMAGE SENSING DEVICE}

This invention relates to a light selective transmission filter, a resin sheet, and a solid-state image sensor. More specifically, the solid-state imaging which has a light selective transmission filter useful for uses, such as a display device component, a mechanical component, an electrical and electronic component, besides an optical member and an opt device member, a resin sheet used for it, and a light selective transmission filter It relates to an element.

A light selective transmission filter is a filter which selectively reduces the transmittance | permeability of the light of a specific wavelength, and an infrared (IR) cut filter, an ultraviolet cut filter, an infrared rays, an ultraviolet cut filter etc. are mentioned according to the wavelength of the light to reduce. Such a light selective transmission filter is useful as an optical filter used for a display device component, a mechanical component, an electrical / electronic component, etc. besides an optical member and an opt device member, for example. For example, as one of typical optical members, there are solid-state imaging devices (also referred to as camera modules) mounted in optical imaging devices such as mobile phone cameras, digital cameras, and digital video cameras. It is common to perform reduction of the optical noise which disturbs, etc. by providing the infrared (IR) cut filter which cuts the infrared rays (especially the near-infrared region of wavelength> 780 nm) used as optical noise.

In the field of the optical member or the like represented by such a solid-state image pickup device, miniaturization is being progressed recently, such as mounting a digital camera module in a mobile phone, and with this, the demand for thinning a light selective transmission filter increases. have. The light selective transmission filter is mainly formed by depositing a metal or the like on a substrate to form an inorganic multilayer film and controlling a refractive index of each wavelength. A glass plate has conventionally been used as the substrate. The technique used as a base material is examined. Recently, application to optical imaging devices that can be used outdoors, such as mobile phones, digital cameras, on-vehicle cameras, and surveillance cameras, has also been considered. However, in their outdoor use, they are resistant to external environments such as direct sunlight exposure. That is, high level of light resistance and heat resistance are required.

As a light selective transmission filter which can be applied to a solid-state image sensor, the near-infrared absorption filter which contains the quaternylene pigment which consists of a specific structure, and is manufactured using a heat and / or a photocurable compound, for example (patent document 1) And a filter produced using a lake pigment having an absorption maximum wavelength at 700 nm to 1100 nm, and a near-infrared absorbing dye-containing curable composition containing a heat and / or photocurable compound (see Patent Document 2). Absorption filters are being developed.

In addition, Patent Document 3 discloses a light selective transmission filter having a thickness of less than 200 µm and having a base material including a reflowable functional film, which is excellent in heat resistance even when sufficiently thin, and is very useful for various applications. A filter is realized. Moreover, the Example of patent document 3 discloses the light selective transmission filter of the form which deposited the reflective IR cut film (dielectric multilayer film) on the base material, ie, a reflective filter.

In addition, attempts have been made to combine absorption filters with reflective filters such as dielectric multilayer films (see, for example, Patent Documents 4 and 5). Patent Document 4 discloses a near-infrared cut filter having a norbornene-based resin substrate containing a near-infrared absorber and a near-infrared reflective film that is a dielectric multilayer film, and when dissolved in a good solvent as a near-infrared absorber, the wavelength of such a solution is 800 to 1000 nm. The use of the compound which has the density | concentration range which the spectral transmittance measured at the optical path length of 1 cm in becomes 60% or less, Preferably it is 30% or less is disclosed. Patent Document 5 discloses an optical filter in which an optical low pass filter layer, an absorption type infrared cut filter layer, and a reflection type infrared cut filter layer are integrally laminated, and is used as an infrared absorbing material for use in an absorption type infrared cut filter layer. The use of the ionic copper compound which has absorption characteristics in the approximate wavelength 700-1000 nm is disclosed.

On the other hand, as a light selective transmission filter for plasma displays (PDP), it is formed by laminating | stacking the composition which disperse | distributed the near-infrared absorbing dye in binder resin on the base material, and the near-infrared absorption filter whose residual amount in this laminated body is 5.0 weight% or less. Is disclosed (see Patent Document 6). In Patent Document 6, such a near-infrared absorbing filter absorbs near-infrared rays emitted from a plasma display and prevents malfunction of electronic devices using a near-infrared remote control. As a near-infrared absorbing dye, a dimonium salt-based compound and Use of fluorine-containing phthalocyanine compounds, dithiol metal complex compounds, and the like are disclosed.

Japanese Unexamined Patent Publication No. 2008-009206 Japanese Unexamined Patent Publication No. 2007-271745 WO2008 / 081892 Publication Japanese Laid-Open Patent Publication 2005-338395 Japanese Laid-Open Patent Publication 2005-345680 Japanese Unexamined Patent Publication No. 2000-227515

As described above, various light selective transmission filters have been studied. In general, reflective filters have excellent light blocking performance, but have an incident angle dependency (also referred to as a viewing angle dependency) in which reflection characteristics change with the incident angle of light. The reduction was a subject. As the filter having no incident angle dependence, an absorption type filter can be cited, but in order to realize sufficient absorption characteristics, a considerable thickness was required. Moreover, although the optical filter which combined the reflection type filter and the absorption type filter is disclosed by patent documents 4 and 5, also in these techniques, it is calculated | required to implement | achieve one more layer reduction and thinning of the incidence angle dependence of blocking performance. As described above, in the related art, there is room for research to obtain a light selective transmission filter that can sufficiently reduce the incident angle dependency of the blocking performance to effectively block light of a specific wavelength and can also respond to the request for thinning. Further, there has been room for research to provide a light selective transmission filter that can exhibit more sufficient performance even in a harsh external environment such as direct sunlight exposure, that is, excellent in high level of light resistance and heat resistance.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described present situation, and the light-selective transmission filter, the light selection of which the incident angle dependence of the blocking characteristics is sufficiently reduced, the light selective transmittance is excellent, sufficient thinning is possible, and the light resistance and heat resistance are particularly excellent. An object of the present invention is to provide a solid-state imaging device having a resin sheet used for the transmission filter and a light selective transmission filter thereof.

As a result of various studies on the light selective transmission filter which is especially useful for a solid-state image sensor, the present inventors etc. pays attention to the use of the pigment which is excellent in the absorption blocking performance of the long wavelength region of visible light to such a light selective transmission filter, As such a pigment | dye, when the conjugated skeleton which it has is nonionic and uses the compound which shows a specific absorption characteristic, and consists of a resin sheet which has a resin layer using the pigment | dye, it is especially excellent in light resistance and heat resistance. It turned out to be a light selective transmission filter. Specifically, as a result of examining the molecular structure and the light resistance and heat resistance in the state in which the pigment is dispersed in the resin component, the pigment having excellent absorption blocking performance in the long wavelength region of visible light is examined. Anion, cation, or zwitterion), the near-infrared absorption performance is changed by light or heat, and in particular, when an ionization (charge separation) portion is present in the conjugated skeleton of the pigment, It was found that the near-infrared absorption performance was significantly reduced. Therefore, even when the reflection film (reflective layer) is further included, in order to obtain a light selective transmission filter having excellent light resistance and heat resistance, the dye to be used is ionized (charged) such as anion, cation, and zwitterion in the conjugated skeleton. It was found that it was necessary to use a pigment having a non-ionic portion, that is, the conjugated skeleton was nonionic. Moreover, when it is set as such a structure, when it further contains a reflection film (reflective layer), it turns out that it becomes a light selective transmission filter which can stably reduce incident angle dependence over a long term, and also uses glass for a base material In comparison with the case, it was also found that the entire light selective transmission filter can be significantly thinned. And it can be found that such a light selective transmission filter is a light selective transmission filter which is very effective especially for lens applications, such as optical use, an opt device use, etc., such as a solid-state image sensor (camera module), and can solve the said problem splendidly. In addition to being present, the present invention has been reached.

When the relationship between the wavelength and the absorbance is represented by a two-dimensional graph of the X-axis and the Y-axis (where the X-axis is the wavelength and the Y-axis is the absorbance), the wavelength at which the absorbance is changed from increasing to decreasing is called the absorption maximum wavelength (absorption Also called peak wavelength). An absorption maximum wavelength (absorption peak wavelength) may have only one according to a compound, and may have two or more. The maximum absorbance among absorption maximum wavelengths (absorption peak wavelength) is called "maximum absorption wavelength (also called maximum absorption peak wavelength)."

That is, this invention is a light selective transmission filter containing a resin sheet, The resin sheet has the resin layer containing a pigment | dye and a resin component, The pigment | dye has the conjugate system skeleton which it has is nonionic, and is 600 It is a light selective transmission filter containing the pigment | dye A which has an absorption maximum wavelength in the wavelength range of -800 nm, and whose at least 1 absorption maximum wavelength exists in 600-730 nm.

This invention is also a resin sheet used for the said light selective transmission filter.

This invention is also a solid-state image sensor which has the said light selective transmission filter, a lens unit part, and a sensor part at least.

Hereinafter, the present invention will be described in detail. Moreover, it is also a preferable aspect of this invention to combine two or three or more of the preferable aspects of this invention described below in a paragraph.

[Resin sheet]

The light selective transmission filter of this invention contains 1 or 2 or more resin sheets.

The resin sheet in the said light selective transmission filter is a resin sheet (it contains film shape) which has a resin layer containing a pigment | dye and a resin component. Although such a resin sheet is very excellent in light resistance and heat resistance, for example, by combining with a reflection film, the viewing angle dependency (also called incident angle dependency) is sufficiently reduced, and it is also possible to provide a light selective transmission filter having sharp transmission and absorption characteristics. have. In addition, when combined with an optical multilayer film suitable as a reflective film, the number of layers of the optical multilayer film can be reduced, and the stress in the multilayer film can be alleviated, so that cracks and cracks of the multilayer film can be sufficiently prevented. The resin sheet used for such a light selective transmission filter of this invention is also one of this invention.

The structure (form) of the said resin sheet is not specifically limited as long as it contains a resin layer, You may include another layer further as needed. Especially, it is preferable to further have a support body. By making a resin sheet into the structure containing a support body and a resin layer (absorption layer), even if it is a support body which is difficult to disperse | distribute a pigment | dye, the effect as a resin sheet of this invention can be provided by coating a resin layer on this surface. In addition, by changing the thickness of the resin layer, the absorption characteristics can be further controlled, and the ultrathin coating of the resin layer gives the effect of the present invention almost without changing the film thickness of the resin sheet with the film thickness of the support. The resin layer may be used for thickness adjustment of the support.

As a form of the said resin sheet, More preferably, it is a form in which the resin layer was formed in one or both surfaces of a support body, More preferably, it is a form in which the resin layer was formed in both surfaces of a support body. Moreover, it is good also as a resin sheet which sandwiched the resin layer with the support film.

In addition, one layer or two or more layers may be sufficient as the resin layer which comprises a resin sheet, and other layers, such as a support body, respectively.

It is preferable that the thickness of the said resin sheet is 1 mm or less. Thereby, the light selective transmission filter of this invention can fully be thinned, and it can respond more to the request of reducing the thickness, such as an optical member. More preferably, it is 500 micrometers or less, More preferably, it is 300 micrometers or less, Especially 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 the support body is 120 micrometers or less.

<Resin layer>

In the said resin sheet, although the resin layer contains a pigment | dye and a resin component, it is preferable that a pigment | dye is disperse | distributed or melt | dissolved in a resin layer. That is, it is preferable that a resin layer is formed of the resin composition of the form which the pigment | dye disperse | distributed or melt | dissolved in the resin composition containing a pigment | dye and a resin component. In the resin composition of such a form, it is preferable to use the solvent-soluble resin mentioned later, a solvent-soluble resin raw material, and / or a liquid resin raw material as a resin component.

In addition, as a pigment | dye and a resin component, 1 type, or 2 or more types can be used, respectively.

- Coloring -

The said pigment | dye contains pigment | dye A which the conjugate frame | skeleton which it has is nonionic, has absorption maximum wavelength in the wavelength range of 600-800 nm, and the at least 1 absorption maximum wavelength exists in 600-730 nm. .

The fact that such a conjugated skeleton of the dye A is nonionic means that all of the conjugated skeletons of the dye are not anionic, cationic, and zwitterionic, i.e., the ionized portion in the conjugated skeleton (no On, cation or zwitterion). When the ionized portion is present in the conjugated skeleton, the near-infrared absorption performance derived from the compound is significantly reduced by light or heat, but the light resistance and heat resistance are expressed by not having the ionized portion in the conjugated skeleton, and the near-infrared absorption performance is improved. It becomes possible to exhibit over a long term.

In addition, having a binary ion means having both a static charge and a negative charge in one molecule. Zwitterions are also called intramolecular salts.

The part other than the conjugated skeleton in the dye A is not limited to nonionicity. For example, the pigment | dye which has a structure which introduce | transduced an anionic group by sulfonic acid group is also contained in the said pigment | dye A whose conjugate system skeleton is nonionic. Among them, preferably, portions other than the conjugated skeleton are also nonionic compounds, whereby the lowering of the near infrared absorption performance can be further suppressed. That is, it is preferable that the said pigment | dye A is a nonionic compound, In other words, it is a compound which does not have anion, a cation, and a zwitterionic moiety (group).

Thus, although the near-infrared absorption performance of a resin sheet (and resin layer) can be made excellent in long-term stability by the non-ionic conjugated frame | skeleton of a pigment | dye, it is guessed by the following mechanism.

The near-infrared absorption of a resin sheet (and resin layer) is considered that the point by the electron transition between the conjugate system orbits of the pigment | dye used for a resin layer is large. In this absorption, although the kind and number of substituents (atomic group) which a pigment | dye has, and a pigment | dye are a metal complex, absorption characteristics, such as an absorption end wavelength and an extinction coefficient, can be controlled to some extent according to the kind of metal ion, etc., but near-infrared rays The light absorption performance of a region is basically largely dependent on the electronic structure of the conjugated electron which a pigment | dye has. Therefore, the stability of the near-infrared absorption performance of a resin sheet (and resin layer) is considered to depend on the stability of the conjugated system of the conjugated skeleton in a pigment | dye. Therefore, although the mechanism of the influence on the stability of the near-infrared absorption performance by the presence or absence of the ionization structure part in a conjugated skeleton is not clear, it is considered as follows.

For example, by heating the resin layer containing a pigment | dye, when the substance which is easy to dissociate to ions, such as water, exists in a resin layer, or it mixes over time, water becomes easy to ionize first in an ionization part. As a result, the anion / cation moiety in the dye strongly interacts or reacts electronically, resulting in the breakdown of the conjugated system, resulting in a decrease in near-infrared absorption performance. Moreover, when light is irradiated to the resin layer containing a pigment | dye, oxygen molecule | numerator is excited by irradiation of light, especially an ultraviolet-ray, and produces | generates a highly reactive state (single singlet oxygen). The ionized portion is likely to react with singlet oxygen, and if reacted, the conjugated system is destroyed, so that the near infrared absorption performance is lowered.

From such a point, it is thought that it is effective to use the compound whose conjugate system skeleton is nonionic as said pigment | dye.

As said compound whose said conjugated skeleton is nonionic, the compound (heterocyclic 5-membered ring aromatic compound) whose compound conjugate is a heterocyclic 5-membered ring structure is preferable from a viewpoint which is excellent in heat resistance and light resistance. Especially, the compound whose heterocyclic 5-membered ring structure is a pyrrole ring is preferable. More preferably, it is a tetrapyrrole compound.

Here, the compound group containing four pyrrole rings is called a tetrapyrrole compound, although there exist some which are cyclic and a linear type, It is more preferable that they are a cyclic tetrapyrrole compound.

The cyclic tetrapyrrole compound means a cyclic compound group including four pyrrole rings, but is preferably a compound containing a structure in which adjacent pyrrole rings are connected via a carbon atom or a nitrogen atom. Specifically, for example, a) four bonds of adjacent pyrrole rings, such as porphyrins, chlorines, etc., are all bonded via one carbon atom, and b) adjacent to phthalocyanines. Compounds in which four bonds of the pyrrole rings are all bonded through one nitrogen atom, c) Of the four bonds of adjacent pyrrole rings, such as choline, three of the bonds are via one carbon atom. The compound etc. which consist of a bond and the other one consists of the bond of carbon atoms which comprise a pyrrole ring are mentioned preferably. In a), porphyrins and chlorine are preferable, phthalocyanine is preferable in b), and choline is preferable in c). That is, as said cyclic tetrapyrrole compound, porphyrins (also called porphyrin dyes), chlorine (also called chlorine dyes), phthalocyanines (also called phthalocyanine dyes) and / or choline (also called choline dyes) ), And among these, porphyrins and / or phthalocyanines are preferable because they are easily obtained industrially. Moreover, it is preferable that the said cyclic tetrapyrrole compound is a metal complex which has a metal ion at the center from a viewpoint which is further excellent in light resistance.

In the said pigment | dye A, as a metal used as a center metal ion, copper is preferable at the point which becomes a resin sheet which is especially excellent in light resistance. Especially bivalent copper (Cu (II)) is preferable. Thereby, even if it raises a pigment | dye concentration, it becomes a resin sheet excellent in light resistance. In addition, zinc is preferred as a metal from the viewpoint that the dye A is easily dissolved and dispersed in a single molecule or associative molecular state, the resin layer can have a particularly high resin layer, and can be sufficiently absorbed even in a thin film. Do. Particularly preferred is divalent zinc (Zn (II)).

As mentioned above, as a metal used as the center metal ion in the pigment | dye A, copper or zinc is especially preferable. As a metal complex which uses these metals as a center metal ion, porphyrins or phthalocyanines are especially preferable, and phthalocyanines are the most preferable.

In addition, porphyrins mean the group of compounds which have a porphyrin skeleton, and the thing in which the hydrogen atom couple | bonded with the carbon atom which comprises a pyrrole ring, and the bonding carbon atom which connects pyrrole rings is substituted by another atom (group) or group. .

The said pigment | dye A is a compound which has an absorption maximum wavelength in the wavelength range of 600-800 nm, and the at least 1 absorption maximum wavelength exists in 600-730 nm.

Here, the absorption maximum wavelength which the said pigment | dye should just be 1 or 2 or more in the 600-800 nm wavelength range, and one of them should just exist in 600-730 nm. By constructing a resin sheet using a compound having such an absorption characteristic, the wavelength region to be blocked can be cut more sharply, and the wavelength selective to be transmitted is excellent in light selective transmittance of showing high transmittance. In addition, when the resin sheet and the reflective film are combined, it is possible to greatly reduce the incident angle dependence of the reflective film. More preferably, it has an absorption maximum wavelength in the 600-800 nm wavelength range, and the at least 1 absorption maximum wavelength exists in 600-710 nm. Moreover, it is preferable that the wavelength (that is, the maximum absorption wavelength) of the peak with the lowest transmittance is 600-730 nm among 1 or 2 or more absorption maximum wavelengths which exist in the 600-800 nm wavelength range. More preferably, the maximum absorption wavelength is 600-710 nm among 1 or 2 or more absorption maximum wavelengths which exist in the wavelength range of 600-800 nm. More preferably, the maximum absorption wavelength is at 660 to 700 nm.

Moreover, when the molecule | numerator which is excellent in planarity like a phthalocyanine type compound exists in the state (association molecule) associated with the case where it exists as a single molecule, the position of an absorption maximum peak may differ. In this application, it is thought that the peak (absorption maximum) derived from a single molecule appears on the long wavelength side, and the peak (absorption maximum) derived from the association molecule appears on the short wavelength side.

Among the said pigment | dye A, the form disperse | distributed to a resin layer at least one part showing the absorption peak derived from an association molecule is preferable at the point which is excellent in the light resistance of a resin sheet. Moreover, the resin sheet in which at least 1 of the absorption maximum peak derived from the association molecule of the pigment | dye A exists in the wavelength range of 600-730 nm is preferable. In other words, it is preferable to make the resin sheet contain the pigment | dye which has the absorption maximum peak derived from an association molecule in the wavelength range of 600-730 nm. More preferably, the resin sheet is made to contain the pigment | dye which has the absorption maximum peak derived from an association molecule in the wavelength range of 600-710 nm.

In addition, from the viewpoint of suppressing the incident angle dependence when combined with the reflective film, at least one of the maximum wavelength derived from a single molecule is 600 to 1 or 2 or more absorption maximum wavelengths present in the wavelength region of 600 to 800 nm. It is preferable to exist in 730 nm (more preferably, 600-710 nm).

Although the absorption maximum wavelength of a pigment | dye can be calculated | required by measuring an absorption spectrum with a conventional method, it can also be calculated | required from the transmittance spectrum of a pigment as another method. In either case, it is preferable to use a solvent dispersion method.

The solvent dispersing method is a 1 cm thick transparent quartz cell filled with a solution (including a dispersion) obtained by dissolving or dispersing a dye in a solvent (for example, chloroform and dimethylacetamide), followed by a spectrophotometer (e.g., For example, it can measure using Shimadzu UV-3100, the Shimadzu Corporation make. When the measurement mode is absorbance, the absorption spectrum of the dye is obtained. When the measurement mode is transmittance, the transmittance spectrum of the dye 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 0.000001-0.01 mass% with respect to 100 mass% of total amounts of a solvent and a pigment, More preferably, it is 0.00001-0.001 mass% It is.

Specifically as said pigment | dye A, it has the structural characteristic and absorption characteristic which were mentioned above. That is, it will not specifically limit, if the conjugated skeleton which it has is nonionic and has an absorption maximum wavelength in the 600-800 nm wavelength range, and the at least 1 absorption maximum wavelength exists in 600-730 nm, As mentioned above, it is preferable to use 1 type, or 2 or more types, such as a porphyrin pigment, a chlorine pigment, a phthalocyanine pigment, and a choline pigment, and especially, using a porphyrin pigment and / or a phthalocyanine pigment. It is more preferable. Moreover, even if it is a compound other than these, if it has said structural characteristic and absorption characteristic, it can use suitably as a pigment | dye of this invention.

As said phthalocyanine type pigment | dye, a metal phthalocyanine complex is preferable, For example, metal elements, such as copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, lead, are made into the center metal. A metal phthalocyanine complex to be mentioned. Among these metal elements, from the viewpoint of better solubility, visible light transmittance, and light resistance, it is preferable to use any one or more of copper, vanadium, and zinc as the center metal. As a center metal, More preferably, it is copper, zinc, or indium, More preferably, it is copper or zinc, More preferably, it is copper. Phthalocyanine type pigment | dye using copper does not deteriorate by light, even if it disperse | distributes to any resin component (binder resin), and has very excellent light resistance. On the other hand, the phthalocyanine complex (phthalocyanine-based dye) containing zinc as a metal element has excellent light solubility in the 400-600 nm region and high light absorption in the 600-800 nm region because of its excellent solubility in the resin component. It is especially preferable because a resin sheet is easy to obtain.

Tetraaza porphyrin etc. are mentioned as said porphyrin type pigment | dye.

Among the phthalocyanine-based dyes, particularly preferably, the following general formula (I):

[Formula 1]

In the formula, R ^a1 to R ^d1 , R ^a2 to R ^d2 , R ^a3 to R ^d3, and R ^a4 to R ^d4 Is the same or different and OR ⁱ which may have a hydrogen atom (H), a fluorine atom (F), and a substituent SR ^j which may have a group or a substituent Group. R ⁱ and R ^j Is the same or different and represents an alkyl group, a phenyl group or a naphthyl group. M represents a metal atom, a metal oxide, or a metal halide.). Thereby, it becomes possible to fully exhibit the effect of this invention. In this manner, the form in which the dye A is a phthalocyanine dye represented by the general formula (I) is also one of the preferred embodiments of the present invention.

In General Formula (I), R ^a1 to R ^d1 , R ^a2 to R ^d2 , R ^a3 to R ^d3, and R ^a4 to R ^d4 are the same or different, and a hydrogen atom (H), a fluorine atom (F), OR OR ⁱ which may have a substituent Group, and OR ⁱ It is preferable that group represents an alkoxy group, a phenoxy group, or a naphthoxy group.

In General Formula (I), R ⁱ and R ^j Is the same or different and represents an alkyl group, a phenyl group or a naphthyl group, but an alkyl group having 1 to 20 carbon atoms is preferable as the alkyl group. More preferably, it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, Especially preferably, it is a C1-C4 alkyl group. R ⁱ and R ^j are particularly preferably a phenyl group.

OR ⁱ Flag and SR ^j The substituent group which may have, for example, an alkoxycarbonyl group (-COOR), a halogen group (halogen atom), a cyano group (-CN), nitro (-NO _2), electron withdrawing group and the like; Electron donating groups such as alkyl groups (-R); These may be mentioned, and these 1 or 2 or more may be included. The electron withdrawing group is preferably an alkoxycarbonyl group, a halogen group or a cyano group, and more preferably a methoxycarbonyl group, an ethoxycarbonyl group, a fluoro group, a chlor group or a cyano group. As the electron donating group, an alkyl group is preferable. Moreover, said OR ⁱ Flag and SR ^j The form in which the substituent which the group may have is a halogen group is a particularly preferred embodiment of the present invention.

Moreover, it is preferable that R which comprises an alkoxycarbonyl group (-COOR) and an alkyl group (-R) is an alkyl group which may have a C1-C8 substituent. More preferably, it is a C1-C4 alkyl group. As an alkoxycarbonyl group, Preferably, they are a methoxycarbonyl group or a methoxyethoxycarbonyl group, As an alkyl group, Preferably they are a methyl group or a dimethyl group. Moreover, as a halogen group, Preferably, they are a fluoro group or a chlor group (chlorine atom).

Preferably as said R <^a1> -R <^d1> , R <^a2> -R <^d2> , R <^a3> -R <^d3>, and R <^a4> -R <^d4> , at least 1 or more of these is OR <^i>. It represents a group. This becomes more excellent in light resistance and solubility.

Also, OR ⁱ The carbon to which the group is bonded may be an α-position carbon (C _α : carbon at positions 1, 4, 8, 11, 15, 18, 22, and 25 of the phthalocyanine ring) in the four aromatic rings of the phthalocyanine skeleton. and β-position carbon (C _β : represents carbon at positions 2, 3, 9, 10, 16, 17, 23, and 24 of the phthalocyanine ring.). Moreover, although the number of OR <^i> groups introduce | transduced is not specifically limited, One or two is preferable for each aromatic ring of a phthalocyanine skeleton. That is, one or two of R ^a1 to R ^d1 , one or two of R ^a2 to R ^d2 , one or two of R ^a3 to R ^d3 , and one or two of R ^a4 to R ^d4 . Dogs are the same or different and OR ⁱ It is preferable that it is a group. Among them, one OR ⁱ at the C _α position Group which has a group, and is otherwise a hydrogen atom; 1 OR ⁱ at C _β Group which has a group and is otherwise a fluorine atom; Two identical or different OR ⁱ at C _β Group which has a group and is otherwise a fluorine atom; It is especially preferable in either form. That is, it is especially preferable that the compound represented by the said general formula (I) is a compound represented with the following general formula (I-1), (I-2) or (I-3).

(2)

OR ^{i in} said (I-1)-(I-3) The groups may be the same or different. OR ^{i in} the general formulas (I-1) to (I-3) Although group is as above-mentioned, it is preferable that it is a phenoxy group or a substituted phenoxy group. The substituent mentioned above is mentioned as a substituent which a substituted phenoxy group has, Especially, a methoxycarbonyl group, a methoxyethoxycarbonyl group, a chlor group (chlorine atom), a methyl group, or a cyano group is especially preferable.

In the above general formula (I), M represents a metal atom, a metal oxide or a metal halide. It does not specifically limit as said metal atom and the metal atom which comprises a metal oxide or a metal halide, For example, copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, Lithium, lead, etc. are mentioned, These 1 type, or 2 or more types can be used. Among them, it is preferable to use at least one of copper, vanadium and zinc as a central metal in view of better solubility, visible light transmittance and light resistance. More preferably copper or zinc. A phthalocyanine type pigment | dye which uses copper as a center metal does not deteriorate by light even if it disperse | distributes to any resin component (binder resin), and has very excellent light resistance. On the other hand, phthalocyanine complexes (phthalocyanine-based dyes) containing zinc as the center metal are excellent in solubility in resin components, have high light transmittance in the wavelength region of 400 to 600 nm, and high in the wavelength region of 600 to 800 nm. Since it is easy to obtain the light selective transmission filter which has light absorptivity, it is especially preferable.

Especially preferable form as a compound represented by said general formula (I-1), (I-2) or (I-3) is represented by Formula (6b), (7b), or (8b) shown by the Example mentioned later. Compound (wherein X and Y are each OR ⁱ Group. M is the same as the above).

The present inventors also found that a difference occurs in the absorption characteristics in the absorption region on the long wavelength side (600 nm or more) of visible light due to the presence form of the phthalocyanine-based dye. Specifically, since the phthalocyanine-based dye has a molecular structure excellent in planarity, the position of the absorption maximum peak differs when present as a single molecule and when present in an associated state (association molecule), and on the long-wavelength side. The peak (absorption maximum) derived from a single molecule discovered that the peak (absorption maximum) derived from an association molecule appears in the short wavelength side, respectively. And it is found out that the association state of the phthalocyanine type pigment | dye in a resin layer can be controlled by the three-dimensional structure of a molecule | numerator, and an electronic state, and the structure represented by the following general formula (i) also in the compound represented by the said General formula (I) In the case of having a, the absorption peak in the short wavelength region close to 600 nm is high due to the fact that the dye becomes easy to take associative molecular structure, and the light can more sufficiently reduce the incident angle dependence when combined with a reflective film, for example. It was found that a selective transmission filter was obtained. That is, the said pigment A is the following general formula (i):

(3)

In the formula, M represents a metal atom, a metal oxide or a metal halide. X ¹ to X ⁴ and Y ¹ to Y ⁴ Is the same or different and OR ⁱ which may have a hydrogen atom (H), a fluorine atom (F) or a substituent Group. OR ⁱ A group represents an alkoxy group, a phenoxy group, or a naphthoxy group. However, at least 4 of X <^1> -X <^4> and Y <^1> -Y <^4> are the same or different, and represent the phenoxy group which has an electron withdrawing group.) The form which is a phthalocyanine type pigment represented by this is also a preferable aspect of this invention. One. Thereby, while being able to fully satisfy the spectroscopic characteristic calculated | required by the light selective transmission filter, the obtained light selective transmission filter becomes what is more excellent in light resistance and heat resistance.

In the general formula (i), X ¹ to X ⁴ and Y ¹ to Y ⁴ OR is the same or different and may have a hydrogen atom (H), a fluorine atom (F) or a substituent OR ⁱ Represents a group, OR ⁱ The group represents an alkoxy group, a phenoxy group or a naphthoxy group, but X ¹ to X ⁴ and Y ¹ to Y ⁴ At least four of them are the same or different and represent a phenoxy group having an electron withdrawing group as a substituent. Where OR ⁱ When the group is an alkoxy group, R ⁱ It is preferable that it is a C1-C20 alkyl group, for example. More preferably, it is a C1-C8 alkyl group, More preferably, it is a C1-C6 alkyl group, Especially preferably, it is a C1-C4 alkyl group.

OR ⁱ About the substituent which the group may have, it is as above-mentioned.

X ¹ to X ⁴ and Y ¹ to Y ⁴ As mentioned above, although at least 4 of these represent the phenoxy group which has an electron withdrawing group, the said electron withdrawing group may be same or different. Moreover, although the number of the electron withdrawing groups in each phenoxy group is not specifically limited, For example, it is preferable that it is 1-4, More preferably, it is 1 or 2 pieces. In addition, when one phenoxy group has two or more electron withdrawing groups, the said electron withdrawing group may be same or different. In addition, the position of the electron withdrawing group in each phenoxy group is not specifically limited.

In the X ¹ ~ X ⁴ and Y ¹ ~ Y portion of ^tetravalent, if a group other than a phenoxy group having an electron withdrawing group, the art group, a hydrogen atom (H), fluorine (F), or may have a substituent OR ⁱ A group (except the phenoxy group which has an electron withdrawing group) may be sufficient. Especially, it is preferable that it is a phenoxy group, the phenoxy group which has an electron-donating group, or a fluorine atom (F), More preferably, it is a fluorine atom (F).

As said X <^1> -X <^4> and Y <^1> -Y <^4> , Preferably, all of X <^1> -X <^4> and Y <^1> -Y <^4> are the same or different, and represent the phenoxy group which has an electron withdrawing group. As a result, due to the higher association of the dye, the wavelength region to be blocked can be sharply blocked, and the light selective transmittance (blocking transmission characteristic) that shows a high transmittance in the wavelength region to be transmitted is further enhanced. Since the light selective permeable filter which can be exhibited can be provided and the incidence angle dependence by a reflection film can be reduced more, it is preferable. Thus, the form which shows the phenoxy group which all X <^1> -X <^4> and Y <^1> -Y <^{4> in} said general formula (i) have the same or different, and an electron withdrawing group is also one of the preferable forms of this invention. .

In General Formula (i), M is the same as M in General Formula (I). The preferred form is also the same.

The phthalocyanine-based dye represented by the general formula (i) further has one or two absorption maximum wavelengths in a wavelength range of 600 to 800 nm, and preferably at least one absorption maximum wavelength is present at 600 to 730 nm. Do. In other words, it is preferable that there is one or two absorption maximum wavelengths in the wavelength range of 600 to 800 nm, and at least one of them exists at 600 to 730 nm. By having such an absorption characteristic, the wavelength selective region to block can be cut more sharply, and the light selective transmittance which shows high transmittance | permeability in the wavelength range to be transmitted becomes more excellent, and such a pigment | dye When the used absorbent sheet is combined with the reflecting film, it becomes possible to significantly reduce the incident angle dependence by the reflecting film.

In the case where the phthalocyanine-based dye represented by the general formula (i) has two absorption maximum wavelengths in the wavelength range of 600 to 800 nm, the wavelength on the shorter wavelength side of the two absorption maximum wavelengths is λ _A1 and the wavelength on the long wavelength side. When λ _A2 is used, λ _A1 is preferably present in a wavelength range of 730 nm or less, and more preferably in a wavelength range of 700 nm or less. Moreover, it is preferable that the minimum of absorption maximum wavelength (lambda) _A1 is 650 nm or more. Moreover, it is preferable to use the pigment | dye whose transmittance | permeability in wavelength 500nm is 90% or more, and the transmittance | permeability in maximum absorption wavelength (lambda) _A1 is 60% or less. The transmittance at the maximum absorption wavelength λ _A1 is more preferably 50% or less, still more preferably 30% or less, particularly preferably 20% or less, and most preferably 10% or less.

When the phthalocyanine-based dye represented by the general formula (i) further evaluates absorbance characteristics by the resin film evaluation method, the wavelength of the peak having the largest absorptivity among the two absorption maximum wavelengths (λ _A1 , λ _A2 ) (that is, It is preferable that the wavelength of the peak with the lowest transmittance) is λ _A1 . Thereby, since it becomes possible to show sharp transmission absorption characteristic on the short wavelength side near 600 nm, it becomes further excellent in light selective transmission.

Moreover, the smaller the smaller the ratio (A _A2 / A _A1 ) of the absorbance at the two absorption maximum wavelengths (λ _A1 , λ _A2 ), the sharper the absorption waveform on the shorter wavelength side than λ _A1 is preferable. Specifically, it is preferable that it is 0.75 or less. If (A _A2 / A _A1 ) is larger than 0.75, there is a fear that the increase in absorption on the shorter wavelength side becomes slower (that is, not sharper) than the maximum absorption wavelength. The absorbance ratio (A _A2 / A _A1 ) is more preferably 0.6 or less, still more preferably 0.5 or less, particularly preferably 0.45 or less. Moreover, it is preferable that the lower limit of (A _A2 / A _A1 ) is 0 or more.

Said "resin film evaluation method" is a method of evaluating absorbance characteristics in the state of the film disperse | distributed or dissolved in the resin component.

The film "dispersed or dissolved in a resin component" is a film composed of a dye and a resin component, and under conditions (λ _A1 , λ _A2 ) in which absorption at two absorption maximum wavelengths (λ _A1 , λ _A2 ) can be evaluated The content of the dye and the thickness of the film may be selected so that the absorbance does not exceed the measurement limit of the spectrophotometer and satisfies the condition under which the absorbance can be measured.

In the said resin film evaluation method, it is preferable that the film | membrane for evaluation has a content rate of the pigment | dye chosen from the range of 0.01-15 mass%, and the thickness of a film | membrane in the range of 0.1-10 micrometers, and the content rate of the pigment | dye in a film | membrane is 3 mass. % And the thickness of the film is more preferably 3 µm.

The film for evaluation can be obtained by including a pigment | dye and a resin component (you may include a solvent as needed), and forming into a transparent base material (glass or a transparent resin film) (coating and drying as needed). By measuring the absorbance of the substrate with a film thus obtained, the absorbances of the dyes A _A1 , A _A2 , and A _A2 / A _A1 Can be obtained.

Here, depending on the combination of a pigment | dye and a resin component, even if the content rate of a pigment | dye and film thickness are changed, the absorption maximum may not be observed in the position of (lambda) _A2 . In this case, the wavelengths in correspondence to the λ _A2 confirming the absorbance (maximum value) A _A1, and the solvent dispersion method of the λ _A1 on the film that can be measured and the absorbance does not saturate absorbance in λ _A1 What is necessary is just to consider the absorbance in A <_A2> , and to calculate | require the ratio A _A2 / A _A1 .

In addition, although it does not specifically limit as a resin component for evaluation, The said pigment | dye uses the at least 1 sort (s) of resin component which can be used as the resin component of this invention mentioned later in the ratio (A _A2 / A _A1 ) mentioned above. It is preferable that it is a pigment | dye to satisfy. As a resin component for evaluation, Preferably it is solvent-soluble resin mentioned later. It is preferable that it is 1 type chosen from the group which consists of a fluorinated aromatic polymer, a poly (amide) imide resin, a polyamide resin, an aramid resin, and a polycycloolefin resin as evaluation resin component. Especially, a fluorinated aromatic polymer or a poly (amide) imide resin is more preferable, More preferably, it is a poly (amide) imide resin, Especially preferably, it is a polyimide resin.

Absorbance can be measured using Shimadzu Corporation make: UV-1800 (measuring machine), for example.

In order to obtain the compound represented by the said General formula (I) (the compound represented by the said General formula (i) is also included.), It is preferable to manufacture according to the method described in Unexamined-Japanese-Patent No. 6-31239 etc., for example. Do. Specifically, 1 type selected from the group which consists of a metal, a metal oxide, a metal carbonyl, a metal halide, and an organic acid metal, and the following general formula (I-i):

[Formula 4]

(Wherein R ^a to R ^d Is the same or different and is a hydrogen atom (H), a fluorine atom (F), an OR ⁱ group or SR ⁱ Group. R ⁱ and R ⁱ Represents the same or different, an alkyl group having 1 to 4 carbon atoms, a phenyl group which may have a substituent, or a naphthyl group which may have a substituent.), In the presence of a solvent-free or organic solvent, It is preferable to obtain by making it react by heating. Especially, it is preferable to make it react in an organic solvent. The cyclization reaction of the phthalonitrile derivative is not particularly limited, and the method described in JP-A-6-31239, JP-A-3721298, JP-3226504, JP-A-2010-77408, and the like. Can be applied alone or as appropriately modified. Substituents and OR ⁱ The specific form of group is as above-mentioned regarding said general formula (I).

In General Formula (Ii), as R ^a to R ^d , preferably, at least one of these is OR ⁱ It represents a group. OR ⁱ introduced Although the number of groups is not specifically limited, One or two is preferable. 1 OR ⁱ Group which has a group, and is otherwise a hydrogen atom; 1 OR ⁱ Group which has a group and is otherwise a fluorine atom; Two identical or different OR ⁱ Group which has a group and is otherwise a fluorine atom; It is especially preferable in either form. That is, it is especially preferable that the phthalonitrile derivative represented by said general formula (Ii) is a compound represented with the following general formula (I-1-i), (I-2-i), or (I-3-i). .

[Chemical Formula 5]

OR ^{i in} General Formula (I-3-i) The groups may be the same or different. OR ^{i in} General Formulas (I-1-i), (I-2-i) and (I-3-i) Although group is as above-mentioned, it is preferable that it is a phenoxy group or a substituted phenoxy group. The substituent mentioned above as a substituent which a substituted phenoxy group has can be mentioned, Especially, a methoxycarbonyl group, a methoxyethoxycarbonyl group, a fluoro group, a chlor group (chlorine atom), a methyl group, or a cyano group is especially preferable.

As a compound especially preferable as a compound represented by said general formula (I-1-i), (I-2-i), or (I-3-i), Formula (6a), (7a) shown by the Example mentioned later Or a compound represented by (8a) (In these formulas, X and Y are OR ⁱ , respectively. Group.).

Among the compounds represented by the general formula (I), in the case of obtaining the phthalocyanine-based dye represented by the general formula (i), the phthalonitrile derivative represented by the general formula (I-i) is, in particular, the following general formula (ii);

Where X ^a and Y ^a Is the same or different and OR ⁱ which may have a hydrogen atom (H), a fluorine atom (F) or a substituent Represents a group, OR ⁱ The group is preferably a phthalonitrile derivative represented by alkoxy group, phenoxy group or naphthoxy group.

In said general formula (ii), as X ^<a> and Y ^<a> , Preferably, at least 1 of these shows the phenoxy group which has an electron withdrawing group. More preferably, X ^a and Y ^a are the same or different and represent a phenoxy group having an electron withdrawing group.

In the reaction, X ^a and Y ^{a are} used as the phthalonitrile derivative represented by the general formula (ii). It is preferable to use at least the compound of the form which at least 1 shows the phenoxy group which has an electron withdrawing group. In addition, the X ^a and Y ^a and all of the type represents a non-electron withdrawing group having a phenoxy group compound, X ^a and Y ^a At least 1 may use together the compound of the form which shows the phenoxy group which has an electron withdrawing group.

The metal, metal oxide, metal carbonyl, metal halide and organic acid metal (hereinafter also referred to as metal compound) are particularly limited as long as the compound represented by the general formula (I) is obtained by reacting with the phthalonitrile derivative. It doesn't happen. For example, metals, such as iron, copper, zinc, vanadium, titanium, indium, magnesium, and tin; Halogen compounds (chlorides, bromide, iodide, etc.) of the metal; Metal oxides (vanadium oxide, titanium oxide, copper oxide, etc.) of the metal; Organic acid metal (acetate, etc.) of the said metal; Complex compounds of the metals (acetylacetonate and the like); Metal carbonyl (carbonyl iron and the like) of the metal; And the like.

Specific examples of the halogen compound include vanadium chloride, titanium chloride, copper chloride, zinc chloride, cobalt chloride, nickel chloride, iron chloride, indium chloride, aluminum chloride, tin chloride, gallium chloride, germanium chloride, magnesium chloride, Copper iodide, zinc iodide, cobalt iodide, indium iodide, aluminum iodide, gallium iodide, copper bromide, zinc bromide, cobalt bromide, aluminum bromide, gallium bromide and the like.

Specific examples of the metal oxides include vanadium monoxide, vanadium trioxide, vanadium tetraoxide, vanadium pentoxide, titanium dioxide, iron monoxide, iron trioxide, iron tetraoxide, manganese oxide, nickel monoxide, cobalt monoxide, cobalt trioxide, Cobalt dioxide, cuprous oxide, cuprous oxide, copper trioxide, palladium oxide, zinc oxide, germanium monoxide, germanium dioxide and the like.

Specifically as said organic acid metal, copper acetate, zinc acetate, cobalt acetate, copper benzoate, zinc benzoate, etc. are mentioned, for example.

Specifically as said metal carbonyl, cobalt carbonyl, iron carbonyl, nickel carbonyl, etc. are mentioned, for example.

Among the above metal compounds, at least one member selected from the group consisting of metals, metal oxides and metal halides is preferable. More preferably, it is a metal halide. More preferably, they are vanadium iodide, vanadium chloride, copper iodide, and zinc iodide. Especially preferably, they are vanadium iodide, vanadium chloride, and zinc iodide.

When zinc iodide is used as the metal compound, the center metal (M) in the general formula (I) is zinc.

When the reaction between the metal compound and the phthalonitrile derivative represented by the general formula (Ii) is carried out in an organic solvent, examples of the organic solvent include benzene, toluene, trimethylbenzene, xylene, nitrobenzene, and monochloro. Inert solvents such as benzene, dichlorobenzene, trichlorobenzene, 1-chloronaphthalene, 1-methylnaphthalene, ethylene glycol and benzonitrile; Aprotic properties such as pyridine, N, N-dimethylformamide, N-methyl-2-pyrrolidinone, N, N-dimethylacetophenone, triethylamine, tri-n-butylamine, dimethyl sulfoxide and sulfolane Polar solvents; Alcoholic solvents such as 1-octanol and diethylene glycol monomethyl ether; 1 type, or 2 or more types, such as these, can be used. Especially, it is preferable to use 1-chloronaphthalene, 1-methylnaphthalene, trimethylbenzene, or benzonitrile. More preferably, it is trimethylbenzene or benzonitrile.

In addition, it is preferable to set the usage-amount of the organic solvent at the time of using a solvent in the quantity which the density | concentration of the phthalonitrile derivative represented by the said General formula (I-i) will be 1-50 mass% normally. And more preferably 10 to 40% by mass.

In the said reaction, it is preferable that the injection amount of the said metal compound shall be 0.8-2 mol with respect to 4 mol of the phthalonitrile derivative represented by the said General formula (I-i). More preferably, it is 1-1.5 mol.

Regarding the above reaction, the reaction temperature is not necessarily constant depending on the kind of the raw material, the kind of the solvent, and other conditions, but is usually preferably 100 to 300 ° C. More preferably, it is 120 degreeC or more, More preferably, it is 130 degreeC or more. More preferably, it is 260 占 폚 or lower, more preferably 240 占 폚 or lower, and particularly preferably 200 占 폚 or lower. Further, the temperature may be increased stepwise to control the exothermic reaction. The reaction time is not particularly limited, but is usually from 2 to 24 hours, more preferably from 5 to 20 hours.

The reaction may be carried out in an air atmosphere, but depending on the type of the metal compound, an inert gas or an oxygen-containing gas atmosphere (for example, nitrogen gas, helium gas, argon gas, or oxygen / nitrogen mixed gas, etc.) may be used. Preferably under distribution).

After the said cyclization reaction, you may perform crystallization, filtration, washing | cleaning, and / or drying according to a conventionally well-known method.

In the said resin layer, although it changes also with the density | concentration (content) of the said pigment | dye A, the thickness of the resin sheet, the resin layer, etc., for example, with respect to 100 mass% of total amounts of a resin component and a pigment | dye, the said pigment | dye A Is preferably 0.001% by mass or more. By using the pigment | dye A, even if the pigment | dye density | concentration in a resin layer is high concentration, it becomes a resin layer which has the outstanding light resistance. More preferably, it is 0.01 mass% or more, More preferably, it is 0.1 mass% or more, Especially preferably, it is 1 mass% or more. However, if the dye concentration is too high, the resin layer may be considerably thin in order to sufficiently transmit the visible light region to be transmitted, which may make it difficult to form a film with a uniform film thickness. From such a viewpoint, it is preferable that it is 20 mass% or less. More preferably, it is 15 mass% or less.

In this invention, another pigment can also be used together with the pigment | dye A mentioned above.

Although the said other pigment | dye should just be pigment | dyes other than the said pigment | dye A, it is preferable to have absorption maximum in the 600-800 nm wavelength range. More preferably, it has absorption maximum in the wavelength range of 650-750 nm.

It is preferable that the said other pigment | dye does not have an absorption maximum substantially in the wavelength range of 400 nm or more and less than 600 nm.

Specifically as said other pigment | dye, For example, phthalocyanine pigment | dye other than the pigment | dye A mentioned above, porphyrin pigment | dye, chlorine pigment | dye, choline pigment | dye, cyanine pigment | dye, quaterylene pigment, squarylium pigment | dye, Naphthalocyanine dyes, nickel complex dyes, copper ion dyes, and the like, and one or two or more thereof can be used. Among these, a phthalocyanine type pigment | dye is preferable from a light resistant and heat resistant viewpoint.

As said other pigment | dye, Preferably when it evaluates by the resin film evaluation method mentioned above, than the maximum absorption wavelength of the above-mentioned pigment | dye A (among these, Preferably, the phthalocyanine-type pigment | dye represented by the said General formula (i)). It is preferable that it is a pigment | dye which has a maximum absorption wavelength in a long wavelength side. Thereby, when used for the light selective transmission filter which further contains a reflective film (reflective layer), it becomes possible to reduce incident angle dependence further. Especially, the phthalocyanine pigment | dye (it is called pigment B) which satisfy | fills at least 1 or more of the following absorption characteristics (1)-(3) is especially preferable. By using such pigment | dye B and the pigment | dye A mentioned above, sufficient absorption band width can be ensured and the light selective transmission filter which is more excellent in light selective transmittance can be provided, and the light selective transparent filter obtained is more durable It is excellent.

(1) It has two absorption maximum wavelengths ((lambda) _B1 , (lambda) _B2 ) in the wavelength range of _650-800nm , and has the largest absorption wavelength (lambda) _B2 on the long wavelength side among them.

(2) Maximum absorption wavelength of dye B (ie, wavelength of peak having the lowest transmittance) [lambda] _B2 is longer than the maximum absorption wavelength [lambda] _A of pigment | dye A mentioned above.

(3) The ratio (A _B2 / A _B1 ) of absorbance at the two absorption maximum wavelengths (λ _B1 , λ _B2 ) is composed of the dye B and the resin component, and the content ratio of the dye B is 3% by mass. 2 or more are satisfied when the absorbance of a phosphorus composition is measured.

Especially as said pigment B, it is a phthalocyanine type pigment | dye which satisfy | fills all said absorption characteristics (1)-(3). Thus, the pigment | dye contained in the resin layer of this invention is a phthalocyanine type pigment | dye which has two absorption maximum wavelengths ((lambda) _B1 , (lambda) _B2 ) in the wavelength range of 650-800nm further, Among them, the maximum absorption wavelength in a long wavelength side dye B having λ _B2 , and the maximum absorption wavelength λ _B2 is longer than the maximum absorption wavelength λ _A of the dye A, and the absorbance at the two absorption maximum wavelengths (λ _B1 , λ _B2 ) When the ratio (A _B2 / A _B1 ) is composed of the dye B and the resin component and the absorbance of the composition in which the content ratio of the dye B is 3% by mass is measured, the form of satisfying two or more is also present. It is one of the preferable forms of invention.

Although the said two absorption maximum wavelengths ((lambda) _B1 , (lambda) _B2 ) should just exist in the wavelength range of 650-800 nm, it is preferable that at least 1 exists in the wavelength range of 650-730 nm. That is, it is preferable that there exist two absorption maximum wavelengths in the wavelength range of 650-800 nm, and at least 1 exists in 650-730 nm. By having such an absorption characteristic, the wavelength selective region to block can be cut more sharply, and the light selective transmittance which shows high transmittance | permeability in the wavelength range to be transmitted becomes more excellent, and such a pigment | dye When the used resin sheet is combined with a reflecting film, it becomes possible to significantly reduce the incident angle dependence by the reflecting film.

Among the two absorption maximum wavelengths, when the wavelength on the short wavelength side is λ _B1 and the wavelength on the long wavelength side is λ _{B 2} , the wavelength of the peak having the largest absorption ratio (that is, the wavelength of the peak having the lowest transmittance) is determined on the long wavelength side. That is, λ _B2 . As a result, it is possible to exhibit sharp transmission absorption characteristics on the short wavelength side close to 600 nm, so that the incident angle dependency can be sufficiently reduced. Moreover, it is preferable that this maximum absorption wavelength (lambda) _B2 exists in the wavelength range of 650-730 nm. More preferably, maximum absorption wavelength (lambda) _B2 exists in the wavelength range of 680-720 nm. The transmittance at the maximum absorption wavelength λ _B2 is preferably 60% or less, more preferably 50% or less, still more preferably 30% or less, and particularly preferably 20% or less.

When the said pigment | dye B also evaluated the absorbance characteristic by the resin film evaluation method, in the two absorption maximum wavelengths ((lambda) _B1 , (lambda) _B2 )), the wavelength of the peak with the largest absorption among these (that is, the peak with the lowest transmittance | permeability). Wavelength) is preferably λ _B2 . Thereby, since it becomes possible to show sharp transmission absorption characteristic on the short wavelength side near 600 nm, it becomes further excellent in light selective transmission. In addition, the larger the ratio (A _B2 / A _B1 ) of absorbance at the two absorption maximum wavelengths (λ _B1 , λ _B2 ), the larger the visible light transmittance of 650 nm or less is improved, and the sharper transmission absorption sharper on the longer wavelength side than 650 nm. It becomes possible to show characteristics. As absorbance ratio (A _B2 / A _B1 ), Preferably it is 2.0 or more, More preferably, it is 2.5 or more, More preferably, it is 3.0 or more. Moreover, although an upper limit is not specifically limited, It is preferable that it is 10 or less and it is easy to obtain industrially.

The said absorbance ( _AB1 , _AB2 ) is a value when the absorbance of the composition which consists of a pigment | dye B and a resin component, and the content rate of the pigment | dye B is 3 mass% is measured. Absorbance can be measured using Shimadzu Corporation make: UV-1800 (measuring machine), for example.

In addition, it is preferable to use polyimide resin for the resin component at the time of measuring the said absorbance ( _AB1 , _AB2 ).

The said "resin film evaluation method" is as having mentioned above.

As said pigment B, what is necessary is just a phthalocyanine type pigment | dye which satisfy | fills at least 1 or more of the above-mentioned absorption characteristics (1)-(3), Specifically, for example, the compound represented by general formula (I) mentioned above 1 type, or 2 or more types of is used preferably.

Wherein R ^a1 to R ^a4 , R ^b1 to R ^b4 , R ^c1 to R ^c4 and R ^d1 to R ^d4 As described above, at least one of these is OR ⁱ Group preferably represents OR ⁱ The carbon to which the group bonds may be α-position carbon or β-position carbon, but it is preferable that it is at least α-position carbon. Among them, OR ⁱ in an average of two or more carbons in α-position carbon (C _α ) The form which group couple | bonded is preferable, More preferably, it is OR ⁱ to one or more alpha-position carbon (C _alpha ) in each aromatic ring. It is a combination of groups. Moreover, it is also preferable that it is a form which the hydrogen atom or the fluorine atom couple | bonded with the average 4 or more carbon among ( _beta ) position carbon (C ( _beta )). More preferably, a hydrogen atom or a fluorine atom is bonded to an average of 6 or more carbons among β-position carbons (C _β ), and more preferably, a hydrogen atom or a fluorine atom is bonded to all carbons of the β-position carbon (C _β ). to be. By setting it as such a form, since it becomes a phthalocyanine type pigment | dye which fully satisfies at least 1 or more of the above-mentioned absorption characteristics (1)-(3), it becomes possible to fully exhibit the effect of this invention.

Moreover, 1 type (s) or 2 or more types of the compound represented by the following general formula (II) is also used preferably.

[Formula 6]

Wherein M &lt; ^{2 &gt;} 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 Is the same or different, and represents substituent (a) represented by the following formula (II-a), or substituent (b) represented by the following formula (II-b). Z ¹ , Z ⁴ , Z ⁵ , Z ⁸ , Z ⁹ , Z ¹² , Z ¹³ and Z ¹⁶ Is the same or different, and represents a fluorine atom or the substituent (b ') represented by a following formula (II-b'). Where 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 to unit 4; In this case, any one to three of the units 1 to 4 represent all two groups (atoms) constituting the unit with a fluorine atom, and the remaining units represent all two groups (atoms) with the substituents ( b ') or one of the two groups (atoms) constituting the unit represents a substituent (b') and the other represents a fluorine atom.

[Formula 7]

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 1-5. R ² Are, the same or different and which may have a substituent carbon atoms, an alkyl group having 1 to 20 carbon atoms which may have a substituent of 1 to 20 alkoxy group, -COOR ^3, or 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 0-4.

R ^{4 in} formula (II-b) Is the same or different, and represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, -COOR ⁵ , or 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 of 0-5.

In formula (II-b '), R ^4' Is the same or different, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an alkoxy group having 1 to 20 carbon atoms which may have a substituent, -COOR ^{5 '} , and a carbon atom having 6 substituents The aryl group of 30 or a halogen atom is represented. R ^{5 '} Represents an alkyl group having 1 to 20 carbon atoms which may have a substituent. n ^{1 '} Is an integer of 0-5.

In the formula (II), M ² Represents a metal atom, a metal oxide or a metal halide, but a preferred form of the metal atom and the metal atom constituting the metal oxide or the metal halide is M in general formula (I) described above. It is the same as the metal atom shown.

As said pigment | dye A and pigment | dye B, 1 type, or 2 or more types of compound represented by following General formula (III) are also used preferably.

[Formula 8]

In the formula, M ³ Represents a metal free, metal atom, metal oxide or metal halide. Z ¹⁷ to Z ³² Is the same or different, a fluorine atom, a chlorine atom, a bromine atom, a substituent (III-a) represented by the following formula (III-a), a substituent (III-b) represented by the following formula (III-b), the following formula ( Substituent (III-c) represented by III-c), Substituent (III-d) represented by following formula (III-d), Substituent (III-e) represented by following formula (III-e), Formula (III- Substituent (III-f) represented by f), Substituent (III-g) represented by following formula (III-g), Group (III-h) derived from 7-hydroxycoumarin, or 2,3-dihydroxy The group (III-i) derived from quinoxaline is shown. Where Z ¹⁷ to Z ³² 6-12 of them are substituents (III-a), (III-c), (III-d), (III-e), (III-f), (III-g), (III-h) and Any of (III-i) is shown, or 9-12 of these are a substituent (III-b), and the remainder represents a fluorine atom, a chlorine atom, or a bromine atom.

[Chemical Formula 9]

In formulas (III-a) and (III-b), R ⁵ Represents a C1-C8 alkoxy group or a halogen atom. R ⁶ Represents a C1-C3 alkylene group. R ⁷ Represents a C1-C8 alkyl group. p is an integer of 0-4. n ² Is an integer of 1-3. m ² is an integer of 1-4.

R in formulas (III-c) and (III-d)⁸ Silver is a hydrogen atom, a C1-C8 alkyl group, or-(R⁶O)_m2R⁷The group represented by is shown. R⁵, p, R⁶, m² And R⁷ Is the same definition as each symbol in said Formula (III-a) and (III-b), respectively.

X ^{1 in} formulas (III-e), (III-f) and (III-g) Represents an oxygen atom or a sulfur atom. Ar represents a phenyl group or naphthyl group which may be substituted by one or more R ⁹ . R ⁹ is the same or different and represents a cyano group, a nitro group, a 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 C1-C8 alkyl group which may be substituted by the halogen atom or the C1-C8 alkoxy group. R ¹¹ Represents a C1-C5 alkylene group. R ¹² Is the same or different, and represents a C1-C8 alkoxy group or a C1-C8 alkyl group.

Here, in general, the extinction coefficient is different depending on the skeleton of the dye, and since it is impossible to define the mass ratio with respect to the dye of the various skeletons, it is difficult to define the ratio of the content of the dye A and the other dye. However, when using the pigment | dye B mentioned above as said other pigment | dye, for example, the mass ratio (color B / colour A) of content of the said pigment | dye B and the pigment | dye A is 80/20-40/60, for example. It is preferable to set it as. By being in this range, it becomes possible to fully exhibit the effect of this invention that it has a more sufficient absorption band width, shows sharp transmission absorption characteristic, and can also fully reduce the incident angle dependency when combined with a reflective film. As mass ratio (color B / color A), More preferably, they are 70 / 30-50 / 50.

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, content of such another pigment | dye is 100 mass of total amounts of a pigment, in order to fully exhibit the effect by this invention. It is preferable that it is 30 mass% or less with respect to%. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less, Especially preferably, it does not contain the said other pigment | substrate substantially.

It is preferable that the said resin layer further contains the compound which has an absorptivity in the wavelength range of 350-400 nm. Thereby, deterioration of the resin sheet (and light selective transmission filter) resulting from the light (almost purple light) of 350-400 nm wavelength range can be fully suppressed.

As a form containing the compound which has an absorptivity in the said wavelength range of 350-400 nm, the said pigment | dye A may be a form which is a compound which has an absorptivity in the 350-400 nm wavelength range, and also it is 350-400 nm separately The form which uses together the compound which has an absorptivity in a wavelength range may be sufficient. As a compound which has an absorptivity in the latter wavelength range of 350-400 nm, it is 1 type of ultraviolet absorbing compounds, such as TINUVIN P, TINUVIN 234, TINUVIN 329, TINUVIN 213, TINUVIN 571, TINUVIN 326 (made by BASF Corporation), for example. Or 2 or more types can be used.

Resin component

In the said resin layer, as a resin component, the resin component which can fully melt | dissolve or disperse a pigment | dye is preferable. That is, it is preferable that the said pigment | dye is disperse | distributed or melt | dissolved uniformly in a resin layer. By appropriately selecting such a resin component, both high transmittance in the wavelength region (for example, visible region) to be transmitted and high absorbance in the wavelength region (for example, infrared region) to be blocked are compatible. It becomes possible.

As said resin component, at least 1 sort (s) chosen from the group which consists of solvent soluble resin, a solvent soluble resin raw material, and a liquid resin raw material is preferable, for example. Since such a resin component has high dispersibility of a pigment | dye, it can form the light absorption film which is more excellent in a light selective absorptivity, and can disperse | distribute a pigment | dye at a high concentration, and can also thin the light selective transmission filter. Moreover, when the said resin component is used, since the resin layer can be formed (film-forming) by the solvent casting method mentioned later, pigment | dye can be disperse | distributed uniformly in high concentration in a resin layer, and a resin layer is formed at comparatively low temperature. can do.

In addition, the said resin layer itself may be solvent soluble or insoluble.

Here, "solvent soluble resin" means resin which is soluble in an organic solvent, For example, it is preferable that it is resin which melt | dissolves 1 mass part or more with respect to 100 mass parts of dimethylacetamide or N-methylpyrrolidone. . In addition, "solvent soluble resin raw material" means solvent soluble resin raw material, ie, resin soluble as a resin raw material, For example, 1 mass part with respect to 100 mass parts of dimethyl acetamide or N-methylpyrrolidone. It is preferable to melt | dissolve abnormally. In addition, "liquid resin raw material" means a liquid resin raw material, ie, a liquid as a resin raw material. The substance is "liquid" means that the viscosity of the substance itself is 100 Pa · s or less at normal temperature (25 ° C). A viscosity can be measured with a Brookfield viscometer.

In addition, the "resin raw material" shall contain the precursor of resin, the raw material of this precursor, and the monomer (curable monomer etc.) for forming resin.

As said resin component, as mentioned above, although at least 1 sort (s) chosen from the group which consists of solvent-soluble resin, a solvent-soluble resin raw material, and a liquid resin raw material is preferable, it is preferable to use solvent-soluble resin among these. When solvent-soluble resin is used, it is excellent in light resistance compared with the case where a solvent-soluble resin raw material and a liquid resin raw material are used. This is because the solvent-soluble resin is less likely to cause deterioration in the absorption performance of the dispersed pigment than the solvent-soluble resin raw material and the liquid resin raw material. As a reason, solvent soluble resin is adjusted from the monomer and precursor, and complete | finish superposition | polymerization and reaction. In addition, purification may be performed. It is thought that the solvent-soluble resin obtained in this way has almost no unreacted substance, a reactive terminal, an ionic group, a catalyst, an acid-base group, etc. which promote deterioration and decomposition of the dye. On the other hand, the solvent-soluble resin raw material and the liquid resin raw material have many factors which accelerate deterioration and decomposition of such a pigment | dye. Moreover, in the state which disperse | distributed the pigment | dye, it is difficult to complete superposition | polymerization and reaction of a solvent-soluble resin raw material and a liquid resin raw material, maintaining the absorption performance and absorption spectrum of a pigment | dye. Not obtained). Therefore, even if the same pigment | dye is disperse | distributed, light resistance of a resin layer changes with a difference of a resin component. Therefore, it is preferable to use solvent soluble resin at least from a light resistant viewpoint.

Specific examples of the solvent-soluble resins include fluorinated aromatic polymers, poly (amide) imide resins, polyamide resins, aramid resins, polycycloolefin resins, and the like. Especially, a fluorinated aromatic polymer and / or poly (amide) imide resin are preferable from a viewpoint which is more excellent in light resistance. More preferably, it is poly (amide) imide resin, More preferably, it is polyimide resin.

The solvent-soluble resin may further be a reactive group capable of crosslinking reaction (curing reaction) (eg, 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 the like). Radical curable group and / or addition curable group).

When using solvent-soluble resin as the said resin component, the solvent-soluble resin may be used as the resin component which comprises the said resin layer as it is, and the thing in which the solvent-soluble resin changed by crosslinking reaction etc. comprises the said resin layer. It may be a resin component.

The amount of the crosslinkable reactive group and the extent to which the crosslinking reaction proceeds 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 is composed of an aromatic ring having at least one fluorine group and a repeating unit comprising 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 A polymer etc. are mentioned, Specifically, For example, polyimide which has a fluorine atom, polyether, polyetherimide, polyether ketone, polyether sulfone, polyamide ether, polyamide, polyether nitrile, polyester Etc. can be mentioned. Among these, it is preferable that it is a polymer which has the aromatic ring which has an at least 1 or more fluorine group, and the repeating unit containing an ether bond as an essential site | part, and is represented by the following general formula (1-1) or (1-2) The polyether ketone which has a fluorine atom containing more preferable is more preferable. Especially, especially fluorinated polyether ketone (FPEK) is preferable.

In addition, the repeating unit represented by General formula (1-1) or (1-2) may be same or different, and may be any form, such as a block phase and a random phase.

[Formula 10]

In 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 greater than or equal to 0, satisfy | fill x + y = 1-8, are the same or different, and show the number of the fluorine atoms couple | bonded with the aromatic ring. n ³ Silver represents a polymerization degree, the inside of the range of 2-5000 is preferable, and the inside of the range of 5-500 is more preferable. In General Formula (1-2), R ¹⁴ Is a C1-C12 alkyl group, a C1-C12 alkoxy group, a C1-C12 alkylamino group, a C1-C12 alkylthio group, a C6-C20 aryl group, C6-C12 which may have a substituent An aryloxy group of 20, an arylamino group of 6 to 20 carbon atoms or an arylthio group of 6 to 20 carbon atoms is represented. R ¹⁵ Represents a divalent organic chain having an aromatic ring having 1 to 150 carbon atoms. z is the number of fluorine atoms couple | bonded with the aromatic ring, and is 1 or 2. n ³ Represents a polymerization degree, the inside of the range of 2-5000 is preferable, and the inside of the range of 5-500 is more preferable.

In the said General formula (1-1), inside of the range of 2-8 is preferable, and x + y has a more preferable inside of the range of 4-8. Moreover, as a position which an ether structure part (-OR <^13> -O-) couple | bonds with an aromatic ring, it is preferable that it is a para position with respect to Z.

In the formulas (1-1) and (1-2), R ¹³ and R ¹⁵ Is a divalent organic chain, but is preferably an organic chain of any one of the following structural formula groups (2) or a combination thereof.

[Formula 11]

In the structural formula group (2), Y ¹ to Y ⁴ Is the same or different and represents a hydrogen group or a substituent, the substituent being a halogen atom or an alkyl group, alkoxy group, alkylamino group, alkylthio group, aryl group, aryloxy group, arylamino group or aryl which may have a substituent A thio group is shown.

As a more preferable specific example of said R <^13> and R <^15> , the organic chain represented by the following structural formula group (3) is mentioned.

[Chemical Formula 12]

In the general formula (1-1), Z represents a divalent chain or a direct bond. As said bivalent chain, it is preferable that it is a chain represented, for example by the following structural formula group (4) (structure formula (4-1)-(4-13)).

[Chemical Formula 13]

In said structural formula group (4), although X is a C1-C50 divalent organic chain, For example, the organic chain represented by the structural formula group (3) mentioned above is mentioned, Especially, a diphenyl ether chain and bisphenol are mentioned. A chain, bisphenol F chain, fluorene chain are preferred.

In R ¹⁴ in the general formula (1-2), the alkyl group is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl or isopentyl , 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, etc. are preferable.

As said alkylamino group, methylamino group, ethylamino group, dimethylamino group, diethylamino group, propylamino group, n-butylamino group, sec-butylamino group, tert- butylamino group, etc. 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.

Examples of the aryl group include 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, Biphenylyl group, benzhydryl group, trityl group, pyrenyl group, etc. are preferable.

Examples of the aryloxy group include phenoxy group, benzyloxy group, hydroxybenzoic acid and esters thereof (for example, methyl ester, ethyl ester, methoxyethyl ester, ethoxyethyl ester, furfuryl ester and phenyl ester). Group, naphthoxy group, o-, m- or p-methylphenoxy group, o-, m- or p-phenylphenoxy group, phenylethynylphenoxy group, cresotinic acid and groups derived from esters thereof are preferable. Do.

As said arylamino group, an anilino group, o-, m- or p- toludino group, 1,2- or 1, 3- xyldino group, o-, m- or p-methoxyanilino group, anthra Nilic acid and the group derived from esters thereof are preferable.

As said arylthio group, a phenylthio group, a phenylmethanethio group, o-, m- or p-tolylthio group, thiosalicylic acid, the group derived from esters, etc. are preferable.

As said R <^14> , the alkoxy group, the aryloxy group, the arylthio group, and the arylamino group which may have a substituent among these are preferable. R ² The double bond or the triple bond may or may not be included in.

As a substituent in R <^2> in the said General formula (1-2), a C1-C12 alkyl group as mentioned above; Halogen atoms such as fluorine, chlorine, bromine and iodine; Cyano group, nitro group, carboxyester group, etc. are preferable. Moreover, the hydrogen of these substituents may or may not be halogenated. Among these, Preferably, a halogen atom and hydrogen may or may not be halogenated, and are methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, and carboxyester group.

The said poly (amide) imide resin means narrow polyimide resin (resin containing an imide bond and not containing an amide bond, and an amide bond here is an imide bond by dehydration reaction of an amic acid. Means an amide bond that cannot form a polyamideimide resin, and a resin containing an amide bond and an imide bond that cannot form an imide bond by dehydration of amic acid. It includes everything.

In addition, the imide bond in polyimide resin is the bond chain which has an amide bond and the carboxyl group adjacent to it normally (In this invention, the bond chain is also called amic acid. Usually, the carbon atom which the amide bond couple | bonded) It is formed by the dehydration reaction of an amide bond and a carboxyl group in ().

When producing a polyimide resin by dehydration reaction from polyamic acid, some amount of amic acid may 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 the dehydration reaction of amic acid. The amide bond which can form an imide bond by this is not included or may be included in a little quantity.

As said solvent-soluble resin, the imide bond content rate (ratio of the imide bond number with respect to 100 mol% of total amounts of the amide bond number and imide bond number which can be imidated by imidation reaction) in polyimide resin is Preference is given to polyimide resins of 80 mol% or more. More preferably, it is 90 mol% or more, More preferably, it is 95 mol% or more, Especially preferably, it is 98 mol% or more.

Here, although polyamideimide resin contains the amide bond and imide bond which cannot form an imide bond by the dehydration reaction of amic acid, the amide bond which can form an imide bond by dehydration reaction of amic acid May or may not contain a small amount. In the case of containing an amide bond capable of forming an imide bond by dehydration of amic acid, the amide bond water (imide bond is formed by dehydration reaction with an amide bond water that cannot form an imide bond by dehydration reaction). As for the content rate of the amide bond which can form an imide bond by the dehydration reaction of amic acid, with respect to the total amount of the sum total of the amide bond number which can be formed) and imide bond number 100 mol%, less than 20 mol% is preferable. Do. More preferably, it is less than 10 mol%, More preferably, it is less than 5 mol%, Especially preferably, it is less than 2 mol%.

The said poly (amide) imide resin is also called the raw material (poly (amide) imide precursor of poly (amide) imide resin obtained by reaction of a polyhydric carboxylic acid compound, a polyvalent amine compound, and / or a polyvalent isocyanate compound. ) Can be obtained by imidization reaction.

It is preferable that the said poly (amide) imide resin also has transparency. In order to improve transparency, the one with less aromatic rings is preferable. Especially, it is preferable to have a structure which substituted the aromatic ring by alicyclic or fatty chains. More preferably, the weight of the aromatic ring in 100% of the total weight is 65% or less, still more preferably 45% or less, and particularly preferably 30% or less.

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

[Formula 14]

In which R ¹⁶ Is the same or different and represents an organic group.) The compound which has a repeating unit represented by these is preferable.

As R <^16> in the said General formula (5), a divalent organic group is preferable, Especially, a C2-C39 divalent organic group is preferable. Moreover, it is preferable that the said organic group contains 1 type, or 2 or more types of hydrocarbon skeleton. As a hydrocarbon backbone, it is preferable that they are aliphatic chain hydrocarbon, aliphatic cyclic hydrocarbon, or aromatic hydrocarbon. The organic group may further have a heterocyclic skeleton.

R ¹⁶ in the general formula (5) further has the same or different two or more selected from the hydrocarbon skeleton and / or the heterocyclic skeleton described above, and they are via a carbon-carbon bond or carbon. It is preferable to include the backbone which couple | bonded through the bonding group different from -carbon bond. As the coupler, for example, -O-, -SO ₂ - may be mentioned, -C ₂ H ₄ O-, -S-, etc. _{-, -CO-, -Si (CH 3} ) 2.

In addition, the same or different things may be sufficient as each R <^16> in the repeating unit represented by the said General formula (5).

The organic group represented by R ¹⁶ may be bonded directly 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- and the like.

In addition, although some or all of the hydrogen atoms in the cyclohexyl ring in General formula (5) may be substituted, it is preferable that they are unsubstituted (all are hydrogen atoms).

The repeating unit represented by the said General formula (5) may be same or different, and may be any form, such as a block form and a random form.

As a preferable specific example of the said poly (amide) imide resin, Neoprem L-3430 (thickness 50 micrometers, 100 micrometers, 200 micrometers etc.) by Mitsubishi Gas Chemical Co., Ltd. is mentioned, for example. Moreover, although this product is a film form, since it is soluble in the organic solvent, it is used suitably as said solvent-soluble resin.

As said solvent-soluble resin raw material or liquid resin raw material, the epoxy compound used as a raw material of an epoxy resin, the vinyl compound ((meth) acrylic compound, a styrene compound, etc.) which is a raw material of vinyl polymer resin, poly (amide), for example And imide precursors. Preferably, it is an epoxy compound and a vinyl type compound.

The said epoxy resin is hardened | cured material of the curable composition containing the compound (epoxy compound) which has an epoxy group. As a form of hardened | cured material, the form formed by light and / or thermosetting an epoxy compound in presence of a cationic curing catalyst, the form of the hardened | cured material obtained by making an epoxy compound react with an additional hardening | curing agent, etc. are mentioned. In the latter, a conventionally known curing accelerator may be used in combination for promoting the curing reaction. As an additional hardening | curing agent, an acid anhydride, a polyhydric phenol compound, a polyhydric amine, etc. are illustrated, for example, Especially, an acid anhydride is preferable.

As said epoxy compound, an aromatic epoxy compound, an aliphatic epoxy compound, an alicyclic epoxy compound, a hydrogenated epoxy compound, etc. are preferable, For example, Fluorene epoxy (Oncoat EX-1) by Osaka Gas Chemical Company; Bisphenol A epoxy compound (Epicoat 828 EL) by the Japan epoxy resin company; Hydrogenated bisphenol A epoxy compound (Epicoat YX8000) by the Japan epoxy resin company; Alicyclic liquid epoxy compound (Celoxide 2021) etc. made by Daicel Industries, Ltd. can be used preferably.

In addition, in this specification, an epoxy group is what contains the oxirane ring which is an ether of a 3-membered ring, and what contains a glycidyl group (including glycidyl ether group and glycidyl ester group) other than a narrow epoxy group. it means.

It is preferable that the curable composition containing the said epoxy compound contains the component (flexible component) which has flexibility. By including a flexible component, it can be set as the resin composition with a sense of unity, such as not shatter | molding at the time of shaping | molding, or peeling off from a board | substrate, a mold, etc., being in shape, being easy to peel off, and having flexibility.

As said flexible component, the compound different from the said epoxy compound may be sufficient, and at least 1 type of the said epoxy compound may be a flexible component.

The said vinyl polymer resin is a polymer obtained by (co) polymerizing a vinyl compound as a polymerization raw material, and an acrylic resin, a styrene resin, an acryl-styrene resin, etc. are illustrated. An acrylic resin is hardened | cured material of the curable composition containing the compound (it is also called a (meth) acryloyl-group containing compound or a (meth) acrylic-type compound) which has a (meth) acryloyl group, and a styrene resin is styrene and divinyl) It is a hardened | cured material of the curable composition containing styrene-type monomers (it is also called a styrene-type compound), such as benzene, and an acryl-styrene resin is the hardened | cured material of the curable composition containing a (meth) acryloyl-group containing compound and a styrene-type monomer. to be. Among the vinyl polymer resins, acrylic resins and acrylic-styrene resins are preferable.

As said (meth) acryloyl-group containing compound, (meth) acrylate monomer, urethane (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, etc. are illustrated preferably. (Meth) acrylate (co) polymer (however, it has (meth) acryloyl group) which (co) polymerized the (meth) acrylate monomer can also be used preferably. Since it can make film formation easy, it contains polymeric oligomers, such as a urethane (meth) acrylate, a polyester (meth) acrylate, and a (meth) acrylate (co) polymer, and a (meth) acrylate monomer. It is preferable to use the composition to make an acrylic resin raw material.

As said acryl-styrene resin raw material, the composition using a styrene monomer further in the preferable aspect of the said acrylic resin raw material is preferable.

The said poly (amide) imide precursor is a raw material for forming a poly (amide) imide resin, ie, a compound used for imidation reaction, For example, a polyamic acid etc. are preferable. Specifically, HPC-7000-30 manufactured by Hitachi Kasei Kogyo Co., etc. is preferably used.

Although it is preferable that the said resin layer is a layer formed with the resin composition containing the said pigment | dye and a resin component, the resin composition may further contain other components as needed. Although other pigment | dye etc. which were mentioned above are mentioned as another component, When other components contain inorganic components, such as a metal oxide, the content is 100 mass% of a resin composition from a viewpoint which is excellent in transparency to visible light. It is preferable that it is less than 50 mass% in the inside. More preferably, it is less than 20 mass%, More preferably, it is less than 5 mass%, Especially preferably, it is less than 1 mass%. Most preferably, the resin composition which forms the said resin layer does not contain an inorganic component substantially.

About the film thickness (thickness) of the said resin layer, thin film formation becomes possible by using the pigment | dye A as mentioned above. It is advantageous in light resistance that it can be thinned in that it is easy to suppress penetration and diffusion of moisture or the like from the thickness direction. It is preferable that the film thickness (thickness) of the said resin layer is 5 micrometers or less. Thereby, the light selective transmission filter can be sufficiently thinned and can meet the low magnification request | requirements of an optical member. More preferably, it is 3 micrometers or less. Moreover, it is preferable that it is 0.5 micrometer or more, More preferably, it is 1 micrometer or more.

Although the said resin layer may be excellent in permeability in the ultraviolet region from the short wavelength region of visible light, when it is set as the ultraviolet cut filter which combined the resin sheet and the reflecting film which reflects an ultraviolet region, in order to reduce the incident angle dependency by a reflecting film It is preferable that the minimum value of the transmittance | permeability of the resin layer in 350-400 nm wavelength range is 20 to 80% from an easy point. For the same reason, it is preferable that the minimum value of the transmittance | permeability in 350-400 nm wavelength range in a resin sheet is 20 to 80%.

Moreover, it is preferable that the said resin layer has absorption maximum wavelength in the wavelength range of 600-800 nm, and the at least 1 absorption maximum wavelength exists in 600-730 nm. Here, the absorption maximum wavelength which the said resin layer has should just be 1 or 2 or more in the 600-800 nm wavelength range, and one of them should just exist in 600-730 nm. By having such absorption characteristics, the wavelength region to be blocked can be cut more sharply, and the light selective transmittance of high transmittance is shown in the wavelength region to be transmitted, and the resin sheet and the reflective film are When combined, it becomes possible to greatly reduce the incident angle dependency by the reflection film. More preferably, at least one absorption maximum wavelength exists in a wavelength range of 710 nm or less, More preferably, it exists in a wavelength range of 700 nm or less. Moreover, it is preferable to exist in a wavelength range of 650 nm or more.

Moreover, it is preferable that the wavelength (namely, the maximum absorption wavelength) of the peak with the lowest transmittance | permeability among the 1 or 2 or more absorption maximum wavelength which exist in the 600-800 nm wavelength range is 600-730 nm. The maximum absorption wavelength is more preferably present in the wavelength range of 730 nm or less, and further preferably present in the wavelength range of 700 nm or less. The maximum absorption wavelength is more preferably present in the wavelength region of 650 nm or more.

Moreover, it is preferable that the transmittance | permeability in the said maximum absorption wavelength is 60% or less, More preferably, it is 50% or less, More preferably, it is 30% or less.

As said resin layer, the aspect (1) which specifically has one absorption maximum wavelength in 600-800 nm, and the absorption maximum wavelength exists in 600-730 nm, for example; Embodiment (2) which has two or more absorption maximum wavelengths in the 600-800 nm wavelength range, and the at least 1 absorption maximum wavelength exists in 600-730 nm; These are mentioned preferably.

In the said aspect (1) and aspect (2), the absorption maximum (maximum absorption) represented by 600-730 nm (preferably 650-730 nm) is the peak with the largest absorption rate of the said pigment | dye A (absorption maximum wavelength (lambda). It is preferable that it is absorption derived from _A1 ). Moreover, in aspect (2), it is preferable that one of other absorption maximum originates from the absorption peak which makes wavelength (lambda) _A2 of the said pigment | dye A the absorption maximum wavelength.

In the resin layer, the absorption of the absorbance in a wavelength of λ _A1 of the dye A to the peak absorption resulting from the absorption peak as the peak absorption wavelength Abs (Q1), the wavelength λ _{A 2} of the specific dye to the peak absorption wavelength peak When the absorbance at the absorption maximum derived from is set to Abs (Q2), the ratio (Abs (Q2) / Abs (Q1)) of these absorbances is preferably 0.61 or less. More preferably, it is 0.60 or less, More preferably, it is 0.50 or less, Especially preferably, it is 0.45 or less. In addition, in the said aspect (1), on the absorption spectrum of a resin layer, although the absorption derived from the absorption peak which makes wavelength (lambda) _A2 of the pigment | dye A the absorption maximum wavelength will not be observed substantially, it corresponds to the wavelength (lambda) _A2 . Using the absorbance Abs (Q2) 'at the wavelength (typically approximately equal to λ _A2 ), the ratio to the absorbance Abs (Q1) (Abs (Q2)' / Abs (Q1)) is equal to the ratio ( It is preferable that it is the same range as Abs (Q2) / Abs (Q1)).

Moreover, it is preferable that the transmittance | permeability in 500 nm of the said resin layer is 80% or more. More preferably, it is 85% or more.

As the absorption transmittance characteristic of the said resin layer, Preferably, the transmittance | permeability (T630) in wavelength 630nm is 50% or more, and the transmittance | permeability (T700) in wavelength 700nm satisfies 50% or less. This is preferable because it can exhibit sharper blocking characteristics. As T630, Preferably it is 55% or more, More preferably, it is 60% or more, As T700, More preferably, it is 45% or less, More preferably, it is 40% or less.

It is preferable that the said resin layer is 10 nm or more in 50-% transmission width (absolute value of the difference of the wavelength of the short wavelength side which shows 50% transmittance, and the wavelength of the long wavelength side) in the absorption band in 600-800 nm. More preferably, it is 20 nm or more, More preferably, it is 30 nm or more.

Although the absorption maximum wavelength etc. of the said resin layer and a resin sheet can be calculated | required by measuring an absorption spectrum by a conventional method, As another method, it can also be calculated | required from the transmittance spectrum of a resin layer and a resin sheet.

When the resin layer has the above-described absorption characteristics, the light selective transmittance is further excellent, and when the absorption sheet containing such a resin layer is combined with the reflection film, the incident angle dependency by the reflection film is further reduced. It becomes possible.

Moreover, the resin sheet containing the said resin layer, and / or the light selective transmission filter containing this resin sheet also have the same absorption transmittance characteristics (absorption maximum wavelength or each said wavelength as the above-mentioned resin layer). Transmittance, etc.) is preferable.

Although it is preferable that a pigment | dye disperse | distributes or melt | dissolves uniformly in a resin layer as above-mentioned in the said resin layer, It is preferable that haze in the visible light region of this resin layer is 10% or less. More preferably, it is 5% or less, More preferably, it is 3% or less, Especially preferably, it is 1% or less. Moreover, in this aspect, it is preferable that the transmittance | permeability in 500 nm of visible light of this resin layer is 60% or more. More preferably, it is 70% or more, More preferably, it is 80% or more, Especially preferably, it is 85% or more.

Moreover, also about the said resin sheet and a light selective transmission filter, it is preferable that the haze in visible region and the transmittance in 500 nm of visible light exist in the range mentioned above, respectively.

The transmittance | permeability can be measured using a spectrophotometer (for example, Shimadzu UV-3100, the Shimadzu Corporation make). It is preferable that the thickness of the resin layer and resin sheet which are used for the measurement of the transmittance | permeability shall be 1-200 micrometers.

<Support>

It is preferable that the said resin sheet has a support body further as mentioned above, but as a support body, a film-shaped thing (support film) is preferable.

It is preferable to use resin or glass which is excellent in transparency as said support body. Especially, since it is easy to be a sheet which is excellent in mechanical strength, especially excellent in mechanical strength even if it thins, a preferable support body is resin. 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. Can be. Among these, a fluorinated aromatic polymer, a poly (amide) imide resin, a polyamide resin, an aramid resin, a cycloolefin resin, an epoxy resin, and / or an acrylic resin is preferable at the point which is excellent in the heat resistance at the time of vapor-depositing a reflection layer. More preferably, at least poly (amide) imide resin is used.

As a preferable combination of the material of the said support body (preferably a support film), and the resin component contained in a resin layer, it is poly (amide) imide resin / poly (amide) imide resin as a support film / resin component, for example. , Poly (amide) imide resin / acrylic resin, poly (amide) imide resin / fluorinated aromatic polymer, polyamide resin / acrylic resin, aramid resin / acrylic resin, cycloolefin resin / acrylic resin and the like. Especially, poly (amide) imide resin / poly (amide) imide resin is preferable, More preferably, polyimide resin / polyimide resin, polyimide resin / polyamideimide resin, or polyamideimide resin / Polyamideimide resin, More preferably, it is a polyimide resin / polyimide resin.

It does not specifically limit as a formation method of the said resin sheet, For example, the resin composition which forms a resin layer is made to the support surface (or the surface of the said other layer, when it has another layer between a support body and a resin layer). In addition to the method of forming by apply | coating, drying, or hardening (it is called a coating method or a coating method), the method of forming by thermopressing the resin film formed from the resin composition with respect to a support body, kneading | mixing method etc. are mentioned. Among these, when obtaining the resin sheet which has a support body and a resin layer, it is preferable to employ | adopt a coating method. That is, it is preferable that the said resin layer is a layer formed by the apply | coating method, and by this, adhesiveness of the said resin layer, a support body, etc. becomes more sufficient. Moreover, when obtaining the resin sheet which does not have a support body, it is preferable to use a coating method, for example, after apply | coating the resin composition which forms a resin layer to a temporary base material, and peeling from the base material, the said resin A sheet can be obtained.

Also in the said coating method, Preferably, it is a solvent casting method, The form which the said resin layer is a layer formed by the solvent casting method is also one of the preferable aspects of this invention. When the solvent cast method is used, since the pigment | dye can be disperse | distributed more uniformly, since the light absorption film which is more excellent in light selective absorptivity can be formed, it is preferable. Moreover, since a pigment | dye can be disperse | distributed to high concentration, thin film formation is possible and it can respond more to the request of low magnification of members, such as a solid-state image sensor. Moreover, since a resin layer can be formed at comparatively low temperature, the pigment | dye with 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 may decompose, and there is a fear that sufficient light absorption may not be obtained. Moreover, there exists a possibility that the dispersibility of a pigment | dye may not become high enough.

In the said solvent casting method, it is preferable to film-form (film-form) a resin layer by apply | coating and drying (curing) the solution obtained by melt | dissolving the resin composition for forming a resin layer in a solvent on a support body. Moreover, when using a liquid resin raw material as a resin component, you may disperse | distribute a pigment | dye directly to this resin raw material, and you may disperse | distribute a pigment | dye after diluting this resin raw material with a solvent.

The solvent (organic solvent) is not particularly limited as long as it can dissolve the resin composition for forming the resin layer. The solvent (organic solvent) can be appropriately selected depending on the type of the resin component or the like. For example, methyl ethyl ketone (2- Ketones such as butanone), methyl isobutyl ketone (4-methyl-2-pentanone), and cyclohexanone; Glycol derivatives such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether, ethylene glycol ethyl ether acetate (ether compound, ester compound, ether ester compound, etc.) ; Amides such as N, N-dimethylacetamide; Esters such as ethyl acetate, propyl acetate and butyl acetate; Pyrrolidones such as N-methyl-pyrrolidone (more specifically, 1-methyl-2-pyrrolidone and the like); Aromatic hydrocarbons such as toluene and xylene; Aliphatic hydrocarbons such as cyclohexane and heptane; Ethers such as diethyl ether and dibutyl ether; Etc. are preferable. More preferably, they are methyl ethyl ketone, ethyl acetate, and N, N- dimethylacetamide.

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

[Reflective film]

It is preferable that the light selective transmission filter of this invention contains a reflection film (also called a reflection layer). Thereby, it becomes possible to become the light selective transmission filter which is more excellent in light selective transmission, the incidence angle dependence of light blocking characteristic is fully reduced, and can realize sufficient thin film. Thus, the form in which the said light selective transmission filter further contains a reflecting film is also one of the preferable aspects of this invention.

It is preferable that it is a film which consists of a multilayer as said reflection film. That is, it is preferable that the said reflection film is an optical multilayer film. Moreover, as an optical multilayer film, the inorganic multilayer film etc. which can control the refractive index of each wavelength are preferable at the point which is excellent in heat resistance. As an inorganic multilayer film, it is preferable that it is a refractive index control multilayer film which alternately laminated the low refractive index material and the high refractive index material on the resin layer, the support body, and other functional material layers by the vacuum deposition method, the sputtering method, or the like. It is also preferable that the reflecting film is a transparent conductive film. As a transparent conductive film, the transparent conductive film as a film | membrane which reflects infrared rays, such as an indium tin oxide (ITO), is preferable. Among these, an inorganic multilayer film is preferable.

As said inorganic multilayer film, the dielectric multilayer film which laminated | stacked the dielectric layer A and the dielectric layer B which has a refractive index higher than the refractive index which dielectric layer A has alternately is preferable.

As the material constituting the dielectric layer A, a material having a refractive index of 1.6 or less can be commonly used, and preferably a material having a refractive index in the range of 1.2 to 1.6 is selected. As such a material, silica, alumina, lanthanum fluoride, magnesium fluoride, sodium aluminum hexafluoride, etc. are preferable, for example.

As the material constituting the dielectric layer B, a material having a refractive index of 1.7 or more can be used, and preferably a material having a refractive index in the range of 1.7 to 2.5 is selected. As such a material, for example, titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide as a main component, and a small amount of titanium oxide, tin oxide, cerium oxide, etc. It is preferable to make it contain.

It is preferable that the thickness of each layer of the said dielectric layer A and the dielectric layer B is 0.1 (lambda) -0.5 (lambda) normally, when the wavelength of the light to block is made into (lambda) (nm). When the thickness is outside this range, the product (n × d) of the refractive index (n) and the film thickness (d) is greatly different from the optical film thickness calculated by λ / 4, and the relationship between the optical properties of reflection and refraction is broken. In particular, there is a possibility that control to block and transmit 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, the dielectric layer A and the dielectric layer B may be formed by a CVD method, a sputtering method, a vacuum deposition method, or the like. By laminating alternately, a dielectric multilayer film can be formed.

The reflective film such as the inorganic multilayer film can be preferably formed by the above method, but the following method can be used to further reduce the possibility that the light selective transmission filter is deformed by curling and cracks are generated. have. That is, specifically, the transfer method of the reflective film which forms a vapor deposition layer in temporary base materials, such as a release process, transfers the vapor deposition layer to the resin sheet used as a base material of a light selective transmission filter, and forms a reflective film is preferable. In this case, it is preferable to form an adhesive layer in the resin sheet.

Moreover, when the said resin sheet is formed of an organic material, specifically a resin composition, after depositing a dielectric layer etc. in the resin sheet (resin composition) of an uncured or semi-hardened state, the method of hardening a resin sheet is preferable. . When such a method is used, the substrate becomes fluid during the cooling after the multilayer deposition, and the liquid phase becomes close to the liquid phase. Therefore, the difference in thermal expansion coefficient between the resin composition and the dielectric layer is not a problem, and the deformation (curl) of the light selective transmission filter is not a problem. Can be suppressed more sufficiently.

As described above, although a vapor deposition method is preferably used for formation of a reflective film (preferably an optical multilayer film, more preferably an inorganic multilayer film) on the resin sheet, the deposition temperature is preferably 100 ° C or higher. More preferably 120 ° C or higher, and even more preferably 150 ° C or higher. When vapor deposition is performed at such a high temperature, there is an advantage that the inorganic film (the inorganic film constituting the inorganic multilayer film) becomes dense and hard, various resistances are improved, and the yield is improved. Therefore, it is very meaningful to use a resin sheet and a pigment which withstand such a vapor deposition temperature. Moreover, it is preferable to use the resin layer or support body film with a low linear expansion coefficient as the resin layer or support film which comprises a resin sheet for vapor deposition at such high temperature. Thereby, the inorganic layer crack by the difference of the linear expansion coefficient of an inorganic and organic can be suppressed more. In addition, when a resin layer or a support film having a low coefficient of linear expansion is used, not only can it be deposited at a high temperature, but even if it is deposited at a low temperature, the difference in the coefficient of linear expansion with the inorganic film is small, so that a solid-state imaging device having a light selective transmission filter In the heating environment or harsh use environment in manufacturing processes, such as a reflow process employ | adopted when manufacturing etc., an inorganic layer crack does not generate | occur | produce by the difference of the linear expansion coefficient of an inorganic and organic.

As a resin layer or support film with low said linear expansion coefficient, it is preferable that a linear expansion coefficient is 60 ppm or less. More preferably, it is 50 ppm or less, More preferably, it is 30 ppm or less, Most preferably, it is 10 ppm or less.

Specific examples of the resin layer or support film having a low coefficient of linear expansion include poly (amide) imide resin, aramid resin, polyamide resin, epoxy resin, polyester resin, organic inorganic hybrid resin, and the like. The form in which the said resin layer or a support film is formed by at least 1 sort (s) chosen from the group which consists of these is one of the preferable aspects of this invention. Moreover, resin is extended | stretched; Inorganic fine particles are dispersed; Using glass crosses; Raise the crosslinking density; Composite; Crystallize; The coefficient of linear expansion can also be lowered by such means.

It is preferable that the said reflective film is formed in at least one surface of the said resin sheet. Although the reflecting film may be formed only in one surface of the said resin sheet, and may be formed in both surfaces, it is preferable to form in both surfaces. Thereby, the curvature of the light selective transmission filter which concerns on this invention, and the crack of a reflective film can fully be reduced. Moreover, when the said resin sheet consists of a resin layer and a support body, it is preferable that a reflecting film is formed in the surface of a resin layer. In particular, a form in which 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 a reflective film made of a support or an inorganic multilayer film is preferable. The light selective transmission filter of such a form becomes especially excellent in light resistance and heat resistance.

As another preferable aspect, the form in which the reflective film is formed in the at least one surface of the resin film different from the said resin sheet, and the said resin sheet is formed in the surface of the reflective film is also mentioned. That is, it is a form formed by laminating | stacking in order of the reflective film and the said resin sheet on the surface of a resin film. It is preferable that the reflecting film is formed 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 thing similar to the support film mentioned above can be used for a resin film, and a preferable aspect is the same as that of the support film.

As mentioned above, it is preferable that the said reflection film is an optical multilayer film, but when the laminated number has the said optical multilayer film only on one surface of the said resin sheet, the range of 10-80 layers is preferable, More preferably, It is the range of 25-50 layers. On the other hand, when it has the said optical multilayer film on both surfaces of the said resin sheet, the laminated number of the said optical multilayer film has a preferable range of 10-80 layer as a total of the laminated number of both sides of a resin sheet, More preferably, 25-50 Range of layers.

Moreover, it is preferable that the thickness of the said reflecting film is 0.5-10 micrometers. More preferably, it is 2-8 micrometers. In the form in which the reflective film is formed on both surfaces of the said resin sheet, it is preferable that the thickness of the sum total of the reflective film of both surfaces is in the said range.

The light selective transmission filter of this invention may have various other functions other than the function of selectively reducing the transmittance | permeability of desired light. For example, in the case of the infrared cut filter which is one of the preferable forms as a light selective transmission filter, the physical properties of the form which has various functions other than infrared cuts, such as a function which shields an ultraviolet-ray, and infrared cut filters, such as toughness and intensity | strength, are improved. The form which has a function to make is mentioned.

Thus, in the aspect which the light selective transmission filter of this invention has another function, it is preferable to form a reflective film in one surface of the said resin sheet, and to form the functional material layer for giving another function to the other surface. . The functional material layer is, for example, by CVD method, sputtering method, vacuum vapor deposition method, directly attaching the functional material layer formed on the resin sheet or formed on the temporary substrate subjected to the release treatment with an adhesive to the resin sheet. It can be obtained by. Moreover, it can also be obtained by apply | coating and drying a liquid composition containing a raw material to the said resin sheet, and forming into a film.

In the light selective transmission filter of the present invention, the thickness (thickness of the total of other layers such as the resin sheet and the reflective film) is preferably 1 mm or less. The thickness of the light selective transmission filter means the maximum thickness of the light selective transmission filter. More preferably, it is 200 micrometers or less from the point which can respond to a thinning request, More preferably, it is 150 micrometers or less, Especially preferably, it is 120 micrometers or less, Most preferably, it is 60 micrometers or less. Moreover, it is preferable that it is 1 micrometer or more from the point which is excellent in reflow property, especially the heat resistance at the temperature of 260 degreeC, More preferably, it is 10 micrometers or more, More preferably, it is 30 micrometers or more. Moreover, it is preferable that the range of the thickness of a light selective transmission filter is 1-150 micrometers, More preferably, it is 10-120 micrometers, More preferably, it is 30-120 micrometers, Especially preferably, it is 30-60 micrometers.

By setting the thickness of the light selective transmission filter to 1 mm or less, the light selective transmission filter can be made smaller and lighter, and can be preferably used for various applications. In particular, it can use preferably for optical uses, such as an optical member. In optical applications, like the other optical members, the light selective transmission filter is also required to be downsized and lightweight. Since the light selective transmission filter of this invention can be 1 mm or less in thickness, thinning can be achieved more, and especially when it is used for lens units, such as an imaging lens, low magnification of a lens unit can be realized. . In other words, when using the 1 mm or less thin light selective transmission filter as an optical member, an 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 CMOS sensor.

1 and 2 schematically show an example of a camera module. In addition, these figures refer to the electronic journal 81st Technical Seminar material.

As shown in FIG. 1, the light selective transmission filter cut | disconnects light of a desired wavelength (light of a wavelength of 700 nm or more, for example in a camera module), and has a role which prevents the malfunction of a CMOS sensor. When the light selective transmission filter is placed in the camera module, the focal length becomes long, so that the back focus is extended and the module becomes large. 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 to increase the module, but the light selective transmission filter is thinned and the focal length is shortened. The module can be made small. Therefore, as an optical path length of an optical size of 1/10 inch, for example, it is preferable to set it as 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 this invention selectively reduces the transmittance | permeability of light. As light to reduce, what is necessary is just between 10 nm-100 micrometers, and it can select according to the use to be used. According to the wavelength of light to reduce, it can be set as an infrared cut filter, an ultraviolet cut filter, an infrared cut, an ultraviolet cut filter, etc. Among these, infrared light of 650 nm-10 micrometers and ultraviolet light of 200-350 nm are reduced, and other than that It is preferable to transmit light. That is, it is preferable that the said light selective transmission filter is an infrared rays cut filter.

The infrared cut filter should just be a filter which has a function which selectively reduces the light of a certain wavelength (range) among the light which has a wavelength of 650 nm-10 micrometers which is an infrared region. As a range of wavelength to selectively reduce, it is preferable that they are 650 nm-2.5 micrometers, 650 nm-1 micrometer, or 800 nm-1 micrometer. A filter for selectively reducing at least one of the wavelengths in these ranges is also included in the infrared cut filter. As a range of wavelength to selectively reduce, it is more preferable that they are 650 nm-1 micrometer which is a near-infrared region.

The ultraviolet cut filter is a filter having a function of blocking ultraviolet rays. It is preferable that it is 200-350 nm as a range of wavelength to selectively reduce.

The infrared rays and the ultraviolet rays cut filter are filters which have a function of blocking both ultraviolet rays and infrared rays. It is preferable that the range of the wavelength to selectively reduce is the same as the above-mentioned.

In the form where the light selective transmission filter of this invention is an infrared cut filter, it is preferable to reduce the transmittance | permeability of infrared rays of 650-1000 nm selectively to 5% or less. It is preferable that the transmittance | permeability of another wavelength range is 70% or more, and it is more preferable that it is 75% or more, but only the transmittance | permeability of a specific wavelength range may be high according to a use of a filter. For example, when using the said infrared cut filter as a camera module, it is preferable that the transmittance | permeability of infrared light is 5% or less, and the transmittance | permeability of 450-600 nm in visible light is 70% or more. More preferably, it is 80% or more, More preferably, it is 85% or more. Moreover, it is preferable that the transmittance | permeability of the light of a wavelength range of 480-550 nm is 85% or more also in visible light, and it is more preferable that it is 90% or more. Moreover, in the said infrared cut filter, As transmittance | permeability of the wavelength (other than an infrared region), More preferably, it is 85% or more, More preferably, it is 90% or more. That is, it is preferable that the said light selective transmission filter is an infrared cut filter whose light transmittance in wavelength is 480-550 nm is 80% or more, and the transmittance in 800-1000 nm is 5% or less.

The transmittance can be measured using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation).

In the form where the light selective transmission filter of this invention is an ultraviolet cut filter, it is preferable to reduce the transmittance | permeability of the ultraviolet-ray of 200-350 nm selectively to 5% or less. It is preferable that it is 70% or more, and, as for the transmittance | permeability of another wavelength range, it is more preferable that it is 75% or more.

In the form where the light selective transmission filter of the present invention is an infrared / ultraviolet cut filter, it is preferable to selectively reduce the infrared light of 650 nm to 10 μm and the ultraviolet light of 200 to 350 nm to 5% or less, and other wavelengths. It is preferable that it is 70% or more, and, as for the transmittance | permeability of an area | region, it is more preferable that it is 75% or more.

The light selective transmission filter is preferably in a form in which a reflective film is formed on at least one surface of a resin sheet having a resin layer containing the dye and the resin component. Can be reduced more sufficiently.

Here, the incident angle dependence of the light blocking property is, for example, a transmittance (for example, 0 °, 20 °, 25 °, 30) in which the incident angle is changed using a spectrophotometer (Shimadzu UV-3100, manufactured by Shimadzu Corporation). The transmittance at the incident angle of 0 ° is the transmittance measured by allowing light to enter from the thickness direction of the light selective transmission filter, and the transmittance at the incident angle of 20 ° is 20 ° with respect to the thickness direction of the light selective transmission filter. It is the transmittance measured by allowing light to enter from the inclined direction.) Can be measured and evaluated by the amount of spectral change.

In addition, the incident angle dependence of the light blocking characteristic needs to be sufficiently reduced by absorption of the absorbing layer, and it is preferable that the transmittance spectrum does not change with respect to the change in the incident angle, or the degree of the change is small. Specifically, even if the angle of incidence 0 ° is changed to 20 ° (more preferably, 25 °), in the region of 80% or more of transmittance, it is preferable that the spectrum of transmittance does not change, more preferably transmittance 70 The spectrum of transmittance does not change in the area | region of% or more, More preferably, the spectrum of transmittance does not change in the area | region of 60% or more of transmittance | permeability. 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, heat resistance and light selective transmission, and can sufficiently reduce the incident angle dependence of the light blocking property, and can sufficiently thin the film. Not only is it useful as a heat ray cut filter etc. mounted to glass, such as a building, but it is also useful as a filter for blocking the optical noise in camera module (also called a solid-state image sensor), and correct | amending visibility. Especially, the light selective transmission filter of this invention is useful as a filter used for camera modules, such as a digital still camera and a camera for a mobile telephone which thinning and weight reduction progress. That is, it is preferable that the said light selective transmission filter is a light selective transmission filter for a solid-state image sensor (camera module).

Although a solid-state image sensor normally comprises a lens unit (imaging lens) part, a light selective transmission filter, and sensor parts, such as CCD and CMOS, the solid-state image sensor (camera module) using the light selective transmission filter of this invention, Usually, it is arrange | positioned between a lens unit (imaging lens) part and a sensor part, such as CCD and CMOS. Thus, the solid-state image sensor which has the light selective transmission filter of this invention, a lens unit part, and a sensor part at least is also one of this invention. Usually, in the solid-state image sensor using the reflective light selective transmission filter, in order to suppress the influence (dependence of color nonuniformity due to incident angle) resulting from incident angle dependence, although a lens unit part is comprised using many lenses, In the solid-state imaging device of the present invention, since the influence caused by the incident angle dependency is sufficiently eliminated by using the above-mentioned light selective transmission filter, the number of lenses constituting the lens unit portion can be reduced, resulting in thinner and lighter weight. Will be.

In addition, the aspect described in WO2008 / 081892 can be preferably used for the lens unit portion.

As said solid-state image sensor, a mobile telephone, a digital camera, a vehicle camera, a surveillance camera, a display element (LED etc.) etc. are mentioned specifically ,, for example. Thus, the mobile telephone camera, the digital camera, the on-vehicle camera, the surveillance camera, and the display element which use the light selective transmission filter of this invention are also contained in the preferable aspect of this invention.

The light selective transmission filter of this invention is the light selective transmission filter which consists of the structure mentioned above, can effectively block the light of a desired wavelength, and was fully reduced in incident angle dependence of light blocking characteristic. Therefore, the solid-state image sensor (camera module) using the light selective transmission filter of this invention can input the image by which generation | occurrence | production of the color nonuniformity by the incident angle which became a subject by the use of the reflection type light selective transmission filter was suppressed. Moreover, since sufficient thin film is also possible, it can use especially preferably for the use which requires thinning and weight reduction. Specifically, it can be used suitably for various uses, such as an opt device use, a display device use, a mechanical component, an electrical and electronic component, and it is especially useful as a light selective transmission filter for lenses, such as an imaging lens, Especially, It is particularly useful as an IR cut filter for camera modules. Moreover, since high light resistance and heat resistance can be exhibited, it is used suitably for the use which requires severe light resistance and heat resistance, such as the use which may be exposed to direct sunlight or a high temperature environment.

1 is a schematic cross-sectional view showing the configuration of a camera module.
Fig. 2 is a schematic diagram showing elongation of the back focus with or without a light selective transmission filter.
3 is a conceptual diagram illustrating a method of measuring transmittance.

Although an Example is given to the following and this invention is demonstrated in more detail, this invention is not limited only to these Examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass%". In addition, light resistance and heat resistance were evaluated according to the following test method.

<Light resistance test method (fluorescent lamp irradiation test)>

About each film, the fluorescent lamp light of roughness 100,000 lux was irradiated for 100 hours at room temperature (25 degreeC). The transmittance before and after irradiation was evaluated, and the change in transmittance was investigated. Specifically, the degree of transmittance change in the transmittance measurement wavelengths of the dyes described in Tables 1-1 to 1-3 was evaluated. Moreover, the sample was installed in the position which distanced 95 mm from the light source using the Marrow line Pride FHF32EX-D-PD by Toshiba Corporation as a light source. The illuminance at the installation position was confirmed with an illuminometer. The transmittance | permeability was measured with the spectrophotometer (Shimadzu UV-3100, the Shimadzu Corporation make).

<Heat resistance test method>

About each film, it installed in 150 degreeC or 200 degreeC oven for 1 hour, and performed the heat resistance test. The transmittance before and after the heat resistance test was evaluated, and the change in transmittance was investigated. Specifically, the degree of transmittance change in the transmittance measurement wavelengths of the dyes described in Tables 1-1 to 1-3 was evaluated. The transmittance | permeability was measured with the spectrophotometer (Shimadzu UV-3100, the Shimadzu Corporation make).

Synthesis Example 1

<Synthesis of alicyclic polyimide>

5 parts of 1,2,4,5-cyclohexanetetracarboxylic acid (manufactured by Aldrich, 95% purity) and 44 parts of acetic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) are charged into the flask, and the reactor is replaced with nitrogen gas while stirring. did. It heated up to the reflux temperature of a solvent in nitrogen gas atmosphere, and refluxed the solvent for 10 minutes. It cooled to room temperature with stirring, and precipitated the crystal | crystallization. The precipitated crystals were solid-liquid separated and dried to obtain crystals of the target product (1,2,4,5-cyclohexanetetracarboxylic dianhydride). 0.89 parts of 4,4'-diaminodiphenyl ether (made by Wako Junyaku) under a stream of nitrogen in a flask equipped with a thermometer, a stirrer, a nitrogen inlet tube, a dropping funnel with side tubes, a Dean Stark and a cooling tube. 7.6 parts of N-methyl-2-pyrrolidone was injected and dissolved, and then 1 part of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in portions over 1 hour in a solid state at room temperature, It stirred at room temperature for 2 hours. 2.6 parts of xylene was added as an azeotropic dehydrating agent, reaction was performed at 180 degreeC for 3 hours, and the product water which refluxed by dean stark and azeotropically was isolate | separated. After distilling off xylene, heating up at 190 degreeC, it cooled and obtained the N-methyl- 2-pyrrolidone solution of polyimide.

Synthesis Example 2

<Synthesis of FPEK (Fluorinated Polyetherketone)>

16.74 parts of BPDE (4,4'-bis (2,3,4,5,6-pentafluorobenzoyl) diphenylether) to a reactor equipped with a thermometer, a cooling tube, a gas introduction tube, and a stirrer, HF 10.5 parts of (9,9-bis (4-hydroxyphenyl) fluorene), 4.34 parts of potassium carbonate and 90 parts of DMAc (dimethylacetamide) were injected. This mixture was heated to 80 ° C. and reacted for 8 hours. After completion of the reaction, the reaction solution was poured into a 1% aqueous acetic acid solution while being stirred vigorously with a blender. The precipitated reactant was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain FPEK, which is a fluorinated aromatic polymer. As for the glass transition point temperature (Tg) of the obtained polymer, 242 degreeC, number average molecular weight (Mn) was 70770, and surface resistance value was 1.0 * 10 <^{18> (} ohm) / cm <2> or more.

In addition, the number average molecular weight in the said synthesis example was measured by the following method.

Gel permeation chromatography (column: two TSKgel Super Multipore HZ-N 4.6 ^* 150, eluent: tetrahydrofuran, standard sample: TSK polystyrene standard) was measured.

&Lt; Synthesis Example of Pigments &gt;

According to the prescription of Unexamined-Japanese-Patent No. 6-31239, the pigment | dye (phthalocyanine pigment | dye; Pc1-Pc15) was synthesize | combined. In addition, the synthesis method of Pc5 is shown in the synthesis example B-10. The synthesis example of Pc7 is shown in the synthesis example B-11. The synthesis example of Pc14 is shown in the synthesis example B-12.

Pc1-Pc8 is a pigment | dye which has a structure represented by Formula (6b) obtained using the phthalonitrile derivative represented by Formula (6a) in Table 1-1.

Pc9-Pc12 are pigment | dyes which have a structure represented by Formula (7b) obtained using the phthalonitrile derivative represented by Formula (7a) in Table 1-2.

Pc13-Pc15 are pigment | dyes which have a structure represented by Formula (8b) obtained using the phthalonitrile derivative represented by Formula (8a) in Table 1-3.

M, X, and Y in Formula (6a)-(8b) are as showing to Table 1-1-1-3 about each pigment | dye. Moreover, the absorption maximum wavelength of each pigment | dye is shown to Tables 1-1 to 1-3. In addition, in the light resistance and heat resistance test in the Example etc. which are mentioned later, the change of the transmittance | permeability was investigated by each transmittance measurement wavelength shown in Table 1-1-1-3 in the pigment | dye used by each Example.

In the table, C _α represents carbon at positions 1, 4, 8, 11, 15, 18, 22, and 25 of the phthalocyanine ring. C _β represents carbon at positions 2, 3, 9, 10, 16, 17, 23, and 24 of the phthalocyanine ring.

[Table 1-1]

[Table 1-2]

[Table 1-3]

Synthesis Example A-1

Synthesis of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile

Into a 500 mL four-neck separable flask, 50 g (0.25 mol) of tetrafluorophthalonitrile, 34.8 g (0.60 mol) of potassium fluoride and 50 g of acetone were added, and further 2,5-dichlorophenol 82.3 was added to the dropping funnel. g (0.50 mol) and acetone 82.3 g were injected. After stirring at -1 degreeC, the acetone solution of 2, 5- dichlorophenol was dripped over about 2 hours from the dropping funnel, and stirring was continued for 2 hours again. Thereafter, the reaction temperature was stirred overnight while slowly rising to room temperature. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtered and 88.8 g (yield 72.7%) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile were obtained by vacuum drying.

Synthesis Example A-2

Synthesis of 4,5-bis (4-butoxyphenoxy) -3,6-difluorophthalonitrile

Into a 500 mL four-neck separable flask was charged 14.90 g (0.074 mol) of tetrafluorophthalonitrile, 9.73 g (0.17 mol) of potassium fluoride and 120 g of acetone, and further 25.00 g of 4-butoxyphenol in a dropping funnel. (0.15 mol) and 87.32 g of acetone were injected. While stirring at about 5 degreeC, the acetone solution of 4-butoxyphenol was dripped over about 2 hours from the dropping funnel, and stirring was continued for 2 hours again. Thereafter, the reaction temperature was stirred overnight while slowly rising to room temperature. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal | crystallization was filtrated and 16.43 g (yield 44.8%) of 4, 5-bis (4-butoxyphenoxy) -3, 6- difluoro phthalonitrile were obtained by vacuum drying.

Synthesis Example A-3

Synthesis of 4,5-bis (6-methoxyethylcarbonyl-2-naphthoxy) -3,6-difluorophthalonitrile

Into a 500 mL four-neck separable flask, 20.00 g (0.100 mol) of tetrafluorophthalonitrile, 30.39 g (0.220 mol) of potassium carbonate and 46.67 g of acetone were added, and further 6-hydroxy-2- was added to the dropping funnel. 49.73 g (0.200 mol) of naphthoic acid methoxyethyl and 350.00 g of acetone were injected. While stirring at 5 degreeC, the acetone solution of 6-hydroxy- 2-naphtho acid methoxyethyl was dripped over about 2 hours from the dropping funnel, and stirring was continued for 2 hours further. Thereafter, the reaction temperature was stirred overnight while slowly rising to room temperature. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtered and 41.8 g (yield 64.1%) of 4,5-bis (6-methoxyethylcarbonyl-2-naphthoxy) -3,6-difluorophthalonitrile were obtained by vacuum drying.

Synthesis Example A-4

Synthesis of 4,5-bis (2,4-dichloro-1-naphthoxy) -3,6-difluorophthalonitrile

Into a 500 mL four-neck separable flask, 11.62 g (0.058 mol) of tetrafluorophthalonitrile, 9.61 g (0.16 mol) of potassium fluoride and 120 g of acetone were added, and further, 2,4-dichloro-1 was added to the dropping funnel. 24.99 g (0.12 mol) of naphthol and 87.32 g of acetone were injected. While stirring at 5 degreeC, the acetone solution of 2, 4- dichloro- 1-naphthol was dripped over about 2 hours from the dropping funnel, and stirring was continued for 2 hours again. Thereafter, the reaction temperature was stirred overnight while slowly rising to room temperature. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtered and 27.20 g (yield 79.9%) of 4,5-bis (2,4-dichloro-1-naphthoxy) -3,6-difluorophthalonitrile were obtained by vacuum drying.

Synthesis Example A-5

Synthesis of 4,5-bis (4-ethoxycarbonylphenoxy) -3,6-difluorophthalonitrile

Into a 500 mL four-neck separable flask, 30.00 g (0.15 mol) of tetrafluorophthalonitrile, 43.52 g (0.315 mol) of potassium carbonate, and 70.00 g of acetone were added, and 50.84 ethyl p-hydroxybenzoate was added to the dropping funnel. g (0.303 mol) and 120.00 g of acetone were injected. After stirring at 5 degreeC, the acetone solution of ethyl p-hydroxybenzoate was dripped over about 2 hours from the dropping funnel, and stirring was continued for 2 hours again. Thereafter, the reaction temperature was stirred overnight while slowly rising to room temperature. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtered and 55.3 g (yield 74.9%) of 4,5-bis (4-ethoxycarbonylphenoxy) -3,6-difluorophthalonitrile were obtained by vacuum drying.

Synthesis Example A-6

Synthesis of 3- (2-chlorophenoxy) phthalonitrile

Into a 500 mL four-neck separable flask was charged 17.3 g (0.10 mol) of 3-nitrophthalonitrile, 13.6 g (0.105 mol) of 2-chlorophenol, 16.6 g (0.12 mol) of potassium carbonate, and 69.3 g of acetonitrile. It stirred at 60 degreeC overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtered and 27.8 g (yield 91.7%) of 3- (2-chlorophenoxy) phthalonitrile were obtained by vacuum drying.

Synthesis Example A-7

Synthesis of 3- (2,6-dimethylphenoxy) phthalonitrile

In a 500 mL four-neck separable flask, 15.0 g (0.087 mol) of 3-nitrophthalonitrile, 11.2 g (0.091 mol) of 2,6-dimethylphenol, 23.9 g (0.17 mol) of potassium carbonate, and 60.0 g of acetonitrile Was injected and stirred overnight at 60 ° C. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtered and 17.5 g (yield 69.9%) of 3- (2,6-dimethylphenoxy) phthalonitrile were obtained by vacuum drying.

Synthesis Example A-8

Synthesis of 3- (2,6-dichlorophenoxy) phthalonitrile

In a 500 mL four-neck separable flask, 15.0 g (0.087 mol) of 3-nitrophthalonitrile, 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 It injected and stirred at 60 degreeC overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtrated and 17.5 g (yield 69.9%) of 3- (2,6-dichlorophenoxy) phthalonitrile were obtained by vacuum drying.

Synthesis Example A-9

Synthesis of 4- (2,6-dichlorophenoxy) phthalonitrile

In a 500 mL four-neck separable flask, 15.0 g (0.087 mol) of 4-nitrophthalonitrile, 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 It injected and stirred at 60 degreeC overnight. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added to recrystallize. The obtained crystal was filtrated and 22.8 g (yield 91.1%) of 4- (2,6-dichlorophenoxy) phthalonitrile were obtained by vacuum drying.

Synthesis Example B-1

[2,3,9,10,16,17,23,24-octakis (2,5-dichlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H Synthesis of, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] vanadium oxide (referred to as Pc16)

In a 200 mL four-necked flask, 60.00 g (0.1234 mol) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-1 and vanadium chloride (III) ) 6.31 g (0.0401 mol), 1,2,4-trimethylbenzene 87.96 g, 9.60 g benzonitrile are injected and under mixed gas (nitrogen: oxygen = 93: 7 (vol%)) bubbling (10 ml / min) It reacted for 24 hours, stirring at 170 degreeC. After completion of the reaction, the reaction solution was added dropwise into 1200 g of methanol to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was stirred and washed again with 600 g of methanol, and suction filtered. The obtained cake was dried at 100 degreeC for 24 hours using the vacuum dryer, and 56.23g of target objects (Pc16) were obtained (yield 90.6%).

Synthesis Example B-2

[2,3,9,10,16,17,23,24-octakis (2,5-dichlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H Synthesis of, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] indium chloride (referred to as Pc17)

In a 200 mL four-necked flask, 5.00 g (0.0103 mol) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-1 and indium chloride (III) ) 0.63 g (0.0028 mol) and 7.50 g of benzonitrile were injected, and it stirred for 24 hours, stirring at 160 degreeC. After the completion of the reaction, the reaction solution was added dropwise into 77.26 g of acetonitrile to precipitate crystals, and after suction filtration, a wet cake was obtained. The obtained cake was stirred and washed again with 19.3 g of acetonitrile and suction filtered. The obtained cake was dried at 100 degreeC for 24 hours using the vacuum dryer, and 2.1 g of target objects (Pc17) were obtained (yield 40.8%).

Synthesis Example B-3

[2,3,9,10,16,17,23,24-octakis (2,5-dichlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H Synthesis of, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] titanium oxide (referred to as Pc18)

5.00 g (0.0103 mol) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile obtained by the synthesis example A-1 in a 200 mL four neck flask, tetraethyl ortho titanate 0.65 g (0.0028 mol) and 11.67 g of 1,2,4-trimethylbenzenes were injected | thrown-in, and it reacted for 24 hours, stirring at 160 degreeC under nitrogen flow (10 mL / min). After the completion of the reaction, the reaction solution was added dropwise into 25 g of methanol to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was stirred and washed again with 25 g of methanol, and suction filtered. After drying the obtained cake at 100 degreeC for 24 hours using the vacuum dryer, 5.1 g of target objects (Pc18) were obtained (yield 98.8%).

Synthesis Example B-4

[2,3,9,10,16,17,23,24-octakis (4-butoxyphenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H, Synthesis of 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (called Pc19)

In a 200 mL four-necked flask, 3.00 g (0.0061 mol) of 4,5-bis (4-butoxyphenoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-2, zinc iodide (II) 0.49 g (0.0015 mol) and 7.50 g of benzonitrile were injected, and it was made to react for 24 hours, stirring at 160 degreeC under nitrogen flow (10 mL / min). After the completion of the reaction, the reaction solution was added dropwise into 31.0 g of methanol corresponding to 10 times the theoretical amount of the phthalocyanine compound to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was stirred and washed again with 15.5 g of methanol corresponding to five times the theoretical amount of the phthalocyanine compound, and suction filtered. The obtained cake was dried at 100 degreeC for 24 hours using the vacuum dryer, and 2.48 g (yield 80.1%) of target objects (Pc19) were obtained.

Synthesis Example B-5

[2,3,9,10,16,17,23,24-octakis (6-methoxyethylcarbonyl-2-naphthoxy) -1,4,8,11,15,18,22,25- Synthesis of octafluoro-29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (called Pc20)

In a 200 ml four-necked flask, 3.00 g (0.0046 mol) of 4,5-bis (6-methoxyethylcarbonyl-2-naphthoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-3 0.44 g (0.0014 mol) of zinc iodide (II) and 4.5 g of benzonitrile were injected, and it was made to react for 24 hours, stirring at 160 degreeC under nitrogen flow (10 mL / min). After completion of the reaction, the same operation as in Synthesis Example B-3 was performed to obtain 2.73 g (yield 88.8%) of the target product (Pc20).

Synthesis Example B-6

[2,3,9,10,16,17,23,24-octakis (2,4-dichloro-1-naphthoxy) -1,4,8,11,15,18,22,25-octafluoro Synthesis of rho-29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (called Pc21)

In a 200 mL four-necked flask, 3.00 g (0.0051 mol) of 4,5-bis (2,4-dichloro-1-naphthoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-4, iodide 0.41 g (0.0013 mol) of zinc (II) and 7.5 g of benzonitrile were injected, and it reacted for 24 hours, stirring at 160 degreeC under nitrogen flow (10 mL / min). After the completion of the reaction, the same operation as in Synthesis Example B-3 was performed to obtain 2.87 g (yield 93.1%) of the target product (Pc21).

Synthesis Example B-7

Synthesis of [ZnPc- ｛β- (2,5-Cl ₂ ) C ₆ H ₃ O｝ ₄ , ｛β- (4-COOC ₂ H ₅ ) C ₆ H ₄ O｝ ₄ F ₈ ] (called Pc22)

In a 200 mL four-necked flask, 4.00 g (0.0082 mol) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-1, Synthesis Example A- 4,5-bis (4-ethoxycarbonylphenoxy) -3,6-difluorophthalonitrile 4.05 g (0.0082 mol) obtained in 5, zinc iodide (II) 1.44 g (0.0045 mol), benzonitrile 12.08 g was injected and made to react for 24 hours, stirring at 160 degreeC under nitrogen flow (10 ml / min). After the completion of the reaction, the same operation as in Synthesis Example B-3 was performed to obtain 7.42 g (yield 89.3%) of the target product (Pc22).

Synthesis Example B-8

Synthesis of [CuPc- ｛β- (2,5-Cl ₂ ) C ₆ H ₃ O｝ ₄ , ｛β- (4-COOC ₂ H ₅ ) C ₆ H ₄ O｝ ₄ F ₈ ] (called Pc23)

In a 200 mL four-necked flask, 4.00 g (0.0082 mol) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-1, Synthesis Example A- 4,5-bis (4-ethoxycarbonylphenoxy) -3,6-difluorophthalonitrile 4.05 g (0.0082 mol) obtained from 5, copper chloride (I) 0.45 g (0.0045 mol), diethylene glycol 12.08 g of monomethyl ether was injected and reacted for 4 hours while stirring at 160 ° C under nitrogen flow (10 ml / min). After the completion of reaction, the same operation as in Synthesis Example B-3 was performed to obtain 6.22 g (yield 74.8%) of the target product (Pc23).

Synthesis Example B-9

Synthesis of [VOPc-Vβ- (2,5-Cl ₂ ) C ₆ H ₃ OV ₄ , Vβ- (4-COOC ₂ H ₅ ) C ₆ H ₄ OV ₄ F ₈ ] (called Pc24)

In a 200 mL four-necked flask, 5.00 g (0.0103 mol) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-1, Synthesis Example A- 5.06 g (0.0103 mol) of 4,5-bis (4-ethoxycarbonylphenoxy) -3,6-difluorophthalonitrile obtained from 5, 0.89 g (0.0057 mol) of vanadium (III) chloride, 1,2 14.75 g of, 4-trimethylbenzene and 1.61 g of benzonitrile were injected and reacted for 24 hours with stirring at 170 ° C under bubbling of mixed gas (nitrogen: oxygen = 93: 7 (vol%)) (2 ml / min). After the completion of the reaction, the same operation as in Synthesis Example B-3 was performed to obtain 6.51 g (yield 62.6%) of the target product (Pc24).

Moreover, the pigment | dye obtained by the synthesis example B-7-B-9 of the structure of the pigment | dye (phthalocyanine pigment | dye; Pc16-Pc21) obtained by the said synthesis examples B-1-B-6 is shown in Table 2-1, and the phthalocyanine pigment | dye The structures of Pc22 to Pc24) are shown in Table 2-2 below.

Here, the "absorption maximum wavelength" shown in Table 2-1-2-2 means the absorption maximum wavelength in "600-710 nm" which is a preferable range of this invention. That is, even if it has a maximum absorption wavelength other than this "600-710 nm" range, the absorption maximum wavelength which exists in the range of "600-710 nm" was described in Table 2-1-2-2.

TABLE 2-1

Table 2-2

Synthesis Example B-10

Synthesis of [C, C, C, 1-tetrakis (2-chlorophenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (called Pc5)

In a 200 mL four-necked flask, 10.19 g (0.040 mol) of 3- (2-chlorophenoxy) phthalonitrile obtained in Synthesis Example A-6, 3.51 g (0.011 mol) of zinc iodide (II), and 23.8 g of benzonitrile Was injected and reacted for 24 hours, stirring at 160 degreeC. After completion of the reaction, the reaction solution was added dropwise into methanol (86 g) corresponding to 20 times the theoretical amount of the phthalocyanine compound to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was stirred and washed again with methanol (43 g) corresponding to 10 times the theoretical amount of the phthalocyanine compound and suction filtered. The obtained cake was dried at 100 degreeC for 24 hours using the vacuum dryer, and 2.74 g of target objects (Pc5) were obtained (yield 25.3%).

Synthesis Example B-11

Of [C, C, C, 1-tetrakis (2,6-dimethylphenoxy) -29H, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] copper (referred to as Pc7) synthesis

In a 200 ml four-necked flask, 4.00 g (0.0161 mol) of 3- (2,6-dimethylphenoxy) phthalonitrile obtained in Synthesis Example A-7, 0.44 g (0.0044 mol) of copper chloride (I), diethylene 9.33 g of glycol monomethyl ether were injected and reacted for 10 hours while stirring at 180 degreeC. After the reaction was completed, the same operation as in Example 1-1 was performed to obtain 2.87 g of the target product (Pc7) (yield 67.44%).

Synthesis Example B-12

[2,3,9,10,16,17,23,24-octakis (2,5-dichlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H , 31H-phthalocyaninato (2-)-N29, N30, N31, N32] zinc (referred to as Pc14)

In a 200 ml four-necked flask, 8.26 g (0.0170 mol) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-1, zinc iodide (II ) 1.42 g (0.0045 mol) and 33.05 g of benzonitrile were injected and reacted for 24 hours with stirring at 160 ° C. After the completion of the reaction, the same operation as in Synthesis Example B-10 was performed to obtain 7.17 g of the target product (Pc14) (yield 84.0%).

Synthesis Example B-13

[2,3,9,10,16,17,23,24-octakis (2,5-dichlorophenoxy) -1,4,8,11,15,18,22,25-octafluoro-29H Synthesis of, 31H-phthalocyaninato (2-)-N29, N30, N31, N32] vanadium oxide (referred to as B-Pc16 ')

In a 100 mL four-necked flask, 15.00 g (0.0309 mol) of 4,5-bis (2,5-dichlorophenoxy) -3,6-difluorophthalonitrile obtained in Synthesis Example A-1 and vanadium chloride (III) ) 1.58 g (0.010 mole), 21.99 g of 1,2,4-trimethylbenzene and 2.40 g of benzonitrile were injected, and M gas (mixed gas of nitrogen and oxygen, 7 vol% of oxygen) at 170 ° C was added to the liquid phase. It was made to react for 18 hours, stirring, blowing. After the completion of the reaction, the same operation as in Synthesis Example B-10 was performed to obtain 13.61 g (yield 87.7%) of the target product (B-Pc16 ').

Synthesis Example B-14

Synthesis of [ZnPc- ｛α- (2,6-Cl ₂ PhO) ₂ H ₆ ｝ ｛β- (2,6-Cl ₂ PhO) ₂ H ₆ ｝] Zinc (Pc25)

In a 200 mL four-necked flask, 2.5 g (0.0086 mol) of 3- (2,6-dichlorophenoxy) phthalonitrile obtained in Synthesis Example A-8 and 4- (2,6- obtained in Synthesis Example A-9 2.5 g (0.0086 mol) of dichlorophenoxy) phthalonitrile, 1.1 g (0.0048 mol) of zinc iodide (II), and 7.5 g of benzonitrile were injected, and it was made to react for 24 hours, stirring at 160 degreeC. After the completion of the reaction, the same operation as in Synthesis Example B-10 was carried out to obtain 4.2 g of the target product (Pc25) (3- (2,6-dichlorophenoxy) phthalonitrile and 4- (2,6-dichlorophenoxy). Yield for phthalonitrile: 79.2%).

Example 1

0.004875 parts of Pc1 was added to the solution of the synthesis example 1, and it melt | dissolved uniformly. This pigment | dye containing polyimide solution was apply | coated to the glass plate, and it baked at 150 degreeC for 3 hours. It peeled off from the glass plate and obtained the phthalocyanine pigment | dye containing polyimide film (thickness 22 micrometers). About this film, light resistance and heat resistance were evaluated in accordance with the above test method. The results are shown in Table 3.

In addition, although the structure of Pc1 is shown in Table 1-1 (formula (6b)), this is the pigment | dye A of this invention (conjugated skeleton which it has is nonionic, and it is the absorption maximum wavelength in the 600-800 nm wavelength range. And a compound whose at least one absorption maximum wavelength is present at 600 to 730 nm.

Example 2

0.004875 parts of Pc2 was added to the solution of the synthesis example 1, and it was made to melt | dissolve uniformly. This pigment | dye containing polyimide solution was apply | coated to the glass plate, and it baked at 150 degreeC for 3 hours. It peeled off from the glass plate and obtained the phthalocyanine pigment | dye containing polyimide film (thickness 21 micrometers). About this film, light resistance and heat resistance were evaluated according to the test method mentioned above. The results are shown in Table 3.

In addition, although the structure of Pc2 was shown to Table 1-1 (formula (6b)), this corresponds to the pigment | dye A of this invention.

Example 3

6 parts of DMAc and 0.00325 parts of Pc1 were added to 1 part of FPEK of Synthesis Example 2, and the mixture was dissolved uniformly. This pigment | dye containing FPEK solution was apply | coated to the glass plate, and it baked at 150 degreeC for 3 hours. It peeled off from the glass plate and obtained the phthalocyanine pigment | dye containing FPEK film (thickness 19 micrometers). About this film, light resistance and heat resistance were evaluated according to the test method mentioned above. The results are shown in Table 3.

Example 4

6 parts of DMAc and 0.00325 parts of Pc2 were added to 1 part of FPEK of Synthesis Example 2, and it was dissolved uniformly. This pigment | dye containing FPEK solution was apply | coated to the glass plate, and it baked at 150 degreeC for 3 hours. It peeled off from the glass plate and obtained the phthalocyanine pigment | dye containing FPEK film (thickness 20 micrometers). About this film, light resistance and heat resistance were evaluated according to the test method mentioned above. The results are shown in Table 3.

Comparative Example 1

In Example 1, instead of Pc1: 0.004875 parts, cyanine-based pigment # 1H-Benzindolium, 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-) (HBFB, cyanine-based dye, absorption maximum wavelength 680 nm) In the same manner as in Example 1, a cyanine dye-containing polyimide film (thickness 21 μm) was obtained. About this film, light resistance and heat resistance were evaluated according to the test method mentioned above. The results are shown in Table 3.

In addition, although the structure of HBFB is shown below, since it has a cation in a conjugated skeleton, it does not correspond to the pigment | dye A in which the conjugated skeleton in this invention is nonionic.

[Formula 15]

Comparative Example 2

In Example 3, a cyanine pigment | dye containing FPEK film (thickness 18 micrometers) was obtained like Example 3 except having used 0.0009 parts of HBFB instead of 0.00325 parts of Pc1. About this film, light resistance and heat resistance were evaluated according to the test method mentioned above. The results are shown in Table 3.

Comparative Example 3

In Example 1, instead of Pc1: 0.004875 parts, a squarylium pigment {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 (S2084, a squarylium pigment | dye, absorption maximum wavelength 668 nm) much the same as Example 1 except having used 0.0010 parts of And the squarylium type pigment | dye containing polyimide film (thickness 20micrometer) was obtained. About this film, light resistance and heat resistance were evaluated according to the test method mentioned above. The results are shown in Table 3.

In addition, although the structure of S2084 is shown below, since it has a zwitterion in a conjugated skeleton, it does not correspond to the pigment | dye A in which the conjugated skeleton in this invention is nonionic.

[Chemical Formula 16]

[Table 3]

Examples 9-21

In Example 1, except having used each pigment | dye shown in Table 4 instead of Pc1 as a pigment | dye, it carried out similarly to Example 1, and obtained the phthalocyanine pigment | dye containing polyimide film (thickness 22 micrometers). About this film, light resistance and heat resistance were evaluated in accordance with the above test method. The results are shown in Table 4.

In addition, although the structure of the pigment | dye (Pc3-Pc15) used in Examples 9-21 was shown to Tables 1-1 to 1-3 (formula (6b), (7b), (8b)), these are the pigment | dye of this invention. Corresponds to A.

[Table 4]

Examples B-1 to B-9

A phthalocyanine pigment | dye containing polyimide film (thickness 22 micrometers) was obtained like Example 1 except having used each pigment | dye shown in Table 5 as a pigment | dye instead of Pc1. About this film, light resistance and heat resistance were evaluated in accordance with the above test method. The results are shown in Table 5.

In addition, although the structure of the pigment | dye (Pc16-Pc21) used in Examples B-1 to B-9 was shown to Tables 2-1 to 2-2 (formula (9b) and (10b)), these are the pigment | dye of this invention. Corresponds to A.

[Table 5]

Example 5

The phthalocyanine pigment | dye containing polyimide film obtained in Example 1 was cut into the rectangle of width 60mm and length 100mm.

On both surfaces of this resin sheet, the multilayer film (referred below) which reflects infrared rays was formed by vapor deposition at the vapor deposition substrate temperature of 150 degreeC, and the light selective transmission filter (optical filter) was manufactured. About this filter, light resistance was evaluated in accordance with the test method mentioned above. The results are shown in Table 6.

The term "multilayer film reflecting infrared rays" is obtained by alternately laminating a silica (SiO ₂ : film thickness of 120 to 190 nm) layer and a titania (TiO ₂ : film thickness of 70 to 120 nm) layer, and these are formed on one side of the resin sheet. Twenty layers were deposited on both sides. Therefore, the sum total of the laminated number of a reflective multilayer film is 40 layers.

Examples 6-8, Comparative Examples 4-6

Instead of the phthalocyanine dye-containing polyimide film obtained in Example 1, except that the film shown in Table 6 was used, it carried out similarly to Example 5, and produced the light selective transmission filter (optical filter), respectively. About each of these filters, light resistance was evaluated according to the test method mentioned above. The results are shown in Table 6.

TABLE 6

The following were confirmed from the said Example and the comparative example.

Tables 3-6 summarize the light resistance and heat resistance test results with respect to the resin sheet.

Example 1, Example 2, Examples 9-21, Comparative Example 1, and Comparative Example 3 are examples in which the dyes of the same binder resin (resin component) are different, but under such a difference, light resistance and heat resistance In contrast, compared with Examples 1, 2 and 9-21, in Comparative Examples 1 and 3, the difference in transmittance before and after light irradiation or heating is remarkably large. Moreover, in Example 3, Example 4, and the comparative example 2, when the pigment | dye of the thing using the same binder resin (resin component) is different, and also compares these light resistance and heat resistance, compared with Examples 3 and 4, In the comparative example 2, the difference of the transmittance | permeability before and behind light irradiation or heating is remarkably large.

Table 6 summarizes the light resistance test results for the light selective transmission filter. Also in Examples 5-8 and Comparative Examples 4-6, the same tendency as the resin sheet was seen.

Here, in the above-mentioned examples, although Pc1-Pc22 is used as a pigment | dye, a conjugated skeleton is nonionic and has an absorption maximum wavelength in the wavelength range of 600-800 nm, The at least 1 absorption maximum wavelength As long as the pigment | dye which exists in this 600-730 nm is used, the mechanism of effect which raises the effect of this invention is the same. That is, an essential feature of the present invention is that the conjugated skeleton of the pigment has a nonionic ion, that is, it does not have an ionizing structure portion and also has a specific absorption characteristic, and thus has the structural characteristics and absorption characteristics. If it is a pigment | dye, even if it is pigment | dyes other than Pc1-Pc22, the effect as shown in the said Example is exhibited. It is understood that the resin sheets (Examples 1 to 4, 9 to 21 and B-1 to B-9) of the present invention exhibit high light resistance and heat resistance and are preferably used as the resin sheet for the light selective transmission filter. there was.

Example 22

100 parts of dimethylacetamides were added to 8 parts of neoprem L-3430 (made by Mitsubishi Gas Chemical Co., Ltd., 50 micrometers thick), and it stirred for 1 hour and made it melt | dissolve. 15 mg of the phthalocyanine compounds (Pc5) obtained above were added to 6.063 g of this solution, mixed and dissolved to adjust the resin coating liquid (resin composition). By applying the obtained resin coating liquid onto a glass substrate with a spin coater and drying at 120 ° C. for 20 minutes, a resin layer (thickness of the dried resin film: 3 μm) was formed to form a sample (coated glass with a resin layer formed on the glass plate). Got it. The absorption spectrum of the obtained sample, ie, the resin sheet (also called an absorption sheet), was measured with a spectrophotometer (Shimadzu Corporation: UV-1800). The results are summarized in Table 7 below.

Examples 23-26

Except having used the phthalocyanine compound shown in Table 7 instead of Pc5, it carried out similarly to Example 22, and obtained the absorption sheet (resin sheet). The absorption spectrum of the obtained absorption sheet was measured with the spectrophotometer (The Shimadzu Corporation make: UV-1800). The results are summarized in Table 7 below.

[Table 7]

In Table 7, Pc5, Pc7, Pc14, Pc16 ', and Pc25 are phthalocyanine type pigment | dyes which have a structure shown by Formula (11) in Table 7.

About M, X, Y, and R ( ^alpha ) in Formula (11), it is as showing in Table 7 about each pigment | dye.

For example, with respect to Pc5, it is R <^alpha> (eight total) in Formula (11) that R <^alpha> is "four 4-chlorophenoxy, four hydrogen", and X and Y are "eight hydrogen". It means that four are 2-chlorophenoxy groups, the remaining R ^α is a hydrogen atom, and both X and Y (total 8) are hydrogen atoms.

In Table 7, Q1, Q2, (lambda) Q1, (lambda) Q2, and Abs (Q2) / Abs (Q1) mean the following, respectively.

Q1: Absorption of short-wavelength side of phthalocyanine

Q2: Long-wave absorption of phthalocyanine

λQ1: Absorption maximum wavelength of short wavelength side absorption of phthalocyanine

λQ2: Absorption maximum wavelength of long wavelength side absorption of phthalocyanine

Abs (Q1): absorbance at λQ1 (Max value of)

Abs (Q2): absorbance at λQ2 (Max value of)

Abs (Q2) / Abs (Q1): Ratio of Abs (Q1) and Abs (Q2)

α-position substituent: a substituent bonded to carbon at positions 1, 4, 8, 11, 15, 18, 22, and 25 of the phthalocyanine ring.

β-position substituent: a substituent bonded to a carbon at positions 2, 3, 9, 10, 16, 17, 23, and 24 of the phthalocyanine ring.

In addition, in the resin sheet of a present Example, only (lambda) Q1 is observed and (lambda) Q2 may not be observed. In such a case, the absorbance at the absorption maximum wavelength which shows if the pigment | dye contained is a non-association state was measured, Abs (Q2) / Abs (Q1) was computed by making the absorbance into Abs (Q2). In this way, when only the absorption maximum was observed for λ Q1, a * mark was given to the λ Q2 column in Table 1 and shown.

Examples 27 and 28 (spectral characteristic measurement in the polyimide which mixed 2 types of pigment | dye)

100 parts of dimethylacetamides were added to 8 parts of neoprem L-3430 (made by Mitsubishi Gas Chemical Co., Ltd., 50 micrometers thick), and it stirred for 1 hour and made it melt | dissolve. The pigment | dye mixture which measured and measured the pigment | dye A and pigment | dye B shown in Table 8 so that a total amount might be 15 mg in 6.063 g of this solution by the mass ratio of Table 8 was prepared, and the resin coating liquid (resin composition) was prepared. . The resin sheet with a resin layer formed on the glass substrate surface was manufactured by apply | coating the obtained resin coating liquid on the glass substrate with a spin coater, and drying at 120 degreeC for 20 minutes. The absorption spectrum of the obtained resin sheet was measured with the spectrophotometer (The Shimadzu Corporation make: UV-1800). The results are summarized in Table 8.

In addition, in each Example, instead of using the pigment | dye A and the pigment | dye B together, except for the point which used only 15 mg of pigment | dye A used by each Example, the resin coating liquid (resin composition) was prepared similarly to each Example, In addition, the absorbent sheet was produced and evaluated in the same manner as in each example, and the results of the evaluation are shown in Table 8.

[Table 8]

When the absorption characteristic of the resin sheets obtained in Examples 27-28 is compared with the absorption characteristic of the resin sheet obtained by using the pigment | dye A alone, a maximum absorption wavelength is contained by further including the pigment | dye B in addition to the pigment | dye A in a resin layer. It is understood that while the transmittance in the film is reduced (absorption rate is increased), the absorption width in the 600 to 800 nm wavelength range is increased.

In addition, "% T_ (lambda) max" and "W (nm)" of Table 8 also originate in the resin sheet which is evaluation object of the absorbance ratio (Abs (Q2) / Abs (Q1)).

In Tables 8 and 9, "λmax" means the maximum absorption wavelength.

An absorption width is a wavelength width in arbitrary transmission intensity.

Here, by combining the resin sheet of the present invention and a reflective film (for example, an optical multilayer film), a light selective transmission filter having sharp transmission absorption characteristics can be provided. In this case, since the reflective film has an incident angle dependence, when the incident angle is large, the transmittance spectrum is changed (shifted to the short wavelength side) as compared with when the incident angle is 0 degrees, but since the resin sheet has no incident angle dependency, sharp transmission absorption characteristics can be maintained. . Moreover, when the absorption width (absorption band width) is wide (large surface), the design conditions of the reflective film are expanded, and the manufacture of the IRC (infrared cut filter) becomes easy.

Examples 29 and 30 (spectral measurement in polyimide mixed with two pigments)

Except having used the dye A and the dye B shown in Table 9, it carried out similarly to Example 27, and produced the resin sheet, and measured the absorption spectrum. The results are summarized in Table 9.

In addition, in each Example, instead of using the pigment | dye A and the pigment | dye B together, except for the point which used only 15 mg of pigment | dye B used by each Example, the resin coating liquid (resin composition) was prepared similarly to each Example, In addition, the absorbent sheet was produced and evaluated in the same manner as in each of the examples.

TABLE 9

When the absorption characteristics of the resin sheets obtained in Examples 29 and 30 are compared with the absorption characteristics of the resin sheet obtained by using the dye B alone, when the dye B is used alone, the transmittance of 630 nm is lowered and shorter wavelength than lambda max. Sharp transmissive absorption characteristics are not obtained, resulting in low light selective transmissivity. In addition to the pigment | dye A in addition to the pigment | dye A in a resin layer, the transmittance | permeability of maximum absorption 630 nm becomes high, the sharp permeation absorption characteristic which is sharper on the short wavelength side than (lambda) max is obtained, and light selective transmittance improves. That is, Table 9 shows that the absorption width in the 600-800 nm wavelength range is increasing.

In addition, "(lambda) max" and "% T" of Table 9 are derived from the resin sheet which is evaluation object.

<Evaluation of Incidence Dependence>

Incident angle dependence was evaluated about the light selective transmission filter obtained in Examples 5-8.

The transmittance | permeability in 200-1100 nm was measured using Shimadzu UV-3100 (made by Shimadzu Corporation). 3, when the light selective transmission filter is provided 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. The light is incident from the thickness direction of the light selective transmission filter. And a 25 ° light selective transmission filter inclined with respect to the incident light (the measured transmission spectrum is also referred to as a 25 ° spectrum. From the direction inclined 25 ° to the thickness direction of the light selective transmission filter). Measurement is made for each incident light).

As a result, although the spectrum is not shown, in the light selective transmission filter (Examples 5-8) which have the resin layer containing the pigment | dye A, in the area | region of 60% or more of transmittance | permeability, there is no change in the spectrum of 0 degrees and 25 degrees. , The dependence of the angle of incidence on the light blocking property was confirmed to be reduced.

Therefore, it turned out that the light selective permeation | transmission filter (Examples 5-8) of this invention can exhibit high light resistance and heat resistance, while reducing the incident angle dependence of a light blocking characteristic.

1: Lens
2: light selective transmission filter
3: sensor
4: light source
5: light selective transmission filter
6: light receiver

Claims (9)

As a light selective transmission filter containing a resin sheet,
The resin sheet has a resin layer containing a dye and a resin component,
The said pigment | dye contains the pigment | dye A in which the conjugate frame | skeleton which it has is nonionic and has absorption maximum wavelength in the wavelength range of 600-800 nm, and the at least 1 absorption maximum wavelength exists in 600-730 nm. The light selective transmission filter characterized by the above-mentioned. The method of claim 1,
The said pigment A is the following general formula (I):
[Formula 1]

In the formula, R ^a1 to R ^d1 , R ^a2 to R ^d2 , R ^a3 to R ^d3, and R ^a4 to R ^d4 Is the same or different and OR ⁱ which may have a hydrogen atom (H), a fluorine atom (F), and a substituent SR ^j which may have a group or a substituent Group. R ⁱ and R ^j Is the same or different and represents an alkyl group, a phenyl group or a naphthyl group. M represents a metal atom, a metal oxide, or a metal halide.) The light selective transmission filter characterized by the above-mentioned. 3. The method of claim 2,
OR ⁱ Flag or SR ^j The substituent which the group may have is a halogen group, The light selective transmission filter characterized by the above-mentioned. The method according to any one of claims 1 to 3,
The light selective transmission filter further comprises a reflective film. The method according to any one of claims 1 to 4,
The said pigment A is the following general formula (i):
(2)

In the formula, M represents a metal atom, a metal oxide or a metal halide. X ¹ to X ⁴ and Y ¹ to Y ⁴ Is the same or different and OR ⁱ which may have a hydrogen atom (H), a fluorine atom (F) or a substituent Group. OR ⁱ A group represents an alkoxy group, a phenoxy group, or a naphthoxy group. However, at least 4 of X <^1> -X <^4> and Y <^1> -Y <^4> are the same or different, and represent the phenoxy group which has an electron withdrawing group.) The light selective transmission filter characterized by the above-mentioned. The method of claim 5, wherein
X ¹ to X ⁴ and Y ¹ to Y ^{4 in} the general formula (i) Are all the same or different, and represent a phenoxy group which has an electron withdrawing group, The light selective transmission filter characterized by the above-mentioned. 7. The method according to any one of claims 1 to 6,
The said dye is a phthalocyanine type pigment | dye which has two absorption maximum wavelengths ((lambda) _B1 , (lambda) _B2 ) in the wavelength range of _{650-800nm further} , and contains the pigment | dye B which has the largest absorption wavelength (lambda) _B2 in the long wavelength side among them. and,
The said maximum absorption wavelength (lambda) _B2 is in a longer wavelength side than the maximum absorption wavelength (lambda) _A of the said pigment | dye A,
The ratio (A _B2 / A _B1 ) of absorbance at the two absorption maximum wavelengths (λ _B1 , λ _B2 ) is composed of the dye B and the resin component, and the content ratio of the dye B is 3% by mass of the composition. The light selective transmission filter which satisfy | fills two or more when absorbance is measured. It is used for the light selective transmission filter in any one of Claims 1-7, The resin sheet characterized by the above-mentioned. The solid-state image sensor which has at least the light selective transmission filter of any one of Claims 1-7, a lens unit part, and a sensor part.

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