JP2016071323A - Near-infrared cut filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-infrared cut filter formed in a way that makes it hard for a laminate laminated on a glass substrate to come off the glass substrate.SOLUTION: A near-infrared cut filter of the present invention comprises a glass substrate, a base layer formed on the glass substrate, and a resin layer provided above the base layer, where the base layer is made of a composition containing a silane coupling agent having an amino group, and the resin layer contains at least either of a polyimide resin and polyamide-imide resin.SELECTED DRAWING: None

Description

  The present invention relates to a near-infrared cut filter including a glass substrate, a base layer provided on the glass substrate, and a resin layer provided above the base layer.

  In recent years, in order to achieve multi-functionality in various fields, such as optical devices such as display elements and image pickup elements, a material having a laminated structure in which various layers are formed on a substrate made of glass or the like has been widely used. Yes. Examples of the layer formed on the substrate include an ITO (tin-doped indium oxide) transparent conductive layer used for a touch panel and the like, an antireflection layer that reduces reflection of light on the substrate surface, and optical noise in the imaging element ( Near) Infrared cut layer and the like.

  The image sensor is also referred to as a solid-state image sensor or an image sensor chip, and is an electronic component that converts light of an object into an electrical signal and outputs it. It is used for elements (LED etc.). Such an image pickup element is usually configured to include a detection element (sensor) such as a CCD (Charge Coupled Device) or a CMOS (Complementary Metal-Oxide Semiconductor) and a lens. There is a demand for reduction of optical noise that hinders the above.

  Conventionally, optical noise in an image sensor has been reduced by using an absorption glass such as blue glass doped with copper ions, a resin filter having a light absorption function or a reflection function for reducing optical noise on a resin component, and the like. It was. However, although the absorbing glass is very excellent in heat resistance, cracks and chipping are likely to occur, and the processability is not sufficient. On the other hand, the resin filter can suppress the occurrence of cracks and chipping and is excellent in workability. On the other hand, the heat resistance is not sufficient as compared with glass, and warpage due to linear expansion is likely to occur. Therefore, in recent years, development of an optical filter having a laminated structure in which a layer having a light absorption function and a reflection function is formed on a substrate such as glass has been advanced.

  As an optical filter having the laminated structure, for example, Patent Document 1 discloses a filter having a glass substrate, an underlayer mainly composed of silicon oxide, and a near infrared absorption layer.

JP 2014-52431 A

  However, in such a filter, the adhesion between the glass substrate and the near-infrared absorbing layer is not sufficient, and it is difficult to say that the filter has sufficient durability.

  This invention is made | formed in view of the above situations, The objective is to provide the near-infrared cut filter formed so that the laminated body laminated | stacked on the glass substrate might not peel easily from a glass substrate. It is in.

  The near-infrared cut filter of the present invention capable of solving the above problems comprises a glass substrate, a base layer provided on the glass substrate, and a resin layer provided above the base layer, The underlayer is formed from a composition containing a silane coupling agent having an amino group, and the resin layer contains at least one of a polyimide resin and a polyamideimide resin.

  The resin layer contains at least one of a phthalocyanine dye and an oxocarbon dye, and the contained dye preferably has an absorption maximum in a wavelength region of 600 to 900 nm.

The polyimide resin is preferably a polyimide resin represented by the following general formula (1).

(In the general formula (1), X ′ and Y ′ each independently contain a monocyclic or condensed polycyclic aliphatic group, or a monocyclic or condensed polycyclic aromatic group, A linking group that may have a substituent having 2 to 39 carbon atoms is shown.)

The polyamideimide resin is preferably a polyamideimide resin represented by the following general formula (2).

(In general formula (2), X ″ represents a trivalent organic group, and Y ″ represents a divalent organic group represented by the following general formula (3) or the following general formula (4).)

(In General Formula (3), R ¹ and R ³ represent a hydrogen atom or a nonionic and inert substituent,
R ² represents CH ₂ , CO, SO ₂ or O. )

(In general formula (4), R ¹ is the same as in general formula (3).)

  The silane coupling agent preferably has a primary amino group.

  The present invention also includes a composition for forming the resin layer of the near infrared cut filter by coating, wherein the composition contains at least one of a polyimide resin and a polyamideimide resin. To do.

  In this specification, “absorption maximum” means that the absorbance changes from increasing to decreasing when the relationship between wavelength and absorbance is represented by a two-dimensional graph with the X axis as the wavelength and the Y axis as the absorbance. Means a vertex.

  According to the present invention, the underlayer contains a silane coupling agent having an amino group, and the resin layer contains at least one of a polyimide resin and a polyamideimide resin, thereby being extremely excellent in peel resistance. It becomes a near-infrared cut filter. Moreover, the deformation | transformation of a near-infrared cut filter decreases by using a glass substrate as a base material. Furthermore, by combining the glass substrate with the base layer and the resin layer, a high-performance near-infrared cut filter with high heat resistance and reduced residual solvent is obtained.

  The near-infrared cut filter of the present invention includes a glass substrate, a base layer provided on the glass substrate, and a resin layer provided above the base layer, and the base layer is a silane cup having an amino group. The resin layer is formed from a composition containing a ring agent, and the resin layer contains at least one of a polyimide resin and a polyamideimide resin (hereinafter referred to as poly (amide) imide resin). Hereinafter, the near-infrared cut filter of the present invention will be described in detail.

(Glass substrate)
The near-infrared cut filter of the present invention has a base layer and a resin layer formed on a glass substrate. By making the substrate glass, the adhesion between the glass substrate and the underlayer is excellent, and the generation of cracks, chipping and warpage of the underlayer and the resin layer (hereinafter referred to as a laminate) can be further suppressed, and A near-infrared cut filter with excellent heat resistance.

The glass substrate may be obtained by containing transition metal ions in a material forming glass. As the transition metal ion, one or more kinds which are usually used as those having light absorption ability may be used. For example, Ag ⁺ , Fe ²⁺ , Co ²⁺ , Ni ²⁺ , Cu ²⁺ , Zn ^{2+ and the} like can be mentioned.

  In addition to the above, borosilicate glass is preferable because it is easy to process and the generation of scratches and foreign matters on the optical surface is suppressed. As the borosilicate glass, a commercially available product can be used, for example, D263 Teco manufactured by SCHOTT or the like. Further, the alkali-free glass containing no alkali component is advantageous in terms of high adhesiveness, weather resistance and the like. And soda-lime glass is particularly preferable because it is inexpensive and easily available, and the surface of the glass substrate is reinforced.

  The magnitude | size of a glass substrate is suitably adjusted according to the magnitude | size used as a near-infrared cut filter, the apparatus to be used, etc. The thickness of the glass substrate is preferably 0.05 mm or more, and more preferably 0.1 mm or more, from the viewpoint of reducing the size and thickness of the apparatus and preventing damage during handling. Moreover, from the point of weight reduction and intensity | strength, it is preferable that it is 0.4 mm or less, and it is more preferable that it is 0.3 mm or less.

(Underlayer)
The underlayer is formed from a composition containing a silane coupling agent having an amino group (hereinafter referred to as an underlayer composition), and the underlayer may be provided only on one side of the glass substrate. It may be provided on both sides. The underlayer may have either a single layer structure or a multilayer structure.

<Silane coupling agent>
The silane coupling agent has an amino group as a reactive group. By including such an amino group-containing silane coupling agent in the composition for the underlayer, the effect of improving the adhesion with the glass substrate and the effect of suppressing the ingress of moisture into the underlayer by the water repellent action As a result, a near-infrared cut filter excellent in heat resistance and heat-and-moisture resistance can be obtained. Specifically, peeling or the like can be suppressed during use in a solder reflow process or in a humid heat environment.
The reactive group other than the amino group preferably has, for example, an alkoxy group, a vinyl group, a (meth) acryloyl group, an oxirane group (oxirane ring), a mercapto group, an isocyanate group, etc., and particularly has an alkoxy group. It is more preferable.

  Specific examples of the amino group-containing silane coupling agent include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-aminopropyltriisopropoxysilane, 3-aminopropylmethyldimethoxysilane, and 3-aminopropyl. Methyldiethoxysilane, 3- (2-aminoethyl) aminopropyltrimethoxysilane, 3- (2-aminoethyl) aminopropylmethyldimethoxysilane, 3- (2-aminoethyl) aminopropyltriethoxysilane, 3- ( 2-aminoethyl) aminopropylmethyldiethoxysilane, 3- (2-aminoethyl) aminopropyltriisopropoxysilane, 3- (6-aminohexyl) aminopropyltrimethoxysilane, 3- (N-ethylamino)- 2-methylpropyltri Toxisilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltrimethoxysilane, N-vinylbenzyl-3-amino Propyltriethoxysilane, N-cyclohexylaminomethyltriethoxysilane, N-cyclohexylaminomethyldiethoxymethylsilane, N-phenylaminomethyltrimethoxysilane, (2-aminoethyl) aminomethyltrimethoxysilane, bis (3-tri Methoxysilylpropyl) amine, N, N′-bis [3- (trimethoxysilyl) propyl] ethylenediamine and the like. The silane coupling agent preferably has at least one of a primary amino group and a secondary amino group, and more preferably has a primary amino group. In particular, it is preferable to use a composition for an underlayer containing a silane coupling agent having a primary amino group because the adhesion to a glass substrate becomes very good. The amino group-containing silane coupling agent preferably has at least one of a methoxy group and an ethoxy group, and among them, a chain (preferably a straight chain having no ring structure) is particularly preferable. In particular, 3-aminopropyltrimethoxysilane and 3- (2-aminoethyl) aminopropyltrimethoxysilane are preferable because they are easily available and provide a base layer that exhibits high adhesion to a glass substrate. Only one type of amino group-containing silane coupling agent may be used, or two or more types may be used.

  Specific examples of the amino group-containing silane coupling agent include KBM-903 (3-aminopropyltrimethoxysilane) manufactured by Shin-Etsu Silicone, Z-6020 (3- (2-aminoethyl) amino manufactured by Toray Dow Corning Co., Ltd. Propyltrimethoxysilane) and the like are preferably used.

  The content of the amino group-containing silane coupling agent in the underlayer composition is preferably 0.00001 to 10% by mass, preferably 0.00005 to 5%, relative to 100% by mass of the underlayer composition (total amount including the solvent). % By mass is more preferable, and 0.0001 to 3% by mass is particularly preferable. By setting it as the content, an underlayer having excellent adhesion to the glass substrate and high heat resistance can be obtained.

<Method for Preparing Composition for Underlayer>
The method for preparing the composition for the underlayer is not particularly limited, and it can be obtained by adding a liquid medium and a catalyst to the amino group-containing silane coupling agent and mixing them by an ordinary method. The liquid medium may be water, alcohol, or the like, and one or more may be used, but water and / or ethanol are preferable. By adding a liquid medium, the alkoxy group in the amino group-containing silane coupling agent is hydrolyzed to form a silanol group, and this silanol group migrates to the glass substrate surface through hydrogen bonding with the hydroxyl group on the glass substrate surface. To do. And the adhesiveness of a glass substrate and a base layer improves by producing | generating a strong covalent bond with the glass substrate surface through the dehydration condensation reaction of a silanol group. The content of the liquid medium in the underlayer composition is preferably 97 to 99.9% by mass, more preferably 98 to 99.5% by mass with respect to 100% by mass of the underlayer composition (total amount including the solvent). preferable.

  Moreover, the catalyst should just act as a catalyst at the time of the hydrolysis reaction of an amino group containing silane coupling agent, and any of an organic acid or an inorganic acid may be sufficient as it. Examples of inorganic acids include sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, etc. Examples of organic acids include formic acid, oxalic acid, fumaric acid, maleic acid, glacial acetic acid, acetic anhydride, propionic acid, and n- Compounds having a carboxylic acid group such as butyric acid; compounds having a sulfur-containing acid group such as an organic sulfonic acid and an esterified product of an organic sulfonic acid (organic sulfate ester, organic sulfite ester), and the like. Can be used. Of these, formic acid is preferably used as the catalyst. The content of the catalyst is preferably 0.0001 to 3% by mass and more preferably 0.001 to 1% by mass with respect to 100% by mass of the composition for the underlayer (total amount including the solvent).

<Formation method of underlayer>
As a method for forming the underlayer, a known method can be used, but a method of forming the underlayer composition (undercoat solution) on a glass substrate by heating and drying is preferable. Specific examples include commonly used methods such as spin coating, casting, roll coating, spray coating, bar coating, dip coating, screen printing, flexographic printing, and inkjet. Among these, the spin coating method is preferable from the viewpoint of reducing the deviation of the coating layer on the substrate. When a coating film is formed by a spin coating method, it is preferable to dry the solvent while rotating the substrate on which the base layer composition is applied at about 500 to 4000 rpm for about 10 to 60 seconds at around room temperature (25 ° C.). . Moreover, it is preferable that the base material (glass substrate) coated with the composition for the underlayer is heated to remove the solvent and cause the silane coupling agent and the base material to chemically react.

  As a method for forming the underlayer, any of the methods described above may be used, but the amount of residual solvent in the underlayer is preferably as small as possible. Specifically, 3 mass% or less is preferable, More preferably, it is 1 mass% or less, More preferably, it is 0.5 mass% or less. When the residual solvent amount exceeds 3% by mass, the underlying layer may be deformed or the characteristics may change over time, and the desired function may not be exhibited. In this invention, since the glass substrate is used as a base material, compared with the case where a film is used as a base material, the composition for base layers is easy to dry and a residual solvent tends to decrease.

(Resin layer)
The resin layer contains at least one of a polyimide resin and a polyamideimide resin. That is, the resin layer forming composition (hereinafter referred to as the resin layer composition) contains at least one of a polyimide resin and a polyamideimide resin.

  The resin layer is preferably on the base layer (the resin layer and the base layer are in contact), but may be formed above the base layer (on the side opposite to the glass substrate). The other layer mentioned later may be laminated between. The resin layer may be provided only on one side of the glass substrate, or may be provided on both sides. Further, the resin layer may have either a single layer structure or a multilayer structure.

<Poly (amide) imide resin>
Poly (amide) imide resins are narrowly defined polyimide resins (resins that contain imide bonds and do not contain amide bonds that cannot form imide bonds by dehydration reaction), and polyamide imide resins (imide bonds and imide bonds by dehydration reaction). And any amide bond that cannot form a bond).

  The poly (amide) imide resin used in the present invention is a solvent-soluble poly (amide) imide resin. In this specification, the solvent-soluble resin refers to a resin that is solvent-soluble. The solvent-soluble resin includes a resin precursor. Further, the resin layer itself may be solvent-soluble or insoluble.

  When the resin layer composition contains a solvent-soluble resin, the light resistance of the filter is easily improved. Solvent-soluble resins are prepared from their monomers and precursors, have undergone polymerization and reaction, and may be further purified. The solvent-soluble resins thus obtained are not yet used to promote deterioration and decomposition of pigments. It is considered that there are almost no reactants, reactive ends, ionic groups, catalysts, acid / basic groups and the like. Therefore, when the pigment | dye is disperse | distributed or dissolved in the composition for resin layers, it is thought that the near-infrared absorption performance of a pigment | dye becomes difficult to fall. And it is preferable to use the polyimide resin which is solvent-soluble resin from a viewpoint of the light resistance improvement of a filter.

  The solvent-soluble resin is not particularly limited as long as it is soluble in an organic solvent. For example, it is preferably a resin that dissolves 1 part by mass or more with respect to 100 parts by mass of N, N-dimethylacetamide, and 5 parts by mass. It is more preferable that the resin be dissolved as described above. Specific examples include polyimide resins, polyamideimide resins and / or precursors thereof, and examples thereof include compounds represented by the following general formula (1) and / or general formula (2).

(In the general formula (1), X ′ and Y ′ each independently contain a monocyclic or condensed polycyclic aliphatic group, or a monocyclic or condensed polycyclic aromatic group, A linking group that may have a substituent having 2 to 39 carbon atoms is shown.)

(In general formula (2), X ″ represents a trivalent organic group, and Y ″ represents a divalent organic group represented by the following general formula (3) or the following general formula (4).)
In the general formula (2), X ″ is preferably an aromatic group or a monocyclic aliphatic group.

(In general formula (3), R ¹ and R ³ represent a hydrogen atom or a nonionic and inert substituent, and R ² represents CH ₂ , CO, SO ₂ or O.)

(In general formula (4), R ¹ is the same as in general formula (3).)

  These solvent-soluble resins are reactive groups that can undergo a crosslinking reaction (curing reaction) (for example, ring-opening polymerizable groups such as epoxy groups, oxetane rings, ethylene sulfide groups, acryloyl groups, methacryloyl groups, vinyl groups). Or a radical curable group such as an addition curable group).

  When the solvent-soluble resin is contained in the resin layer composition, the solvent-soluble resin itself may constitute the resin layer, or the solvent-soluble resin changed by a crosslinking reaction or the like may constitute the resin layer. .

  The imide bond in the narrowly defined polyimide resin is usually formed by a dehydration reaction between the amide bond and the carboxyl group in a polyamic acid having a bond chain having an amide bond and a carboxyl group adjacent thereto. However, after an imide bond is generated from the polyamic acid by a dehydration reaction, a slight amount of amide bond and carboxyl group may remain in the molecule.

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

  Although it will not specifically limit if it is a compound which has an imide bond as a polyimide resin, It is preferable that it is a compound (polymer) which has a repeating unit represented by following General formula (5).

(In General Formula (5), R ⁴ represents a divalent organic group having 2 to 39 carbon atoms.)

R ⁴ in the general formula (5) is preferably an organic group having 2 to 39 carbon atoms, divalent aliphatic, alicyclic, aromatic, or a combination thereof. The organic group represented by R ⁴ may be directly bonded to a nitrogen atom, and as a bonding group, —O—, —SO ₂ —, —CO—, —CH ₂ —, —C (CH ₃ ) _{2 -, - Si (CH 3} ) 2 -, - C 2 H 4 O -, - S- , etc. may be included. The repeating unit represented by the general formula (5) may be the same or different, and the polymer having the repeating unit represented by the general formula (5) is in any form such as block or random. May be.

  The polyamideimide resin is preferably a compound having an amide group in the polymer main chain of polyimide (for example, a copolymer), for example, a partial structure represented by the general formula (6) or the general formula (7). It is a polymer as a repeating unit.

(In the general formula (6), R represents a divalent organic group represented by the general formula (3) or the general formula (4).)

(In the general formula (7), R represents a divalent organic group represented by the general formula (3) or the general formula (4).)

  As the polyamideimide resin, the polyamideimide resin disclosed in JP 2011-213849 A can be used. Moreover, as a polyamideimide resin, a commercial item can also be used, for example, the Toyobo company make Viromax (trademark) series is mentioned.

  The content of the poly (amide) imide resin in the resin layer composition is preferably 1 to 30% by mass, more preferably 2 to 100% by mass with respect to 100% by mass of the resin layer composition (total amount including the solvent). It is 20 mass%, More preferably, it is 3-10 mass%.

<Near-infrared absorbing dye>
In the resin layer composition, it is preferable that the near-infrared absorbing dye contains a dye having an absorption maximum in the wavelength range of 600 to 900 nm (hereinafter also referred to as a specific dye). By including such a specific dye, light (transmitted light) particularly in a region of 600 nm to 1000 nm can be reduced, and optical noise caused by this can be removed. As a result, a suitable performance for reducing optical noise, such as high visible light transmittance and excellent blocking performance in the near infrared region, can be obtained. The specific dye is more preferably a dye having an absorption maximum in a wavelength range of 600 to 800 nm, and more preferably a dye having an absorption maximum in a wavelength range of 650 to 750 nm.

  The specific dye may have a plurality of absorption maxima in the wavelength region of 600 to 900 nm. Of the absorption maximums in the wavelength range of 600 to 900 nm, the absorption maximum on the shortest wavelength side is preferably in the wavelength range of 650 to 750 nm. The specific dye is also preferably one having no absorption maximum in a wavelength region of 400 nm or more and less than 600 nm.

  In the resin layer composition, the near infrared absorbing dye is preferably dispersed or dissolved in the resin layer composition, and the near infrared absorbing dye is dissolved and contained in the resin layer composition. Is more preferable. That is, it is preferable that the near-infrared absorbing dye is dissolved in a resin component (binder resin) or a solvent contained in the resin layer composition. By using a poly (amide) imide resin that is solvent-soluble together with such a near-infrared absorbing dye, a resin layer in which the dye is uniformly dispersed at a high concentration can be formed. 1 type (s) or 2 or more types can be used for a near-infrared absorption pigment | dye.

  The near infrared absorbing dye is preferably a dye having a π electron bond in the molecule. The dye having a π electron bond in the molecule is preferably a compound containing an aromatic ring. More preferably, it is a compound containing two or more aromatic rings in one molecule. And it is especially preferable that the pigment | dye which has (pi) electron bond in the said molecule | numerator is what has an absorption maximum in the wavelength range mentioned above, ie, a specific pigment | dye.

  Examples of the dye having a π-electron bond in the molecule include, for example, phthalocyanine compounds, oxocarbon compounds, porphyrin compounds, cyanine compounds, quaterylene compounds, naphthalocyanine compounds, nickel complex compounds, azo compounds, A diimonium type compound is mentioned, These 1 type (s) or 2 or more types can be used. From the viewpoint of heat resistance, weather resistance, permeability, and compatibility with the poly (amide) imide resin used in the present invention, phthalocyanine compounds and / or oxocarbon compounds are particularly preferable. Examples of such a dye include the dye disclosed in International Publication No. 2013/054864, JP-A-2014-59550, and the like, the squarylium dye represented by Formula (9) described later, and Formula (10). Examples include croconium dyes.

<Phthalocyanine compounds>
The phthalocyanine compound is preferably a metal phthalocyanine complex, for example, a metal element such as copper, zinc, indium, cobalt, vanadium, iron, nickel, tin, silver, magnesium, sodium, lithium, lead and the like as a central metal. Metal phthalocyanine complexes. Among these metal elements, one or more of copper, vanadium, and zinc is more excellent in solubility or dispersibility (for example, solubility or dispersibility in a resin component), visible light transmittance, and light resistance. A phthalocyanine compound having a central metal as the central metal is preferred, and a phthalocyanine compound having at least one of copper and zinc as the central metal is more preferred. In particular, a phthalocyanine complex having copper as a central metal is not deteriorated by light even when dispersed in any resin component, and has very excellent light resistance. Moreover, the phthalocyanine complex which uses zinc as a central metal is excellent in the solubility with respect to a resin component, and it is easy to obtain a near-infrared cut filter with higher light selective permeability.

  Among the phthalocyanine compounds, a compound represented by the following general formula (8) is particularly preferable. When the resin layer composition containing such a compound is used, it is possible to obtain a near-infrared cut filter that can further prevent cracks, chipping, and warpage, and can sufficiently withstand high-temperature deposition. In addition, when such a near-infrared cut filter is applied to an imaging device, the occurrence of flare and ghost can be sufficiently suppressed, and incident angle dependency that can be a problem when combined with a reflective film is sufficiently reduced. You can also. Further, when such a near-infrared cut filter is provided with, for example, a reflection film or an interference film, it is possible to exhibit light selective transmission close to the sensitivity of the human eye. And after the synthesis | combination of the said phthalocyanine type compound, you may perform crystallization, filtration, washing | cleaning, drying, etc. according to a well-known method.

(In the general formula, M represents a metal atom, a metal oxide, or a metal halide. R ^{a1 to} R ^a4 , R ^b1 to ^b4 , R ^{c1 to} R ^c4, and R ^{d1 to} R ^d4 are the same or different groups. And represents a hydrogen atom (H), a fluorine atom (F), a chlorine atom (Cl), a bromine atom (Br), an iodine atom (I), or an OR ⁱ group which may have a substituent. ^{The i} group represents an alkoxy group, a phenoxy group, a naphthoxy group, or a chlorophenoxy group (for example, a substituent E in the chemical formula (15) described later or a substituent I in the chemical formula (17)).

  A preferred form of the compound represented by the general formula (8) is, for example, phthalocyanine described in Chinese Patent Application No. 10392438.

  The oxocarbon-based compound is a compound containing one or more cyclic oxocarbon groups composed only of carbon and oxygen. In the present invention, the oxocarbon-based dye is used as a near-infrared absorbing dye. It is preferable to use (preferably an organic compound). Details of the oxocarbon-based compound will be described later.

The resin layer composition may also contain two or more pigments. Among these, the two or more dyes include a specific dye α and a specific dye β having different absorption characteristics, and at least one of the specific dye α and the specific dye β is a phthalocyanine dye or an oxocarbon dye, and the specific dye When the absorption spectrum of a resin layer composed of α and a resin component (binder resin) is measured, the absorption maximum is shown in the wavelength ranges of 600 to 650 nm and 680 to 750 nm, respectively. When the absorption spectrum of the resin layer composed of the resin component is measured, it is preferable that the absorption maximum be exhibited in the wavelength range of 650 to 680 nm. As a result, when the near-infrared cut filter of the present invention is applied to an imaging device, a sufficient light absorption width can be secured, and the occurrence of flare and ghost can be sufficiently suppressed, and there is a problem when combined with a reflective film. The incident angle dependency that can be reduced can be sufficiently reduced. Further, when the near-infrared cut filter is provided with, for example, a reflection film or an interference film, it is possible to exhibit light selective transmission close to the sensitivity of the human eye. In addition, the specific dye α is preferably a phthalocyanine dye or an oxocarbon dye, more preferably the specific dye α and the specific dye β are both a phthalocyanine dye or an oxocarbon dye, and the specific dye α and the specific dye. β is a phthalocyanine compound represented by the general formula (8) described above, a squarylium compound represented by the general formula (9) described later, or a croconium compound represented by the general formula (10) described later. More preferably.
In addition, in order to supplement near infrared absorption performance near a wavelength of 850 nm, a phthalocyanine compound other than the specific dye, a dithiol compound, an oxocarbon compound other than the specific dye, and the like can be used in combination.

  The content of the specific dye in the resin layer composition is preferably 0.05 to 30% by mass, more preferably 0.00%, with respect to 100% by mass of the resin layer composition (resin corresponding to the solid content). It is 05-10 mass%, More preferably, it is 0.5-5 mass%.

  The resin layer composition may contain a pigment other than the specific pigment. For example, a dye having a characteristic absorption at a specific wavelength in each of the near-infrared, infrared, ultraviolet, and visible light bands other than the wavelength range of 600 to 900 nm may be appropriately selected according to the intended use, and for various uses of optical materials. Can be applied. For example, in order to improve light resistance, a UV-absorbing dye such as benzophenone or benzotriazole may be used together.

  The content of the dye other than the specific dye is preferably 50% by mass or less with respect to 100% by mass of the total amount of the dye. More preferably, it is 20 mass% or less, More preferably, it is 10 mass% or less. In other words, the specific dye is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more with respect to 100% by mass of the total amount of the dye.

  The total amount of the dye is preferably 0.05% by mass or more and 35% by mass or less with respect to 100% by mass of the resin layer composition (resin corresponding to the solid content). Thereby, it becomes possible to obtain a cured product (resin layer) having higher visible light transmittance and superior in blocking performance in the near infrared region. The lower limit of the total amount of the dye is more preferably 0.1% by mass or more, further preferably 0.3% by mass or more, particularly preferably 0.5% by mass or more, and most preferably 1% by mass or more. Moreover, as an upper limit, More preferably, it is 30 mass% or less, More preferably, it is 25 mass% or less, Most preferably, it is 20 mass% or less.

<Oxocarbon compounds>
The oxocarbon compound preferably includes at least one of a squarylium compound and a croconium compound.

  The structure of the squarylium-based compound is not particularly limited, and examples thereof include a compound represented by the following formula (9).

(In Formula (9), at least one of R ^e1 and R ^e2 represents a heterocyclic ring which may have a substituent or an aromatic ring which may have a substituent.)

  The structure of the croconium-based compound is not particularly limited, and examples thereof include a compound represented by the following formula (10).

(In Formula (10), at least one of R ^e3 and R ^e4 represents a heterocyclic ring which may have a substituent or an aromatic ring which may have a substituent.)

Examples of the heterocyclic ring include an aromatic heterocyclic ring and an alicyclic heterocyclic ring.
Examples of the aromatic heterocycle include a 5-membered or 6-membered monocyclic aromatic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom, and a sulfur atom, and a condensed 2- to 8-membered ring. And a condensed aromatic heterocycle having at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more specifically, a pyridine ring, a pyrazine ring, a pyrimidine ring, Pyridazine ring, quinoline ring, isoquinoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, naphthyridine ring, cinnoline ring, pyrrole ring, pyrazole ring, imidazole ring, triazole ring, tetrazole ring, thiophene ring, furan ring, thiazole ring, oxazole ring , Indole ring, isoindole ring, indazole ring, benzimidazole ring, benztriazole ring, Zochiazoru ring, benzoxazole ring, purine ring, carbazole ring.

  The alicyclic heterocycle includes, for example, a 5-membered or 6-membered monocyclic alicyclic heterocycle containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and a 3- to 8-membered ring. And a condensed alicyclic heterocyclic ring containing at least one atom selected from a nitrogen atom, an oxygen atom and a sulfur atom, and more specifically, a pyrrolidine ring, a piperidine, etc. Ring, piperazine ring, morpholine ring, thiomorpholine ring, homopiperidine ring, homopiperazine ring, tetrahydropyridine ring, tetrahydroquinoline ring, tetrahydroisoquinoline ring, tetrahydrofuran ring, tetrahydropyran ring, dihydrobenzofuran ring, tetrahydrocarbazole ring, etc. .

  As an aromatic ring, a C6-C14 thing is mentioned, For example, a benzene ring, a naphthalene ring, an anthracene ring etc. are mentioned.

  The substituent of the heterocyclic ring or aromatic ring may be the same or different and may be 1 to 5 substituents such as hydroxyl group, carboxyl group, nitro group, alkoxy group, alkyloxycarbonyl group, amide group, sulfonamide group, alkyl Group, aralkyl group, cyano group, halogen atom, -R '= R "-Ar (R' and R" are the same and represent N or CH, Ar represents a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group And an aryl group which may be substituted with a substituent selected from the group consisting of an alkyl group optionally substituted with a halogen group, a cyano group and a halogen atom). Examples of the substituent of the alkyl group or the alkoxy group include the same or different 1 to 3 substituents such as a hydroxyl group, a carboxyl group, a nitro group, an alkoxy group, an aryl group, and a halogen atom.

  Among them, a 5-membered or 6-membered heterocyclic ring which may have a substituent or a 5-membered or 6-membered aromatic ring which may have a substituent is preferable.

  The oxocarbon-based compound preferably includes at least one of a squarylium-based compound having the structure of the above formula (9) and a croconium-based compound having the structure of the above formula (10), and has the structure of the above formula (9). It is more preferable to include a squarylium-based compound, and it is more preferable to include a squarylium-based compound having the structure of the above formula (9).

<Squarylium compound (squarylium dye)>
In the squarylium-based compound, R ^e1 and R ^e2 in the above formula (9) are each independently a specific structural unit represented by the following formula (11) or a specific structural unit represented by the following formula (12). It is particularly preferred. R ^e1 and R ^e2 may be the same or different.

(In Formula (11), Ring A is a 4- to 9-membered unsaturated hydrocarbon ring.
X and Y are each independently an organic group or a polar functional group.
n is an integer of 0 to 6 and m or less (where m is a value obtained by subtracting 3 from the number of members of ring A), and when n is 2 or more, a plurality of Ys are the same. It may be different or different.
Ring B is an optionally substituted aromatic hydrocarbon ring, aromatic heterocyclic ring or condensed ring containing these ring structures.
In addition, * represents the coupling | bond part with a 4-membered ring in Formula (9). )

(In the formula (12), R ^f1 , R ^f2 , R ^f4 and R ^f5 are each independently an organic group, a polar functional group or a hydrogen atom, and R ^f3 is an organic group or polar functional group containing a nitrogen atom. And at least one of R ^f1 and R ^f5 is an organic group or a polar functional group containing a nitrogen atom or an oxygen atom.
In addition, * represents the coupling | bond part with a 4-membered ring in Formula (9). )

  Hereinafter, the details of Expression (11) and Expression (12) will be described.

  In formula (11), * represents a binding site to the squarylium skeleton represented by formula (9), and the carbon atom (carbon atom indicated by the arrow in the above formula (11)) bonded to the squarylium skeleton is a hydrocarbon. It is characterized in that it forms a ring (ring A).

  In formula (11), ring A is an unsaturated hydrocarbon ring having 4 to 9 members. Ring A is an unsaturated hydrocarbon having at least one double bond between the carbon atom bonded to the squarylium skeleton (in the above formula (11), the carbon atom indicated by the arrow) and the carbon atom constituting the pyrrole ring. The ring may be a ring and may have an unsaturated bond (preferably a double bond) in addition to the double bond, but preferably the ring A has one double bond. . Ring A is preferably a 5- to 8-membered ring, more preferably a 6- to 8-membered ring.

  Examples of the structure of ring A include cyclobutene, cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene, cycloheptene, cycloheptadiene, cycloheptatriene, cyclooctene, cyclooctadiene, cyclooctatriene, cyclononene, cyclononadiene, cyclononatriene, Examples include cycloalkene structures such as cyclononatetraene. Of these, cycloalkane monoenes such as cyclopentene, cyclohexene, cycloheptene, and cyclooctene are preferable.

  In formula (11), for example, n is an integer of 0 to 6 and is m or less (where m is a value obtained by subtracting 3 from the number of members of ring A). n is preferably an integer of 0 to 5, more preferably an integer of 0 to 3, and still more preferably an integer of 0 to 2. When n is 1 or more, the hydrogen atom bonded to the carbon atom constituting the ring A is substituted with Y.

In formula (11), X and Y are organic groups or polar functional groups. Examples of the organic group as X and Y include, for example, alkyl group, alkoxy group, alkylthiooxy group (alkylthio group), alkyloxycarbonyl group, alkylsulfonyl group, aryl group, aralkyl group, aryloxy group, arylthiooxy Examples include a group (arylthio group), an aryloxycarbonyl group, an arylsulfonyl group, an amide group (—NHCOR), a sulfonamide group (—NHSO ₂ R), a carboxy group (carboxylic acid group), and a cyano group. Examples of the polar functional group include a halogeno group, a hydroxyl group, a nitro group, an amino group, and a sulfo group (sulfonic acid group).

  As an organic group or polar functional group which is an example of X, an alkyl group, an alkyloxycarbonyl group or an aryl group is preferable, and an alkyl group or an aryl group is more preferable. In this case, the number of carbon atoms of the alkyl group is preferably 1 to 6 if it is a linear or branched alkyl group, more preferably 1 to 4, and 4 to 7 if it is an alicyclic alkyl group. Preferably, it is 5-6. 6-10 are preferable and, as for carbon number of an aryl group, More preferably, it is 6-8. Specifically, preferred examples of the organic group or polar functional group of X include a methyl group, an ethyl group, an isopropyl group, an isobutyl group, a t-butyl group, a cyclopentyl group, a cyclohexyl group, and a phenyl group.

As the organic group or polar functional group as an example of Y, among the above, an alkyl group, an alkoxy group, a halogeno group, a phenyl group, an alkoxycarbonyl group (ester group), an amide group, a sulfonamide group, and a hydroxyl group are preferable. An alkyl group or a hydroxyl group is preferable. In this case, 1-5 are preferable, as for carbon number of an alkyl group, More preferably, it is 1-3, More preferably, it is 1-2. Specifically, preferred examples of the organic group or polar functional group as Y include a methyl group, an ethyl group, and a hydroxyl group.
When n is 2 or more and a plurality of Y are present, each Y may be the same or different. When n is 2 or more, a plurality of Ys may be bonded to different carbon atoms, or two Ys may be bonded to one carbon atom.

  In formula (11), ring B is an aromatic hydrocarbon ring, an aromatic heterocycle, or a condensed ring containing these ring structures, which may have a substituent. Examples of the ring B include rings having the structures of the following formulas (A-1) to (A-12), and rings in which one or more hydrogen atoms of these rings are substituted with an arbitrary substituent. Among these, a benzene ring (A-1), a naphthalene ring (A-2, A-3), or a ring substituted with the following substituents is preferable, and a benzene ring (A-1) or a benzene ring (A- A ring in which the following substituent is substituted in 1) is more preferable. Here, examples of the substituent include the groups described above as the organic group or polar functional group as examples of X and Y, and among them, an alkyl group (particularly preferably a linear or straight chain having 1 to 4 carbon atoms) Branched alkyl group), aryl group, alkoxy group; alkylthio group (particularly preferably 1 to 2 carbon atoms), electron donating group such as amino group, amide group, sulfonamide group, halogeno group (particularly preferred is chloro Group, a bromo group, etc.), an alkoxycarbonyl group (ester group), a carboxy group (carboxylic acid group), a sulfo group (sulfonic acid group), a nitro group and the like are preferable, and an electron attractive group is particularly preferable. The number of substituents in ring B may be one or two or more.

  The above formulas (A-1) to (A-12) represent the ring B including a part of the pyrrole ring. For example, the formula (A-1) is indicated by an arrow a in the figure below. The β-position carbon atom of the pyrrole ring and the α-position carbon atom of the pyrrole ring indicated by the arrow b in the following formula are represented.

Note that R ^e1 and R ^e2 which are specific structural units in the formula (9) having a squarylium skeleton may be the same structure or different.

  A particularly preferred squarylium-based compound has a squarylium skeleton of formula (9), and in the structural unit of formula (11), ring A is cyclohexene, cycloheptene, or cyclooctene, and X is an alkyl having 1 to 4 carbon atoms. A compound in which ring B is a benzene ring (A-1) or a naphthalene ring (A-2, A-3). In this particularly preferred oxocarbon compound, when ring B has a substituent, the substituent is preferably an alkyl group, a trihalogenomethyl group, a phenyl group, an alkoxy group, a cyano group, a carboxyl group, or a halogeno group.

  Although the manufacturing method of the squarylium type compound which has a specific structural unit shown by the said Formula (11) which is one of the suitable squarylium type compounds used for this invention is not specifically limited, For example, following formula (13):

  (In formula (13), ring A, ring B, X, Y, and n are the same as those in formula (11)). A pyrrole ring-containing compound represented by the formula is used as an intermediate raw material, and this is reacted with squaric acid. be able to.

The pyrrole ring-containing compound used as an intermediate raw material can be synthesized by appropriately adopting known synthetic techniques. For example, a pyrrole ring-containing compound can be synthesized by a synthesis method described in the following paper.
SAJJADIFAR ET AL: 'New 3H-Indole Synthesis by Fischer's Method. Part I.' Molecules 2010, no. 15, April 2010, pages 2491-2498

  In addition, the squarylium compound having the specific structural unit represented by the above formula (11) can be synthesized by appropriately adopting a known synthesis method in which a pyrrole ring-containing compound and squaric acid are reacted. For example, a squarylium compound is synthesized by a synthesis method described in a paper such as Serguei Miltsov et al. (“New Cyanine Dyes: Norindosquarocyanines”, Tetrahedron Letters, Volume 40, Issue 21, May 21, 1999, p. 4067-4068). can do.

  The obtained squarylium-based compound can be appropriately purified by known purification means such as filtration, silica gel column chromatography, alumina column chromatography, sublimation purification, recrystallization, and crystallization as necessary.

  In Formula (12), * represents a binding site to the squarylium skeleton represented by Formula (9), and the carbon atom (carbon atom indicated by an arrow in Formula (12)) bound to the squarylium skeleton is It is characterized in that it forms an aromatic ring.

In formula (12), at least one of R ^f1 and R ^f5 is an organic group or a polar functional group containing a nitrogen atom or an oxygen atom. Preferably, one of R ^f1 and R ^f5 is —NHR ^g1 or a hydroxyl group, and the other is a hydrogen atom, a hydroxyl group, a halogen atom, an alkyl or alkoxy group having 1 to 6 carbon atoms, —NR ^g2 R ^g3 , Or ^-NRg4 . R ^{g1 to} R ^g3 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, —S (═O) ₂ —R ^g5 , or —C (═O) —R ^g6 (R ^g5 , R ^g6 is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl or araryl group having 6 to 11 carbon atoms. R ^g4 is a cycloalkyl group having 3 to 9 members, or a part of —CH ₂ — in the cycloalkyl group is —O—, —S—, —Se—, —S (═O) _2. —, —C (═O) —, or —NR ^g7 — (R ^g7 is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 11 carbon atoms, or A cycloalkyl group having 3 to 9 members and substituted with an (araryl group). R ^f1 and R ^f5 are preferably either —NHR ^g1 or a hydroxyl group.

In Formula (12), R ^f2 and R ^f4 are each independently an organic group, a polar functional group, or a hydrogen atom. Examples of the organic group as an example of R ^f2 and R ^f4 include an alkyl group, an alkoxy group, an alkylthiooxy group (alkylthio group), an alkyloxycarbonyl group, an alkylsulfonyl group, an aryl group, an aralkyl group, an aryloxy group, and an aryl group. Examples include a ruthiooxy group (arylthio group), an aryloxycarbonyl group, an arylsulfonyl group, an amide group (—NHCOR), a sulfonamide group (—NHSO ₂ R), a carboxy group (carboxylic acid group), and a cyano group. Examples of the polar functional group include a halogeno group, a hydroxyl group, a nitro group, an amino group, and a sulfo group (sulfonic acid group).

In Formula (12), R ^f3 is an organic group or a polar functional group containing a nitrogen atom, and R ^f3 is preferably NR ^g8 R ^g9 or NR ^g10 . R ^g8 and R ^g9 are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or —C (═O) —R ^g11 (R ^g11 may have a hydrogen atom or a substituent. A good alkyl group having 1 to 20 carbon atoms, or an aryl group or araryl group having 6 to 11 carbon atoms). R ^g10 is a cycloalkyl group having 3 to 9 members, or a part of —CH ₂ — in the cycloalkyl group is —O—, —S—, ^—Se— , —S (═O) _2. The number of members substituted with —, —C (═O) —, —CHR ^g12 — or —CR ^g13 R ^g14 — (R ^{g12 to} R ^g14 are each an alkyl group having 1 to 5 carbon atoms) is 3 to 9 members. A cycloalkyl group; When R ^f3 is NR ^g10 , R ^f3 may be bonded to R ^f2 or R ^f4 to form a ring.

  In addition, in Formula (12), although the structure of the squarylium type compound which has a benzene ring which has a substituent is shown, the squarylium type compound which has polycyclic aromatic hydrocarbons, such as a naphthalene ring, may be sufficient. A squarylium-based compound having a polycyclic aromatic hydrocarbon can be a dye having an absorption maximum in a relatively large wavelength region (around 800 nm).

  The method for producing a squarylium compound having a specific structural unit represented by the above formula (12), which is one of the preferred squarylium compounds used in the present invention, is not particularly limited, and a known synthesis method is appropriately employed. Can be synthesized.

<Croconium-based compounds (croconium-based dyes)>
As the croconium-based compound, in the above formula (10), R ^e3 and R ^e4 are more preferably each independently a structural unit represented by the following formula (11). R ^e3 and R ^e4 may be the same or different.

(In the formula (11),
Ring A is a 4-9 membered unsaturated hydrocarbon ring.
X and Y are each independently an organic group or a polar functional group.
n is an integer of 0 to 6 and m or less (where m is a value obtained by subtracting 3 from the number of members of ring A), and when n is 2 or more, a plurality of Ys are the same. It may be different or different.
Ring B is an optionally substituted aromatic hydrocarbon ring, aromatic heterocyclic ring or condensed ring containing these ring structures.
In addition, * represents the coupling | bond part with the 5-membered ring in Formula (10). )

<Solvent>
It is preferable that the composition for resin layers contains the solvent from a viewpoint of improving applicability | paintability. Solvents are not particularly limited, but monoalcohols; glycols; cyclic ethers; glycol monoethers; glycol ethers; esters of glycol monoethers (for example, propylene glycol monomethyl ether acetate); alkyl esters; ketones Aromatic hydrocarbons; halogenated aromatic hydrocarbons; aliphatic hydrocarbons; amides; For the resin layer composition containing a phthalocyanine-based compound, among those described above, PGMEA (2-acetoxy-1-methoxypropane), N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylacetamide, Cyclopentanone is particularly preferred. In addition, since the oxocarbon-based compound has high durability in a solvent having a small dipole moment, a solvent having a dipole moment of 4D or less is used for the resin layer composition containing the oxocarbon-based compound. Preferably, a solvent having a dipole moment of 3.5D or less is more preferable, and a solvent having a dipole moment of 3D or less is particularly preferable. As specific examples of such a solvent, for example, cyclopentanone, o-dichlorobenzene, PGMEA, ethylcyclohexane, xylene, trimethylbenzene, limonene and the like are preferable. Among the above-mentioned, cyclopentanone, o-dichlorobenzene, trimethylbenzene, ethylcyclohexane, xylene, and limonene are particularly preferable.
These solvent may be used by 1 type and may be used as 2 or more types of mixed solvents. Moreover, it is preferable that the water content in a solvent is 5 mass% or less.

  The content of the solvent in the resin layer composition is preferably 100 to 4000 parts by mass, more preferably 300 to 3000 parts by mass, and further preferably 500 to 2000 parts by mass with respect to 100 parts by mass of the resin. is there.

<Method for preparing resin layer composition>
The preparation method of the composition for resin layers is not specifically limited, It can obtain by mixing the said containing component by a normal method. When mixing the components, if necessary, each component or mixture can be heated and mixed to achieve a uniform composition. As heating temperature, Preferably it is 20-140 degreeC, More preferably, it is 40-120 degreeC.

  As a mixing method, it can prepare by mixing and dispersing using various mixers and dispersers. A dispersion process and a mixing process are not specifically limited, What is necessary is just to perform by a normal method. Further, it may further include other steps that are normally performed.

  In preparing the resin layer composition, the order of adding and mixing the components can be selected as appropriate. After adding and mixing the dye to the poly (amide) imide resin, a solvent may be further added and mixed, or the poly (amide) imide resin and the dye may be added to the solvent and mixed.

<Method for forming resin layer>
As a method for forming the resin layer, a method in which the resin layer composition is applied on a glass substrate on which an underlayer has been formed and dried by heating is suitable. The resin layer is preferably formed by coating, specifically, spin coating method, casting method, roll coating method, spray coating method, bar coating method, dip coating method, screen printing method, flexographic printing method, inkjet method. From the viewpoint of reducing the deviation of the coating layer on the substrate, the spin coating method is more preferable. When forming a coating film by the spin coat method, the solvent is (semi-) dried while rotating the base material coated with the resin layer composition at 500 to 4000 rpm for about 10 to 60 seconds at around room temperature (25 ° C.). However, the (semi) drying of the solvent may be performed at other than the rotation. Here, (semi) drying may mean that the solvent may be completely removed or a trace amount of residual solvent may be contained.

(Near-infrared cut filter)
The near-infrared cut filter of the present invention has an anti-reflection and / or anti-glare layer and an anti-scratch performance for reducing reflection of a fluorescent lamp or the like on the outside air, in addition to the glass substrate, the base layer, and the resin layer. A layer having a transparent layer, a transparent substrate having other functions, glass, a filter, or the like may be laminated. Moreover, the near-infrared cut filter of this invention is equipped with the layer (henceforth a general layer) containing resin other than a polyimide resin and a polyamidoimide resin other than a glass substrate, a base layer, and a resin layer, or multiple layers. The general layer may be provided at any position as long as it is above the base layer. For example, the general layer may be provided between the base layer and the resin layer, or may be provided on the resin layer. When the resin layer has a multilayer structure, the general layer is formed on the resin layer. Although it may be provided so that it may be pinched | interposed, it is preferable that the general layer is provided on the resin layer.

  In the present invention, it is preferable that a near-infrared reflective film is further laminated. The near-infrared reflective film is a film having the ability to reflect near-infrared light. Examples of such a near-infrared reflective film include an aluminum vapor-deposited film, a noble metal thin film, a resin film in which metal oxide fine particles mainly containing indium oxide and containing a small amount of tin oxide are dispersed, a high refractive index material layer, and a low refractive index. A dielectric multilayer film or the like in which material layers are alternately stacked can be used. The near-infrared reflective film may be provided on one side of the glass substrate or on both sides. When it is provided on one side, it is excellent in production cost and manufacturability, and when it is provided on both sides, it is possible to obtain a near-infrared cut filter having high strength and less warpage. Furthermore, by laminating such a near-infrared reflective film, a filter that can cut near-infrared rays more reliably can be obtained.

  Among the near-infrared reflective films, it is preferable to use a dielectric multilayer film in which high refractive index material layers and low refractive index material layers are alternately laminated. As a material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of 1.7 to 2.5 is usually selected. Examples of the material constituting the high refractive index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; silicon nitride Nitrides such as oxides, mixtures of the nitrides and the like, and those doped with metals or carbon such as aluminum or copper (for example, tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO)), etc. Can be mentioned. As a material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of 1.2 to 1.6 is usually selected. Examples of the material constituting the low refractive index material layer include silica, alumina, lanthanum fluoride, magnesium fluoride, and aluminum hexafluoride sodium.

(Other)
The composition for base layers and the composition for resin layers may contain a suitable additive according to the objective. For example, you may contain in the range of 0.00001 mass% or more and 10 mass% or less with respect to 100 mass% of total amount (solid content) of each said composition. Specific examples of additives include curing agents, leveling agents, pigments, pigment dispersants, UV absorbers, antioxidants, viscosity modifiers, light stabilizers, metal deactivators, peroxide decomposing agents, and fillers. Agent, reinforcing material, plasticizer, lubricant, anticorrosive agent, rust preventive agent, emulsifier, mold demolding agent, fluorescent whitening agent, organic flameproofing agent, inorganic flameproofing agent, anti-dripping agent, melt flow modifier , Antistatic agent, slipping agent, adhesion promoter, antifouling agent, surfactant, antifoaming agent, polymerization inhibitor, photosensitizer, surface improver, (near) infrared cut agent, silane coupling Examples include adhesion improvers, heat stabilizers, antibacterial and antifungal agents, flame retardants and the like other than the agents.
Moreover, the composition for base layers and the composition for resin layers may contain arbitrary appropriate organic fine particles or inorganic fine particles. Typically, these organic fine particles or inorganic fine particles are used for imparting a function (refractive index, conductivity, etc.) according to the purpose.
Specific examples of fine particles useful for increasing the refractive index of the resin layer and imparting conductivity include zinc oxide, titanium oxide, zirconium oxide, aluminum oxide, tin oxide, tin-doped indium oxide, antimony-doped tin oxide, indium-doped zinc oxide, and oxidation. Examples include indium and antimony oxide. Specific examples of the fine particles useful for lowering the refractive index of the resin layer include magnesium fluoride, silica, and hollow silica. Specific examples of the fine particles useful for imparting antiglare properties include inorganic particles such as calcium carbonate, barium sulfate, talc and kaolin; silicone resin, melamine resin, benzoguanamine resin, acrylic resin, polystyrene resin and the like in addition to the fine particles described above. And organic fine particles such as copolymer resins. These fine particles may be used alone or in combination of two or more.

Hereinafter, the present invention will be described in detail based on examples. However, the following examples are not intended to limit the present invention, and all modifications made without departing from the spirit of the preceding and following descriptions are included in the technical scope of the present invention.
Hereinafter, “%” indicates “mass%”, and “part” indicates “part by mass”.

  First, the evaluation method used in the examples will be described below.

(PCT (Pressure Cooker Test) test)
With respect to the test material (resin layer laminated substrate), the resin layer provided in the test material was cut with a cutter (A-300 manufactured by NTT), and 10 crosscut lines were arranged at intervals of 2 mm in each of the vertical and horizontal rows. By providing 81 squares of 4 mm ^2, a sample substrate for evaluation was produced. Next, the sample substrate for evaluation was placed in a high-pressure, high-temperature, high-humidity tank (personal pressure cooker PC-242HS-E (manufactured by Hirayama Seisakusho), operation mode 1) at 120 ° C., 2 atm and 100% humidity for 15 hours or 50 hours. Subsequently, at room temperature, a tape (3M (3M) Scotch (registered trademark) transparent adhesive tape, transparent beautiful color (registered trademark)) was applied so that air would not enter, and left for 10 seconds. Thereafter, the tape was peeled from the substrate within 1 second and evaluated according to the following criteria. Note that the tape was peeled off so that the peeling force was constant in any of the cells.
○: No peeling occurred in one square among the squares of the produced 81 square.
Δ: Peeling occurred in 1 to 9 squares out of the produced 81 squares.
X: Peeling occurred in 10 to 81 squares among the squares of 81 squares produced.

(Polyimide resin A)
A flask is charged with 5 parts of 1,2,4,5-cyclohexanetetracarboxylic acid (manufactured by Aldrich, purity 95%) and 44 parts of acetic anhydride (manufactured by Wako Pure Chemical Industries), and the reactor is filled with nitrogen gas while stirring. Replaced. The temperature was raised to the reflux temperature of the solvent under a nitrogen gas atmosphere, and the solvent was refluxed for 10 minutes. Thereafter, the mixture was cooled to room temperature with stirring to precipitate crystals. The precipitated crystals were separated into solid and liquid and dried to obtain crystals of the desired product (1,2,4,5-cyclohexanetetracarboxylic dianhydride). Subsequently, 4,4′-diaminodiphenyl ether (manufactured by Wako Pure Chemical Industries, Ltd.) 0.89 under a nitrogen stream in a flask equipped with a thermometer, stirrer, nitrogen introducing tube, dropping funnel with side tube, Dean Stark, and cooling tube. And 7.6 parts of N-methyl-2-pyrrolidone as a solvent were dissolved, and then 1 part of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was kept solid at room temperature for 1 hour. Over a period of 2 hours and stirred at room temperature for 2 hours. 2.6 parts of xylene as an azeotropic dehydrating agent was added and reacted at 180 ° C. for 3 hours, and the product water refluxed by Dean Stark was azeotropically separated. Xylene was distilled off while the temperature was raised to 190 ° C., followed by cooling to obtain an N-methyl-2-pyrrolidone solution of polyimide. This N-methyl-2-pyrrolidone solution was further diluted with γ-butyrolactone to obtain a polyimide resin solution having a solid content of 3%. 1 part of this polyimide resin solution was reprecipitated with 50 parts of methanol and separated into solid and liquid. The solid-liquid separated polyimide resin was dissolved in γ-butyrolactone to obtain a polyimide resin solution having a solid content of 3% again, and re-precipitated with 50 parts of methanol in the same manner as described above, followed by solid-liquid separation. The resin obtained by reprecipitation was dried to obtain polyimide resin A.

(Polyamideimide resin B)
A glass container equipped with a stirrer, a thermometer, and a nitrogen gas inlet tube was charged with 27.63 g (0.138 mol) of 4,4-oxydianiline, 300 g of dimethylacetamide (DMAc), and 13.96 g (0.138 mol) of triethylamine. And stirred for a certain time to prepare a uniform solution. To this homogeneous solution, 30.00 g (0.138 mol) of anhydrous cyclohexanetricarboxylic acid chloride was slowly added so as not to exceed 40 ° C. while cooling with ice. After the addition was completed, the ice cooling was stopped and the reaction was allowed to proceed at room temperature for 2 hours. Then, 0.21 g (0.002 mol) of aniline was added, and the mixture was further stirred for 30 minutes to prepare a polyamide solution having a viscosity of 19 ps. To the polyamide solution thus prepared, 26 mL of acetic anhydride and 12 mL of pyridine were added and stirred at 55 ° C. for 2 hours to perform imidization. The obtained reaction solution was added to a water / methanol mixed solution, and the obtained powder was washed with water and dried to obtain a polyamideimide resin B.

(Phthalocyanine D)
<Process for producing intermediate C>
A 1000 ml four-necked separable flask was charged with 54 g (0.27 mol) of tetrafluorophthalonitrile, 34.5 g (0.59 mol) of potassium fluoride, and 126 g of acetone, and 3-chloro-4-hydroxybenzoate was added to the dropping funnel. 127 g (0.55 mol) of acid methoxyethyl ester and 216 g of acetone were charged. Specifically, the 3-chloro-4-hydroxybenzoic acid methoxyethyl ester solution was dropped from the dropping funnel over about 2 hours while stirring the reaction vessel under ice-cooling, and stirring was further continued for 2 hours. Then, it stirred overnight, raising reaction temperature to room temperature slowly. The reaction solution was filtered, acetone was distilled off from the filtrate with a rotary evaporator, and methanol was added for recrystallization. The obtained crystals were filtered and vacuum-dried to obtain 108.7 g of intermediate C (yield 64.8%). The reaction in the production process of this intermediate C is simplified and shown in the following chemical formula (14).

<Production process of phthalocyanine D>
A 200 ml four-necked flask was charged with 20.0 g (0.032 mol) of the intermediate C, 2.57 g (0.0081 mol) of zinc (II) iodide, and 30.0 g of benzonitrile, and stirred at 160 ° C. After reacting for 24 hours, 52.7 g of methyl cellosolve was added to prepare a reaction solution. This reaction solution was dropped into a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was again stirred and washed with a mixed solution of methanol and water, suction filtered, and then dried at 90 ° C. for 24 hours using a vacuum dryer, and 17.78 g ( Yield 86.7%). The reaction in the production process of this phthalocyanine D is simplified and shown in the following chemical formula (15).

  The phthalocyanine D has a structure in which the substituent E shown in the chemical formula (15) is substituted on each of the portions indicated by “*” (total 8) in the main skeleton in the structure.

(Phthalocyanine G)
<Process for producing intermediate F>
In a 1000 ml three-necked reaction vessel, 100 g (0.58 mol) of 3-nitrophthalonitrile, 159.7 g (1.16 mol) of potassium carbonate, 104.6 g (0.64 mol) of 2,6-dichlorophenol, and 400 g of acetonitrile are added. Prepared. After stirring and reacting at 60 ° C. overnight, the reaction solution was filtered, acetonitrile was removed from the filtrate by a rotary evaporator, and recrystallization was performed by adding methanol. The obtained crystals were filtered and vacuum-dried to obtain 100.9 g of Intermediate F (yield 60.2%).
The reaction in the production process of this intermediate F is simplified and shown in the following chemical formula (16).

<Production process of phthalocyanine G>
A 300 ml four-necked flask was charged with 60.0 g (0.21 mol) of the intermediate F, 5.65 g (0.057 mol) of copper (I) chloride, and 140.0 g of diethylene glycol monomethyl ether while stirring at 160 ° C. After reacting for 24 hours, 100.0 g of methyl cellosolve was added to prepare a reaction solution. This reaction solution was dropped into a mixed solution of methanol and water to precipitate crystals, and a wet cake was obtained after suction filtration. The obtained cake was again stirred and washed with a mixed solution of methanol and water, suction filtered, and then dried at 90 ° C. for 24 hours using a vacuum dryer, to obtain 51.48 g of the target phthalocyanine G ( Yield 80.4%). The reaction in the production process of phthalocyanine G is simplified and shown in the following chemical formula (17).

  In the structure, phthalocyanine G is substituted with the substituent I shown on the right side in four of the parts indicated by “*” in the main skeleton (total 8) and the substituents shown on the lower side in the remaining four ( That is, the hydrogen atoms are each substituted or bonded. Further, phthalocyanine G has absorption maximums at 630 nm and 701 nm, and the wavelength having the largest absorbance (absorption maximum wavelength) is 701 nm.

  The structural formulas of squarylium compounds 01 to 09 used in the examples are shown below. The squarylium compounds 01 to 06 were produced by the synthesis methods described in the papers mentioned in the specification. The squarylium compounds 07 and 08 were prepared by the method described below. As the squarylium compound 09, a squarylium compound disclosed in Formula 17 of US Pat. No. 5,543,086 was used.

(Method for producing squarylium compound 07)
1) Production process of intermediate raw material 07-1 (1- (3-nitrophenyl) piperidine) In a 200 mL two-necked flask, 7.06 g (0.050 mol) of 3-fluoronitrobenzene and 12.77 g (0.150 mol) of piperidine The mixture was allowed to react for 12 hours under reflux conditions while stirring with a magnetic stirrer under nitrogen flow (5 mL / min). After completion of the reaction, the solution was cooled to room temperature, and then the reaction solution was added to ion exchanged water and extracted with ethyl acetate. The obtained organic layer is concentrated by an evaporator, and the concentrated solution is purified by column chromatography on silica gel (developing solvent: ethyl acetate) to obtain an intermediate raw material 07-1 (1- (3-nitrophenyl) as a target product. 10.15 g (piperidine) (yield based on 3-fluoronitrobenzene: 98.4 mol%) was obtained.

2) Production Step of Intermediate Raw Material 07-2 (1- (3-Aminophenyl) piperidine) In a 200 mL two-necked flask, 10.11 g (0.049 mol) of Intermediate Raw Materials 07-1 and 40.91 g (0.181 mol) ) And a concentrated hydrochloric acid (204 g) as a solvent, and stirred under a nitrogen flow (5 mL / min) with a magnetic stirrer at an internal temperature of 100 ° C. for 30 minutes. Reacted. After completion of the reaction, the solution was cooled to room temperature, and white crystals obtained by filtration were obtained. The obtained crystals were added to a 20% by mass aqueous sodium hydroxide solution for neutralization, and then extracted with ethyl acetate. The obtained organic layer is concentrated with an evaporator, and the concentrated solution is purified by column chromatography on silica gel (developing solvent: ethyl acetate) to obtain an intermediate raw material 07-2 (1- (3-aminophenyl) as a target product. 7.9 g (piperidine) (yield based on intermediate raw material 07-1: 91.0 mol%) was obtained.

3) Production process of intermediate raw material 07-3 (4-methyl-N- (3- (piperidin-1-yl) phenyl) benzenesulfonamide) In a 200 mL two-necked flask, 1.55 g (0.009 mol) of intermediate A raw material composition consisting of raw material 07-2, 1.97 g (0.010 mol) tosyl chloride and 1.74 g (0.017 mol) triethylamine, and 40 g of chloroform as a solvent were added, and under nitrogen flow (5 mL / min ), And allowed to react for 12 hours at room temperature with stirring using a magnetic stirrer. After completion of the reaction, the reaction solution was added to ion-exchanged water and extracted with ethyl acetate. The obtained organic layer is concentrated with an evaporator, and the concentrated solution is purified by column chromatography on silica gel (developing solvent: ethyl acetate) to obtain the intermediate product 07-3 (4-methyl-N- (3 -(Piperidin-1-yl) phenyl) benzenesulfonamide) 2.6 g (yield based on intermediate raw material 07-2: 98.1 mol%) was obtained.

4) Production process of squarylium compound 07 In a 300 mL three-necked flask, a raw material composition consisting of 2.31 g (0.008 mol) of intermediate raw material 07-3, 0.43 g (0.004 mol) of squaric acid, and 1 as a solvent Add 23 g butanol and 23 g toluene, stir with a magnetic stirrer under nitrogen flow (5 mL / min), and remove the eluted water using a Dean-Stark apparatus for 3 hours under reflux conditions Reacted. After completion of the reaction, the reaction solution was concentrated with an evaporator, the solvent was distilled off, and 50 g of methanol was added for crystallization. The precipitated crystals were obtained by filtration, and the cake was rinsed with methanol to obtain a wet cake. The obtained washed cake was dried at 60 ° C. for 12 hours using a vacuum dryer to obtain 0.82 g (yield based on squaric acid: 29.5 mol%) of the target product squarylium compound 07.
The reaction in the production process of the squarylium compound 07 is simplified and shown below.

(Method for producing squarylium compound 08)
1) Production process of intermediate raw material 08-1 (1- (3-nitrophenyl) morpholine) Production process of intermediate raw material 07-1 except that 13.07 g (0.150 mol) of morpholine was used as the raw material composition. In the same manner, 8.25 g (yield based on 3-fluoronitrobenzene: 79.2 mol%) of intermediate raw material 08-1 (1- (3-nitrophenyl) morpholine) was obtained.

2) Production process of intermediate raw material 08-2 (1- (3-aminophenyl) morpholine) Intermediate raw material 07- except that 8.25 g (0.040 mol) of intermediate raw material 08-1 was used as a raw material composition. 2.28 g of intermediate raw material 08-2 (1- (3-aminophenyl) morpholine) (yield with respect to intermediate raw material 08-1: 32.3 mol%) was obtained by a method similar to that in Step 2.

3) Production step of intermediate raw material 08-3 (2,2,2-trifluoro-N- (3-morpholinophenyl) acetamide) As raw material composition, 1.38 g (0.008 mol) of intermediate raw material 08-2, Except for using 3.19 g (0.015 mol) of trifluoroacetic anhydride, intermediate raw material 08-3 (2,2,2-trifluoro-N -(3-morpholinophenyl) acetamide) (2.0 g, yield based on intermediate raw material 08-2: 96.0 mol%) was obtained.

4) Production process of squarylium compound 08 As the raw material composition, 0% of squarylium compound 08 was prepared in the same manner as the production process of squarylium compound 07 except that 2.0 g (0.007 mol) of intermediate raw material 08-3 was used. .64 g (yield based on squaric acid: 23.7 mol%) was obtained.

(Underlayer composition (undercoat solution))
<Preparation of undercoat solution>
Mixtures P to S were prepared by mixing and dissolving a predetermined amount of a silane coupling agent, ethanol, water, and a formic acid aqueous solution at the composition ratio shown in Table 1. Next, 1 part of each of the mixed liquids P to S was diluted and dissolved with 99 parts of ethanol. 1-4 were produced. Undercoat liquid No. 1-4 are as shown in Table 2. In addition, the following four are used as a silane coupling agent.
Shin-Etsu Silicone KBM-903 (3-aminopropyltrimethoxysilane)
Z-6020 (3- (2-aminoethyl) aminopropyltrimethoxysilane) manufactured by Toray Dow Corning
Z-6040 (3-glycidoxypropyltrimethoxysilane) manufactured by Toray Dow Corning
Z-6043 (2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) manufactured by Toray Dow Corning

Example 1
<Application of undercoat solution>
1 cc of the undercoat solution was dropped on a glass substrate (D263 Teco, manufactured by SCHOTT, 60 mm × 60 mm × 0.3 mm), and then 2200 rotations (rpm) using a spin coater (1H-D7 manufactured by Mikasa Co., Ltd.) over 3 seconds. ) And held at that number of rotations for 20 seconds, and then a base layer was formed so as to achieve 0 rotations (rpm) over 3 seconds. The glass substrate after forming the underlayer was dried at 100 ° C. for 10 minutes using a precision thermostat (DH611 manufactured by Yamato Kagaku Co., Ltd.) to obtain a glass substrate provided with the underlayer (hereinafter referred to as an underlayer laminated substrate). .

<Application of composition solution for resin layer>
8 parts of phthalocyanine D having an absorption maximum wavelength of 670 nm was mixed and dissolved in a solution of 100 parts of polyimide resin A and 1900 parts of γ-butyrolactone (GBL) to prepare a resin layer composition solution. After 0.6 cc of this resin layer composition solution was dropped on the underlayer of the underlayer laminated substrate (on the side opposite to the underlayer), a spin coater (1H-D7 manufactured by Mikasa Co., Ltd.) was used for 0.2 seconds. Over 1000 seconds (rpm), the resin layer was formed in such a manner that the number of rotations was maintained for 10 seconds, followed by 0 rotation (rpm) over 0.2 seconds. The glass substrate on which the resin layer was formed was subjected to initial drying at 100 ° C. for 3 minutes using a precision thermostat (DH611 manufactured by Yamato Kagaku Co., Ltd.) and then additional drying at 200 ° C. for 30 minutes to provide an underlayer and a resin layer. A glass substrate (hereinafter referred to as a resin layer laminated substrate) was obtained. The thickness of the resin layer after drying was 1 μm. In addition, the film thickness of the resin layer after drying measured the thickness of the resin layer laminated substrate and the thickness of the base layer laminated glass substrate using a micrometer, and the difference between the two is the film thickness of the resin layer after drying. did. Moreover, the absorption spectrum (transmission spectrum) of the resin layer laminated substrate was measured using a spectrophotometer (Shimadzu Corporation UV-3100), and the wavelength at which the absorption maximum was reached was defined as the maximum absorption wavelength.

(Examples 2 to 12, Comparative Examples 1 to 10)
In Example 1, the types of undercoat liquid, the types and amounts of resins, the types and amounts of pigments, the types and amounts of solvents, the temperature of initial drying, and the temperature and time of additional drying are as shown in Tables 3 and 4 A resin layer laminated substrate was obtained in the same manner as in Example 1 except for changing to. In addition to the polyimide resin A and the polyamideimide resin B, the following two resins are also used as the resin.
UDEL (registered trademark) P-1700 NT11 (polysulfone resin) manufactured by Solvay Specialty Polymers
Arton (registered trademark) resin (cyclic olefin resin) manufactured by JSR
The PCT test was done using the obtained resin layer laminated substrate. The composition of the resin layer laminated substrate and the results of the PCT test are summarized in Tables 3 and 4 below.

(Reference Example 1)
Based on the knowledge obtained in the present invention, a resin layer composition solution prepared in Example 1 was further added to a silane coupling agent (Shin-Etsu Silicone Co., Ltd.) on an uncoated glass substrate (D263 Teco manufactured by SCHOTT). After suspending 0.6 cc of the silane coupling agent-containing composition solution to which KBM-903 (manufactured KBM-903) was added, the spin coater (1H-D7 manufactured by Mikasa Co., Ltd.) was used to achieve 1000 rotations (rpm) over 0.2 seconds. The resin layer was formed by maintaining the number of rotations for 10 seconds and then rotating to 0 rotations (rpm) over 0.2 seconds. Specifically, the silane coupling agent-containing composition solution was prepared by mixing 8 parts of phthalocyanine D having an absorption maximum wavelength of 670 nm with a solution of 100 parts of polyimide resin A and 1900 parts of γ-butyrolactone (GBL). It was prepared by adding 3 parts of a ring agent (KBM-903 manufactured by Shin-Etsu Silicone).
The glass substrate on which the resin layer is formed is first dried at 100 ° C. for 3 minutes using a precision thermostat (DH611 manufactured by Yamato Scientific Co., Ltd.), and then additionally dried at 200 ° C. for 30 minutes. Obtained. As a result of performing a PCT test on the obtained test sample, the adhesion was good. The composition of the resin layer laminated substrate and the results of the PCT test are summarized in Table 5 below.
Therefore, a near-infrared absorbing dye, an amino group-containing silane coupling agent, and a poly (amide) imide resin that is a solvent-soluble resin are all contained in one composition solution, and a resin layer formed from the composition solution is provided. The usefulness of the near-infrared cut filter (without undercoat) was also confirmed.

  Since the near-infrared cut filter of the present invention is excellent in peel resistance, it can be used in various fields such as optical devices such as a display element and an imaging element. For example, it can be used for electronic parts such as a mobile phone camera, a digital camera, an in-vehicle camera, a surveillance camera, and a display element (LED, etc.).

Claims (6)

A near-infrared cut filter comprising a glass substrate, a base layer provided on the glass substrate, and a resin layer provided above the base layer,
The underlayer is formed from a composition containing a silane coupling agent having an amino group,
The near-infrared cut filter, wherein the resin layer contains at least one of a polyimide resin and a polyamideimide resin.   The near-infrared cut filter according to claim 1, wherein the resin layer contains at least one of a phthalocyanine dye and an oxocarbon dye, and the contained dye has an absorption maximum in a wavelength region of 600 to 900 nm. The near-infrared cut filter according to claim 1, wherein the polyimide resin is a polyimide resin represented by the following general formula (1).

(In the general formula (1), X ′ and Y ′ each independently contain a monocyclic or condensed polycyclic aliphatic group, or a monocyclic or condensed polycyclic aromatic group, A linking group that may have a substituent having 2 to 39 carbon atoms is shown.) The near-infrared cut filter according to claim 1 or 2, wherein the polyamide-imide resin is a polyamide-imide resin represented by the following general formula (2).

(In general formula (2), X ″ represents a trivalent organic group, and Y ″ represents a divalent organic group represented by the following general formula (3) or the following general formula (4).)

(In General Formula (3), R ¹ and R ³ represent a hydrogen atom or a nonionic and inert substituent,
R ² represents CH ₂ , CO, SO ₂ or O. )

(In general formula (4), R ¹ is the same as in general formula (3).)   The near-infrared cut filter according to claim 1, wherein the silane coupling agent has a primary amino group.   It is a composition for forming the said resin layer of the near-infrared cut filter of any one of Claims 1-5 by coating, Comprising: The said composition contains at least one of a polyimide resin and a polyamide-imide resin. A composition characterized by comprising: