KR101578963B1 - Near-infrared ray cut filter and apparatus using near-infrared ray cut filter - Google Patents

Abstract

An object of the present invention is to obtain a near infrared ray blocking filter having a wide viewing angle, excellent near infrared ray shielding ability, low hygroscopicity, and free from foreign matter and warpage.
The near-infrared cut filter of the present invention is characterized by having a resin substrate (I) containing a compound (I) having a structure derived from a compound represented by the following formula (I).
(I)

Description

[0001] The present invention relates to a near-infrared cut filter and a near-infrared cut filter,

The present invention relates to a near-IR blocking filter. To a near infrared ray blocking filter which can be preferably used as a visibility correction filter for a solid-state image pickup device such as a CCD or a CMOS.

2. Description of the Related Art In recent years, a television equipped with a plasma display panel (PDP) has been commercialized and widely used in general households. This PDP is a display that operates using plasma discharge, but it is known that near infrared rays (wavelength: 800 to 1000 nm) are generated during plasma discharge.

On the other hand, in the home, near infrared rays are often used for information exchange of a remote controller of household appliances such as a television, a stereo or an air conditioner, and a personal computer, and the near infrared rays generated by the PDP may cause malfunction of these devices It is usually pointed out that it is high.

Therefore, most of the commercially available PDPs have a filter function for blocking near infrared rays, which are generated by the front plate itself.

CCD or CMOS image sensors, which are solid-state image pickup devices for color images, are used for video cameras, digital still cameras, mobile phones equipped with camera functions, etc. However, these solid-state image pickup devices use a silicon photodiode having sensitivity to near- It is necessary to perform visibility correction, and a near-infrared ray cut filter is often used.

As such a near-infrared ray cut filter, those manufactured by various methods have been used conventionally. For example, a transparent substrate made of glass or the like is coated with a metal such as silver to reflect near infrared rays, a transparent resin such as acrylic resin or polycarbonate resin is added with a near infrared absorbing dye, and the like have.

However, the near-infrared cut filter in which a metal is deposited on a glass substrate has a problem in that it is costly to manufacture, and glass fragments of the substrate are mixed as a foreign material at the time of cutting. Further, even in the case of using an inorganic material as the base material, there has been a limit in coping with recent thickness reduction and miniaturization of the solid-state image pickup device.

Japanese Patent Application Laid-Open No. 6-200113 (Patent Document 1) discloses a near-IR blocking filter using a transparent resin as a base material and containing a near-infrared absorbing dye in the transparent resin.

However, the near infrared ray shielding filter described in Patent Document 1 has a case in which the near infrared ray absorbing ability is not necessarily sufficient.

The present applicant has proposed a near infrared ray shielding filter having a norbornene resin substrate and a near infrared ray reflecting film in Japanese Patent Laid-Open Publication No. 2005-338395 (Patent Document 2).

Japanese Unexamined Patent Publication (Kokai) No. 6-200113 Japanese Patent Application Laid-Open No. 2005-338395

The near infrared ray shielding filter described in Patent Document 2 has excellent near infrared ray shielding ability, moisture absorption resistance and impact resistance, but a sufficient viewing angle can not be obtained.

It is an object of the present invention to obtain a near-infrared ray blocking filter which can be preferably used for a solid-state imaging device such as CCD, CMOS, etc., which has wide viewing angle, excellent near infrared ray blocking ability, low hygroscopicity, no foreign substance or warpage. Still another object of the present invention is to provide a solid-state imaging device which is thin and excellent in impact resistance.

The near-infrared cut filter according to the present invention is characterized by having a resin substrate (I) containing a compound (I) having a structure derived from a compound represented by the following formula (I).

(I)

Wherein R ^a , R ^b and Y satisfy the following (i) or (ii)

(i) R ^a independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an -NR ^e R ^f group (R ^e and R ^f each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) And,

R ^b each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, -NR ^g R ^h group (R ^g and R ^h are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or -C (O) R ⁱ (R ⁱ represents an alkyl group having 1 to 5 carbon atoms)) or a hydroxy group,

Y represents an -NR ^j R ^k group wherein each of R ^j and R ^k independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group, To 12 aromatic hydrocarbon groups, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom is substituted with an alkyl group).

(ii) one of the two R ^{a on} one benzene ring is bonded to Y on the same benzene ring to form a heterocyclic ring containing 5 or 6 constituent atoms and at least one nitrogen atom,

R ^b and R ^a not involved in the bond are each independently the same as R ^b and R ^a in the above (i)

The near-infrared cut filter according to the present invention preferably has a transmittance satisfying the following (A) to (D).

(A) an average value of transmittance in a wavelength range of 430 to 580 nm measured from the vertical direction of the near-infrared cut filter is 75% or more

(B) an average value of the transmittance when measured from the vertical direction of the near-infrared cut filter at a wavelength of 800 to 1000 nm is not more than 20%

(C) the longest wavelength (Xa) in which the transmittance is 70% when measured from the vertical direction of the near-IR cut filter in the wavelength region of 800 nm or less, and the longest wavelength (Xa) measured from the vertical direction of the near- The absolute value of the difference between the shortest wavelength (Xb) in which the transmittance is 30% in one case is less than 75 nm

(D) a value (Ya) of the wavelength at which the transmittance is 50% when measured from the vertical direction of the near-IR cut filter in a wavelength range of 560 to 800 nm and an angle of 30 DEG with respect to the vertical direction of the near- The absolute value of the difference in the value (Yb) of the wavelength at which the transmittance in one case is 50% is less than 15 nm

It is preferable that the resin substrate (I) satisfies the following (E) and (F).

(E) Absorption maximum at wavelength of 600 to 800 nm

(F) a longest wavelength (Za) at an absorption maximum or less at which the transmittance is 70% when measured from the vertical direction of the substrate in a wavelength range of 430 to 800 nm, and Direction, the absolute value of the difference between the shortest wavelength (Zb) in which the transmittance is 30% and the absolute value of the difference is less than 75 nm

The compound represented by Formula (I) is preferably a compound represented by Formula (II).

≪

Wherein R ^a and R ^b each independently have the same meaning as (i) in the above formula (I), R ^c each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an arbitrary hydrogen atom as a functional group A substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom is substituted with an alkyl group.

The resin substrate (I) is preferably a substrate comprising a cyclic olefin resin or an aromatic polyether resin.

The cyclic olefin resin is preferably a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula X ₀ and a monomer represented by the following formula Y ₀ .

<Formula X _0>

(In the formula X ₀ , R ^x1 to R ^x4 each independently represent an atom or a group selected from the following (i ') to (viii'), k ^x , m ^x and p ^x each independently represent 0 or a positive integer Lt; / RTI &gt;

(i ') hydrogen atom

(ii ') a halogen atom

(iii ') a trialkylsilyl group

(iv ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a connecting group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom

(v ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms

(vi ') polar group (except (iv'))

(vii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form an alkylidene group, and R ^x1 to R ^{x4, which} are not involved in the bond, Represents an atom or a group selected from

(viii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by bonding each other, and R ^x1 to R ^{x4, which} are not involved in the bond, (Vi), or a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding R ^x2 and R ^x3 to each other, and R ^x1 to R ^{x4 which} are not involved in the bond are each independently Represents an atom or a group selected from (i ') to (vi').

<Y ₀ >

(In the formula Y ₀ , R ^y1 and R ^y2 each independently represent an atom or a group selected from the above (i ') to (vi'), or represent the following (ix '), and K ^y and P ^y are independently Lt; 0 &gt; or a positive integer)

(ix ') represents a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding of R ^y1 and R ^y2 to each other

The aromatic polyether resin preferably has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2).

(Wherein R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represent an integer of 0 to 4)

(Formula (2) of, R ¹ to R ⁴ and a to d are each independently the same meaning as R ¹ to R ⁴ and a to d in the formula 1, Y is a single bond, -SO ₂ - or> C = O R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, g and h each independently represent an integer of 0 to 4, m is 0 or 1, , Provided that when m is 0, R &lt; ⁷ &gt; is not a cyano group)

The aromatic polyether resin preferably further has at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4).

(Wherein R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z is a single bond, -O-, -S-, -SO ₂ -,> C = O, -CONH -, -COO- or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1)

(Formula (4) ^{of, R 7, R 8, Y} , m, and g and h are each independently the same meaning as ^{R 7, R 8, Y,} m, g , and h in the formula 2, R ^5, R ^6, Z, n, e and f are each independently the same as R ⁵ , R ⁶ , Z, n, e and f in the above formula (3)

The compound (I) is preferably contained in an amount of 0.01 to 10.0 parts by weight based on 100 parts by weight of the resin.

The near-infrared cut filter according to the present invention can be preferably used for a solid-state imaging device.

The solid-state image pickup device and the camera module according to the present invention are characterized by having the near-IR cut filter.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to produce a near infrared ray shielding filter having small incident angle dependence of absorption (transmission) wavelength, wide viewing angle, excellent near infrared ray shielding ability, low hygroscopicity, and free from foreign matters and warpage.

Further, according to the present invention, the solid-state imaging device, the camera module and the like can be made thinner and smaller.

1 (a) is a schematic cross-sectional view showing an example of a conventional camera module. 1 (b) is a schematic cross-sectional view showing an example of a camera module when the near-infrared cut filter 6 'obtained in the present invention is used.
2 is a schematic view showing a method of measuring the transmittance in the case where the near-infrared cut filter is measured from the vertical direction.
3 is a schematic diagram showing a method of measuring the transmittance when measured from an angle of 30 DEG with respect to the vertical direction of the near-infrared cut-off filter.

Hereinafter, the present invention will be described in detail.

[Near infrared ray filter]

The near infrared ray blocking filter according to the present invention is a filter containing a compound (I) having a structure derived from a compound having a squarylium structure (hereinafter also referred to as "compound (I ')" It is preferable to have the resin substrate (I) having the following resin substrate (I) and the following near-infrared reflecting film.

Since the near-infrared cut filter has such a resin substrate, it becomes a near-infrared cut filter having a small dependence on the incident angle.

&Quot; resin substrate (I) &quot;

It is preferable that the resin substrate (I) comprises the compound (I) and satisfies the following (E) and (F).

(E) the absorption maximum in the wavelength range of 600 to 800 nm.

When the absorption maximum wavelength of the substrate is within this range, the substrate can selectively and effectively block the near infrared rays.

(F) a longest wavelength (Za) at an absorption maximum or less at which the transmittance is 70% when measured from the vertical direction of the substrate in a wavelength range of 430 to 800 nm, and (| Za-Zb |) of the difference of the shortest wavelength (Zb) in which the transmittance is 30% as measured from the direction is less than 75 nm, preferably less than 50 nm, more preferably less than 30 nm Value.

When the absolute value of the absorption maximum wavelength of the resin substrate I and the difference between (Za) and (Zb) is in the above range, the wavelengths Za and Zb near the wavelength region of the near- The transmittance is rapidly changed.

When such a substrate is used for a near-IR blocking filter, the absolute value of the difference between (Ya) and (Yb) of the filter becomes small, the dependence of the incident wavelength on the incident angle is small, A wide NIR filter can be obtained.

In addition, when the near-infrared cut filter using such a substrate is used for a lens unit such as a camera module, it is preferable because the lens unit can be lowered (lowered).

The average transmittance of the substrate when the thickness of the resin substrate containing the compound (I) is 100 占 퐉 is 50% or more in a so-called visible light region of 400 to 700 nm in wavelength, Or more, preferably 65% or more.

The thickness of the resin substrate I may be suitably selected in accordance with the intended use and is not particularly limited, but it is preferable to adjust the thickness of the substrate to satisfy the above requirements (E) and (F), more preferably 250 To 50 m, more preferably from 200 to 50 m, and particularly preferably from 150 to 80 m.

When the thickness of the resin substrate (I) is within the above range, the near-infrared cut filter using the substrate can be miniaturized and lightweight, and can be suitably used for various applications such as solid state imaging devices. Particularly, when the lens unit is used in a lens unit such as a camera module, it is preferable because the lens unit can be downsized.

&Lt; Compound (I) >

The compound (I) has a structure derived from the compound (I '). The compound (I) is preferably a dye having a squarylium structure.

(I)

Wherein R ^a , R ^b and Y satisfy the following (i) or (ii)

(i) R ^a independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an -NR ^e R ^f group (R ^e and R ^f each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) And,

R ^b each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, -NR ^g R ^h group (R ^g and R ^h are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or -C (O) R ⁱ (R ⁱ represents an alkyl group having 1 to 5 carbon atoms)) or a hydroxy group,

Y represents an -NR ^j R ^k group wherein each of R ^j and R ^k independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group, To 12 aromatic hydrocarbon groups, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom is substituted with an alkyl group).

(ii) one of the two R ^{a on} one benzene ring is bonded to Y on the same benzene ring to form a heterocyclic ring containing 5 or 6 constituent atoms and at least one nitrogen atom, and R ^b and R ^a being not involved in the coupling are each independently the same meaning as R ^b, and R ^a in the (i)]

Examples of the alkyl group having 1 to 8 carbon atoms represented by R ^a include a methyl group (Me), an ethyl group (Et), an n-propyl group (n-Pr), an i- Butyl group (t-Bu), pentyl group and hexyl group, and arbitrary hydrogen atoms of these groups may be substituted with a methyl group and an ethyl group.

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^e and R ^f in the -NR ^e R ^f group include methyl, ethyl, n-propyl, i-propyl, n-butyl, And a pentyl group.

Examples of the alkyl group having 1 to 5 carbon atoms for R ^b include a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s-butyl group,

Examples of the alkyl group having 1 to 5 carbon atoms represented by R ^g and R ^h in the -NR ^g R ^h group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, And a pentyl group.

Examples of R ⁱ in the -C (O) R ⁱ group include methyl, ethyl, n-propyl, i-propyl, n-butyl, have.

Examples of the aliphatic hydrocarbon group having 1 to 8 carbon atoms for R ^j and R ^k in the -NR ^j R ^k group include methyl, ethyl, n-propyl, i-propyl, n-butyl, Chain aliphatic hydrocarbon groups such as a butyl group, a pentyl group and a hexyl group; And cyclic aliphatic hydrocarbon groups such as cyclopentyl group and cyclohexyl group.

As the substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom of R ^j and R ^k in the -NR ^j R ^k group is substituted by a functional group, any hydrogen atom of the above-mentioned chain aliphatic hydrocarbon group may be replaced by -NR'R " (R 'and R''represent a chain aliphatic hydrocarbon group such as a methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, A substituted aliphatic hydrocarbon group substituted with a functional group such as CN, -OH, -OR (R represents a methyl group, an ethyl group and a propyl group); And a substituted cyclic aliphatic hydrocarbon group in which any hydrogen atom of the cyclic aliphatic hydrocarbon group is substituted with a methyl group or an ethyl group.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms of R ^j and R ^k in the -NR ^j R ^k group include a phenyl group and the like.

As the substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom of R ^j and R ^k in the -NR ^j R ^k group is substituted with an alkyl group, any hydrogen atom of the phenyl group is preferably a methyl group, ethyl group, n-propyl group, i A substituted phenyl group substituted with a chain aliphatic hydrocarbon group such as a propyl group, an n-butyl group, an s-butyl group, a t-butyl group and a pentyl group.

As the heterocycle having at least one nitrogen atom of 5 or 6 constituent atoms in which one of the two R ^a on one benzene ring in the above formula (I) is bonded to Y on the same benzene ring, For example, pyrrolidine, pyrrole, imidazole, pyrazole, piperidine, pyridine, piperazine, pyridazine, pyrimidine and pyrazine. Of these heterocyclic rings, a heterocyclic ring constituting a corresponding heterocyclic ring and in which one adjacent atom of the carbon atom constituting the benzene ring is a nitrogen atom is preferable, and pyrrolidine is more preferable.

The compound (I ') includes, for example, a compound (I-2) having a resonance structure having a structure represented by the following formula (I-1). Examples of the compound (I ') include the compound (I-1) and the compound (I-2).

The compound (I) is a compound having a spectral transmittance at an absorption maximum when the transmittance of a solution obtained by dissolving the compound (I) in its good solvent is measured (optical path length is 1 cm) Is preferably 30% or less, irrespective of the amount of the compound (I) contained in the solution, and when the transmittance of the solution obtained by dissolving the compound (I) in its good solvent is measured The transmittance is 30% at a wavelength not less than 580 nm and the longest wavelength at or below the absorption maximum at which the transmittance becomes 70% in the wavelength range of 430 to 800 nm, Is preferably a compound which has an absolute value of the difference of the shortest wavelength which is shorter than 75 nm, preferably less than 65 nm, more preferably less than 55 nm.

In addition, in the conventional near-IR blocking filter, the compound (I) has a slope with a steep slope of its transmittance curve, that the absorption region in the near-infrared region is narrow, (I) can not withstand the molding temperature of the glass. Therefore, a near-infrared ray blocking filter having a small dependency on the incident angle as in the present invention has not been obtained.

Since the resin substrate (I) containing the compound (I) has the characteristics of the above (E) and (F), the near- . Therefore, it is possible to obtain a near-infrared ray blocking filter having small incident angle dependency and a wide viewing angle.

In addition, when a near-infrared reflective film to be described later is provided on the resin substrate I by vapor deposition or the like, the viewing angle of the near-infrared cut filter is narrowed, and the performance is deteriorated. However, the resin substrate (I) It is possible to prevent deterioration of the performance of the near-IR cut filter that can be caused by providing the near-infrared reflective film. Therefore, even when the near-infrared ray reflective film is provided on the resin substrate I by vapor deposition or the like, a near-infrared ray cut filter having a stable absorption wavelength region that does not depend on the incident angle of the incident light can be obtained.

In the present invention, it is preferable that the compound (I ') is a compound represented by the following formula (II).

&Lt;

Wherein R ^a and R ^b have the same meanings as in the above formula (i), R ^c each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a carbon number in which an arbitrary hydrogen atom is substituted with a functional group A substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom is substituted with an alkyl group.

An aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^c in the formula (II), a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group, an aromatic hydrocarbon group having 6 to 12 carbon atoms, , An aliphatic hydrocarbon group having 1 to 8 carbon atoms represented by R ^j and R ^k in the -NR ^j R ^k group, an aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group , Aromatic hydrocarbon groups having 6 to 12 carbon atoms, and groups similar to those exemplified for the substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom is substituted with an alkyl group.

The compound (II) may also be a compound represented by the following formula (II-1) which is a resonance structure thereof.

Examples of the compound represented by the above formula (II) include the following (a-1) to (a-19). In addition, a compound "Ac" represents a -C (O) -CH _3.

Among them, when the compound (a-10) is dissolved in methylene chloride and the spectral transmittance (optical path length: 1 cm) of the solution obtained by dissolving the compound (a-10) in methylene chloride at a concentration of 0.0001 part by weight is measured, 0.04 parts by weight of a compound (a-10), 100 parts by weight of a cyclic olefin-based resin "ATON G" manufactured by JSR Kabushiki Kaisha, 20% by weight of a resin obtained by adding methylene chloride, Phosphoric acid solution was cast on a smooth glass plate, dried at 20 占 폚 for 8 hours, peeled off from the glass plate, and dried at 100 占 폚 for 8 hours under reduced pressure. When the transmittance is measured, the longest wavelength at which the transmittance becomes 70% in the wavelength range of 430 to 800 nm, the longest at the absorption maximum or smaller, and the shortest transmittance at 30% in the wavelength range of 580 nm or more Since the absolute value of the difference is less than sheets of 55 nm, it is preferred in that the incident angle dependence of the wavelength of the absorption (transmission) is small, can be prepared a wide viewing angle, near-infrared light blocking filter.

In the present invention, the compound (I) can be synthesized by a generally known method, and can be synthesized, for example, by the method described in Japanese Patent Application Laid-Open No. 1-228960.

In the present invention, the amount of the compound (I) to be used is preferably appropriately selected so that the resin substrate (I) satisfies the above conditions (E) and (F) Is preferably 0.01 to 10.0 parts by weight, more preferably 0.01 to 8.0 parts by weight, particularly preferably 0.01 to 5.0 parts by weight, based on 100 parts by weight of the resin used.

When the amount of the compound (I) is within the above range, a near infrared ray blocking filter having a small incident angle dependence of the absorption wavelength, a wide viewing angle, a near infrared ray shielding ability, and excellent transmittance and strength in the range of 430 to 580 nm can be obtained.

When the amount of the compound (I) is larger than the above range, a near infrared ray blocking filter in which the properties of the compound (I) are stronger can be obtained. However, when the transmittance in the range of 430 to 580 nm is lower than the desired value If the amount of the compound (I) used is less than the above range, a near infrared ray shielding filter having a high transmittance in the range of 430 to 580 nm can be obtained There is a possibility that the characteristics of the compound (I) may be difficult to appear, the dependence of the incident wavelength on the incident angle is small, and it may be difficult to obtain a resin substrate or a near infrared ray shielding filter having a wide viewing angle.

<Resin>

The resin substrate (I) used in the present invention may comprise the compound (I) and a resin, and the resin is preferably a transparent resin. Such a resin is not particularly limited as long as it does not impair the effect of the present invention. For example, the dielectric multi-layer film is formed by high-temperature vapor deposition at a deposition temperature of 100 deg. C or higher while ensuring thermal stability and moldability into a film A resin having a glass transition temperature (Tg) of preferably 110 to 380 DEG C, more preferably 110 to 370 DEG C, and still more preferably 120 to 360 DEG C can be mentioned. When the glass transition temperature of the resin is 120 deg. C or higher, preferably 130 deg. C or higher, more preferably 140 deg. C or higher, a film capable of vapor-depositing the dielectric multilayer film at a higher temperature is obtained.

As the resin, a resin having a total light transmittance at a thickness of 0.1 mm is preferably 75 to 94%, more preferably 78 to 94%, and particularly preferably 80 to 94%. When the total light transmittance is in this range, the resulting substrate exhibits good transparency as an optical film.

Examples of such a resin include a resin such as a cyclic olefin resin, a polyether resin, a polyarylate resin (PAR), a polysulfone resin (PSF), a polyether sulfone resin (PES), a polyparaphenylene resin (PC), poly (ethylene naphthalate) (PEN), and organic-inorganic hybrid resins such as poly (arylene ether) phosphine oxide resin (PEPO), polyimide resin (PPI), polyamideimide resin Inorganic nano hybrid materials.

Use of a cyclic olefin resin or aromatic polyether resin having high transparency among the above resins is preferable because the transmittance of the visible light region is particularly high. These resins are preferable because they are low in hygroscopicity and hardly warped.

When a norbornene resin or an aromatic polyether resin is used as the resin, the dispersibility of the compound (I) to the norbornene resin is favorable, so that a substrate having uniform optical characteristics and excellent moldability can be obtained .

<Cyclic Olefin Resin>

As the transparent resin to be used in the present invention, a cyclic olefin-based resin can be mentioned. The cyclic olefin resin is not particularly limited, but may be, for example, a resin obtained by polymerizing at least one monomer selected from the group consisting of a monomer represented by the following formula X ₀ and a monomer represented by the following formula Y ₀ , A resin obtained by hydrogenating the resin obtained above can be used.

<Formula X _0>

(In the formula X ₀ , R ^x1 to R ^x4 each independently represent an atom or a group selected from the following (i ') to (viii'), k ^x , m ^x and p ^x each independently represent 0 or a positive integer Lt; / RTI &gt;

(i ') hydrogen atom

(ii ') a halogen atom

(iii ') a trialkylsilyl group

(iv ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a connecting group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom

(v ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms

(vi ') polar group (except (iv'))

(vii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form an alkylidene group, and R ^x1 to R ^{x4, which} are not involved in the bond, Represents an atom or a group selected from

(viii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by bonding each other, and R ^x1 to R ^{x4, which} are not involved in the bond, (Vi), or a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding R ^x2 and R ^x3 to each other, and R ^x1 to R ^{x4 which} are not involved in the bond are each independently Represents an atom or a group selected from (i ') to (vi').

<Y ₀ >

(In the formula Y ₀ , R ^y1 and R ^y2 each independently represent an atom or a group selected from the above (i ') to (vi'), or represent the following (ix '), and K ^y and P ^y are independently Lt; 0 &gt; or a positive integer)

(ix ') represents a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by bonding of R ^y1 and R ^y2 to each other

Examples of the halogen atom (ii ') include a fluorine atom, a chlorine atom and a bromine atom.

Examples of the trialkylsilyl group (iii ') include a trialkylsilyl group having 1 to 12 carbon atoms, preferably a trialkylsilyl group having 1 to 6 carbon atoms. Examples of such a trialkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a triisopropylsilyl group.

Examples of the linking group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom include a carbonyl group (-CO-), an oxycarbonyl group (-OCO-), a carbonyloxy group (-COO-), a sulfonyl group (-SO ₂ - ), ether bond (-O-), thioether bond (-S-), an imino group (-NH-), amide bond (-NHCO-, -CONH-), and siloxane bond (-OSi (R) ₂ - ( (Wherein R is an alkyl group such as methyl or ethyl)), and the substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms in (iv ') may be a group including a plurality of these linking groups.

(* -COO-) and siloxane bonds (-OSi (R) ₂ -) are preferable in view of the dispersibility and solubility of the compound (I) and the adhesion and adhesion to the near- desirable. Provided that * is bonded to the ring of the formula X ₀ .

The substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms is preferably a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and examples thereof include an alkyl group such as methyl group, ethyl group and propyl group; A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; Aromatic hydrocarbon groups such as phenyl group, biphenyl group and phenylethyl group; An alkenyl group such as a vinyl group, an allyl group and a propenyl group, and the like. Of these groups, a methyl group and an ethyl group are preferable in terms of heat stability.

Examples of the substituent include a hydroxyl group and a halogen atom.

The (vi ') polar group includes, for example, a hydroxy group; An alkoxy group having 1 to 10 carbon atoms such as methoxy group and ethoxy group; A carbonyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; Cyano; An amino group; Acyl; Sulfo group; A carboxyl group and the like.

Examples of the alkylidene group formed by combining R ^x1 and R ^x2 or R ^x3 and R ^x4 with each other include a methylidene group, an ethylidene group, and a propylidene group.

A monocyclic or polycyclic hydrocarbon ring or heterocyclic ring formed by combining R ^x1 and R ^x2 or R ^x3 and R ^x4 , a monocyclic hydrocarbon ring or heterocyclic ring formed by bonding R ^x2 and R ^x3 , and R ^y1 and R ^y2 Examples of the monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocycle formed by combining with each other include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclobutenylene, cyclopentenylene, cyclohexenylene , Cycloheptenylene, phenylene, naphthylene, and the like.

k ^x , m ^x , p ^x , k ^y , and p ^y are each independently an integer of 0 to 3. More preferably, k ^x + m ^x + p ^x is an integer of 0 to 4, more preferably k ^x + m ^x + p ^x is an integer of 0 to 2, and particularly preferably k ^x + m ^x + p ^x is 1. k ^y + p ^y is preferably an integer of 0 to 4, and k ^y + p ^y is more preferably an integer of 0 to 2. It is preferable that a cyclic olefin monomer having m ^x = 0 and k ^x + p ^x = 1 is used because a resin having a high glass transition temperature and excellent mechanical strength can be obtained.

Specific examples of the cyclic olefin-based monomer represented by the formula X ₀ or Y ₀ include, but are not limited to, the following compounds.

· Bicyclo [2.2.1] hept-2-ene (norbornene)

· 5-Methyl-bicyclo [2.2.1] hept-2-ene

· 5-Ethyl-bicyclo [2.2.1] hept-2-ene

· 5-Propylbicyclo [2.2.1] hept-2-ene

· 5-Butylbicyclo [2.2.1] hept-2-ene

· 5-t-Butylbicyclo [2.2.1] hept-2-ene

· 5-Isobutylbicyclo [2.2.1] hept-2-ene

Pentylbicyclo [2.2.1] hept-2-ene

5-hexylbicyclo [2.2.1] hept-2-ene

· 5-heptylbicyclo [2.2.1] hept-2-ene

· 5-Octylbicyclo [2.2.1] hept-2-ene

· 5-Decylbicyclo [2.2.1] hept-2-ene

Dodecylbicyclo [2.2.1] hept-2-ene

5-Cyclohexyl-bicyclo [2.2.1] hept-2-ene

· 5-Phenyl-bicyclo [2.2.1] hept-2-ene

· 5- (4-biphenyl) -bicyclo [2.2.1] hept-2-ene

· 5-Methoxycarbonyl-bicyclo [2.2.1] hept-2-ene

· 5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene

· 5-Phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene

· 5-Phenylcarbonyloxy-bicyclo [2.2.1] hept-2-ene

· 5-Methyl-5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenoxycarbonyl-bicyclo [2.2.1] hept-2-ene

5-Methyl-5-phenoxyethylcarbonyl-bicyclo [2.2.1] hept-2-ene

· 5-vinyl-bicyclo [2.2.1] hept-2-ene

· 5-Ethylidene-bicyclo [2.2.1] hept-2-ene

· 5-Trimethoxysilyl-bicyclo [2.2.1] hept-2-ene

5-triethoxysilyl-bicyclo [2.2.1] hept-2-ene

· 5,5-Dimethyl-bicyclo [2.2.1] hept-2-ene

5,6-Dimethyl-bicyclo [2.2.1] hept-2-ene

· 5-Fluoro-bicyclo [2.2.1] hept-2-ene

· 5-Chloro-bicyclo [2.2.1] hept-2-ene

Bromo-bicyclo [2.2.1] hept-2-ene

· 5,6-Difluoro-bicyclo [2.2.1] hept-2-ene

· 5,6-Dichloro-bicyclo [2.2.1] hept-2-ene

· 5,6-dibromo-bicyclo [2.2.1] hept-2-ene

· 5-Hydroxy-bicyclo [2.2.1] hept-2-ene

· 5-Hydroxyethyl-bicyclo [2.2.1] hept-2-ene

· 5-Cyano-bicyclo [2.2.1] hept-2-ene

· 5-Amino-bicyclo [2.2.1] hept-2-ene

Tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

Tricyclo [4.4.0.1 ^2,5 ] undec-3-ene

· 7-Methyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Ethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Cyclohexyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Phenyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7- (4-biphenyl) -tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8-Dimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8,9-Trimethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 8-Methyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene

· 8-Phenyl-tricyclo [4.4.0.1 ^2,5 ] undec-3-ene

· 7-Fluoro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Chloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Bromo-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7,8-Dichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

7,8,9-Trichloro-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Chloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Dichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-trichloromethyl-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Hydroxy-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Cyano-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· 7-Amino-tricyclo [4.3.0.1 ^2,5 ] dec-3-ene

· Tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

- pentacyclo [7.4.0.1 ^2,5 .1 ^8,11 .0 ^7,12 ] pentadec-3-ene

· 8-Methyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-ethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Cyclohexyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Phenyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8- (4-biphenyl) -tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-phenylcarbonyloxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-Methyl-8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-Methyl-8-phenoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Methyl-8-phenoxyethylcarbonyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-vinyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-ethylidene-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

- 8,8-Dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

- 8,9-Dimethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Fluoro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Chloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Bromo-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8,8-Dichloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

- 8,9-Dichloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8,8,9,9-tetrachloro-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Hydroxy-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

8-Methyl-8-hydroxyethyl-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Cyano-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

· 8-Amino-tetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene

These cyclic olefin monomers may be used singly or in combination of two or more.

The kind and amount of the cyclic olefin-based monomer used in the present invention are appropriately selected depending on the properties required for the obtained resin.

Among them, when a compound having a structure containing at least one atom selected from an oxygen atom, a sulfur atom, a nitrogen atom and a silicon atom in the molecule (hereinafter referred to as a "polar structure") is used, I) is excellent in dispersibility and excellent in adhesiveness and adhesiveness to other materials (near-infrared ray reflective film, etc.). In particular, in the general formula X ₀ , R ^x1 and R ^x3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, preferably a hydrogen atom or a methyl group, and any one of R ^x2 and R ^x4 is a group having a polar structure , And the other is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms, is preferable because it has low absorption (wettability). A resin obtained by polymerizing a compound in which one of R ^y1 and R ^y2 is a group having a polar structure and the other is a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms is preferable because it has low absorption (wettability). The cyclic olefin-based monomer, in which the group having the polar structure is a group represented by the following formula Z ₀ , is preferably used because it is easy to balance the heat resistance and the absorption (wettability) of the obtained resin.

<Z ₀ >

- (CH _{2) z} COOR

(In the formula Z ₀ , R represents a substituted or unsubstituted hydrocarbon group having 1 to 15 carbon atoms, and z is 0 or an integer of 1 to 10)

It is preferable that z is 0 or an integer of 1 to 3 because the glass transition temperature of the obtained hydrogenated product becomes higher as the value of z in the above formula Z ₀ is smaller and the heat resistance is excellent. . In the formula (Z ₀₎ , the greater the number of carbon atoms in the above formula Z ₀ , the lower the absorption (wettability) of the hydrogenated product of the obtained polymer tends to decrease. However, since the glass transition temperature tends to decrease, To 10 carbon atoms, and particularly preferably a hydrocarbon group having 1 to 6 carbon atoms.

Further, in the above formula X ₀ indicating that if the alkyl group, especially a methyl group having 1 to 3 carbon atoms bonded to the carbon atoms bonded to a group represented by the formula Z _0, because it tends to be excellent in balance between heat resistance and absorption (s), compound desirable. In addition, in the above formula X ₀ , the compound in which m ^x is 0 and k ^x + p ^x is 1 has high reactivity and a polymer can be obtained at a high yield, that a hydrogenated polymer having high heat resistance can be obtained, It is preferably used in terms of easiness of operation.

The cyclic olefin-based resin may be a polymer obtained by copolymerizing the cyclic olefin-based monomer and a monomer copolymerizable with the monomer within a range not to impair the effect of the present invention.

Examples of the copolymerizable monomers include cyclic olefins such as cyclobutene, cyclopentene, cycloheptene, cyclooctene and cyclododecene, noncondensates such as 1,4-cyclooctadiene, dicyclopentadiene and cyclododecatriene And cyclic polyenes.

These copolymerizable monomers may be used alone or in combination of two or more.

The method of polymerizing the cyclic olefin-based monomer is not particularly limited as far as the polymerization of the monomer is possible, but the polymerization can be carried out by, for example, ring-opening polymerization or addition polymerization.

The polymer obtained by the ring-opening polymerization reaction has an olefinic unsaturated bond in its molecule. Further, in the addition polymerization reaction, the polymer sometimes has an olefinic unsaturated bond in its molecule. When the olefinically unsaturated bond is present in the polymer molecule as described above, the olefinic unsaturated bond may cause deterioration such as coloration or gelation with time. Therefore, the hydrogenation reaction for converting the olefinic unsaturated bond into the saturated bond is carried out .

The hydrogenation reaction can be carried out in a conventional manner, that is, by adding a hydrogenation catalyst known to a solution of a polymer having olefinic unsaturated bonds, and adding hydrogen gas of atmospheric pressure to 300 atm, preferably 3 to 200 atm, Deg.] C, preferably 20 to 180 [deg.] C.

The hydrogenation rate of the hydrogenated polymer is 500 MHz, and the ratio of hydrogen added to the olefinically unsaturated bond obtained by ¹ H-NMR is usually 50% or more, preferably 70% or more, more preferably 90% or more, , Preferably not less than 98%, and most preferably not less than 99%. The higher the hydrogenation rate, the better the stability against heat and light, and the more stable the characteristics over a long period of time.

<Aromatic polyether-based resin>

As the transparent resin used in the present invention, an aromatic polyether-based resin can be mentioned. Examples of the aromatic polyether resin include, but not limited to, a structural unit represented by the following formula (hereinafter also referred to as a "structural unit (1)") and a structural unit represented by the following formula (Hereinafter also referred to as "resin (1)") having at least one structural unit (hereinafter also referred to as "structural unit (1-2)") selected from the group consisting of desirable. The substrate obtained from such a resin is excellent in heat resistance and mechanical strength, and is excellent in transparency and surface smoothness.

&Lt; Formula 1 >

(Wherein R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms, a to d each independently represent an integer of 0 to 4, preferably 0 or 1)

Examples of the monovalent organic group having 1 to 12 carbon atoms include a monovalent hydrocarbon group having 1 to 12 carbon atoms and a monovalent organic group having 1 to 12 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom .

Examples of the monovalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched hydrocarbon group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms.

The linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferably a linear or branched hydrocarbon group having 1 to 8 carbon atoms, more preferably a linear or branched hydrocarbon group having 1 to 5 carbon atoms.

Preferred examples of the linear or branched hydrocarbon group include a methyl group, an ethyl group, a n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert- And an n-heptyl group.

The alicyclic hydrocarbon group having 3 to 12 carbon atoms is preferably an alicyclic hydrocarbon group having 3 to 8 carbon atoms, and more preferably an alicyclic hydrocarbon group having 3 or 4 carbon atoms.

Preferable specific examples of the alicyclic hydrocarbon group having 3 to 12 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group; And cycloalkenyl groups such as a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group. The bonding site of the alicyclic hydrocarbon group may be any carbon on the alicyclic ring.

Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenyl group, a biphenyl group and a naphthyl group. The bonding site of the aromatic hydrocarbon group may be any carbon on the aromatic ring.

Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom include an organic group composed of a hydrogen atom, a carbon atom and an oxygen atom. Among them, an ether bond, a carbonyl group or an organic group having 1 to 12 carbon atoms in total and consisting of an ester bond and a hydrocarbon group Can be preferably used.

Examples of the organic group having 1 to 12 carbon atoms in total having an ether bond include an alkoxy group having 1 to 12 carbon atoms, an alkenyloxy group having 2 to 12 carbon atoms, an alkynyloxy group having 2 to 12 carbon atoms, an aryloxy group having 6 to 12 carbon atoms, An alkoxyalkyl group having 1 to 12 carbon atoms, and the like. Specific examples include methoxy, ethoxy, propoxy, isopropyloxy, butoxy, phenoxy, propenyloxy, cyclohexyloxy and methoxymethyl.

Examples of the organic group having 1 to 12 carbon atoms having a carbonyl group include acyl groups having 2 to 12 carbon atoms. Specific examples thereof include an acetyl group, a propionyl group, an isopropionyl group, and a benzoyl group.

Examples of the organic group having 1 to 12 carbon atoms in total having an ester bond include an acyloxy group having 2 to 12 carbon atoms. Specific examples thereof include an acetyloxy group, a propionyloxy group, an isopropionyloxy group and a benzoyloxy group.

Examples of the organic group having 1 to 12 carbon atoms including a nitrogen atom include an organic group composed of a hydrogen atom, a carbon atom and a nitrogen atom. Specific examples thereof include a cyano group, an imidazole group, a triazole group, a benzimidazole group and a benztriazole group .

Examples of the organic group having 1 to 12 carbon atoms including an oxygen atom and a nitrogen atom include organic groups composed of a hydrogen atom, a carbon atom, an oxygen atom and a nitrogen atom, and specific examples thereof include oxazole group, oxadiazole group, benzoxazole group and benzoxazole Diazo group and the like.

R ¹ to R ⁴ in the above formula (1) are preferably a monovalent hydrocarbon group of 1 to 12 carbon atoms in terms of absorption (wettability) of the resin (1), more preferably an aromatic hydrocarbon group of 6 to 12 carbon atoms, desirable.

(2)

(In the formula 2, R ¹ to R ⁴ and a to d are each independently the same meaning as R ¹ to R ⁴ and a to d in the formula 1, Y is a single bond, -SO ₂ - or> C = O, R ⁷ and R ⁸ are each independently a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, m is 0 or 1, provided that when m is 0, R ⁷ is cyano , G and h each independently represent an integer of 0 to 4, preferably 0)

Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic groups having 1 to 12 carbon atoms in the above formula (1).

The resin (1) has a molar ratio of the structural unit (1) to the structural unit (2), provided that the sum of both (structural unit (1) + structural unit (2) (1): structural unit (2) = 50: 50 to 100: 0, and the structural unit (1): structural unit (2) = 70:30 to 100: 0 , More preferably structural unit (1): structural unit (2) = 80: 20 to 100: 0.

Here, the mechanical properties refer to properties such as tensile strength, elongation at break and tensile elastic modulus of the resin.

The resin (1) may be at least one structural unit selected from the group consisting of a structural unit represented by the following formula (3) and a structural unit represented by the following formula (4) ). When the resin (1) has such a structural unit (3-4), the mechanical properties of the substrate including the resin (1) are improved, which is preferable.

(3)

(Wherein R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z is a single bond, -O-, -S-, -SO ₂ -,> C = O, - CONH-, -COO- or a divalent organic group of 1 to 12 carbon atoms, n represents 0 or 1, e and f each independently represent an integer of 0 to 4, preferably 0)

Examples of the monovalent organic group having 1 to 12 carbon atoms include the same organic groups as the monovalent organic groups having 1 to 12 carbon atoms in the above formula (1).

Examples of the divalent organic group having 1 to 12 carbon atoms include divalent hydrocarbon groups having 1 to 12 carbon atoms, divalent halogenated hydrocarbon groups having 1 to 12 carbon atoms, at least one atom selected from the group consisting of oxygen atoms and nitrogen atoms A divalent organic group having 1 to 12 carbon atoms, and a divalent halogenated organic group having 1 to 12 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom.

Examples of the divalent hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a divalent aromatic hydrocarbon group having 6 to 12 carbon atoms. .

Examples of the straight or branched divalent hydrocarbon group having 1 to 12 carbon atoms include methylene, ethylene, trimethylene, isopropylidene, pentamethylene, hexamethylene and heptamethylene.

Examples of the bivalent alicyclic hydrocarbon group having 3 to 12 carbon atoms include a cycloalkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group and a cyclohexylene group; And cycloalkenylene groups such as cyclopentenylene, cyclopentenylene, cyclohexenylene and the like.

Examples of the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms include a phenylene group, a naphthylene group and a biphenylene group.

Examples of the divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a linear or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms, and a divalent halogenated aromatic group having 6 to 12 carbon atoms And a hydrocarbon group.

Examples of the straight or branched divalent halogenated hydrocarbon group having 1 to 12 carbon atoms include a difluoromethylene group, a dichloromethylene group, a tetrafluoroethylene group, a tetrachlorethylene group, a hexafluorotrimethylene group, a hexachlorotrimethylene group, A hexafluoroisopropylidene group, and a hexachloroisopropylidene group.

Examples of the divalent halogenated alicyclic hydrocarbon group having 3 to 12 carbon atoms include groups in which at least a part of hydrogen atoms of the groups exemplified as the divalent alicyclic hydrocarbon groups having 3 to 12 carbon atoms are substituted with fluorine, chlorine, bromine or iodine atoms And the like.

Examples of the divalent halogenated aromatic hydrocarbon group having 6 to 12 carbon atoms include groups in which at least a part of hydrogen atoms of the groups exemplified as the divalent aromatic hydrocarbon group having 6 to 12 carbon atoms are substituted with fluorine, chlorine, bromine or iodine atoms .

Examples of the organic group having 1 to 12 carbon atoms and containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom include an organic group composed of a hydrogen atom, a carbon atom and an oxygen atom and / or a nitrogen atom, A carbonyl group, a divalent organic group having a total of 1 to 12 carbon atoms having an ester bond or an amide bond and a hydrocarbon group, and the like.

As the divalent halogenated organic group having 1 to 12 carbon atoms and containing at least one kind of atom selected from the group consisting of an oxygen atom and a nitrogen atom, specifically, a divalent halogenated organic group containing at least one atom selected from the group consisting of an oxygen atom and a nitrogen atom And groups in which at least a part of the hydrogen atoms of the groups exemplified in the divalent organic group having 1 to 12 carbon atoms are substituted with a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

Z in the formula (3) is preferably a single bond, -O-, -SO ₂ -,> C = O or a divalent organic group having 1 to 12 carbon atoms. In view of the wettability of the resin (1) More preferably a divalent hydrocarbon group having 1 to 12 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms.

&Lt; Formula 4 >

(In the formula ^{4, R 7, R 8,} Y, m, and g and h are each independently the same meaning as ^{R 7, R 8, Y,} m, g , and h in the formula 2, R ^5, R ⁶ , Z, n, e and f are each independently the same as R ⁵ , R ⁶ , Z, n, e and f in the above formula (3), and R ⁷ is not a cyano group when m is 0)

Wherein the sum of the molar ratio of the structural unit (1-2) to the structural unit (3-4) (provided that the sum of the protons ((1-2) + (3-4)) is 100) (1-2) :( 3-4) = 50: 50 to 100: 0, and (1-2) :( 3-4) = 70: 30 to 70: 30 from the viewpoints of optical characteristics, heat resistance, More preferably 100: 0, and even more preferably (1-2) :( 3-4) = 80: 20 to 100: 0.

Here, the mechanical properties refer to properties such as tensile strength, elongation at break and tensile elastic modulus of the resin.

The resin (1) preferably contains the structural unit (1-2) and the structural unit (3-4) in an amount of 70 mol% or more in the total structural units from the viewpoints of optical characteristics, heat resistance and mechanical properties, More preferably 95 mol% or more of the structural units.

The resin (1) can be produced, for example, by reacting a compound represented by the following formula (5) (hereinafter also referred to as "compound (5)") and a compound represented by the following formula (Hereinafter also referred to as a "component (B)") comprising at least one compound selected from the group consisting of a compound represented by the following general formula (hereinafter also referred to as "component (A)") In an organic solvent.

(In the above formula (5), X independently represents a halogen atom, preferably a fluorine atom)

(Wherein the formula (7) ^{of, R 7, R 8, Y} , m, g , and h are each independently the same meaning as ^{R 7, R 8, Y,} m, g , and h in the formula 2, X is the independent Is the same as X in formula (5), provided that when m is 0, R &lt; ⁷ &gt; is not a cyano group)

(Wherein R ^A independently represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, a methanesulfonyl group or a trifluoromethylsulfonyl group, preferably a hydrogen atom, and R ¹ to R ⁴ And a to d are each independently the same as R ¹ to R ⁴ and a to d in the above formula (1)

Specific examples of the compound (5) include 2,6-difluorobenzonitrile (DFBN), 2,5-difluorobenzonitrile, 2,4-difluorobenzonitrile, 2,6-dichlorobenzonitrile, 2,5-dichlorobenzonitrile, 2,4-dichlorobenzonitrile, and reactive derivatives thereof. Particularly, 2,6-difluorobenzonitrile and 2,6-dichlorobenzonitrile are preferably used from the viewpoints of reactivity and economical efficiency. These compounds may be used in combination of two or more.

Specific examples of the compound represented by the general formula (6) (hereinafter also referred to as "compound (6)") include 9,9-bis (4-hydroxyphenyl) fluorene (BPFL), 9,9- 4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis (4-hydroxy-3-cyclohexylphenyl) fluorene, and reactive derivatives thereof, and the like can be given . Of the above-mentioned compounds, 9,9-bis (4-hydroxyphenyl) fluorene and 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene are preferably used. These compounds may be used in combination of two or more.

Specific examples of the compound (7) include 4,4'-difluorobenzophenone, 4,4'-difluorodiphenylsulfone (DFDS), 2,4'-difluorobenzophenone, 2,4'- Difluorodiphenylsulfone, 2,2'-difluorobenzophenone, 2,2'-difluorodiphenylsulfone, 3,3'-dinitro-4,4'-difluorobenzophenone, 3,3 '-Dinitro-4,4'-difluorodiphenylsulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenylsulfone, 2,4'-dichlorobenzophenone, 2,4'-dichloro Diphenyl sulfone, 2,2'-dichlorobenzophenone, 2,2'-dichlorodiphenyl sulfone, 3,3'-dinitro-4,4'-dichlorobenzophenone and 3,3'-dinitro- 4'-dichlorodiphenyl sulfone, and the like. Of these, 4,4'-difluorobenzophenone and 4,4'-difluorodiphenyl sulfone are preferable. These compounds may be used in combination of two or more.

At least one compound selected from the group consisting of the compound (5) and the compound (7) is contained in an amount of 80 to 100 mol%, preferably 90 to 100 mol% in 100 mol% of the component (A) It is more preferable that it is included.

The component (B) preferably contains a compound represented by the following formula (8), if necessary. The content of the compound (6) in the component (B) is preferably 50 mol% to 100 mol%, more preferably 80 mol% to 100 mol%, and 90 mol% to 100 mol% Is more preferable.

(In the formula ^{8, R 5, R 6,} Z, n, e , and f are each independently the same meaning as ^{R 5, R 6, Z,} n, e and f in the formula 3, R ^A is independently And R &lt; ^A &gt; in formula (6)

Examples of the compound represented by Formula 8 include hydroquinone, resorcinol, 2-phenylhydroquinone, 4,4'-biphenol, 3,3'-biphenol, 4,4'-dihydroxydiphenyl sulfone, Dihydroxydiphenyl sulfone, 4'-dihydroxybenzophenone, 3,3'-dihydroxybenzophenone, 1,1'-bi-2-naphthol, 1,1'- 4-naphthol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2- 1,3,3,3-hexafluoropropane, and reactive derivatives thereof. Among the above-mentioned compounds, preferred are resorcinol, 4,4'-biphenol, 2,2-bis (4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2- (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane is preferable, and 4,4'-biphenol is preferably used from the viewpoints of reactivity and mechanical properties. These compounds may be used in combination of two or more.

More specifically, the resin (1) can be synthesized by the following method (I ').

Method (I '):

(B) is reacted with an alkali metal compound in an organic solvent to obtain an alkali metal salt of the component (B) (the compound (6) and / or the compound (8) or the like), and then the obtained alkali metal salt is reacted with the component (A) . Further, the alkali metal salt of the component (B) and the component (A) may be reacted by reacting the component (B) and the alkali metal compound in the presence of the component (A).

Examples of the alkali metal compound used in the reaction include alkali metals such as lithium, potassium and sodium; Alkali metal hydrides such as lithium hydride, potassium hydride and sodium hydride; Alkali hydroxides such as lithium hydroxide, potassium hydroxide and sodium hydroxide; Alkali metal carbonates such as lithium carbonate, potassium carbonate and sodium carbonate; And alkali metal hydrogencarbonates such as lithium hydrogen carbonate, potassium hydrogencarbonate and sodium hydrogencarbonate. These may be used alone or in combination of two or more.

The amount of the metal atom in the alkali metal compound is usually 1 to 3 times, preferably 1.1 to 2 times, and more preferably 1.2 to 1.5 times, based on all -OR ^A in the component (B) It is used in an amount that is equivalent to double.

Examples of the organic solvent used in the reaction include N, N-dimethylacetamide (DMAc), N, N-dimethylformamide, N-methyl-2-pyrrolidone, , and the alkoxy group (the number of carbon atoms in the alkoxy group, the number of carbon atoms in the alkoxy group, the number of carbon atoms in the alkoxy group, the number of carbon atoms in the alkoxy group 1 to 4) and trialkoxybenzene (having 1 to 4 carbon atoms in the alkoxy group). Of these solvents, polar organic solvents having a high dielectric constant such as N-methyl-2-pyrrolidone, N, N-dimethylacetamide, sulfolane, diphenylsulfone and dimethylsulfoxide are particularly preferably used. These organic solvents may be used alone or in combination of two or more.

The reaction may be carried out in the presence of a solvent such as benzene, toluene, xylene, hexane, cyclohexane, octane, chlorobenzene, dioxane, tetrahydrofuran, anisole and phenetole.

The proportion of the component (A) and the component (B) is preferably 45 mol% or more and 55 mol% or less when the total amount of the component (A) and the component (B) is 100 mol% Preferably 50 mol% or more to 52 mol% or less, more preferably 50 mol% or more and 52 mol% or less, and the component (B) is preferably 45 mol% or more and 55 mol% or less, more preferably 48 mol% Or more and 50 mol% or less, and more preferably 48 mol% or more and less than 50 mol%.

Further, the reaction temperature is preferably in the range of 60 占 폚 to 250 占 폚, more preferably 80 占 폚 to 200 占 폚. The reaction time is preferably in the range of 15 minutes to 100 hours, more preferably 1 hour to 24 hours.

The resin (1) has a glass transition temperature (Tg) of preferably 230 to 350 ° C, more preferably 240 to 330 ° C, more preferably 250 to 300 &lt; 0 &gt; C.

The glass transition temperature of the resin (1) can be measured by a differential scanning calorimeter (DSC6200, manufactured by Sigma-Aldrich) using a Model 8230 DSC measuring apparatus (temperature raising rate: 20 ° C / 20 DEG C / min) and the like.

The resin (1) had a weight average molecular weight in terms of polystyrene measured by a GPC apparatus HLC-8220 manufactured by Toso Co., Ltd. (column: TSK gel? -M, developing solvent: tetrahydrofuran (hereinafter also referred to as "THF" Mw) is preferably from 5,000 to 500,000, more preferably from 15,000 to 400,000, and still more preferably from 30,000 to 300,000.

The resin (1) has a thermal decomposition temperature measured by thermogravimetric analysis (TGA) of preferably 450 ° C or higher, more preferably 475 ° C or higher, and still more preferably 490 ° C or higher.

&Lt; Polyimide resin &

As the transparent resin usable in the present invention, a polyimide resin can be mentioned.

The polyimide resin is not particularly limited and may be a polymer containing an imide bond in a repeating unit. For example, the polyimide resin can be synthesized by a method disclosed in Japanese Patent Application Laid-Open No. 2008-163107.

Commercially available products of the transparent resin usable in the present invention include the following commercially available products. Examples of commercially available products of cyclic olefin resins include Aton manufactured by JSR Kabushiki Kaisha, Zeonor manufactured by Nippon Zeon Co., Ltd., APEL manufactured by Mitsui Chemicals, Inc., and TOPAS manufactured by Polyplastics Co., Ltd. As a commercially available product of polyethersulfone resin, Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. and the like can be mentioned. And Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd. as a commercially available polyimide resin. As a commercially available polycarbonate resin, there can be mentioned Pure Aces, manufactured by Deijin Kabushiki Kaisha. As a commercially available product of the organic-inorganic nano hybrid material, Shin-Nittsu Chemical Industries Co., Ltd. and the like can be mentioned.

<Other ingredients>

To the resin substrate (I), additives such as antioxidants, ultraviolet absorbers, dyes and pigments for absorbing near infrared rays, and metal complex system compounds may be further added within the range not impairing the effect of the present invention. When the resin substrate (I) is produced by the solution casting method described later, the resin substrate (I) can be easily produced by adding a leveling agent or a defoaming agent. These other components may be used alone, or two or more of them may be used in combination.

Examples of the antioxidant include 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di- Methane and tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane.

Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

These additives may be mixed with the resin or the like when the resin substrate (I) is produced, or may be added when the resin is produced. The addition amount is appropriately selected depending on the desired characteristics, but it is usually 0.01 to 5.0 parts by weight, preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the resin.

&Lt; Process for producing resin substrate (I) containing compound (I) >

The resin substrate (I) to be used in the present invention can be formed, for example, by melt molding or casting. If necessary, after coating, a coating agent such as an antireflective agent, a hard coating agent and / . &Lt; / RTI &gt;

(A) melt molding

The resin substrate (I) is obtained by melt molding a pellet obtained by melt kneading the resin with the compound (I) and / or the compound (I '); A method of melt-molding the resin and a resin composition containing the compound (I) and / or the compound (I '); A method of melt-molding the pellets obtained by removing the solvent from the resin composition comprising the compound (I) and / or the compound (I '), the resin, and the solvent. Examples of the melt molding method include injection molding, melt extrusion molding, or blow molding.

(B) Casting

The resin substrate (I) can be obtained by casting a resin composition comprising the compound (I) and / or the compound (I '), the resin and the solvent onto a suitable substrate and removing the solvent, an antireflective agent, Or a coating agent such as an antistatic agent and a resin composition containing a compound (I) and / or a compound (I ') on a suitable substrate, a coating agent such as an antireflective agent, a hard coating agent and / And / or a compound (I ') on a suitable substrate and curing, drying, and the like.

For example, the above-mentioned resin composition is coated on a substrate such as a glass plate, a steel belt, a steel drum or a polyester film, or a transparent resin such as a cyclic olefin resin film, and the solvent is dried to obtain a coating film. Whereby a resin substrate (I) can be obtained. Further, as long as the effect of the present invention is not impaired, a laminate of the base material and the coating film may be used as the resin substrate (I) without peeling the coating film from the base material. The above-mentioned resin composition may be coated on an optical component such as a glass plate, quartz or transparent plastic, and the solvent may be dried, or a coating agent, a solvent and a compound (I) and / or a compound (I ' , The resin substrate I may be directly formed on the optical component by curing and drying the resin composition.

The amount of the residual solvent in the resin substrate (I) obtained by the above method is preferably as small as possible, usually 3 wt% or less, preferably 1 wt% or less, more preferably 0.5 wt% or less. If the amount of the residual solvent is more than 3% by weight, the resin substrate I may be deformed or its characteristics may change over time, and the desired function may not be exhibited.

«Near infrared ray reflective film»

The near-infrared reflecting film used in the present invention is a film having an ability to reflect near infrared rays. Examples of such a near-infrared reflective film include an aluminum vapor deposition film, a noble metal thin film, a resin film in which metal oxide fine particles containing indium oxide as a main component and containing a small amount of tin oxide are dispersed, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated Can be used.

Since the near-infrared ray blocking filter of the present invention has such a near-infrared ray reflecting film, it has the following characteristic (B) in particular. Therefore, a filter capable of sufficiently blocking the near-infrared rays can be obtained.

In the present invention, the near-infrared reflection film may be provided on one side of the resin substrate (I) or on both sides thereof. It is possible to obtain a near infrared ray shielding filter which is excellent in manufacturing cost and easy to manufacture and has a high strength when installed on both sides and which is less prone to warpage.

Among these near-infrared reflective films, a dielectric multilayer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated can be preferably used.

As the material constituting the high refractive index material layer, a material having a refractive index of 1.7 or more can be used, and a material having a refractive index range of usually 1.7 to 2.5 is selected.

Examples of these materials include titanium oxide, zirconium oxide, tantalum pentoxide, niobium pentoxide, lanthanum oxide, yttrium oxide, zinc oxide, zinc sulfide and indium oxide, (For example, 0 to 10% with respect to the main component).

As the material constituting the low refractive index material layer, a material having a refractive index of 1.6 or less can be used, and a material having a refractive index range of usually 1.2 to 1.6 is selected.

These materials include, for example, silica, alumina, lanthanum fluoride, magnesium fluoride, and aluminum sodium hexafluoride.

The method of laminating the high refractive index material layer and the low refractive index material layer is not particularly limited as long as a dielectric multilayer film in which these material layers are laminated is formed. For example, a dielectric multi-layer film in which a high refractive index material layer and a low refractive index material layer are alternately laminated is formed on the resin substrate I by direct CVD, sputtering, vacuum deposition, ion assist deposition, ion plating or the like .

The thickness of each of the layers of the high refractive index material layer and the low refractive index material layer is preferably 0.1 to 0.5 [lambda] when the near infrared ray wavelength to be intercepted is [lambda] (nm). When the thickness is within this range, the optical film thickness, in which the product of the refractive index (n) and the film thickness d (nxd) is? / 4 and the thickness of each layer of the high refractive index material layer and the low refractive index material layer There is a tendency that the blocking and transmission of a specific wavelength can be easily controlled from the relationship of optical characteristics of reflection and refraction.

It is also preferable that the number of layers in the dielectric multilayer film is 5 to 60 layers, preferably 10 to 50 layers.

When warping occurs in the substrate when the dielectric multilayer film is formed, a method of forming a dielectric multilayer film on both surfaces of the substrate or irradiating an electromagnetic wave such as ultraviolet ray to the surface of the substrate on which the dielectric multilayer film is formed is performed I can take it. Further, in the case of irradiating electromagnetic waves, irradiation may be performed during formation of the dielectric multilayer film, or irradiation may be separately performed after formation.

«Other functions»

The near-infrared cut filter of the present invention may be provided between a near infrared ray reflective film such as a resin substrate (I) and a dielectric multilayer film or the like, a surface opposite to a surface on which the near infrared ray reflective film of the resin substrate (I) A hard coating film or the like for the purpose of improving the surface hardness of the resin substrate I, improving the chemical resistance, preventing the electrification, and removing the damage, on the surface of the near infrared ray reflective film opposite to the surface on which the resin substrate I is provided A functional film such as an antistatic film can be suitably provided. The near-infrared cut filter of the present invention may include one layer of the functional film or may include two or more layers. When the near-infrared cut filter of the present invention includes two or more layers comprising the functional film, the same layer may include two or more layers, or two or more different layers may be included.

The method for laminating the functional film is not particularly limited, but a method of melt-molding a coating agent such as an antireflective agent, a hard coating agent and / or an antistatic agent on the resin substrate I or the near-infrared reflecting film as described above, Method. Further, the curable composition containing the above-mentioned coating agent-forming material or the like may be coated on a resin substrate (I) or an infrared reflective film with a bar coater or the like and then cured by ultraviolet irradiation or the like.

Examples of the coating agent include ultraviolet (UV) / electron beam (EB) curable resin and thermosetting resin, and examples thereof include urethane, urethane acrylate, acrylate, epoxy and epoxy acrylate resins. Examples of the curable composition corresponding to these coating agents include urethane-based, urethane acrylate-based, acrylate-based, epoxy-based and epoxyacrylate-based curable compositions.

Examples of the component contained in the urethane-based or urethane acrylate-based curable composition include tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, bis (2- hydroxyethyl) isocyanurate di (Meth) acrylate, and oligourethane (meth) acrylates having two or more (meth) acryloyl groups in the molecule. However, the present invention is not limited to these examples. These components may be used alone, or two or more of them may be used in combination. An oligomer or polymer such as polyurethane (meth) acrylate may also be blended.

Examples of the acrylate-based curable composition include, but are not limited to, compositions containing (meth) acrylic esters and vinyl compounds.

Specific examples of the (meth) acrylic esters include, for example,

Isobornyl (meth) acrylate,

Boron (meth) acrylate,

Tricyclodecanyl (meth) acrylate,

Dicyclopentanyl (meth) acrylate,

Dicyclopentenyl (meth) acrylate,

Cyclohexyl (meth) acrylate,

Benzyl (meth) acrylate,

4-butylcyclohexyl (meth) acrylate,

Acryloylmorpholine,

2-hydroxyethyl (meth) acrylate,

2-hydroxypropyl (meth) acrylate,

2-hydroxybutyl (meth) acrylate,

Methyl (meth) acrylate,

Ethyl (meth) acrylate,

Propyl (meth) acrylate,

Isopropyl (meth) acrylate,

Butyl (meth) acrylate,

Amyl (meth) acrylate,

Isobutyl (meth) acrylate,

t-butyl (meth) acrylate,

Pentyl (meth) acrylate,

Isoamyl (meth) acrylate,

Hexyl (meth) acrylate,

Heptyl (meth) acrylate,

Octyl (meth) acrylate,

Isooctyl (meth) acrylate,

2-ethylhexyl (meth) acrylate,

Nonyl (meth) acrylate,

Decyl (meth) acrylate,

Isodecyl (meth) acrylate,

Undecyl (meth) acrylate,

Dodecyl (meth) acrylate,

Lauryl (meth) acrylate,

Stearyl (meth) acrylate,

Isostearyl (meth) acrylate,

Tetrahydrofurfuryl (meth) acrylate,

Butoxyethyl (meth) acrylate,

Ethoxydiethylene glycol (meth) acrylate,

Polyethylene glycol mono (meth) acrylate,

Polypropylene glycol mono (meth) acrylate,

Methoxyethylene glycol (meth) acrylate,

Ethoxyethyl (meth) acrylate,

Methoxypolyethylene glycol (meth) acrylate,

Methoxypolypropylene glycol (meth) acrylate,

Diacetone (meth) acrylamide,

Isobutoxymethyl (meth) acrylamide,

N, N-dimethyl (meth) acrylamide,

t-octyl (meth) acrylamide,

Dimethylaminoethyl (meth) acrylate,

Diethylaminoethyl (meth) acrylate,

7-amino-3,7-dimethyloctyl (meth) acrylate,

N, N-diethyl (meth) acrylamide,

N, N-dimethylaminopropyl (meth) acrylamide,

Phenoxyethyl (meth) acrylate,

Phenoxy-2-methylethyl (meth) acrylate,

Phenoxyethoxyethyl (meth) acrylate,

3-phenoxy-2-hydroxypropyl (meth) acrylate,

2-phenylphenoxyethyl (meth) acrylate,

4-phenylphenoxyethyl (meth) acrylate,

2-hydroxy-3-phenoxypropyl (meth) acrylate,

p-cumylphenol ethylene oxide-modified (meth) acrylate,

2-bromophenoxyethyl (meth) acrylate,

4-bromophenoxyethyl (meth) acrylate,

2,4-dibromophenoxyethyl (meth) acrylate,

2,6-dibromophenoxyethyl (meth) acrylate,

2,4,6-tribromophenoxyethyl (meth) acrylate,

Trimethylolpropane tri (meth) acrylate,

Trimethylolpropane trioxyethyl (meth) acrylate,

Ditrimethylolpropane tetra (meth) acrylate,

Pentaerythritol tri (meth) acrylate,

Pentaerythritol tetra (meth) acrylate,

Dipentaerythritol penta (meth) acrylate,

Dipentaerythritol hexa (meth) acrylate,

Glycerin tri (meth) acrylate,

Ethylene glycol di (meth) acrylate,

Tetraethylene glycol di (meth) acrylate,

Tripropylene glycol di (meth) acrylate

1,3-butanediol di (meth) acrylate,

1,4-butanediol di (meth) acrylate,

1,6-hexanediol di (meth) acrylate,

1,9-nonanediol (meth) acrylate,

Neopentyl glycol di (meth) acrylate,

Diethylene glycol di (meth) acrylate,

Triethylene glycol di (meth) acrylate,

Dipropylene glycol di (meth) acrylate,

Cyclohexyl (meth) acrylate,

Dicyclopentenyl (meth) acrylate,

Dicyclopentanyl (meth) acrylate,

Dicyclopentanyloxyethyl (meth) acrylate,

Isobornyl (meth) acrylate,

Tricyclodecanedimethylol di (meth) acrylate,

Tricyclodecane methanol (meth) acrylate,

Tricyclodecane dimethanol di (meth) acrylate,

Tetracyclodecanedimethylol di (meth) acrylate,

The poly (meth) acrylates of the ethylene oxide or propylene oxide adduct of the starting alcohols when these compounds are prepared,

Oligoester (meth) acrylates having two or more (meth) acryloyl groups in the molecule, and

Oligo ether (meth) acrylates

However, the present invention is not limited to these examples. These components may be used alone, or two or more of them may be used in combination. An oligomer or polymer such as polyester (meth) acrylate may also be blended.

Examples of the vinyl compounds include vinyl acetate, vinyl propionate, divinylbenzene, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and the like. no. These components may be used alone, or two or more of them may be used in combination.

The components contained in the epoxy-based and epoxyacrylate-based curable compositions are not particularly limited, and examples thereof include glycidyl (meth) acrylate, methylglycidyl (meth) acrylate, two or more (meth) acryloyl (Meth) acrylates having an epoxy group-containing unsaturated bond. These components may be used alone, or two or more of them may be used in combination. An oligomer or polymer such as polyepoxy (meth) acrylate may also be blended.

Examples of commercially available products of the coating agent (curable composition containing a coating-forming material and the like) include LCH, LAS, manufactured by Toyo Ink Seisakusho Co., Ltd., Beamset manufactured by Arakawa Chemical Industries, Ltd., EBECRYL manufactured by Daicel- , And Obstar manufactured by JSR Corporation.

The curable composition may also contain a polymerization initiator. As the polymerization initiator, known photopolymerization initiators or thermal polymerization initiators may be used, and a photopolymerization initiator and a thermal polymerization initiator may be used in combination.

Specific examples of the polymerization initiator are not particularly limited,

1-hydroxycyclohexyl phenyl ketone,

2,2-dimethoxy-2-phenylacetophenone,

Xanthon,

Fluorenone,

Benzaldehyde,

Anthraquinone,

Triphenylamine,

Carbazole,

3-methylacetophenone,

4-chlorobenzophenone,

4,4'-dimethoxybenzophenone,

4,4'-diaminobenzophenone,

Michalil Ketone,

Benzoin propyl ether,

Benzoin ethyl ether,

Benzyl dimethyl ketal,

1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-

Hydroxy-2-methyl-1-phenylpropan-1-one,

Thioxanthon,

Diethylthioxanthone,

2-isopropylthioxanthone,

2-chlorothioxanthone,

Methyl-1- [4- (methylthio) phenyl] -2-morpholino-propan-

2,4,6-trimethylbenzoyldiphenylphosphine oxide,

Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylporphineoxide.

Of these, 1-hydroxycyclohexyl phenyl ketone is preferred.

These polymerization initiators may be used alone, or two or more of them may be used in combination.

As commercial products thereof, Irgacure 184, 369, 651, 500, 907, CGI1700, CGI1750, CGI1850, CG24-61, DAROCURE TPO (manufactured by Ciba Specialty Chemicals), Lucirin LR8728 DauroCure 1116 and 1173 (manufactured by Merck), and Ubecryl P36 (manufactured by UCB Co., Ltd.).

In the curable composition, the blending ratio of the polymerization initiator is preferably 0.1 to 10% by weight, more preferably 0.5 to 10% by weight, and still more preferably 1 to 5% by weight, based on 100% by weight of the total amount of the curable composition. When the blending ratio of the polymerization initiator is within the above range, a functional film such as an antireflection film, a hard coating film or an antistatic film having excellent hardening properties and handling properties of the curable composition and having desired hardness can be obtained.

An organic solvent may be added to the curable composition as a solvent, or a known one may be used. Specific examples of the organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol, and octanol; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; Esters such as ethyl acetate, butyl acetate, ethyl lactate,? -Butyrolactone, propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; And amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone, or two or more of them may be used in combination.

The thickness of the functional film is preferably 0.1 탆 to 20 탆, more preferably 0.5 탆 to 10 탆, and particularly preferably 0.7 탆 to 5 탆.

Further, for the purpose of enhancing the adhesion between the resin substrate I and the functional film and / or the near-infrared reflecting film or the adhesion between the functional film and the near-infrared reflecting film, the surface of the resin substrate I or the functional film is subjected to surface treatment such as corona treatment or plasma treatment Processing may be performed.

«NIR filter»

The near-infrared cut filter of the present invention preferably has a light transmittance satisfying the following (A) to (D).

(A) It is preferable that the average value of the transmittance measured from the vertical direction of the near-infrared cut filter in the wavelength range of 430 to 580 nm is 75% or more, preferably 78% or more, more preferably 80% or more . In the present invention, a near infrared ray blocking filter having a high transmittance at 430 to 580 nm can be obtained by using a resin having a high total light transmittance at a thickness of 0.1 mm and a compound (I) having no absorption at the wavelength range.

When the near-infrared blocking filter is used in a filter for visibility correction in a lens unit such as a solid-state imaging device or a camera module, it is preferable that the average value of the transmittance at a wavelength of 430 to 580 nm is in the above range and the transmittance is constant in this wavelength range.

It is preferable that the average value of the transmittance in the wavelength range of 430 to 580 nm is as high as possible. When the average value of the transmittance is high, the intensity of the light passing through the filter is sufficiently secured, and thus it can be suitably used for the above applications.

On the other hand, if the average value of the transmittance in the wavelength range of 430 to 580 nm is low, the intensity of the light passing through the filter is not sufficiently secured, which may result in failure to suitably use for the above applications.

(B) It is preferable that the average value of the transmittance measured from the vertical direction of the near infrared ray cut filter in the wavelength range of 800 to 1000 nm is 20% or less, preferably 15% or less, more preferably 10% or less Do. In the present invention, a near-infrared ray reflection filter having a high near-infrared reflection ability is provided on the resin substrate (I) to obtain a near-infrared ray filter having a sufficiently low transmittance at a wavelength of 800 to 1000 nm.

Since the near-IR blocking filter of the present invention selectively reduces the wavelength (near 800 nm) of near-infrared rays, it is preferable that the average value of the transmittance in the range of 800 to 1000 nm is low. When the average value of the transmittance is low, the near-infrared cut filter can sufficiently block the near-infrared rays.

On the other hand, if the average value of the transmittance in the wavelength range of 800 to 1000 nm is high, the filter can not sufficiently block near infrared rays, and if the filter is used in a PDP or the like, malfunction of electronic devices in the vicinity of the PDP in the home can not be prevented .

(C) the longest wavelength (Xa) in which the transmittance is 70% when measured from the vertical direction of the near-IR cut filter in the wavelength region of 800 nm or less, and the longest wavelength (Xa) measured from the vertical direction of the near- (| Xa-Xb |) of the difference of the shortest wavelength Xb where the transmittance in one case is 30% takes a value of less than 75 nm, preferably less than 72 nm, more preferably less than 70 nm . In the present invention, by using the compound (I), a near infrared ray blocking filter having an absolute value of a wavelength difference having a predetermined transmittance in the predetermined range can be obtained.

When the absolute value of the difference between (Xa) and (Xb) of the near-infrared ray cut filter is in the above range, the transmittance is rapidly changed between the wavelengths Xa and Xb near the wavelength range of near infrared rays, And the absolute value of the difference between (Ya) and (Yb) is small, so that the dependence of the incident wavelength on the incident angle is small and the near-IR blocking filter having a wide viewing angle can be obtained.

(D) a value (Ya) of the wavelength at which the transmittance is 50% when measured from the vertical direction of the near-IR cut filter in the range of 560 to 800 nm, preferably 580 to 800 nm, (Ya-Yb |) of the difference in the value (Yb) of the wavelength at which the transmittance is 50% when measured from an angle of 30 degrees with respect to the direction is less than 15 nm, preferably less than 13 nm, It is preferable to take a value of less than 10 nm.

In the present invention, by using the compound (I), a near infrared ray blocking filter having an absolute value of a wavelength difference having a predetermined transmittance in the predetermined range can be obtained.

When the absolute value of the difference between (Ya) and (Yb) is in the above range in the wavelength range of 560 to 800 nm, when the filter is used in a PDP or the like, even when viewing the display from the oblique direction, It is possible to obtain a near-infrared ray blocking filter which exhibits brightness and color tone equivalent to those of the near-infrared ray filter and has a small dependency on the incident angle of the absorption wavelength and a wide viewing angle.

On the other hand, when a near infrared ray blocking filter having an absolute value of the difference between (Ya) and (Yb) of 15 nm or more is used in a PDP or the like, the brightness is remarkably reduced, the color tone is reversed, There is a possibility that it can not be suitably used for the above use.

Here, the "viewing angle" refers to an index indicating to what degree an image can be normally viewed when viewing a display or the like from top, bottom, left, and right.

In the present invention, when the near-infrared cut-off filter is viewed from above, below, and from left to right, it is an index indicating to what extent an image can be normally viewed.

In order to judge whether or not it can be normally viewed, in the present invention, the value Ya of the wavelength at which the transmittance is 50% when measured from the vertical direction of the filter in the wavelength range of 560 to 800 nm, The absolute value of the difference of the value Yb of the wavelength at which the transmittance is 50% when measured from an angle of 30 DEG is less than 15 nm.

The thickness of the near-infrared cut filter is preferably adjusted so that the transmittance of the filter satisfies the above (A) to (D), and is not particularly limited, but is preferably 50 to 250 占 퐉, more preferably 50 to 200 占 퐉 , More preferably 80 to 150 mu m.

When the thickness of the near-IR blocking filter is within the above range, the filter can be made smaller and lighter, and can be suitably used for various applications such as solid-state imaging devices. Particularly, when the lens unit is used in a lens unit such as a camera module, it is preferable because the lens unit can be downsized.

&Lt; Use of near-IR blocking filter >

The near-IR blocking filter obtained in the present invention has a wide viewing angle and excellent near-infrared blocking ability. Therefore, it is useful for correcting the visual sensitivity of solid-state image pickup devices such as CCDs and CMOSs of camera modules. In particular, a digital still camera, a camera for a mobile phone, a digital video camera, a PC camera, a surveillance camera, a camera for a car, a television, a car navigation device, a portable information terminal, a personal computer, Authentication systems, digital music players, toy robots and toys. It is also useful as a heat ray cut filter or the like mounted on a glass such as an automobile or a building.

Here, the case of using the near-infrared cut filter obtained in the present invention in a camera module will be described in detail.

1 is a schematic cross-sectional view of a camera module.

1 (b) is a schematic cross-sectional view showing one of the structures of a camera module which can be taken when the near-infrared cut-off filter 6 'obtained in the present invention is used. FIG. 1A is a schematic cross-sectional view of the structure of a conventional camera module, to be.

1 (b), the near-infrared cut filter 6 'obtained in the present invention is used in the upper portion of the lens 5. However, the near-infrared cut filter 6' It may be used between the lens 5 and the sensor 7 as well.

In the conventional camera module, light has to be incident almost perpendicularly to the near-infrared cut filter 6. Therefore, it is necessary to arrange the filter 6 between the lens 5 and the sensor 7.

Here, since the sensor 7 is highly sensitive and may not operate correctly even if only about 5 占 퐉 of dust or dirt comes in contact with the sensor 7, the filter 6 used in the upper part of the sensor 7 may be contaminated with dust or dust It does not occur, and it is necessary that it does not contain foreign matter. In addition, it is necessary to set a predetermined distance between the filter 6 and the sensor 7 from the characteristics of the sensor 7, which is one cause of obstructing the lowering of the camera module.

In contrast, in the near-infrared cut filter 6 'obtained in the present invention, the absolute value of the difference between (Ya) and (Yb) is 15 nm or less. That is, since there is no large difference between the light incident from the vertical direction of the filter 6 'and the transmission wavelength of light incident from 30 ° with respect to the vertical direction of the filter 6' (the incident angle dependence of the absorption , The filter 6 'does not need to be disposed between the lens 5 and the sensor 7, and may be arranged on the top of the lens.

Therefore, when the near-infrared cut filter 6 'obtained in the present invention is used in a camera module, handling of the camera module becomes easy, and a predetermined gap is required between the filter 6' and the sensor 7 It is possible to lower the camera module.

[Example]

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited to these examples. "Parts" means "parts by weight" unless otherwise specified.

First, a method of measuring each property value and a method of evaluating properties will be described.

(1) Molecular weight:

Using a gel permeation chromatography (GPC) apparatus (150C type) manufactured by WATERS, equipped with an H-type column manufactured by Toso Co., a weight average of the o-dichlorobenzene solvent in terms of standard polystyrene The molecular weight (Mw) and the number average molecular weight (Mn) were measured.

(2) Glass transition temperature (Tg):

(DSC6200) manufactured by Esuye ANA NanoTechnology Co., Ltd. under the temperature raising rate: 20 DEG C per minute and under nitrogen gas flow.

(3) Saturated absorption rate:

A test piece having a thickness of 3 mm, a length of 50 mm and a width of 50 mm was prepared from the resin obtained in Synthesis Example according to ASTM D570, and the obtained test piece was immersed in water at 23 캜 for one week. Respectively.

(4) Spectral transmittance:

(U-4100, manufactured by Hitachi High-Technologies Co., Ltd.).

Here, the transmittance measured from the vertical direction of the near-infrared cutoff filter was measured as the light transmitted perpendicularly to the filter as shown in Fig.

The transmittance of the near infrared ray blocking filter measured from an angle of 30 DEG with respect to the vertical direction was measured as the light transmitted through the filter at an angle of 30 DEG with respect to the vertical direction of the filter as shown in Fig.

The transmittance is measured using the spectrophotometer under the condition that light is incident perpendicularly on the substrate and the filter, except when measuring (Yb). (Yb) is measured using the spectrophotometer under the condition that light is incident at an angle of 30 degrees with respect to the vertical direction of the filter.

[Synthesis Example 1]

100 parts of 8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ] dodec-3-ene (hereinafter also referred to as "DNM" , 18 parts of 1-hexene (molecular weight regulator) and 300 parts of toluene (solvent for ring opening polymerization reaction) were charged in a nitrogen-purged reaction vessel, and the solution was heated to 80 占 폚. Subsequently, 0.2 part of a toluene solution of triethyl aluminum (0.6 mol / l) as a polymerization catalyst and 0.9 part of a toluene solution of methanol-denatured tungsten hexachloride (concentration 0.025 mol / l) were added to the solution in the reaction vessel, Followed by heating and stirring at 80 DEG C for 3 hours to effect ring-opening polymerization reaction to obtain a ring-opening polymer solution. The polymerization conversion rate in this polymerization reaction was 97%.

<Formula a>

In this way, In 1,000 parts of the resulting ring-opening polymer solution in the autoclave, and the ring-opening polymer solution to RuHCl (CO) [P (C 6 H 5) 3] was added to 0.12 parts _3, and a hydrogen gas pressure of 100 kg / cm ^2, the reaction And the mixture was heated and stirred under the conditions of a temperature of 165 캜 for 3 hours to carry out a hydrogenation reaction.

After the obtained reaction solution (hydrogenated polymer solution) was cooled, the hydrogen gas was depressurized. The reaction solution was poured into a large amount of methanol to separate and recover a solid product, which was then dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The resin A had a number average molecular weight (Mn) of 32,000, a weight average molecular weight (Mw) of 137,000, and a glass transition temperature (Tg) of 165 占 폚.

[Synthesis Example 2]

Dehydrated cyclohexane having a water content of 6 ppm was added to a 1 L stainless autoclave thoroughly dried and replaced with nitrogen. 420.4 g, p-xylene; 180.2 g of 5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene; 48.75 mmol (10.43 g) and bicyclo [2.2.1] hept-2-ene; 1,425 mmol (134.1 g) were charged, and gaseous ethylene was charged so that the autoclave internal pressure became 0.1 MPa. Thereafter, the autoclave was heated to 75 캜.

2-ethylhexanoic acid palladium (as Pd atom); 0.003 mg atom and tricyclohexylphosphine; 0.0015 mmol were dissolved in toluene; 10 ml, and reacted at 25 DEG C for 1 hour to prepare a solution. The whole amount of this solution and triphenylcarbenium pentafluorophenylborate; 0.00315 mmol were added in this order to an autoclave heated to 75 ° C to initiate polymerization.

5-trimethoxysilyl-bicyclo [2.2.1] hept-2-ene was added to the autoclave at room temperature for 10 minutes. After 90 minutes of polymerization, 11.25 mmol (2.41 g) 0.80 g) and 3.75 mmol in total, four times.

After the polymerization reaction was carried out at 75 캜 for 4 hours, tributylamine; 1 ml was added to terminate the polymerization to obtain a solution of the addition polymer B having a solid content of 19.9% by weight. A part of the solution of the addition polymer B was put into isopropanol, and solidified and dried to obtain an addition polymer B (hereinafter also referred to as "resin B").

As a result of the 270 MHz-nuclear magnetic resonance analysis ( ¹ H-NMR analysis) of the resin B, the ratio of the structural units derived from 5-trimethoxysilyl-bicyclo [2.2.1] hept- (Mn) of 74,000, a weight average molecular weight (Mw) of 185,000, a glass transition temperature (Tg) of 360 占 폚, and a saturation absorption rate of 0.35%.

[Synthesis Example 3]

10.0 parts by weight (0.05 mol) of 4,4'-diaminodiphenyl ether was added to a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introducing tube, a side loading dropping funnel, a Dean Stark tube, After dissolving in 85 parts by weight of N-methyl-2-pyrrolidone as a solvent, 11.2 parts by weight (0.05 mole) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was reacted at room temperature for 1 hour And the mixture was stirred at room temperature for 2 hours.

Subsequently, 30.0 parts by weight of xylene as an azeotropic dehydration solvent was added and the temperature was raised to 180 DEG C, followed by reaction for 3 hours, and xylene was refluxed with a Dean-Stark tube to separate the azeotropic product. After 3 hours, it was confirmed that the outflow of water was completed, and the xylene was distilled off while raising the temperature to 190 DEG C over 1 hour. After recovering 29.0 parts by weight, the mixture was air-cooled until the internal temperature reached 60 DEG C, And 105.4 parts by weight of a methyl-2-pyrrolidone solution (hereinafter also referred to as "polyimide solution C").

[Synthesis Example 4]

A 3 L four-necked flask was charged with 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, 125.65 g (0.250 mol) of 9,9-bis (3-phenyl- 443 g (0.300 mol) of N, N-dimethylacetamide (hereinafter also referred to as "DMAc") and 111 g of toluene were added. Then, a thermometer, a stirrer, a three-way cock equipped with a nitrogen inlet tube, a Dean Stark tube and a cooling tube were attached to a four-necked flask.

Subsequently, the inside of the flask was purged with nitrogen, and the obtained solution was reacted at 140 DEG C for 3 hours, and the resulting water was frequently removed from the Dean-Stark tube. When the production of water was no longer observed, the temperature was gradually raised to 160 DEG C and the reaction was carried out at that temperature for 6 hours.

After cooling to room temperature (25 DEG C), the resulting salt was removed by filtration, the filtrate was re-precipitated by adding methanol, and the filtrate (residue) was isolated by filtration. The obtained filtrate was vacuum-dried overnight at 60 캜 to obtain white powder D (hereinafter referred to as Resin D) (yield: 95.67 g, yield: 95%).

The structure of the obtained polymer was analyzed. The results showed that the characteristic absorption of the infrared absorption spectrum was 3035 (CH stretching), 2229 cm ^-1 (CN), 1574 cm ^-1 , 1499 cm ^-1 (aromatic cyclic skeleton absorption) and 1240 cm ^-1 (-O-) . The resin D had a number average molecular weight (Mn) of 67,000, a weight average molecular weight (Mw) of 146,000, and a glass transition temperature (Tg) of 275 deg. The obtained polymer had the above structural unit (1).

[Synthesis Example 5]

Except that 87.60 g (0.250 mol) of 9,9-bis (4-hydroxyphenyl) fluorene was used instead of 125.65 g (0.250 mol) of 9,9-bis , Synthesis was carried out in the same manner as in Synthesis Example 4 to obtain Resin E. The resin E had a number average molecular weight (Mn) of 75,000, a weight average molecular weight (Mw) of 188,000, and a glass transition temperature (Tg) of 285 ° C.

[Synthesis Example 6]

Instead of 125.65 g (0.250 mol) of 9,9-bis (3-phenyl-4-hydroxyphenyl) fluorene, 78.84 g (0.225 mol) of 9,9- -Bis (4-hydroxyphenyl) cyclohexane (6.71 g, 0.025 mol) was used in place of the bis (4-hydroxyphenyl) cyclohexane. The resin F had a number average molecular weight (Mn) of 36,000, a weight average molecular weight (Mw) of 78,000, and a glass transition temperature (Tg) of 260 占 폚.

[Synthesis Example 7]

Except that 78.84 g (0.250 mol) of 4,4-difluorodiphenyl sulfone (DFDS) was used instead of 35.12 g (0.253 mol) of 2,6-difluorobenzonitrile, G was obtained. The resin G had a number average molecular weight (Mn) of 37,000, a weight average molecular weight (Mw) of 132,000, and a glass transition temperature (Tg) of 265 deg.

[Example 1]

100 parts by weight of a cyclic olefin resin "ATON G" manufactured by JSR Corporation, 0.04 part by weight of a squarylium compound "a-10", and methylene chloride were added to a vessel to prepare a solution (ex1 ).

Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled coating film was dried at 100 占 폚 under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

The spectral transmittance of this substrate was measured, and the absorption maximum wavelength and (Za) and (Zb) were obtained. The results are shown in Table 1.

The maximum absorption wavelength of this substrate was 699 nm. It is also possible to use the longest wavelength (Za) at which the transmittance becomes 70% in the wavelength range of 430 to 800 nm, the longest wavelength (Za) at the absorption maximum or less and the shortest wavelength (Zb) at which the transmittance becomes 30% The absolute value of the difference (| Za-Zb |) was 45 nm.

Subsequently, a multilayer evaporated film (silica (SiO ₂ : film thickness: 83 to 199 nm) and titania (TiO ₂ : film thickness: 101 to 125 nm) were alternately deposited on one surface of the substrate to reflect near infrared rays at a deposition temperature of 100 ° C. be formed are laminated, the laminated number 20] the formation, the multi-layer deposited film that reflects near-infrared rays at a deposition temperature of 100 ℃ on the other surface of the substrate [the silica (SiO _2: film thickness of 77 to 189 nm) layer and a titania (TiO _2: Layer thickness: 84 to 118 nm) were laminated alternately, to form a near infrared ray shielding filter having a thickness of 0.105 mm. (Xa), (Xb), (Ya) and (Yb) were obtained by measuring the spectral transmittance of the near-infrared cut filter. The results are shown in Table 1.

The average value of the transmittance at a wavelength of 430 to 580 nm was 91% and the mean value of the transmittance at a wavelength of 800 to 1000 nm was 1% or less.

(Xa) of the difference between the longest wavelength Xa where the transmittance is 70% in the wavelength region of 800 nm or less and the shortest wavelength Xb where the transmittance is 30% in the wavelength region of 580 nm or more in wavelength, Xb |) was 39 nm.

In addition, the transmittance when measured from the vertical direction of the filter at a wavelength of 560 to 800 nm from the value Ya of the transmittance of 50% and the angle of 30 from the vertical direction of the filter The absolute value (| Ya-Yb |) of the difference of the value (Yb) of the wavelength of 50% was 3 nm.

[Example 2]

(SiO ₂ : thickness of 120 to 190 nm) layer and a layer of titania (SiO ₂ ) having a thickness of 0.1 mm, 60 mm length and 60 mm width obtained in Example 1 and reflecting near infrared rays at a deposition temperature of 100 ° C TiO ₂ : film thickness 70 to 120 nm) layers alternately stacked, the lamination number of 40) was formed to obtain a near-infrared ray blocking filter with a thickness of 0.104 mm. Table 1 also shows the results of evaluations conducted in the same manner as in Example 1.

[Example 3]

100 parts by weight of cyclic olefin resin "Aton G" manufactured by JSR Corporation, 0.02 part by weight of squarylium compound "a-10" and methylene chloride were added to the vessel to obtain a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled coating film was dried at 100 占 폚 under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. The results are shown in Table 1.

[Example 4]

100 parts by weight of a cyclic olefin resin "ATON G" manufactured by JSR Corporation, 0.04 parts by weight of a squarylium compound "a-10" and methylene chloride were added to the vessel to obtain a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled coating film was dried at 100 占 폚 under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

On both sides of the substrate, a hard coating agent "BISETEC" manufactured by Arakawa Chemical Industries, Ltd. was coated with a bar coater so that the film thickness after curing became 0.002 mm and then cured by UV irradiation to form a film having a thickness of 0.104 mm, A substrate of 60 mm was obtained.

Further, in the same manner as in Example 1, a near infrared ray cut filter having a thickness of 0.109 mm was produced from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 5]

100 parts by weight of a cyclic olefin resin "Zeonor 1420R" manufactured by Nippon Zeon Co., Ltd., 0.40 parts by weight of a squarylium compound "a-10", and 7: 3 mixed solution of cyclohexane and xylene were added to a vessel, A solution having a resin concentration of 20% was obtained. Subsequently, the solution was cast on a smooth glass plate, dried at 60 DEG C for 8 hours and at 80 DEG C for 8 hours, and then peeled off from the glass plate. The peeled coating film was dried at 100 DEG C for 24 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 6]

100 parts by weight of a cycloolefin resin "APEL # 6015" manufactured by Mitsui Chemicals, Inc., 0.24 parts by weight of a squarylium compound "a-10", and 99: 1 by weight of a mixed solution of cyclohexane and methylene chloride Thereby obtaining a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 40 DEG C for 4 hours and at 60 DEG C for 4 hours, and then peeled off from the glass plate. The peeled coating film was dried at 100 占 폚 under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 7]

100 parts by weight of a polycarbonate resin "PUREACE ", a squarylium compound" a-10 ", 0.02 part by weight, and methylene chloride were added to a vessel to prepare a solution having a resin concentration of 20% . Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled coating film was dried at 100 占 폚 under reduced pressure for 8 hours to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 8]

100 parts by weight of polyether sulfone "FS-1300 " manufactured by Sumitomo Bakelite Co., Ltd., 0.05 part by weight of squarylium compound" a-10 ", and N-methyl- A solution having a resin concentration of 20% was obtained. Subsequently, the solution was cast on a smooth glass plate, dried at 60 ° C for 4 hours and at 80 ° C for 4 hours, and then peeled off from the glass plate. The peeled coating film was dried at 120 캜 for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 9]

A substrate having a thickness of 0.1 mm, a length of 60 mm, and a width of 60 mm was obtained in the same manner as in Example 1, except that the resin A obtained in Synthesis Example 1 was used in place of the cyclic olefin resin "Aton G" manufactured by JSR Kabushiki Kaisha .

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 10]

100 parts by weight of the resin B obtained in Synthesis Example 2, 0.24 parts by weight of the squarylium compound "a-10", and toluene were added to a vessel to obtain a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. A substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm was obtained in the same manner as in Example 1, except that the peeled coating film was dried under reduced pressure at 120 ° C for 8 hours.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 11]

100 parts by weight of the polyimide solution C obtained in Synthesis Example 3 and 0.05 part by weight of the squarylium compound "a-10" with respect to 100 parts by weight of the solid content of the polyimide solution C were added to a vessel to obtain a solution having a solid content of 18% &Lt; / RTI &gt; Subsequently, the solution was cast on a smooth glass plate, dried at 60 ° C for 4 hours and at 80 ° C for 4 hours, and then peeled off from the glass plate. The peeled coating film was dried at 120 캜 for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 12]

100 parts by weight of the resin D obtained in Synthesis Example 4, 0.05 part by weight of a squarylium compound "a-10" and methylene chloride were added to a vessel to obtain a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled resin was dried at 100 DEG C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 13]

100 parts by weight of the resin E obtained in Synthesis Example 5, 0.05 part by weight of a squarylium compound "a-10" and methylene chloride were added to a vessel to obtain a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled resin was dried at 100 DEG C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 14]

100 parts by weight of the resin F obtained in Synthesis Example 6, 0.05 part by weight of the squarylium compound "a-10" and methylene chloride were added to a vessel to obtain a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled resin was dried at 100 DEG C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 15]

100 parts by weight of the resin G obtained in Synthesis Example 7, 0.05 part by weight of the squarylium compound "a-10" and methylene chloride were added to a vessel to obtain a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled resin was dried at 100 DEG C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Example 16]

100 parts by weight of the resin A obtained in Synthesis Example 1, 0.04 part by weight of the squarylium compound "a-10" and methylene chloride were added to a vessel to obtain a solution having a resin concentration of 20%. Subsequently, the solution was cast on a smooth glass plate, dried at 20 DEG C for 8 hours, and then peeled off from the glass plate. The peeled resin was dried at 100 DEG C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a length of 60 mm and a width of 60 mm.

A composition obtained by mixing tricyclodecane dimethanol diacrylate and methyl ethyl ketone in a ratio of 50:50 on both sides of the substrate was applied by a bar coater so that the film thickness after drying was 0.002 mm, and then cured by UV irradiation A substrate having a thickness of 0.104 mm, a length of 60 mm, and a width of 60 mm was obtained.

Further, in the same manner as in Example 1, a near infrared ray cut filter having a thickness of 0.109 mm was produced from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Comparative Example 1]

Except that a solution having a resin concentration of 20% obtained by dissolving the resin A obtained in Synthesis Example 1 in methylene chloride was used in place of the solution (ex1), the thickness was 0.1 mm, the length was 60 mm, the width was 60 mm Was obtained.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Comparative Example 2]

Except that SIR159 (manufactured by Mitsui Chemicals Co., Ltd.), which is a nickel complex compound having no squarylium structure, was used in place of the squarylium-based compound "a-10" 60 mm and a width of 60 mm.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

[Comparative Example 3]

Except that SDB3535 (manufactured by HWSANDS), which is a cyanine dye having no squarylium structure, was used in place of the squarylium-based compound "a-10" A substrate having a width of 60 mm was obtained.

In the same manner as in Example 1, a near infrared ray shielding filter having a thickness of 0.105 mm was prepared from this substrate. Table 1 shows the results of evaluation in the same manner as in Example 1.

The near-infrared ray blocking filter of the present invention may be used in a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, a car camera, a television, a car navigation system, a portable information terminal, a personal computer, , Portable game machines, fingerprint authentication systems, digital music players, toy robots, and toys.

It can also be suitably used as a heat-ray cut filter mounted on glass, such as a car or a building.

1: Camera module
2: lens barrel
3: Flexible substrate
4: hollow package
5: Lens
6: NIR filter
6 ': The near-infrared cut filter
7: CCD or CMOS image sensor
8: NIR filter
9: Spectrophotometer

Claims (12)

(I) containing a compound (I) having a structure derived from a compound having an absorption maximum at a wavelength of 600 to 800 nm represented by the following formula (I) and a near infrared ray reflecting film, Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
(A) an average value of transmittance in a wavelength range of 430 to 580 nm measured from the vertical direction of the near-infrared cut filter is 75% or more
(D) a value (Ya) of the wavelength at which the transmittance is 50% when measured from the vertical direction of the near-IR cut filter in a wavelength range of 560 to 800 nm and an angle of 30 DEG with respect to the vertical direction of the near- The absolute value of the difference in the value (Yb) of the wavelength at which the transmittance in one case is 50% is less than 15 nm
(I)

Wherein R ^a , R ^b and Y satisfy the following (i) or (ii)
(i) R ^a independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an -NR ^e R ^f group (R ^e and R ^f each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms) And,
R ^b each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, -NR ^g R ^h group (R ^g and R ^h are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or -C (O) R ⁱ (R ⁱ represents an alkyl group having 1 to 5 carbon atoms)) or a hydroxy group,
Y represents an -NR ^j R ^k group wherein each of R ^j and R ^k independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, a substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms in which any hydrogen atom is substituted with a functional group, To 12 aromatic hydrocarbon groups, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom is substituted with an alkyl group).
(ii) one of the two R ^{a on} one benzene ring is bonded to Y on the same benzene ring to form a heterocyclic ring containing 5 or 6 constituent atoms and at least one nitrogen atom,
R ^b and R ^a not involved in the bond are each independently the same as R ^b and R ^a in the above (i) The near-infrared cut-off filter according to claim 1, wherein the transmittance satisfies the following (B) and (C).
(B) an average value of the transmittance when measured from the vertical direction of the near-infrared cut filter at a wavelength of 800 to 1000 nm is not more than 20%
(C) the longest wavelength (Xa) in which the transmittance is 70% when measured from the vertical direction of the near-IR cut filter in the wavelength region of 800 nm or less, and the longest wavelength (Xa) measured from the vertical direction of the near- The absolute value of the difference between the shortest wavelength (Xb) in which the transmittance is 30% in one case is less than 75 nm The near infrared ray blocking filter according to claim 1, wherein the resin substrate (I) satisfies the following (E) and (F).
(E) Absorption maximum at wavelength of 600 to 800 nm
(F) a longest wavelength (Za) at an absorption maximum or less at which the transmittance is 70% when measured from the vertical direction of the substrate in a wavelength range of 430 to 800 nm, and Direction, the absolute value of the difference between the shortest wavelength (Zb) in which the transmittance is 30% and the absolute value of the difference is less than 75 nm The near-infrared cut filter according to claim 1, wherein the compound represented by the formula (I) is a compound represented by the following formula (II).
&Lt;

Wherein R ^a and R ^b each independently have the same meaning as (i) in the above formula (I), R ^c each independently represents a hydrogen atom, an aliphatic hydrocarbon group having 1 to 8 carbon atoms, an arbitrary hydrogen atom as a functional group A substituted aliphatic hydrocarbon group having 1 to 8 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a substituted aromatic hydrocarbon group having 6 to 12 carbon atoms in which any hydrogen atom is substituted with an alkyl group. The near infrared ray blocking filter according to claim 1, wherein the resin substrate (I) is a substrate comprising a cyclic olefin resin or an aromatic polyether resin. The cyclic olefin resin according to claim 5, wherein the cyclic olefin resin is a resin obtained from at least one monomer selected from the group consisting of a monomer represented by the following formula X ₀ and a monomer represented by the following formula: Y ₀ .
<Formula X _0>

(In the formula X ₀ , R ^x1 to R ^x4 each independently represent an atom or a group selected from the following (i ') to (viii'), k ^x , m ^x and p ^x each independently represent 0 or a positive integer Lt; / RTI >
(i ') hydrogen atom
(ii ') a halogen atom
(iii ') a trialkylsilyl group
(iv ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms having a connecting group containing an oxygen atom, a sulfur atom, a nitrogen atom or a silicon atom
(v ') a substituted or unsubstituted hydrocarbon group having 1 to 30 carbon atoms
(vi ') polar group (except (iv'))
(vii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are bonded to each other to form an alkylidene group, and R ^x1 to R ^{x4, which} are not involved in the bond, Represents an atom or a group selected from
(viii ') R ^x1 and R ^x2 or R ^x3 and R ^x4 are a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by bonding each other, and R ^x1 to R ^{x4, which} are not involved in the bond, (Vi), or a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding R ^x2 and R ^x3 to each other, and R ^x1 to R ^{x4 which} are not involved in the bond are each independently Represents an atom or a group selected from (i ') to (vi') above)
<Y ₀ >

(In the formula Y ₀ , R ^y1 and R ^y2 each independently represent an atom or a group selected from the above (i ') to (vi'), or represent the following (ix '), and K ^y and P ^y are independently Represents 0 or a positive integer:
(ix ') represents a monocyclic or polycyclic alicyclic hydrocarbon, aromatic hydrocarbon or heterocyclic ring formed by combining R ^y1 and R ^y2 ) 6. The filter according to claim 5, wherein the aromatic polyether resin has at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2) .
&Lt; Formula 1 >

(Wherein R ¹ to R ⁴ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and a to d each independently represent an integer of 0 to 4)
(2)

(Formula (2) of, R ¹ to R ⁴ and a to d are each independently the same meaning as R ¹ to R ⁴ and a to d in the formula 1, Y is a single bond, -SO ₂ - or> C = O R ⁷ and R ⁸ each independently represent a halogen atom, a monovalent organic group having 1 to 12 carbon atoms or a nitro group, g and h each independently represent an integer of 0 to 4, m is 0 or 1, , Provided that when m is 0, R &lt; ⁷ > is not a cyano group) The aromatic polyether resin according to claim 7, wherein the aromatic polyether resin further has at least one structural unit selected from the group consisting of a structural unit represented by the following general formula (3) and a structural unit represented by the following general formula (4) filter.
(3)

(Wherein R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z is a single bond, -O-, -S-, -SO ₂ -,> C = O, -CONH -, -COO- or a divalent organic group having 1 to 12 carbon atoms, e and f each independently represent an integer of 0 to 4, and n represents 0 or 1)
&Lt; Formula 4 >

(Formula (4) ^{of, R 7, R 8, Y} , m, and g and h are each independently the same meaning as ^{R 7, R 8, Y,} m, g , and h in the formula 2, R ^5, R ^6, Z, n, e and f are each independently the same as R ⁵ , R ⁶ , Z, n, e and f in the above formula (3) The near-infrared cut filter according to claim 5, wherein the compound (I) is contained in an amount of 0.01 to 10.0 parts by weight based on 100 parts by weight of the resin. The near-infrared cut filter according to claim 1, wherein the near-infrared cut filter is for a solid-state image pickup device. A solid-state imaging device comprising the near-infrared cut-off filter according to any one of claims 1 to 10. A camera module comprising the near-infrared cut filter according to any one of claims 1 to 10.

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