JP2016164670A - Near-infrared ray cut filter and method for manufacturing near-infrared ray cut filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a near-infrared ray cut filter which does not cost too much, and is excellent in incident angle dependence and heat resistance.SOLUTION: A near-infrared ray cut filter comprises on a glass substrate: an organic polymer layer; and a near-infrared ray reflecting film made of a dielectric multilayer film.SELECTED DRAWING: None

Description

  The present invention relates to a near-infrared cut filter and a method for manufacturing a near-infrared cut filter. More specifically, the present invention has a structure in which an organic polymer layer and a near-infrared reflective layer made of a dielectric multilayer film are laminated on a glass substrate, and in particular, a visibility correction filter for a solid-state imaging device such as a CCD or CMOS. It is related with the near-infrared cut off filter suitable as.

  In recent years, televisions equipped with plasma display panels (PDPs) have been commercialized and have become widespread in ordinary households. This PDP is a display that operates using plasma discharge, but it is known that near infrared rays (wavelength: 800 to 1,000 nm) are generated during plasma discharge.

  On the other hand, in homes, near-infrared rays are often used for remote control of home appliances such as TVs, stereos or air conditioners, and also for information exchange by personal computers. It has always been pointed out that it is likely to cause malfunctions.

Therefore, many commercially available PDPs are provided with a filter function for cutting near infrared rays emitted from the front plate.
In addition, CCDs and CMOS image sensors, which are solid-state image pickup devices for color images, are used in video cameras, digital still cameras, mobile phones with camera functions, etc., and these solid-state image pickup devices are sensitive to near-infrared light at their light receiving parts. Therefore, it is necessary to correct visibility, and a near-infrared cut filter is often used.

As such a near-infrared cut filter, a type using a dielectric multilayer film and a type using a near-infrared absorber are known.
As a type of near infrared cut filter using a dielectric multilayer film, there are a type using a glass substrate as a base material (for example, Patent Document 1) and a type using a resin film (for example, Patent Document 2). However, near-infrared cut filters using glass as a substrate tend to have poor incident angle dependency. On the other hand, near-infrared cut filters using a resin as a base material tend to have poor reflow suitability.
In addition, the type using a near-infrared absorber has a problem that the cost is high and most of the near-infrared cut filter is made of glass, so that it is inferior in processing suitability and lightness.

JP 2011-121792 A JP 2009-258362 A

  An object of the present invention is to solve the above-mentioned problems of the prior art, and an object thereof is to provide a near-infrared cut filter that is not costly and has excellent incident angle dependency and heat resistance.

Based on the above problems, the inventor of the present application has made intensive studies. As a result, the above-mentioned problem can be obtained by forming a laminated body having a glass substrate, an organic polymer resin layer, and a near-infrared reflective film composed of a dielectric multilayer film. I found that the problem could be solved. Specifically, the above problems have been solved by means described in the following <1>, preferably <2> to <15>.
<1> A near-infrared cut filter having an organic polymer layer and a near-infrared reflective film made of a dielectric multilayer film on a glass substrate.
<2> The near-infrared cut filter according to <1>, wherein the organic polymer layer contains a near-infrared absorber.
<3> The glass substrate, the organic polymer layer, and the dielectric multilayer film are provided in this order, or the glass substrate, the dielectric multilayer film, and the organic polymer layer are provided in this order, according to <1> or <2> Near-infrared cut filter.
<4> The near-infrared cut filter according to any one of <1> to <3>, wherein the organic polymer layer is formed by spin coating.
<5> The near-infrared cut filter according to any one of <1> to <4>, wherein the organic polymer layer includes a polyimide resin.
<6> The near-infrared cut filter according to <5>, wherein the polyimide resin has a repeating unit represented by the following general formula (1) and / or general formula (2).
General formula (1)
(In general formula (1), R ¹ represents a tetravalent organic group. A plurality of R ¹ may be the same or different from each other. R ² represents a divalent organic group. R ² may be the same or different from each other, provided that at least one of the plurality of R ² is a group having an alicyclic group, and R ³ is a hydrogen atom or a carbon number of 1 to 20, respectively. Represents an organic group of
General formula (2)
(In the general formula, X and Y each contain a monocyclic or condensed polycyclic aliphatic group or a monocyclic or condensed polycyclic aromatic group, and have 4 carbon atoms. Represents a linking group of ˜30.)
<7> The polyimide resin is a polymer having a repeating unit represented by the general formula (2), and at least one of X and Y in the general formula (2) is monocyclic or condensed polycyclic. The near-infrared cut filter according to <6>, which is an aliphatic group.
<8> The polyimide resin is a polymer having a repeating unit represented by the general formula (2), wherein X in the general formula (2) is an aromatic group, and Y is monocyclic or condensed polycyclic. The near-infrared cut filter according to <6>, which is an aliphatic group of the formula.
<9> An organic polymer layer is formed on a glass substrate, and then a dielectric multilayer film is formed on the surface of the organic polymer layer by vapor deposition. Any one of <1> to <8> The near-infrared cut filter described.
<10> A near-infrared reflective film made of a dielectric multilayer film is formed on a glass substrate by vapor deposition, and then an organic polymer layer is formed on the surface of the near-infrared reflective film. <1> to <8 > The near-infrared cut filter of any one of>.
<11> The near-infrared cut filter according to any one of <1> to <10>, wherein the organic polymer layer is a layer formed by curing a curable composition.
<12> The near-infrared cut filter according to <11>, wherein the organic polymer layer is obtained by curing a curable composition containing a polymerizable monomer.
<13> One of the low refractive index layers includes silica (SiO ₂ ), and one of the high refractive index layers includes titania (TiO ₂ ), according to any one of <1> to <12>. Near-infrared cut filter.
<14> A solid-state imaging device using the near-infrared cut filter according to any one of <1> to <13>.
<15> The method for producing a near-infrared cut filter according to any one of <1> to <13>, comprising forming a dielectric multilayer film by vapor deposition.
<16> The method for producing a near-infrared cut filter according to <15>, comprising forming the organic polymer layer by spin coating.

  According to the present invention, it has become possible to provide a near-infrared cut filter that is not costly and that has excellent incident angle dependency and heat resistance.

It is the schematic which shows an example of the near-infrared filter of this invention. It is the schematic which shows another example of the near-infrared filter of this invention.

  Hereinafter, the contents of the present invention will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.

The near-infrared cut filter of the present invention is characterized by having an organic polymer layer and a near-infrared reflective film made of a dielectric multilayer film on a glass substrate. Hereinafter, the near infrared cut filter of the present invention will be described in detail.
FIG. 1 is a schematic cross-sectional view of an example of the near-infrared cut filter of the present invention, where 1 is a glass substrate, 2 is a near-infrared reflective film made of a dielectric multilayer film, and 3 is an organic polymer layer. ing. In this embodiment, a near-infrared reflective film 2 made of a dielectric multilayer film is provided on one surface of a glass substrate, and an organic polymer layer 3 is provided on the surface. The organic polymer layer 3 contains a near infrared absorber 4. However, in the present invention, the near-infrared absorber 4 does not necessarily have to be added. Further, in the present embodiment, the near-infrared reflective film 2 made of a dielectric multilayer film is also provided on the opposite surface of the glass substrate 1. However, in the present invention, it is sufficient that the near-infrared reflective film 2 composed of the organic polymer layer 3 and the dielectric multilayer film is provided on one surface of the glass substrate, and the surface on the opposite side of the glass substrate 1 is not necessarily required. The dielectric multilayer film is not essential. If it is provided on both sides, the symmetry of the layer structure increases, so that the substrate is not easily distorted. Conversely, the near-infrared reflective film 2 composed of the organic polymer layer 3 and the dielectric multilayer film may be provided on both surfaces of the glass substrate.
FIG. 2 is a schematic cross-sectional view of another example of the near-infrared cut filter of the present invention, and the reference numerals in the figure are the same as those in FIG. In the embodiment of FIG. 2, the organic polymer layer 3 is provided on the surface of the glass substrate 1, and the near-infrared reflective film 2 made of a dielectric multilayer film is provided on the surface. The organic polymer layer 3 contains a near infrared absorber 4. However, in the present invention, the near-infrared absorber 4 does not necessarily have to be added. Further, in the present embodiment, the near-infrared reflective film 2 made of a dielectric multilayer film is also provided on the opposite surface of the glass substrate 1. However, in the present invention, it is sufficient that the near-infrared reflective film 2 composed of the organic polymer layer 3 and the dielectric multilayer film is provided on one surface of the glass substrate, and the surface on the opposite side of the glass substrate 1 is not necessarily required. The dielectric multilayer film is not essential. If provided on both sides, the symmetry of the layer structure increases, so that the substrate is less likely to be distorted. Conversely, the near-infrared reflective film 2 composed of the organic polymer layer 3 and the dielectric multilayer film may be provided on both surfaces of the glass substrate.
The near-infrared cut filter of the present invention may have other constituent layers in any of the embodiments, but substantially includes a glass substrate, a near-infrared reflective film made of a dielectric multilayer film, and It is preferably composed of an organic polymer layer, and more preferably composed of one glass substrate, a near-infrared reflective film composed of one dielectric multilayer film, and two organic polymer layers.

  0.01-1 mm is preferable and, as for the total thickness of the near-infrared cut filter of this invention, 0.03-0.5 mm is more preferable.

<Glass substrate>
The kind of glass substrate in the present invention is not particularly defined, and a known glass substrate used for a near infrared cut filter can be widely used. As thickness of a glass substrate, 0.01-1 mm is preferable, 0.02-0.5 mm is more preferable, 0.03-0.2 mm is further more preferable.
It is preferable that the glass substrate used by this invention does not contain a near-infrared absorber substantially. “Substantially not containing” means not actively adding, for example, 1% by mass or less of the glass substrate.

<Organic polymer layer>
The type of the organic polymer layer in the present invention is not particularly defined, but preferably has high heat resistance. When the heat resistance is high, the organic polymer layer is not easily damaged even when a dielectric multilayer film is formed on the surface of the organic polymer layer by vapor deposition. For example, the glass transition temperature of the organic polymer layer is preferably 250 ° C. or higher, and more preferably 300 ° C. or higher. The upper limit is not particularly defined, but is, for example, 450 ° C. or lower.
The thickness of the organic polymer layer is preferably 0.1 to 10 μm, and more preferably 0.3 to 5 μm. The organic polymer layer may be composed of one layer or may be composed of two or more layers.

  The organic polymer layer preferably comprises 95% by mass or more of an organic polymer. The organic polymer layer preferably used in the present invention is preferably a layer mainly composed of a polyimide resin or a layer obtained by curing a curable composition by polymerization.

  The organic polymer layer is preferably formed by applying a composition obtained by blending an organic polymer with various additives (for example, a near-infrared absorber) into a film shape by coating and curing.

  As various additives mix | blended with the organic polymer layer in this invention, a near-infrared absorber, surfactant, antioxidant, and a heat stabilizer are illustrated, and it is preferable that a near-infrared absorber is included at least.

<Near infrared absorber>
The organic polymer layer in the present invention preferably contains a near infrared absorber. Examples of near-infrared absorbers include squarylium dyes, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, quatarylene dyes, dithiol metal complex dyes, transition metal oxide compounds, and “e-ex-color IR- 10 "," EEX COLOR IR-12 "," EEX COLOR IR-14 "," EEX COLOR HA-1 "," EEX COLOR HA-14 "(all trade names, manufactured by Nippon Shokubai Co., Ltd.), “SIR-128”, “SIR-130”, “SIR-132”, “SIR-152”, “SIR-159”, “SIR-162” (all trade names, manufactured by Mitsui Chemicals), “Kayasorb IRG” -022 "," Kayasorb IRG-023 "," Kayasorb IRG-040 "(all trade names, Nippon Kayaku Co., Ltd.) ), “CIR-1081” (trade name, manufactured by Nippon Carlit), “NIR-IM1”, “NIR-AM1” (all trade names, manufactured by Nagase ChemteX), cesium tungsten oxide compound (Sumitomo Metal Mining Co., Ltd.) , Lumogen IR765, Lumogen IR788 (BASF), ARS670T, IRA800, IRA850, IRA868 (Exciton) are preferred.
Spectral characteristics can be remarkably improved by adding a near-infrared absorber. The addition amount of the near-infrared absorber is preferably contained in the organic polymer layer in a proportion of 0.1 to 50% by weight, more preferably in a proportion of 0.5 to 30% by weight, More preferably, it is contained in a proportion of 10% by weight.

<Polyimide resin>
The polyimide resin used in the present invention is not particularly defined, and known polyimide resins can be widely used. In the present invention, a polymer having a repeating unit represented by the following general formula (1) and / or general formula (2) is preferable.
General formula (1)
(In general formula (1), R ¹ represents a tetravalent organic group. A plurality of R ¹ may be the same or different from each other. R ² represents a divalent organic group. R ² may be the same as or different from each other, provided that at least one of the plurality of R ² is a group having an alicyclic group, and R ³ represents a hydrogen atom or an organic group, respectively. )

(A) Resin having a repeating unit of the general formula (1) The repeating unit represented by the general formula (1) includes the two carbonyl groups sandwiched between two carbonyl groups in the general formula (1). structure and acid component is composed of a general formula (1) -NH-R ² -NH- represented by partial structure a is a diamine component in.
The tetravalent organic group R ¹ preferably has 4 to 30 carbon atoms, and more preferably a tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group. . A plurality of R ¹ present in the resin (a) may be the same or different.
Examples of the monocyclic aromatic group in the tetravalent organic group R ¹ include a benzene ring group and a pyridine ring group.
Examples of the condensed polycyclic aromatic group in the tetravalent organic group R ¹ include a naphthalene ring group and a perylene ring group.
Examples of the monocyclic aliphatic group in the tetravalent organic group R ¹ include a cyclobutane ring group, a cyclopentane ring group, and a cyclohexane ring group.
Examples of the condensed polycyclic aliphatic group in the tetravalent organic group R ¹ include a bicyclo [2.2.1] heptane ring group, a bicyclo [2.2.2] octane ring group, and a bicyclo [2.2. 2] An oct-7-ene ring group and the like can be mentioned.
As the tetravalent linking group having a monocyclic or condensed polycyclic aliphatic group or aromatic group for the tetravalent organic group R ¹ , the above-mentioned monocyclic or condensed polycyclic aliphatic group or The aromatic group itself may be used, but a plurality of monocyclic or condensed polycyclic aliphatic groups or aromatic groups are linked via a single bond or a divalent linking group, and 4 as R ¹ A valent linking group may be formed.
As the divalent linking group, an alkylene group (preferably an alkylene group having 1 to 6 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, etc.), an oxygen atom, a sulfur atom, a divalent sulfone group, an ester bond. , Ketone group, amide group and the like.

Specific examples of the acid component having a group derived from at least four carboxyl groups with R ¹ as a nucleus include pyromellitic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2, 3,3 ′, 4′-biphenyltetracarboxylic anhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic anhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 2 , 2 ′, 3,3′-benzophenonetetracarboxylic anhydride, 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, 1,2,5,6-naphthalenetetracarboxylic anhydride, 2, 3,6,7-naphthalenetetracarboxylic anhydride, 2,3,5,6-pyridinetetracarboxylic anhydride, 3,4,9,10-perylenetetracarboxylic anhydride, (trifluoromethyl) pyromellit Acid anhydride, di (trifluoromethyl) pyromellitic acid anhydride, di (heptafluoropropyl) pyromellitic acid anhydride, pentafluoroethylpyromellitic acid anhydride, bis [3,5-di (trifluoromethyl) phenoxy Pyromellitic anhydride, 3,3 ′, 4,4′-tetracarboxydiphenyl ether dianhydride, 2,3 ′, 3,4′-tetracarboxydiphenyl ether dianhydride, 3,3 ′, 4,4 ′ -Tetracarboxydiphenylmethane dianhydride, 3,3 ', 4,4'-tetracarboxydiphenylsulfone dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-Dicarboxyphenyl) hexafluoropropane dianhydride, 5,5′-bis (trifluoromethyl) -3,3 ′, 4,4′-tetracar Xibiphenyl dianhydride, 2,2 ′, 5,5′-tetrakis (trifluoromethyl) -3,3 ′, 4,4′-tetracarboxybiphenyl dianhydride, 5,5′-bis (trifluoromethyl) ) -3,3 ′, 4,4′-tetracarboxydiphenyl ether dianhydride, 5,5′-bis (trifluoromethyl) -3,3 ′, 4,4′-tetracarboxybenzophenone dianhydride, bis [ (Trifluoromethyl) dicarboxyphenoxy] benzene dianhydride, bis (dicarboxyphenoxy) bis (trifluoromethyl) benzene dianhydride, bis (dicarboxyphenoxy) tetrakis (trifluoromethyl) benzene dianhydride, 2, 2-bis [4- (3,4-dicarboxyphenoxy) phenyl] propane dianhydride, 2,2-bis (4- (3,4-dicarboxy) Phenoxy) phenyl) hexafluoropropane dianhydride, 5,5 '- [p-phenylene bis (oxycarbonyl)] and component derived from an aromatic, such as di-phthalic anhydride tetracarboxylic acid anhydride,
Cyclobutanetetracarboxylic anhydride, cyclopentanetetracarboxylic anhydride, cyclohexanetetracarboxylic anhydride, 1,2,4,5-cyclohexanetetracarboxylic acid, bicyclo [2.2.1] heptane-2,3 5,6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic acid, or bicyclo [2.2.2] oct-7-ene-2,3,5 , 6-tetracarboxylic acid, bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride, Examples include components derived from aliphatic tetracarboxylic anhydrides such as (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic dianhydride.

Preferably, a component derived from pyromellitic acid anhydride, a component derived from 3,3 ′, 4,4′-biphenyltetracarboxylic acid anhydride, 2,3,3 ′, 4′-biphenyltetracarboxylic acid anhydride A component derived from 2,2 ′, 3,3′-biphenyltetracarboxylic anhydride, a component derived from 3,3 ′, 4,4′-benzophenonetetracarboxylic anhydride, 4,4 Component derived from '-(hexafluoroisopropylidene) diphthalic anhydride, component derived from 3,3', 4,4'-tetracarboxydiphenyl ether dianhydride, 1,2,5,6-naphthalenetetracarboxylic A component derived from an acid anhydride, a component derived from 5,5 ′-[p-phenylenebis (oxycarbonyl)] diphthalic anhydride, a component derived from cyclobutanetetracarboxylic anhydride, Component derived from tantetracarboxylic anhydride, component derived from bicyclo [2.2.2] octane-2,3,5,6-tetracarboxylic dianhydride, (1S, 2S, 4R, 5R)- A component derived from cyclohexanetetracarboxylic dianhydride, a component derived from (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic dianhydride, more preferably a component derived from pyromellitic acid anhydride, 3 , 3 ′, 4,4′-component derived from biphenyltetracarboxylic anhydride, component derived from 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride, derived from cyclobutanetetracarboxylic anhydride Component, component derived from 3,3 ′, 4,4′-tetracarboxydiphenyl ether dianhydride, component derived from cyclopentanetetracarboxylic anhydride A component derived from 5,5 ′-[p-phenylenebis (oxycarbonyl)] diphthalic anhydride, a component derived from (1S, 2S, 4R, 5R) -cyclohexanetetracarboxylic dianhydride, (1R, It is a component derived from 2S, 4S, 5R) -cyclohexanetetracarboxylic dianhydride. By using these, good solvent solubility, alkali dissolution rate, transparency, and stress characteristics can be realized.
The content of the acid component derived from the compound having four carboxyl groups with R ¹ as a nucleus in the resin (a) is 20 to 70 mol% with respect to all repeating units constituting the resin (a). It is preferable that it is 30 to 60 mol%.

Examples of the divalent organic group R ² include a divalent group having an alicyclic group, a divalent group having an aromatic group, and a divalent group containing a silicon atom. A plurality of R ² present in the resin (a) may be the same or different.
Hereinafter, diamine the R ² at the core when the divalent group having a R ² is alicyclic group also available that alicyclic diamine component, when R ² is a divalent group having an aromatic group the diamine component of R ² to the core of, sometimes called the aromatic diamine component, the diamine component of the R ² at the core when the divalent group R ² contains a silicon atom, that silicon diamine There is also.

At least one of R ^{2 in} the diamine component present in plural in the resin (a) is a divalent group having an alicyclic group. When the resin (a) contains a diamine component having an alicyclic group, good solvent solubility and transparency can be realized.
The alicyclic group that R ² may have is preferably a divalent alicyclic group having 3 to 20 carbon atoms, such as a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or bicyclo [2.2. 1] Polycyclic cycloalkylene groups such as a heptylene group, norbornylene group, tetracyclodecanylene group, tetracyclododecanylene group, adamantylene group, and the like can be given.
The divalent group having an alicyclic group for R ² may be the alicyclic group itself, but a plurality of alicyclic groups are alkylene groups (C1-C6 alkylene groups are preferred, Methylene group, ethylene group, propylene group, etc.) may be linked to form a divalent group having an alicyclic group as R ² , and the amino group and alicyclic group in the diamine component are alkylene groups. You may connect with.
The alicyclic group and alkylene group which can constitute a divalent group having an alicyclic group may have a substituent, and as such a substituent, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) ), Halogen atoms and the like.
Particularly preferred diamine components having an alicyclic structure having R ² as a nucleus include a 5-amino-1,3,3-trimethylcyclohexanemethylamine component, a cis-1,4-cyclohexanediamine component, and trans-1,4- Cyclohexanediamine component, 1,4-cyclohexanediamine component (cis, trans mixture), 4,4′-methylenebis (cyclohexylamine) component and its 3,3′-dimethyl-substituted product, bis (aminomethyl) bicyclo [2.2 .1] heptane component, 1,3-diaminoadamantane component, 3,3′-diamino-1,1′-biadamantyl component, 4,4′-hexafluoroisopropylidenebis (cyclohexylamine) component, Of which, 3,3′-diamino-1,1′-biadamantyl component, trans-1,4-cyclohe From the viewpoint of San diamine component to lower the stress.
The content of the alicyclic diamine component having two amino groups with R ² as a nucleus in the resin (a) is 20 to 70 mol% with respect to all repeating units constituting the resin (a). Preferably, it is 30-60 mol%.

The aromatic group in the divalent group having an aromatic group for R ² is preferably an aromatic group having 5 to 16 carbon atoms, and examples thereof include a phenylene group and a naphthylene group. Further, the aromatic group may contain a hetero atom such as a nitrogen atom or an oxygen atom, and examples thereof include a divalent benzoxazole group.
The divalent group having an aromatic group for R ² may be the aromatic group itself, but a plurality of aromatic groups are linked via a single bond or a divalent linking group, and R ² The divalent group which has an aromatic group as may be formed, and the amino group in the diamine component and the aromatic group may be linked via a divalent linking group.
As the divalent linking group, an alkylene group (preferably an alkylene group having 1 to 6 carbon atoms, for example, a methylene group, an ethylene group, a propylene group, etc.), an oxygen atom, a sulfur atom, a divalent sulfone group, an ester bond. , Ketone group, amide group and the like.
The aromatic group and alkylene group which can constitute a divalent group having an aromatic group may have a substituent, and as such a substituent, an alkyl group (preferably an alkyl group having 1 to 4 carbon atoms) ), An alkoxy group such as a halogen atom and a methoxy group, and an aryl group such as a cyano group and a phenyl group.
Specific examples of the aromatic diamine component having R ² as a core include, for example, an m-phenylenediamine component, a p-phenylenediamine component, a 2,4-tolylenediamine component, a 3,3′-diaminodiphenyl ether component, 3, 4'-diaminodiphenyl ether component, 4,4'-diaminodiphenyl ether component, 3,3'-diaminodiphenyl sulfone component, 4,4'-diaminodiphenyl sulfone component, 3,4'-diaminodiphenyl sulfone component, 3,3 ' -Diaminodiphenylmethane component, 4,4'-diaminodiphenylmethane component, 3,4'-diaminodiphenylmethane component, 4,4'-diaminodiphenylsulfide component, 3,3'-diaminodiphenylketone component, 4,4'-diaminodiphenyl Ketone component, 3,4′-diaminodiphenyl ketone component, 2, '-Bis (4-aminophenyl) propane component, 2,2'-bis (4-aminophenyl) hexafluoropropane component, 1,3-bis (3-aminophenoxy) benzene component, 1,3-bis (4 -Aminophenoxy) benzene component, 1,4-bis (4-aminophenoxy) benzene component, 4-methyl-2,4-bis (4-aminophenyl) -1-pentene component, 4-methyl-2,4- Bis (4-aminophenyl) -2-pentene component, 1,4-bis (α, α-dimethyl-4-aminobenzyl) benzene component, imino-di-p-phenylenediamine component, 1,5-diaminonaphthalene component 2,6-diaminonaphthalene component, 4-methyl-2,4-bis (4-aminophenyl) pentane component, 5 (or 6) -amino-1- (4-aminophenyl) 1,3,3-trimethylindane component, bis (p-aminophenyl) phosphine oxide component, 4,4′-diaminoazobenzene component, 4,4′-diaminodiphenylurea component, 4,4′-bis (4-amino) Phenoxy) biphenyl component, 2,2-bis [4- (4-aminophenoxy) phenyl] propane component, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane component, 2,2-bis [4- (3-aminophenoxy) phenyl] benzophenone component, 4,4′-bis (4-aminophenoxy) diphenylsulfone component, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) ) Phenoxy] benzophenone component, 4,4′-bis [4- (α, α-dimethyl-4-aminobenzyl) phenoxy] diphenylsulfone 4,4′-diaminobiphenyl component, 4,4′-diaminobenzophenone component, phenylindanediamine component, 3,3′-dimethoxy-4,4′-diaminobiphenyl component, 3,3′-dimethyl-4, 4'-diaminobiphenyl component, 2,2'-dimethyl 4,4'-diaminobiphenyl component, 2,2'-bis (trifluoromethyl) benzidine component, o-toluidine sulfone component, 2,2-bis (4- Aminophenoxyphenyl) propane component, bis (4-aminophenoxyphenyl) sulfone component, bis (4-aminophenoxyphenyl) sulfide component, 1,4- (4-aminophenoxyphenyl) benzene component, 1,3- (4- Aminophenoxyphenyl) benzene component, 9,9-bis (4-aminophenyl) fluorene component, 4,4′-di (3-aminophenoxy) diphenylsulfone component, 4,4′-diaminobenzanilide component, 4-aminophenyl-4′-aminophenylbenzoate component, bis (4-aminophenyl) terephthalate component, 2- (4-aminophenyl) ) Benzoxazol-5-ylamine, 4,4 ″ -diamino-p-terphenyl component, etc., and the hydrogen atom of the aromatic nucleus of these aromatic diamines is a chlorine atom, a fluorine atom, a bromine atom, a methyl group, a methoxy group , A structure substituted with at least one group or atom selected from the group consisting of a cyano group and a phenyl group.
Particularly preferred aromatic diamine components include p-phenylenediamine component, 4,4′-diaminodiphenyl ether component, 3,3′-diaminodiphenylsulfone component, 4,4′-diaminodiphenylsulfone component, and 2,2′-bis. (4-aminophenyl) hexafluoropropane component, 1,4-bis (4-aminophenoxy) benzene component, imino-di-p-phenylenediamine component, 4,4′-diaminobiphenyl component, 4,4′-diamino Benzophenone component, 3,3′-dimethoxy-4,4′-diaminobiphenyl component, 3,3′-dimethyl-4,4′-diaminobiphenyl component, 2,2′-dimethyl 4,4′-diaminobiphenyl component, 2,2′-bis (trifluoromethyl) benzidine component, o-toluidine sulfone component, 2,2-bis (4-amino Nophenoxyphenyl) propane component, 9,9-bis (4-aminophenyl) fluorene component, 4,4′-di- (3-aminophenoxy) diphenylsulfone component, 4,4′-diaminobenzanilide component, 4- Aminophenyl-4′-aminophenylbenzoate component, bis (4-aminophenyl) terephthalate, 2- (4-aminophenyl) benzoxazol-5-ylamine component, 4,4 ″ -diamino-p-terphenyl component A film having good toughness and low stress can be obtained.
The diamine component may be substituted with a hydroxyl group. Examples of such bisaminophenol component include 3,3′-dihydroxybenzidine component, 3,3′-diamino-4,4′-dihydroxybiphenyl component, and 4,4′-diamino-3,3′-dihydroxy. Biphenyl component, 3,3′-diamino-4,4′-dihydroxydiphenylsulfone component, 4,4′-diamino-3,3′-dihydroxydiphenylsulfone component, bis- (3-amino-4-hydroxyphenyl) methane Component, 2,2-bis- (3-amino-4-hydroxyphenyl) propane component, 2,2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane component, 2,2-bis- (4 -Amino-3-hydroxyphenyl) hexafluoropropane component, bis- (4-amino-3-hydroxyphenyl) methane component, 2 2-bis- (4-amino-3-hydroxyphenyl) propane component, 4,4′-diamino-3,3′-dihydroxybenzophenone component, 3,3′-diamino-4,4′-dihydroxybenzophenone component, 4 , 4′-diamino-3,3′-dihydroxydiphenyl ether component, 3,3′-diamino-4,4′-dihydroxydiphenyl ether component, 1,4-diamino-2,5-dihydroxybenzene component, 1,3-diamino Examples include -2,4-dihydroxybenzene component and 1,3-diamino-4,6-dihydroxybenzene component. These bisaminophenol components may be used alone or in combination.

Among these bisaminophenol structures, a particularly preferred embodiment is that R ² in the general formula (1) is a divalent group having an aromatic group selected from the following.

In the above formula, X ₁ represents —O—, —S—, —C (CF ₃ ) ₂ —, —CH ₂ —, —SO ₂ —, —NHCO—. * Represents a bonding position with —NH— or —OH bonded to R ² in the general formula (1). In the above structure, —NH— and —OH bonded to R ² are bonded to each other in the ortho position (adjacent position).
The content of the aromatic diamine component having two amino groups with R ² as the nucleus in the resin (a) is 5 to 40 mol% with respect to all repeating units constituting the resin (a). Preferably, it is 10 to 30 mol%.

Further, the R ² in order to enhance the adhesion to the substrate can be a silicon diamine component as the diamine component to the nucleus. Examples include bis (4-aminophenyl) dimethylsilane component, bis (4-aminophenyl) tetramethylsiloxane component, bis (4-aminophenyl) tetramethyldisiloxane component, bis (γ-aminopropyl) tetramethyl. Examples thereof include a disiloxane component, a 1,4-bis (γ-aminopropyldimethylsilyl) benzene component, a bis (4-aminobutyl) tetramethyldisiloxane component, and a bis (γ-aminopropyl) tetraphenyldisiloxane component.
The following structure can also be mentioned as a silicon diamine component.

In the above formula, R ₅ and R ₆ represent a divalent organic group, and R ₇ and R ₈ represent a monovalent organic group. Several R < ₇ > may mutually be same or different. Several R < ₈ > may mutually be same or different.
Examples of the divalent organic group represented by R ₅ and R ₆ include an optionally substituted linear or branched alkylene group having 1 to 20 carbon atoms, a phenylene group having 6 to 20 carbon atoms, and carbon. This represents a divalent alicyclic group having a number of 3 to 20 or a group formed by combining these.
The monovalent organic group represented by R ₇ and R ₈ represents a linear or branched alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, which may have a substituent. .
More specifically, the following can be mentioned.

The content of the silicon diamine component having at least two amino groups with R ² as a nucleus in the resin (a) is 5 to 40 mol% with respect to all repeating units constituting the resin (a). Preferably, it is 10 to 30 mol%.

Examples of the organic group represented by R ³ preferably have 1 to 20 carbon atoms. Specifically, the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, silicon atom containing group, -CORc (Rc is an alkyl group, an aryl group, a cycloalkyl group), - SO ₂ Rd (Rd represents an alkyl group, an aryl group, a cycloalkyl group, o- quinonediazide group), or a group formed by combining them Can be mentioned.

The alkyl group represented by R ³ may have a substituent, and is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom, sulfur atom, nitrogen atom in the alkyl chain You may have. Specifically, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-octyl group, n-dodecyl group, n-tetradecyl group, n-octadecyl group And a branched alkyl group such as a linear alkyl group such as isopropyl group, isobutyl group, t-butyl group, neopentyl group, and 2-ethylhexyl group. Examples of the substituent include a cyano group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group.

The cycloalkyl group represented by R ³ may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, may be polycyclic, and has an oxygen atom in the ring. Also good. Specific examples include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, and the like.

The aryl group represented by R ³ may have a substituent and is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.

The aralkyl group represented by R ³ may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms, for example, a benzyl group, a phenethyl group, a naphthylmethyl group, or a naphthylethyl group. Can be mentioned.

The alkoxy group represented by R ³ may have a substituent, preferably an alkoxy group having 1 to 20 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, A pentyloxy group, a hexyloxy group, a heptyloxy group, etc. are mentioned.

The silicon atom-containing group represented by R ³ is not particularly limited as long as silicon is contained, but a silyloxy group (trimethylsilyloxy, triethylsilyloxy, t-butyldimethylsilyloxy) is preferable.

Examples of the alkenyl group represented by R ³ include a group having a double bond at an arbitrary position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group or silicon atom-containing group. C1-C12 is preferable and C1-C6 is more preferable. For example, a vinyl group and an allyl group are preferable.

Examples of the alkynyl group represented by R ³ include a group having a triple bond at an arbitrary position of the alkyl group, cycloalkyl group, aryl group, aralkyl group, alkoxy group, and silicon atom-containing group. C1-C12 is preferable and C1-C6 is more preferable. For example, an ethynyl group and a propargyl group are preferable.

In the present invention, a hydrogen atom and an organic group can be mixed in R ³ . It is preferable that it is 100 mol%-20 mol% with respect to all R < ³ > in resin (a), respectively, and it is more preferable that 100 mol%-40 mol% are organic groups.
Moreover, in this invention, terminal blocker can be made to react with the terminal of the polymer which has the repeating unit represented by General formula (1) as a main component. As the end-capping agent, monoamine, acid anhydride, monocarboxylic acid, monoacid chloride compound, monoactive ester compound and the like can be used. By making terminal blocker react, it is preferable at the point which can control the repeating number of a repeating unit, ie, molecular weight, in a preferable range. Furthermore, acid deactivation due to neutralization of the terminal amine and the generated acid can be suppressed by the terminal blocking agent. In addition, by reacting an end-capping agent at the terminal, various organic groups such as a crosslinking reactive group having a carbon-carbon unsaturated bond can be introduced as the terminal group.

  Monoamines used for the end capping agents are 5-amino-8-hydroxyquinoline, 4-amino-8-hydroxyquinoline, 1-hydroxy-8-aminonaphthalene, 1-hydroxy-7-aminonaphthalene, 1-hydroxy- 6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-2-aminonaphthalene, 1-amino-7-hydroxynaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 2-hydroxy-4-aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 1-amino-2 -Hydroxynaphthalene, 1-carboxy-8-amino Phthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 1-carboxy-4-aminonaphthalene, 1-carboxy-3-aminonaphthalene, 1-carboxy 2-aminonaphthalene, 1-amino-7-carboxynaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-carboxy-4-aminonaphthalene 2-carboxy-3-aminonaphthalene, 1-amino-2-carboxynaphthalene, 2-aminonicotinic acid, 4-aminonicotinic acid, 5-aminonicotinic acid, 6-aminonicotinic acid, 4-aminosalicylic acid, 5- Aminosalicylic acid, 6-aminosalicylic acid, 3-a No-O-toluic acid, amelide, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-aminobenzene Amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 5-amino-8-mercaptoquinoline, 4-amino-8-mercaptoquinoline, 1-mercapto-8-aminonaphthalene 1-mercapto-7-aminonaphthalene, 1-mercapto-6-aminonaphthalene, 1-mercapto-5-aminonaphthalene, 1-mercapto-4-aminonaphthalene, 1-mercapto-3-aminonaphthalene, 1-mercapto- 2-aminonaphthalene, 1-amino-7-mercaptonaphthalene 2-mercapto-7-aminonaphthalene, 2-mercapto-6-aminonaphthalene, 2-mercapto-5-aminonaphthalene, 2-mercapto-4-aminonaphthalene, 2-mercapto-3-aminonaphthalene, 1-amino 2-mercaptonaphthalene, 3-amino-4,6-dimercaptopyrimidine, 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline 2,4-diethynylaniline, 2,5-diethynylaniline, 2,6-diethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline, 1-ethynyl-2-aminonaphthalene, 1-ethynyl-3-aminonaphthalene, 1-ethynyl-4-aminonaphthalene 1-ethynyl-5-aminonaphthalene, 1-ethynyl-6-aminonaphthalene, 1-ethynyl-7-aminonaphthalene, 1-ethynyl-8-aminonaphthalene, 2-ethynyl-1-aminonaphthalene, 2-ethynyl-3 -Aminonaphthalene, 2-ethynyl-4-aminonaphthalene, 2-ethynyl-5-aminonaphthalene, 2-ethynyl-6-aminonaphthalene, 2-ethynyl-7-aminonaphthalene, 2-ethynyl-8-aminonaphthalene, 3 , 5-diethynyl-1-aminonaphthalene, 3,5-diethynyl-2-aminonaphthalene, 3,6-diethynyl-1-aminonaphthalene, 3,6-diethynyl-2-aminonaphthalene, 3,7-diethynyl-1 -Aminonaphthalene, 3,7-diethynyl-2-aminonaphthalene, 4,8-diethini 1-aminonaphthalene, 4,8-diethynyl-2-Amino-naphthalene, but it is not limited thereto.

  Of these, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2 -Hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5 Aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4- Aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2- Aminothiophenol, 3-aminothiophenol, 4-aminothiophenol, 3-ethynylaniline, 4-ethynylaniline, 3,4-diethynylaniline, 3,5-diethynylaniline and the like are preferable.

  Acid anhydrides, monocarboxylic acids, monoacid chloride compounds, and active ester compounds used as end-capping agents are phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, 3-hydroxyphthalic anhydride Acid anhydrides such as 2-carboxyphenol, 3-carboxyphenol, 4-carboxyphenol, 2-carboxythiophenol, 3-carboxythiophenol, 4-carboxythiophenol, 1-hydroxy-8-carboxynaphthalene, 1- Hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-hydroxy-4-carboxynaphthalene, 1-hydroxy-3-carboxynaphthalene, 1-hydroxy-2-carboxyl Naphthalene, 1-mercapto-8-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxynaphthalene, 1-mercapto-5-carboxynaphthalene, 1-mercapto-4-carboxynaphthalene, 1-mercapto -3-carboxynaphthalene, 1-mercapto-2-carboxynaphthalene, 2-carboxybenzenesulfonic acid, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 2-ethynylbenzoic acid, 3-ethynylbenzoic acid, 4- Ethynylbenzoic acid, 2,4-diethynylbenzoic acid, 2,5-diethynylbenzoic acid, 2,6-diethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynylbenzoic acid, 2-ethynyl-1- Naphthoic acid, 3-ethynyl-1-na Toeic acid, 4-ethynyl-1-naphthoic acid, 5-ethynyl-1-naphthoic acid, 6-ethynyl-1-naphthoic acid, 7-ethynyl-1-naphthoic acid, 8-ethynyl-1-naphthoic acid, 2- Ethynyl-2-naphthoic acid, 3-ethynyl-2-naphthoic acid, 4-ethynyl-2-naphthoic acid, 5-ethynyl-2-naphthoic acid, 6-ethynyl-2-naphthoic acid, 7-ethynyl-2-naphthoic acid Acids, monocarboxylic acids such as 8-ethynyl-2-naphthoic acid, and monoacid chloride compounds in which these carboxyl groups are acid chloride, and terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 3-hydroxyphthalic acid, 5-norbornene-2,3-dicarboxylic acid, 1,2-dicarboxynaphthalene, 1,3-dicarboxynaphthalene, 1,4-dicarboxyl Sinaphthalene, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1,7-dicarboxynaphthalene, 1,8-dicarboxynaphthalene, 2,3-dicarboxynaphthalene, 2,6-dicarboxynaphthalene , Monoacid chloride compounds in which only the monocarboxyl group of dicarboxylic acids such as 2,7-dicarboxynaphthalene is acid chloride, monoacid chloride compounds and N-hydroxybenzotriazole or N-hydroxy-5-norbornene-2,3- Examples include active ester compounds obtained by reaction with dicarboximide.

  Of these, phthalic anhydride, maleic anhydride, nadic anhydride, cyclohexanedicarboxylic anhydride, acid anhydrides such as 3-hydroxyphthalic anhydride, 3-carboxyphenol, 4-carboxyphenol, 3-carboxythiophenol 4-carboxythiophenol, 1-hydroxy-7-carboxynaphthalene, 1-hydroxy-6-carboxynaphthalene, 1-hydroxy-5-carboxynaphthalene, 1-mercapto-7-carboxynaphthalene, 1-mercapto-6-carboxy Naphthalene, 1-mercapto-5-carboxynaphthalene, 3-carboxybenzenesulfonic acid, 4-carboxybenzenesulfonic acid, 3-ethynylbenzoic acid, 4-ethynylbenzoic acid, 3,4-diethynylbenzoic acid, 3,5-diethynyl benzoic acid Monocarboxylic acids, and monoacid chloride compounds in which these carboxyl groups are converted to an acid chloride, terephthalic acid, phthalic acid, maleic acid, cyclohexanedicarboxylic acid, 1,5-dicarboxynaphthalene, 1,6-dicarboxynaphthalene, 1 , 7-dicarboxynaphthalene, 2,6-dicarboxynaphthalene and the like monocarboxylic acid compounds in which only the monocarboxyl group of the dicarboxylic acid is converted to acid chloride, monoacid chloride compound and N-hydroxybenzotriazole or N-hydroxy-5- Active ester compounds obtained by reaction with norbornene-2,3-dicarboximide are preferred.

  The introduction ratio of the monoamine used for the end-capping agent is preferably in the range of 0.1 to 60 mol%, particularly preferably 5 to 50 mol%, based on the total amine component. The introduction ratio of the compound selected from the acid anhydride, monocarboxylic acid, monoacid chloride compound and monoactive ester compound used as the end-capping agent is in the range of 0.1 to 100 mol% with respect to the diamine component. Preferably, it is 5-90 mol% especially preferably. A plurality of different terminal groups may be introduced by reacting a plurality of terminal blocking agents.

The end-capping agent introduced into the polymer can be easily detected by the following method. For example, a polymer having an end-capping agent introduced therein is dissolved in an acidic solution and decomposed into an amine component and an acid anhydride component that are constituent units of the polymer. By measuring this with gas chromatography (GC) or NMR, the end-capping agent can be easily detected. In addition, it can be easily detected by directly measuring the polymer component into which the end-capping agent has been introduced by pyrolysis gas chromatography (PGC), infrared spectrum and ¹³ CNMR spectrum.

General formula (2)
(In the general formula, X and Y each contain a monocyclic or condensed polycyclic aliphatic group or a monocyclic or condensed polycyclic aromatic group, and have 4 carbon atoms. Represents a linking group of ˜30.X and Y may be composed of one ring structure or may have a plurality of ring structures.)
At least one of X and Y in the general formula (2) is preferably a monocyclic or condensed polycyclic aliphatic group, X is an aromatic group, and Y is monocyclic or condensed polycyclic. The polymer which is an aliphatic group is more preferable.
X is more preferably an aromatic ring, a cyclohexane ring or a bicyclo ring, which may have a substituent. Y is more preferably exemplified by an aromatic ring, a cyclohexane ring and a bicyclo ring, which may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, and an alkoxy group.
By using the polymer having the repeating unit represented by the general formula (2), the adhesion with the near-infrared reflective film can be improved.

  Examples of the polyimide resin used in the present invention include those described in JP-A-2006-213827, JP-A-2006-117910, and the like.

It is preferable that the polyimide resin used for this invention has as a main component the repeating unit represented by General formula (1) and / or the repeating unit represented by General formula (2). The main component referred to here means that 70 mol% or more of the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) is contained. More preferably, it is 80 mol% or more, and most preferably 90 mol% or more.
The resin used in the present invention may be a copolymer of the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) and another repeating unit, or Further, it may be a mixture of a plurality of resins containing the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2).
Further, the resin containing the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) and the repeating unit represented by the general formula (1) and / or the general formula (1) It may be a mixture with a resin not containing the repeating unit represented by 2). In this case, the resin containing the repeating unit represented by the general formula (1) and / or the repeating unit represented by the general formula (2) preferably contains 50% by mass or more, and contains 75% by mass or more. It is more preferable.
The type and amount of the repeating unit used for copolymerization or mixing is preferably selected within a range that does not impair the heat resistance of the polymer obtained by the final heat treatment.

The polyimide resin used in the present invention has a mass average molecular weight of preferably 200,000 or less, more preferably 1,000 to 200,000, and more preferably 2,000 to 100,000 from the viewpoint of film properties and the like. 3,000 to 100,000 is particularly preferable. By setting this molecular weight range, a film having low mechanical stress and excellent mechanical properties can be obtained. In the present invention, the molecular weight is measured by gel permeation chromatography and can be determined using a standard polystyrene calibration curve.
The dispersity (molecular weight distribution) is preferably 1.0 to 4.0, and more preferably 1.0 to 3.5.

  As a method of forming the polyamide resin on the film, a known method can be adopted, and for example, the description of paragraph numbers 0058 to 0070 of JP-A-2006-213827 can be referred to.

<Layer formed by curing a curable composition>
The organic polymer layer in the present invention is also preferably a layer formed by curing a curable composition by polymerization. The curable composition preferably contains a binder and a polymerizable compound.

The binder is preferably a linear organic polymer and soluble in an organic solvent.
Examples of such linear organic high molecular polymers include polymers having a carboxylic acid in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, and JP-B-54-. No. 25957, JP-A-59-53836, JP-A-59-71048, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, etc. Examples thereof include polymers, maleic acid copolymers, partially esterified maleic acid copolymers, and acidic cellulose derivatives having a carboxylic acid in the side chain are also useful. Moreover, as a linear organic high molecular polymer, the polymer as described in paragraph number [0227]-[0234] paragraph of Unexamined-Japanese-Patent No. 2008-292970 is mentioned.

  In addition to those described above, the binder in the present invention includes a polymer having a hydroxyl group added with an acid anhydride, a polyhydroxystyrene resin, a polysiloxane resin, and poly (2-hydroxyethyl (meth) acrylate). Polyvinyl pyrrolidone, polyethylene oxide, polyvinyl alcohol, etc. are also useful. Further, the linear organic high molecular polymer may be a copolymer of hydrophilic monomers. Examples include alkoxyalkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate, (meth) acrylamide, N-methylol acrylamide, secondary or tertiary alkyl acrylamide, dialkylaminoalkyl (meth). Acrylate, morpholine (meth) acrylate, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinyltriazole, methyl (meth) acrylate, ethyl (meth) acrylate, branched or linear propyl (meth) acrylate, branched or straight Examples include butyl (meth) acrylate of a chain, phenoxyhydroxypropyl (meth) acrylate, and the like. Other hydrophilic monomers include tetrahydrofurfuryl group, phosphoric acid group, phosphoric ester group, quaternary ammonium base, ethyleneoxy chain, propyleneoxy chain, sulfonic acid group and groups derived from salts thereof, morpholinoethyl group, etc. Monomers comprising it are also useful.

The binder may have a polymerizable group in the side chain in order to improve the crosslinking efficiency, for example, a polymer containing an allyl group, a (meth) acryl group, an allyloxyalkyl group, etc. in the side chain. Is also useful. Examples of the above-mentioned polymer containing a polymerizable group include: Dynar NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing polyurethane acrylic oligomer. Diamond Shamrock Co. Ltd., manufactured by Viscort R-264, KS resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series, Plaxel CF200 series (all manufactured by Daicel Chemical Industry Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like.
In addition, in order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

  As the binder, it is also preferable to use a polymer (a) obtained by polymerizing a compound represented by the following general formula (E-1) (hereinafter sometimes referred to as “ether dimer”).

In formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or an optionally substituted hydrocarbon group having 1 to 25 carbon atoms.

When the curable composition used in the present invention contains the polymer (a), the heat resistance and transparency of a cured coating film formed using the composition are further improved.
In the general formula (E-1) showing the ether dimer, the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R ¹ and R ² is not particularly limited, For example, straight chain such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, t-amyl group, stearyl group, lauryl v, 2-ethylhexyl group, etc. Or branched alkyl group; aryl group such as phenyl group; cyclohexyl group, t-butylcyclohexyl group, dicyclopentadienyl group, tricyclodecanyl group, isobornyl group, adamantyl group, 2-methyl-2-adamantyl group , An alicyclic group such as 1-methoxyethyl group, 1-ethoxyethyl group, etc., an alkyl group substituted by alkoxy; an aryl group such as benzyl group; Alkyl group; and the like.
Among these, a group containing a primary or secondary carbon that is difficult to be removed by an acid or heat, such as a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group, is particularly preferable in terms of heat resistance.
R ¹ and R ² may be the same type of substituent or different substituents.

  Specific examples of the ether dimer include dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, (N-propyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isopropyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (n-butyl) ) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (isobutyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butyl) -2, 2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-amyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di Stearyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (lauryl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (2-ethylhexyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-methoxyethyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (1-ethoxyethyl) -2 , 2 ′-[oxybis (methylene)] bis-2-propenoate, dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diphenyl-2,2 ′-[oxybis (methylene)] bis- 2-propenoate, dicyclohexyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (t-butylcyclohexyl) 2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (dicyclopentadienyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, di (tricyclodecanyl) -2,2 '-[oxybis (methylene)] bis-2-propenoate, di (isobornyl) -2,2'-[oxybis (methylene)] bis-2-propenoate, diadamantyl-2,2 '-[oxybis (Methylene)] bis-2-propenoate, di (2-methyl-2-adamantyl) -2,2 ′-[oxybis (methylene)] bis-2-propenoate, and the like. Among these, dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, diethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2′- [Oxybis (methylene)] bis-2-propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate are preferred. These ether dimers may be only one kind or two or more kinds.

The binder is preferably a polymer having an epoxy group.
In order to introduce an epoxy group into the binder, for example, a monomer having an epoxy group (hereinafter also referred to as “monomer for introducing an epoxy group”) may be polymerized as a monomer component. Examples of the monomer having an epoxy group include glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, o- (or m-, or p-) vinylbenzyl glycidyl ether, and the like. These monomers for introducing an epoxy group may be only one type or two or more types.

  In the curable composition of the present invention, from the viewpoint of heat resistance, it is also preferable to use a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin.

  Examples of the acrylic resin include a copolymer made of a monomer selected from benzyl (meth) acrylate, (meth) acrylic acid, hydroxyethyl (meth) acrylate, (meth) acrylamide, and the like, and a commercially available KS resist 106 ( Osaka Organic Chemical Industry Co., Ltd.) and Cyclomer P Series (Daicel Chemical Industries, Ltd.) are preferred.

(Phenolic resin)
Moreover, a phenol resin can also be used as a binder in this invention. As this phenol resin, a novolak resin, a vinyl polymer, etc. are mentioned, for example.
Examples of the novolac resin include those obtained by condensing phenols and aldehydes in the presence of an acid catalyst. Examples of the phenols include phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, and bisphenol A.
Examples of the aldehydes include formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, and benzaldehyde.
The said phenols and aldehydes can be used individually or in combination of 2 or more types.

  Specific examples of the novolak resin include, for example, a condensation product of metacresol, paracresol or a mixture thereof and formalin.

  The novolak resin may be adjusted in molecular weight distribution by means of fractionation or the like. Moreover, you may mix the low molecular weight component which has phenolic hydroxyl groups, such as bisphenol C and bisphenol A, with the said novolak resin.

The binder in the present invention described above is preferably a polymer having a mass average molecular weight (polystyrene equivalent value measured by GPC method) of 1000 to 2 × 10 ⁵ , more preferably 2000 to 1 × 10 ⁵ . 5000 to 5 × 10 ⁴ polymers are particularly preferred.

<Polymerizable compound>
The composition of the present invention preferably contains a polymerizable compound.
Examples of the polymerizable compound include addition polymerizable compounds having at least one ethylenically unsaturated double bond. Specifically, it is selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more. Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the present invention. These may be any of chemical forms such as monomers, prepolymers, that is, dimers, trimers and oligomers, or a mixture thereof and a (co) polymer thereof. The polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.

Examples of monomers and their (co) polymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and these (Co) polymers, preferably esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds, and their (co) It is a polymer. Also, addition reaction products of monofunctional or polyfunctional isocyanates or epoxies with unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as hydroxyl group, amino group, mercapto group, monofunctional or polyfunctional. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, and further a halogen group A substitution reaction product of an unsaturated carboxylic acid ester or amide having a detachable substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.
As these specific compounds, the compounds described in paragraphs 0095 to 0108 of JP-A-2009-288705 can also be suitably used in the present invention.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

  Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate. Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate. Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, JP-A-59-5241, and JP-A-2-226149. Those having the aromatic skeleton described above and those having an amino group described in JP-A-1-165613 are also preferably used. Furthermore, the ester monomers described above can also be used as a mixture.

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

  In addition, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable, and specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (E) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (E)
(However, R ⁴ and R ⁵ represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, JP-B-56-17654, Urethane compounds having an ethylene oxide skeleton described in JP-B-62-39417 and JP-B-62-39418 are also suitable. Furthermore, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 can be used. Commercially available polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA- 306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Further, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337 and JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like can also be mentioned. . In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, Journal of Japan Adhesion Association vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

  In the present invention, from the viewpoint of curing sensitivity, it preferably contains two or more ethylenically unsaturated bonds, and more preferably contains three or more. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoint, bisphenol A diacrylate, bisphenol A diacrylate EO modified product, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product, etc. are mentioned as preferable ones. Also, as commercially available products, urethane oligomer UAS-10, UAB-140 (Sanyo Kokusaku Pulp Co., Ltd.) Made), DPHA-40H (made by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (made by Kyoeisha).

  Among them, bisphenol A diacrylate EO modified product, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified product, Dipentaerythritol hexaacrylate EO modified products such as DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 are commercially available products. (Manufactured by Kyoeisha) is more preferred.

  In addition, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned. Other examples of polybasic acid-modified acrylic oligomers manufactured by Toagosei include M-510 and M-520.

(C) Only 1 type may be used for a polymeric compound and it may use 2 or more types together.
The content of the polymerizable compound (C) in the colored curable composition of the present invention is preferably in the range of 4 to 80% by mass, and more preferably in the range of 7 to 50% by mass in terms of solid content. preferable.
In particular, when the film thickness is 0.8 μm or less, the addition amount is preferably 7 to 40% by mass in the total solid content, and particularly effective in the range of 6 to 25% by mass.

  The polymerizable compound is also preferably a compound having at least one addition-polymerizable ethylene group as a polymerizable monomer and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure. Examples include monofunctional acrylates and methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethanetri (Meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (Meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) iso (Meth) acrylate obtained by adding ethylene oxide or propylene oxide to polyfunctional alcohols such as anurate, glycerin and trimethylolethane, JP-B-48-41708, JP-B-50-6034, JP-A-51- Urethane acrylates as described in JP-B-37193, polyester acrylates and epoxy resins described in JP-A-48-64183, JP-B-49-43191 and JP-B-52-30490 Mention may be made of polyfunctional acrylates and methacrylates such as epoxy acrylates, which are reaction products with (meth) acrylic acid, and mixtures thereof. Among these, dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product); Nippon Kayaku Co., Ltd. Dipentaerythritol penta (meth) acrylate (manufactured by KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (manufactured by KAYARAD DPHA; Nippon Kayaku Co., Ltd.) And a structure in which these (meth) acryloyl groups are interposed via ethylene glycol and propylene glycol residues. These oligomer types can also be used.

  In addition to the above, radically polymerizable monomers represented by the following general formulas (MO-1) to (MO-5) can also be suitably used. In the formula, when T or G is an oxyalkylene group, the terminal on the carbon atom side is bonded to R, X and W.

In the said general formula, n is 0-14 and m is 1-8. A plurality of R, X, T, and G present in one molecule may be the same or different.
Specific examples of the radical polymerizable monomer represented by the above general formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP2007-26979A. Can also be suitably used in the present invention.

  As for content in the composition of the polymeric compound demonstrated above, 5-90 mass% is preferable with respect to solid content of a composition, 10-80 mass% is more preferable, 15-50 mass% is especially preferable. . When the content is within the above range, it is possible to maintain a sufficient degree of cure and elution of the unexposed area, maintain a sufficient degree of cure of the exposed area, and significantly reduce the elution of the unexposed area. Can be prevented.

<(C) Radical polymerization initiator>
The curable composition used in the present invention preferably further contains a radical polymerization initiator from the viewpoint of further improving sensitivity.
The photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. It may be an activator that generates active radicals, or may be an initiator that initiates cationic polymerization according to the type of monomer.
The photopolymerization initiator preferably contains at least one component having a molecular extinction coefficient of at least about 50 within a range of about 300 to 800 nm (more preferably 330 to 500 nm).

  Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime. Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.

  Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969), a compound described in British Patent 1388492, a compound described in JP-A-53-133428, a compound described in German Patent 3337024, F.I. C. J. Schaefer et al. Org. Chem. 29, 1527 (1964), compounds described in JP-A-62-258241, compounds described in JP-A-5-281728, compounds described in JP-A-5-34920, US Pat. No. 4,221,976 And the compounds described in the book.

  Examples of the compound described in US Pat. No. 4,221,976 include compounds having an oxadiazole skeleton (for example, 2-trichloromethyl-5-phenyl-1,3,4-oxadiazole, 2- Trichloromethyl-5- (4-chlorophenyl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1,3,4-oxadiazole, 2-trichloromethyl-5 -(2-naphthyl) -1,3,4-oxadiazole, 2-tribromomethyl-5-phenyl-1,3,4-oxadiazole, 2-tribromomethyl-5- (2-naphthyl) -1,3,4-oxadiazole; 2-trichloromethyl-5-styryl-1,3,4-oxadiazole, 2-trichloromethyl-5- (4-chlorostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (4-methoxystyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (1-naphthyl) -1, 3,4-oxadiazole, 2-trichloromethyl-5- (4-n-butoxystyryl) -1,3,4-oxadiazole, 2-tripromomethyl-5-styryl-1,3,4 Oxadiazole, etc.).

  In addition, as photopolymerization initiators other than those described above, polyhalogen compounds (for example, 9-phenylacridine, 1,7-bis (9,9′-acridinyl) heptane, etc.), N-phenylglycine (for example, Carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone, etc.), coumarins (for example, 3- (2-benzofuroyl) -7-diethylaminocoumarin, 3- (2-benzofuroyl) -7- (1-pyrrolidinyl) ) Coumarin, 3-benzoyl-7-diethylaminocoumarin, 3- (2-methoxybenzoyl) -7-diethylaminocoumarin, 3- (4-dimethylaminobenzoyl) -7-diethylaminocoumarin, 3,3′-carbonylbis (5 , 7-di-n-propoxycoumarin), 3,3′-carbo Rubis (7-diethylaminocoumarin), 3-benzoyl-7-methoxycoumarin, 3- (2-furoyl) -7-diethylaminocoumarin, 3- (4-diethylaminocinnamoyl) -7-diethylaminocoumarin, 7-methoxy-3 -(3-pyridylcarbonyl) coumarin, 3-benzoyl-5,7-dipropoxycoumarin, 7-benzotriazol-2-ylcoumarin, JP-A-5-19475, JP-A-7-271028, JP 2002-363206, JP-A 2002-363207, JP-A 2002-363208, JP-A 2002-363209, etc.), acylphosphine oxides (for example, bis (2,4 , 6-Trimethylbenzoyl) -phenylphosphite Oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, Lucirin TPO, etc.), metallocenes (for example, bis (η5-2,4-cyclopentadien-1-yl)- Bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium, η5-cyclopentadienyl-η6-cumenyl-iron (1 +)-hexafluorophosphate (1-), etc.) Examples thereof include compounds described in JP-A-53-133428, JP-B-57-1819, JP-A-57-6096, and US Pat. No. 3,615,455.

  Examples of the ketone compound include benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 4-methoxybenzophenone, 2-chlorobenzophenone, 4-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, 2-ethoxycarbonylbenzolphenone, benzophenonetetracarboxylic acid or tetramethyl ester thereof, 4,4′-bis (dialkylamino) benzophenone (for example, 4,4′-bis (dimethylamino) benzophenone, 4,4′- Bisdicyclohexylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4,4′-bis (dihydroxyethylamino) benzophenone, 4-methoxy-4′-dimethylamino Nzophenone, 4,4'-dimethoxybenzophenone, 4-dimethylaminobenzophenone, 4-dimethylaminoacetophenone, benzyl, anthraquinone, 2-t-butylanthraquinone, 2-methylanthraquinone, phenanthraquinone, xanthone, thioxanthone, 2-chloro -Thioxanthone, 2,4-diethylthioxanthone, fluorenone, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -1-butanone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino -1-propanone, 2-hydroxy-2-methyl- [4- (1-methylvinyl) phenyl] propanol oligomer, benzoin, benzoin ethers (for example, benzoin methyl ether, benzoin ethyl ether, In propyl ether, benzoin isopropyl ether, benzoin phenyl ether, benzyl dimethyl ketal), acridone, chloro acridone, N- methyl acridone, N- butyl acridone, N- butyl - such as chloro acrylic pyrrolidone.

As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
As the hydroxyacetophenone-based initiator, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used. As an aminoacetophenone-based initiator, commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used. As the aminoacetophenone-based initiator, a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used. As the acylphosphine-based initiator, commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.

  More preferred examples of the photopolymerization initiator include oxime compounds. Specific examples of the oxime initiator include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.

  Examples of oxime compounds such as oxime derivatives that are preferably used as a photopolymerization initiator in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutane-2-one, and 3-propionyloxyimino. Butan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4 -Toluenesulfonyloxy) iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one and the like.

Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660), J.M. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, compounds described in JP-A No. 2000-66385, compounds described in JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
IRGACURE-OXE01 (manufactured by BASF) and IRGACURE-OXE02 (manufactured by BASF) are also preferably used as commercial products.

  Further, as oxime ester compounds other than those described above, compounds described in JP-T 2009-519904, in which an oxime is linked to the N-position of carbazole, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, A compound described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced into the dye moiety, a ketoxime compound described in International Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule The compound described in U.S. Pat. No. 7,556,910, the compound described in JP 2009-221114 A having an absorption maximum at 405 nm and good sensitivity to a g-line light source, and the like may be used.

Preferably, it can also be suitably used for the cyclic oxime compounds described in JP2007-231000A and JP2007-322744A. Among the cyclic oxime compounds, the cyclic oxime compounds fused to carbazole dyes described in JP2010-32985A and JP2010-185072A are particularly preferable in terms of high light absorption and high sensitivity.
In addition, the compound described in JP-A-2009-242469 having an unsaturated bond at a specific site of the oxime compound can achieve high sensitivity by regenerating an active radical from a polymerization inert radical, and can be suitably used. .

  Most preferably, an oxime compound having a specific substituent described in JP-A-2007-269977 and an oxime compound having a thioaryl group described in JP-A-2009-191061 are exemplified.

<Near-infrared reflective film>
The near-infrared cut filter of the present invention has a near-infrared reflective film made of a dielectric multilayer film. The dielectric multilayer film preferably has a structure in which low refractive index layers and high refractive index layers are alternately stacked. By having such a dielectric multilayer film on at least one surface of the glass substrate, a near-infrared cut filter having an excellent ability to reflect near-infrared rays can be obtained. Further, the difference in refractive index between the high refractive index layer and the low refractive index layer is preferably 0.5 or more, and more preferably 1.0 or more. When the difference in refractive index is 1.0 or more, the wavelength range of the near infrared region that can be cut is widened, and a filter with more excellent near infrared ray cutting performance can be obtained.

<High refractive index layer>
As a refractive index of the material which comprises a high refractive index layer, it is 1.6 or less normally, and 1.2-1.6 are preferable. Examples of such a material include silica (SiO ₂ ), alumina, lanthanum fluoride, magnesium fluoride, sodium hexafluoroaluminum, and the like, and silica is preferable.

<Low refractive index layer>
As a refractive index of the material which comprises a low-refractive-index layer, it is 1.7 or more normally, and 1.7-2.5 are preferable. Examples of such materials include titanium oxide (titania (TiO ₂ )), zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide, indium oxide, and the like as main components. Examples thereof include titanium oxide (titania (TiO ₂ )), tin oxide, cerium oxide and the like in a small amount. Preferred are titania (TiO ₂ ), ITO (tin-doped indium oxide) and ATO (antimony-doped tin oxide). In particular, when ITO (tin-doped indium oxide) and ATO (antimony-doped tin oxide) are used, the electromagnetic wave region can be cut, which is more effective.

<Lamination method>
The method of laminating the high-refractive index layer and the low-refractive index layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, by a CVD method, a sputtering method, a vapor deposition method, or the like. A dielectric multilayer film can be formed by alternately laminating high refractive index layers and low refractive index layers. Especially in this invention, since it can manufacture by a vapor deposition method, there exists a merit that productivity improves. It is preferable that the substrate temperature at the time of vapor deposition is 120-300 degreeC.

  The thicknesses of the high-refractive index layer and the low-refractive index layer are usually 0.1λ to 0.5λ of the near infrared wavelength λ (nm) to be blocked. If the thickness is out of the above 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. There is a tendency that the relationship between the optical characteristics is broken, and control for blocking / transmitting a specific wavelength cannot be performed.

  When the dielectric multilayer film is provided only on one surface of the glass substrate, the number of laminated layers of the high refractive index layer and the low refractive index layer is usually 10 to 80 layers, preferably 10 to 30 layers. On the other hand, when the dielectric multilayer film is provided on both surfaces of the glass substrate, the number of laminated layers is generally 10 to 80 layers, preferably 10 to 30 layers as the whole number of laminated layers on both surfaces of the substrate.

The near-infrared cut filter according to the present invention has an excellent near-infrared cut ability, is excellent in heat resistance, and is less likely to cause distortion and cracking. Therefore, it is useful not only as a heat ray cut filter attached to glass of automobiles or buildings, but also particularly useful for correcting the visibility of solid-state image sensors such as CCDs and CMOSs in digital still cameras and mobile phone cameras. Therefore, it can be suitably used for applications that require high-temperature adhesion during product incorporation, use in a high-temperature region, and the like.
Moreover, it can use preferably also for an organic EL element, a solar cell element, etc.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below.

Example 1
(1) Synthesis of polyamic acid (polyimide precursor, dope A) In a 200 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, 2,2′-dimethyl-4,4′-diaminobiphenyl (Wakayama Seiki ( Co., Ltd.) 10.615 g was added and dissolved in 120.64 g of N-methyl-2-pyrrolidone, and then (1R, 2S, 4S, 5R) -cyclohexanetetracarboxylic dianhydride (Iwatani) at 2 ° C. under ice cooling. 10.675 g (manufactured by Gas Co., Ltd.) was added. When the reaction was carried out at 4 ° C. for 1 hour and then at 25 ° C. for 24 hours, a transparent polyamic acid solution was obtained. When the obtained solution was analyzed by GPC, Mw = 3.71 × 10 ⁴ and Mn = 2.02 × 10 ⁴ (dope A).
GPC measurement was performed by directly connecting three HPC-8220GPC (manufactured by Tosoh Corporation), guard column: TSKguardcolumn SuperAW-H, column: TSKgel SuperAWM-H, column temperature of 50 ° C., and sample concentration of 0.5 mass%. 20 μl of 2-pyrrolidone solution was injected, and N-methyl-2-pyrrolidone solution (containing LiBr (10 mM) and H ₃ PO ₄ (10 mM)) as an elution solvent was allowed to flow at a flow rate of 0.35 ml per minute to detect RI. This was done by detecting the sample peak with the apparatus. Mw and Mn were calculated using a calibration curve prepared using standard polystyrene.
To 10 g of the obtained polyamic acid resin solution, 0.1 g of quatarylene dye Lumogen IR-765 (manufactured by BASF) was added, stirred and mixed, and filtered with a 0.25 um PP filter to obtain a liquid resin composition It was.

(2) Production of film Next, the liquid resin composition obtained in (1) was spin-coated on a glass substrate at 2000 rpm, and was heated and dried at 100 ° C. to obtain a polymer film having a thickness of 5 μm. Next, it heated at 300 degreeC for 1 hour. When the substrate was observed with an optical microscope, no foreign matter, unevenness or repellency was found, and the appearance was good.

(3) Deposition The SiO ₂ layer and the TiO ₂ layer are alternately deposited on the obtained base film at a substrate temperature of 280 ° C. by the electron beam evaporation (EB) method, and both sides of the dielectric multilayer film are formed. To obtain a laminated film with a dielectric multilayer film. The dielectric multilayer film layer formed on the base film had a layer configuration of one layer of 110 to 120 nm and 18 layers on one side (the outermost layer was an SiO ₂ layer).
The total thickness of the obtained near-infrared cut filter was about 0.2 mm.

(4) Evaluation <Spectral characteristic evaluation>
The spectral characteristics on the long wavelength side of the IR cut filter were evaluated using a phase difference measuring device (COBRA-WR, manufactured by Oji Scientific). The incident angle is changed perpendicularly to the film surface (angle 0 degree) and 35 degrees, and the wavelength shift amount at which the transmittance is 50% on the high wavelength side in the p-polarized transmission band (visible light region) is less than 25 nm. ○, 25 nm or more and less than 30 nm are shown as Δ, and 30 nm or more are shown as ×.

<Heat resistance>
The IR cut filter was cut into 2 cm × 2 cm and heated on a hot plate at 260 ° C. for 3 minutes. Before and after heating, using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation), the spectrum in the wavelength region of 400-1100 nm was measured at an incident angle of 0 degree, and the area of spectral transmittance before and after heating. The amount of change in the integral value of .largecircle. Is less than 5%, .largecircle.

Example 2
The same procedure as in Example 1 was performed except that the synthesis of polyamic acid was changed as follows.
In a 5000 mL flask equipped with a thermometer, a stirrer, and a nitrogen introduction tube, trans-1,4-cyclohexanediamine (manufactured by Iwatani Gas Co., Ltd.) (123.42 g) was placed and NMP (N-methyl-2-pyrrolidone) After being dissolved in (2399.4 g), 3,3 ′, 4,4′-biphenyltetracarboxylic anhydride (manufactured by Mitsubishi Chemical Corporation) (300.00 g) was added. The mixture was stirred at 60 ° C. for 4 hours and then allowed to cool to room temperature. Next, phthalic anhydride (30.27 g) was added and stirred at room temperature for 10 hours to obtain a colorless and transparent polyamic acid solution. When the obtained solution was analyzed by GPC, Mw = 1.68 × 10 ⁴ , Mn = 0.62 × 10 ⁴ , and Mw / Mn = 2.71.
The total thickness of the obtained near-infrared cut filter was about 0.2 mm.

Example 3
The following compounds were mixed and dissolved to prepare a curable composition.
-Cyclohexanone 80 parts by weight-Lumogen IR788 (BASF) 0.2 parts by weight-KAYARAD DPHA (manufactured by Nippon Kayaku, polymerizable compound) 7.78 parts by weight-Photopolymerization initiator 2.00 parts by weight CGI-242 ( BASF, oxime initiator)
-Resin (benzyl methacrylate / methacrylic acid = 80/20, Mw = 30000) 10.00 parts by weight-Surfactant (F-781 manufactured by DIC Corporation) 0.02 parts by weight

A SiO ₂ layer and a TiO ₂ layer are alternately deposited on a glass substrate by an electron beam evaporation (EB) method at a substrate temperature of 280 ° C. to form a dielectric multilayer film on both sides. A laminated film with a film was obtained. The dielectric multilayer film layer formed on the base film had a layer configuration of one layer of 110 to 120 nm and 18 layers on one side (the outermost layer was an SiO ₂ layer).
Next, the curable composition was spin-coated on a glass substrate, dried at 100 ° C. for 2 minutes, and further heated at 200 ° C. for 5 minutes.
The total thickness of the obtained near-infrared cut filter was about 0.2 mm.

Comparative Example 1
On the glass substrate, SiO ₂ layer and TiO ₂ layer are alternately deposited by electron beam evaporation (EB) method to form a dielectric multilayer film on both sides to obtain a multilayer film with a dielectric multilayer film. It was. The dielectric multilayer film layer formed on the base film had a layer configuration of one layer of 110 to 120 nm and 18 layers on one side (the outermost layer was an SiO ₂ layer).

Comparative Example 2
Instead of polyamic acid, the dope was changed to the following to form a film.
A norbornene-based resin “ZEONOR 1400R” manufactured by Nippon Zeon Co., Ltd. was dissolved by adding a 7: 3 mixed solution of cyclohexane and xylene to obtain a solution having a solid content of 20% (Dope E). After adding and stirring and mixing a quartalylene dye (LumogenIR765, manufactured by BASF) (0.1 g) to the dope E (10 g), the mixture was cast on a smooth glass plate at 60 ° C. for 8 hours at 80 ° C. After drying for 8 hours, it peeled off from the glass plate. The peeled resin was further dried at 100 ° C. under reduced pressure for 24 hours.
On the obtained base film, an SiO ₂ layer and a TiO ₂ layer are alternately deposited by an electron beam deposition (EB) method at a substrate temperature of 200 ° C., and a dielectric multilayer film is formed on both sides. A laminated film with a dielectric multilayer film was obtained. The dielectric multilayer film layer formed on the base film had a layer configuration of one layer of 70 to 180 nm and 18 layers on one side (the outermost layer was a SiO ₂ layer).

DESCRIPTION OF SYMBOLS 1 Glass substrate 2 Near-infrared reflective film which consists of dielectric multilayers 3 Organic polymer resin layer 4 Near-infrared absorber

Claims (20)

A near-infrared cut filter having an organic polymer layer and a near-infrared reflective film made of a dielectric multilayer film on a glass substrate,
The organic polymer layer includes a polyimide resin and a near infrared absorber,
The dielectric multilayer film has a structure in which low refractive index layers and high refractive index layers are alternately stacked,
The near-infrared cut filter whose said polyimide resin is a polymer which has a repeating unit represented by following General formula (2).
General formula (2)
(In the general formula, X represents an aromatic group having 4 to 30 carbon atoms, and Y represents a monocyclic or condensed polycyclic aliphatic group having 4 to 30 carbon atoms. Represents.)   The near-infrared cut filter according to claim 1, wherein X in the general formula (2) represents an unsubstituted aromatic group having 4 to 30 carbon atoms. X in the general formula (2) represents an unsubstituted aromatic group having 4 to 30 carbon atoms,
The near-infrared cut filter according to claim 1, wherein Y represents a monocyclic or condensed polycyclic unsubstituted aliphatic group having 4 to 30 carbon atoms. A near-infrared cut filter having an organic polymer layer and a near-infrared reflective film made of a dielectric multilayer film on a glass substrate,
The organic polymer layer is a layer formed by curing a curable composition containing a polymerizable monomer having an ethylenically unsaturated double bond, a binder, a radical photopolymerization initiator, and a near infrared absorber. Yes,
The near-infrared absorber is at least one selected from squarylium dyes, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, quatarylene dyes, dithiol metal complex dyes, and transition metal oxide compounds. Infrared cut filter.   The near-infrared cut filter according to claim 4, wherein the polymerizable monomer includes a polymerizable monomer having three or more ethylenically unsaturated double bonds. The near-infrared cut filter according to claim 4, wherein the polymerizable monomer includes a polymerizable monomer represented by the following general formulas (MO-1) to (MO-5);
In the formula, n is 0 to 14, and m is 1 to 8. A plurality of R and T present in one molecule may be the same or different; in the formula, when T is an oxyalkylene group, the terminal on the carbon atom side is bonded to R. The near-infrared cut filter according to any one of claims 4 to 6, wherein the binder contains a polymer obtained by polymerizing a compound represented by the following general formula (E-1).
(In formula (E-1), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.)   The near-infrared cut filter according to any one of claims 4 to 7, wherein the radical photopolymerization initiator is an oxime photopolymerization initiator.   The near-infrared cut filter according to any one of claims 4 to 8, wherein the curable composition further comprises a surfactant.   The shift amount of the wavelength at which the transmittance is 50% on the high wavelength side in the p-polarized transmission band in the visible light range, obtained by changing the incident angle to 0 ° and 35 ° with respect to the film surface of the near infrared cut filter. The near-infrared cut filter of any one of Claims 1-9 whose is less than 30 nm.   A near-infrared cut filter was cut out to 2 cm × 2 cm, heated on a hot plate at 260 ° C. for 3 minutes, and the spectrum in the wavelength region of 400-1100 nm before and after heating was measured at an incident angle of 0 degree. The near-infrared cut filter according to any one of claims 1 to 10, wherein a change amount of an integrated value of the area is less than 10%.   The near-infrared cut filter according to any one of claims 1 to 11, wherein the glass transition temperature of the organic polymer layer is 250 ° C or higher.   The near-infrared cut filter according to claim 1, wherein the organic polymer layer has a thickness of 0.1 to 10 μm.   The near-infrared absorber is at least one selected from squarylium dyes, cyanine dyes, phthalocyanine dyes, naphthalocyanine dyes, quatarylene dyes, dithiol metal complex dyes and transition metal oxide compounds. Item 2. The near infrared cut filter according to Item 1.   The glass substrate, the organic polymer layer, and the dielectric multilayer film are provided in this order, or the glass substrate, the dielectric multilayer film, and the organic polymer layer are provided in this order. Near-infrared cut filter.   The near-infrared cut filter according to any one of claims 4 to 9, wherein the dielectric multilayer film has a structure in which low refractive index layers and high refractive index layers are alternately laminated. The near-infrared cut filter according to claim 1 or 16, wherein one of the low refractive index layers includes silica (SiO ₂ ), and one of the high refractive index layers includes titania (TiO ₂ ).   The solid-state image sensor using the near-infrared cut filter of any one of Claims 1-17.   The manufacturing method of the near-infrared cut filter of any one of Claims 1-17 including forming a dielectric multilayer by vapor deposition.   The manufacturing method of the near-infrared cut filter of Claim 19 including forming an organic polymer layer by spin coating.