TWI582173B - Optical filter, solid imaging apparatus, camera module and resin composition - Google Patents

Description

Filter, solid-state camera, camera module, and resin composition Object

The present invention relates to a filter and a device using the same. More specifically, it relates to a filter including a specific solvent-soluble pigment compound, and a solid-state imaging device and a camera module using the same.

A charge-coupling device (CCD) that uses a solid-state imaging device as a color image in a solid-state imaging device such as a video camera, a digital still camera, or a camera-equipped mobile phone. Or a complementary metal-oxide-semiconductor (CMOS) image sensor, wherein the solid-state imaging device uses a germanium photodiode that is sensitive to near-infrared rays that are invisible to the human eye in the light receiving portion thereof. (silicon photodiode). For these solid-state imaging elements, it is necessary to perform visual sensitivity correction so that the human eye looks natural in color, and in many cases, a filter that selectively transmits or cuts light of a specific wavelength range (for example, a near-infrared cut filter) is used. .

As such a near-infrared cut filter, those manufactured by various methods have been used. For example, it is known to use a transparent resin as a substrate and to make it transparent. A near-infrared cut filter including a near-infrared absorbing dye in a bright resin (see, for example, Patent Document 1), and a near-infrared cut filter using a phthalocyanine-based compound as a near-infrared absorbing dye is widely known (for example, see Patent Document 2).

However, the maximum absorption wavelength of a typical phthalocyanine-based compound is usually 650 nm to less than 700 nm, and if it is set to a long wavelength shift of the maximum absorption wavelength, it is moved to a wavelength range particularly suitable for use as a solid-state imaging device (700 nm~ The structure of 800 nm) has a problem that the visible transmittance on the short-wavelength side near 430 nm to 460 nm is remarkably lowered.

As a method of shifting the maximum absorption of the phthalocyanine-based compound by a long wavelength, it is generally known to introduce an alkoxy group or an electron-donating group such as an alkyl-substituted amine group or an alkylthio group into a phthalocyanine ring. (for example, refer to Patent Document 3). However, if such a substituent is bonded to the phthalocyanine ring, a charge transfer transition from the non-consensus electron pair on the substituent to the phthalocyanine ring occurs, and the visible range on the short-wavelength side is generated by the transition. The absorption is caused, so the transmittance near 430 nm to 460 nm is particularly lowered.

Further, it is known that a general phthalocyanine-based compound easily forms a H-associated state in which the rings are stacked on each other in a resin. When the phthalocyanine-based compound is H-associated, a wide waveform having a weak absorption intensity near the maximum absorption is present as in the spectrum described in Example 1 of JP-A-2013-083915 (Patent Document 4). The optical characteristics required for the use of the solid-state imaging device cannot be achieved.

[Prior Art Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 6-200113

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2013-064975

[Patent Document 3] Japanese Patent No. 4287923

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2013-083915

An object of the present invention is to provide an improvement in the disadvantages of a filter such as a conventional near-infrared cut filter, which has sufficient absorption intensity in a wavelength range of around 700 nm to 750 nm and on a short wavelength side. A filter having excellent transmittance in the visible wavelength range and a device using the filter.

The present inventors have conducted intensive studies to achieve the above-mentioned problems, and as a result, it has been found that by applying a phthalocyanine-based compound having a specific structure, it is possible to obtain a target maximum absorption wavelength and an absorption intensity in a resin, and to absorb near-infrared rays. The present invention is completed by a filter having excellent characteristics and visible transmittance. An example of the aspect of the invention is shown below.

[1] A filter comprising: a transparent resin substrate comprising a compound (A) represented by the following formula (I); and a near-infrared reflective film formed on at least one surface of the substrate.

[Chemical 1]

In the formula (I), M represents 2 hydrogen atoms, 2 monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom; a plurality of R _a independently It represents L ^1, a plurality of R _b independently represent a hydrogen atom, a halogen atom, L ¹ or -SO ^₂ -L _2; L ¹ represented by the following L ^a, L ^b or L ^c, L ² represented by the following L ^a, L ^b , L ^c , L ^d or L ^e ; (L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms

(L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms

(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms

(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms

(L ^e ) a heterocyclic group having 3 to 14 carbon atoms

The L ^a ~L ^e may further have an aliphatic hydrocarbon group selected from carbon atoms 1 to 12, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and a carbon number of 6 At least one substituent L in the group consisting of an aromatic hydrocarbon group of ~14, a heterocyclic group having 3 to 14 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.

[2] The optical filter according to [1], wherein, in the formula (I), M is a divalent transition metal belonging to Group 4 to Group 12 of the periodic table and the fourth to fifth periods a trivalent or tetravalent metal halide or a tetravalent metal oxide; R _{a is} independently an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 6 carbon atoms, a cyclopentyl group or a ring. Hexyl; R _{b is} independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a cyclopentyl group, a cyclohexyl group or -SO ₂ -L ² ; and L ² is an alkyl group having 1 to 6 carbon atoms; 6 to 12 aromatic hydrocarbon groups or 3 to 6 carbon heterocyclic groups.

[3] The optical filter according to the item [1], wherein the transparent resin constituting the transparent resin substrate is selected from the group consisting of a cyclic olefin resin, an aromatic polyether resin, and a polysiloxane. Amine resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamine resin, polyarylate resin, polysulfone resin, polyether oxime Resin, polyparaphenylene resin, polyamidoximine resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy At least one of a group consisting of a resin, an allyl ester resin, and a sesquioxan resin.

[4] The optical filter according to any one of [1], wherein the near-infrared reflective film is formed on both surfaces of the substrate.

[5] The optical filter according to any one of [1] to [4], which is for a solid-state imaging device.

[6] A solid-state imaging device comprising the optical filter according to any one of [1] to [5].

[7] A camera module comprising the optical filter according to any one of [1] to [5].

[8] A resin composition comprising the compound (A) represented by the following formula (I), and a cyclic olefin resin, an aromatic polyether resin, a polyamidene resin, and a fluorene polycarbonate. Resin, bismuth polyester resin, polycarbonate resin, polyamido resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyparaphenylene resin, polyamidoximine Resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin and sesquiterpene oxide resin At least one resin in the group.

In the formula (I), M represents 2 hydrogen atoms, 2 monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom; a plurality of R _a independently It represents L ^1, a plurality of R _b independently represent a hydrogen atom, a halogen atom, L ¹ or -SO ^₂ -L _2; L ¹ represented by the following L ^a, L ^b or L ^c, L ² represented by the following L ^a, L ^b , L ^c , L ^d or L ^e ; (L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms

(L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms

(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms

(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms

(L ^e ) a heterocyclic group having 3 to 14 carbon atoms

The L ^a ~L ^e may further have an aliphatic hydrocarbon group selected from carbon atoms 1 to 12, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and a carbon number of 6 At least one substituent L in the group consisting of an aromatic hydrocarbon group of ~14, a heterocyclic group having 3 to 14 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.

According to the present invention, it is possible to provide a filter having low incident angle dependency, light resistance, near-infrared absorption characteristics in the vicinity of 700 nm to 750 nm, and excellent transmittance characteristics in the visible wavelength range.

1‧‧‧ Filter

2‧‧‧Spectrophotometer

3‧‧‧Light

Fig. 1(a) is a schematic view showing a method of measuring transmittance in a case where the filter is measured in the vertical direction. Fig. 1(b) is a schematic view showing a method of measuring the transmittance in the case of measuring at an angle of 30° with respect to the vertical direction of the filter.

Hereinafter, the present invention will be specifically described.

The optical filter of the present invention has a transparent resin substrate containing a phthalocyanine-based compound (compound (A)) represented by a specific structure, and a substrate formed on the substrate. A near-infrared reflective film on one side.

[Transparent resin substrate]

The transparent resin substrate (hereinafter also referred to as "resin substrate") constituting the optical filter of the present invention may be a single layer or a plurality of layers (in the case of a plurality of layers, for example, it is configured to be laminated on a resin substrate as a base) The outer layer of the cured resin, etc.) contains at least one compound (A) as a near-infrared absorbing pigment, and the maximum absorption is in the range of 700 nm to 800 nm, more preferably 705 nm to 750 nm, and the transmittance at the maximum absorption wavelength is higher. Preferably, it is 10% or less, and further preferably 8% or less. When the transmittance of the maximum absorption wavelength or the maximum absorption wavelength of the substrate is within such a range, the substrate can selectively cut off near-infrared rays efficiently, and when a near-infrared reflective film is formed on the surface of the transparent resin substrate, It can reduce the incident angle dependence of the optical characteristics near the visible wavelength to the near-infrared wavelength range.

According to the use of the camera module or the like, there is a case where the average transmittance of the substrate when the thickness of the resin substrate containing the compound (A) is 100 μm in the so-called visible light range of 400 nm to 700 nm. More than %, preferably more than 65%.

The thickness of the resin substrate can be appropriately selected depending on the intended use, and is not particularly limited. It is preferably adjusted such that the substrate has an improvement in incident angle as described above, and more preferably 30 μm to 250 μm. It is 40 μm to 200 μm, and particularly preferably 50 μm to 150 μm.

When the thickness of the resin substrate is within the above range, the filter using the substrate can be reduced in size and weight, and can be preferably used in various applications such as a solid-state imaging device. In particular, when the resin substrate is used for a lens unit such as a camera module, it is preferable to reduce the thickness of the lens unit.

In addition to the compound (A), the resin substrate may further contain a group selected from the group consisting of a squary sulphate-based compound and a phthalocyanine-based compound and a cyanine-based compound other than the compound (A). At least one near-infrared absorbing pigment (X) in the group. By using such a resin substrate, the incident angle dependency in the visible wavelength range to the near-infrared wavelength range can be further reduced, and the waveform of the absorption band can be made narrower, and a filter having a wide viewing angle can be obtained.

The compound (A) and the near-infrared absorbing pigment (X) may be contained in the same layer or may be contained in different layers. In the case of being contained in the same layer, for example, a form in which both the compound (A) and the near-infrared absorbing dye (X) are contained in a resin substrate as a base is included, and when it is contained in a different layer, for example, A form in which a layer containing the near-infrared absorbing dye (X) is laminated on a resin substrate containing the compound (A).

The compound (A) and the near-infrared absorbing pigment (X) are preferably contained in the same layer, and in this case, it is easier to control the compound (A) and the near-infrared rays than in the case of being contained in a different layer. The content ratio of the absorbing pigment (X).

<compound (A)>

The compound (A) is a phthalocyanine compound represented by the following formula (I).

[Chemical 3]

In the formula (I), M represents 2 hydrogen atoms, 2 monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom; a plurality of R _a independently It represents L ^1, a plurality of R _b independently represent a hydrogen atom, a halogen atom, L ¹ or -SO ^₂ -L _2; L ¹ represented by the following L ^a, L ^b or L ^c, L ² represented by the following L ^a, L ^b , L ^c , L ^d or L ^e ; (L ^a ) an aliphatic hydrocarbon group having 1 to 12 carbon atoms

(L ^b ) a halogen-substituted alkyl group having 1 to 12 carbon atoms

(L ^c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms

(L ^d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms

(L ^e ) a heterocyclic group having 3 to 14 carbon atoms

The L ^a ~L ^e may further have an aliphatic hydrocarbon group selected from carbon atoms 1 to 12, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, and a carbon number of 6 At least one substituent L in the group consisting of an aromatic hydrocarbon group of ~14, a heterocyclic group having 3 to 14 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms.

With respect to the above-mentioned L ^a to L ^e , the total number of carbon atoms having a substituent is preferably 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the carbon number is more than the above range, the synthesis of the dye may become difficult, and the absorption strength per unit weight tends to be small.

Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms of L ^a and L include methyl (Me), ethyl (Et), n-propyl (n-Pr), and isopropyl (i-Pr). ), n-butyl (n-Bu), second butyl (s-Bu), tert-butyl (t-Bu), pentyl, hexyl, octyl, decyl, decyl and dodecyl Alkyl; vinyl, 1-propenyl, 2-propenyl, butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl, hexenyl and octyl An alkenyl group such as an alkenyl group; and an alkynyl group such as an ethynyl group, a propynyl group, a butynyl group, a 2-methyl-1-propynyl group, a hexynyl group, and an octynyl group.

Examples of the halogen-substituted alkyl group having 1 to 12 carbon atoms of L ^b and L include trichloromethyl, trifluoromethyl, 1,1-dichloroethyl, pentachloroethyl and five. Fluoroethyl, heptachloropropyl and heptafluoropropyl.

Examples of the alicyclic hydrocarbon group having 3 to 14 carbon atoms of L ^c and L include a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and a cyclooctyl group; and a norbornyl group; And polycyclic alicyclic groups such as adamantyl.

Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms of L ^d and L include a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, and a 1-naphthalene group. Base, 2-naphthyl, anthracenyl, phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl and biphenyl.

Examples of the heterocyclic group having 3 to 14 carbon atoms of L ^e and L include furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, and thiadiazole. Anthraquinone, porphyrin, indolenine, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquine a heterocyclic group such as a porphyrin, an acridine, a morpholine or a morphazine.

As the L ^a , a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a second butyl group, a third butyl group, a pentyl group, a hexyl group, an octyl group or a 4-phenyl group are preferable. Further, 2-cyclohexylethyl, more preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, t-butyl, hexyl.

As the L ^b , preferred is trichloromethyl, pentachloroethyl, trifluoromethyl, pentafluoroethyl, 5-cyclohexyl-2,2,3,3-tetrafluoropentyl, more preferably Trichloromethyl, pentachloroethyl, trifluoromethyl, pentafluoroethyl.

The L ^{c is} preferably a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group or a 4-phenylcycloheptyl group, more preferably a cyclopentyl group, a cyclohexyl group, or 4 - Ethylcyclohexyl.

As the L ^d , a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 3,5-di-tert-butylphenyl group are preferable. , 4-cyclopentylphenyl, 2,3,6-triphenylphenyl, 2,3,4,5,6-pentaphenylphenyl, more preferably phenyl, tolyl, xylyl, Mesitylene, cumenyl, 2,3,4,5,6-pentaphenylphenyl.

The L ^{e is} preferably a group containing furan, thiophene, pyrrole, anthracene, porphyrin, pyrene, benzofuran, benzothiophene, morpholine, more preferably furan, thiophene or pyrrole. a group of morpholine.

The L ^a to L ^e may further have at least one atom or group selected from the group consisting of a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, and an amine group. Examples thereof include 4-sulfobutyl group, 4-cyanobutyl group, 5-carboxypentyl group, 5-aminopentyl group, 3-hydroxypropyl group, 2-phosphonylethyl group, and 6-amine. Base-2,2-dicyclohexyl, 2-chloro-4-hydroxybutyl, 2-cyanocyclobutyl, 3-hydroxycyclopentyl, 3-carboxycyclopentyl, 4-aminocyclohexyl, 4 -hydroxycyclohexyl, 4-hydroxyphenyl, 2-hydroxynaphthyl, 4-aminophenyl, 2,3,4,5,6-pentafluorophenyl, 4-nitrophenyl, 3-3-yl A group of a pyrrolidine, 2-hydroxyethoxy, 3-cyanopropoxy, 4-fluorobenzylidene, 2-hydroxyethoxycarbonyl, 4-cyanobutoxycarbonyl.

In the above, examples of the monovalent metal atom include Li, Na, K, Rb, and Cs.

In the above M, examples of the divalent metal atom include Be, Mg, Ca, Ba, Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Zn, Cd, and Hg. Sn, Pb, etc.

In the above M, as the substituted metal atom containing a trivalent metal atom, Al-F, Al-Cl, Al-Br, Al-I, Ga-F, Ga-Cl, Ga-Br, Ga may be mentioned. -I, In-F, In-Cl, In-Br, In-I, Tl-F, Tl-Cl, Tl-Br, Tl-I, Fe-Cl, Ru-Cl, Mn-OH, and the like.

The M, as the metal atom comprises a substituted tetravalent metal atom include _{TiF 2, TiCl 2, TiBr 2} , TiI 2, ZrCl 2, HfCl 2, CrCl 2, SiF 2, SiCl 2, SiBr 2 _{, SiI 2, GeF 2, GeCl} 2, GeBr 2, GeI 2, SnF 2, SnCl 2, SnBr 2, SnI 2, Zr (OH) 2, Hf (OH) 2, Mn (OH) 2, Si (OH) ₂ , Ge(OH) ₂ , Sn(OH) ₂ , TiR ₂ , CrR ₂ , SiR ₂ , GeR ₂ , SnR ₂ , Ti(OR) ₂ , Cr(OR) ₂ , Si(OR) ₂ , Ge(OR ₂ , Sn(OR) ₂ (R represents an aliphatic group or an aromatic group), TiO, VO, MnO, or the like.

As the M, a divalent transition metal, a trivalent or tetravalent metal halide or a tetravalent metal oxide belonging to Group 4 to Group 12 of the periodic table and the fourth to fifth cycles is preferable. Among them, Cu, Ni, Co, Zn, TiO, and VO are more preferable, and Cu and VO are particularly preferable from the viewpoint of achieving high visible light transmittance and pigment stability.

The R _a is preferably an alkyl group having 1 to 10 carbon atoms or a fluorine atom having 1 to 6 carbon atoms from the viewpoint of easiness of synthesis or solubility of the compound (A) in an organic solvent. The alkyl group, the cyclopentyl group or the cyclohexyl group is more preferably an alkyl group having 1 to 10 carbon atoms, particularly preferably an alkyl group having 3 to 8 carbon atoms.

The R _b is preferably a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a cyclopentyl group or a ring, from the viewpoint of easiness of synthesis or stability of the compound (A). Hexyl or -SO ₂ -L ² (L ^{2 is} preferably an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or a heterocyclic group having 3 to 6 carbon atoms), more preferably a hydrogen atom or An alkyl group having 1 to 6 carbon atoms.

A method of synthesizing the compound (A) by a cyclization reaction such as a phthalonitrile derivative represented by the following formula (II), and the obtained phthalocyanine-based compound is as follows. (II-1)~ a mixture of four isomers of the formula (II-4). In the present invention, only one isomer is exemplified for one phthalocyanine-based compound unless otherwise specified, but the other three isomers may be used in the same manner. Further, the isomers may also be used separately as needed, and in the present invention, a mixture of isomers is used in total.

[Chemical 4]

The specific example of the compound (A) is not particularly limited as long as it satisfies the conditions described in the above formula (I), and examples thereof include the following table having the basic skeleton represented by the following formula (I-1). The compound (a-1) to the compound (a-35) described in 1.

[Chemical 6]

[Table 1] Table 1

The compound (A) can be synthesized by a generally known method, for example, It is synthesized by the method described in Japanese Patent No. 4,081,149, "Phase-Chemistry and Function" (IPC, 1997), and Japanese Patent Laid-Open No. Hei 2-138382.

In the resin substrate, the content of the compound (A) in the resin layer is preferably from 0.01 part by weight to 5.0 parts by weight, more preferably from 0.02 part by weight to 3.5% by weight based on 100 parts by weight of the transparent resin used for producing the resin substrate. It is particularly preferably 0.03 parts by weight to 2.5 parts by weight. When the content of the compound (A) is within the above range, both good near-infrared absorption characteristics and high visible light transmittance can be obtained.

<Near infrared absorbing pigment (X)>

The near-infrared absorbing pigment (X) is at least one selected from the group consisting of a squarylium-based compound, a phthalocyanine-based compound, and a cyanine-based compound, and particularly preferably a squaraine-based compound. The maximum absorption wavelength of the near-infrared absorbing pigment (X) is preferably 620 nm or more, more preferably 650 nm or more, particularly preferably 670 nm or more, and preferably less than 800 nm, more preferably 750 nm or less, still more preferably 730 nm or less, and It is desirable that the maximum absorption wavelength of the compound (A) contained at the same time has a maximum absorption on the shorter wavelength side. If the maximum absorption wavelength is within such a wavelength range, the absorption band can be made narrower, and the absorption band of the near-infrared absorbing pigment can be sufficiently expanded, thereby achieving better incident angle dependency improvement performance or ghost reduction. effect.

In the resin substrate, the content of the near-infrared absorbing pigment (X) in the resin layer is preferably 0.01 parts by weight to 5.0 parts by weight, more preferably 0.02% by weight based on 100 parts by weight of the transparent resin used for producing the resin substrate. It is preferably 3.5 parts by weight, particularly preferably 0.03 parts by weight to 2.5 parts by weight. If the content of the near infrared absorbing pigment is in the Within the range, it has good near-infrared absorption characteristics and high visible light transmittance.

"Squaraine Cyanine Compound"

The squarylium-based compound preferably contains at least one selected from the group consisting of a squaraine-based compound represented by the formula (III-1) and a squaraine-based compound represented by the formula (III-2).

In the formula (III-1), R ^m , R ⁿ and Y satisfy the conditions of the following (i) or (ii).

Condition (i)

The plurality of R ^m each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or a -NR ^e R ^f group. R ^e and R ^f each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e .

The plurality of R ⁿ each independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphoric acid group, a -L ¹ or a -NR ^g R ^h group. R ^g and R ^h each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d , -L ^e or -C(O)R ⁱ group (R ⁱ represents -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ).

A plurality of Y independently represent the -NR ^j R ^k basis. R ^j and R ^k each independently represent a hydrogen atom, -L ^a , -L ^b , -L ^c , -L ^d or -L ^e .

The ^{L 1, L a, L b} , L c, L d, L e are each independently defined as in the formula (I), ^{L 1, L a, L b} , L c, L d, L e is The same meaning.

Condition (ii)

At least one of the two R ^m on one benzene ring is bonded to Y on the same benzene ring to form a hetero ring having at least one nitrogen atom and having a number of 5 or 6 atoms, and the hetero ring may have a substitution. The radicals, R ⁿ and R ^m not participating in the formation of the heterocyclic ring are each independently of the same meaning as R ⁿ and R ^m of the above (i).

In the formula (III-2), X represents -O-, -S-, -Se-, -N(R ^c )- or -C(R ^d R ^d )-; and a plurality of R ^c each independently represent a hydrogen atom , -L ^a , -L ^b , -L ^c , -L ^d or -L ^e ; a plurality of R ^d independently represent a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a phosphate group , -L ¹ or -NR ^e R ^f group, adjacent R ^d may also be bonded to each other to form a ring which may have a substituent; L ^a ~L ^e , L ¹ and L ^a as defined in the formula (I) ~ L ^e, L ¹ have the same meaning, R ^e, and R ^f of the (i) of R ^e and R ^f is the same meaning.

The substituents on the four-membered ring bonded to the center of the squaraine-based compound may be the same or different, and are preferably synthesized in the same manner, which is preferable.

The squarylium-based compound may be synthesized by a generally known method. For example, Japanese Patent Laid-Open No. Hei 1-228960, Japanese Patent Laid-Open No. 2001-40234, Japanese Patent No. 3196383, and the like can be used. The method described is synthesized.

"Phthalocyanine Compounds"

As the phthalocyanine-based compound, a compound of any structure generally known other than the compound (A) can be used, and for example, the method described in Japanese Patent No. 4081149 or "Phthalocyanine-Chemistry and Function" (IPC, 1997) can be used. To synthesize.

"Cyanine Compound"

As the cyanine compound, a compound of any structure generally known can be used, and for example, it can be synthesized by the method described in JP-A-2009-108267.

<Transparent Resin>

The resin substrate is composed of a transparent resin and a compound (A).

The transparent resin is not particularly limited as long as it does not impair the effects of the present invention. For example, in order to ensure thermal stability and formability of the film, it is possible to form a high-temperature steam which can be carried out at a vapor deposition temperature of 100 ° C or higher. The film which is plated to form the dielectric multilayer film may, for example, be a resin having a glass transition temperature (Tg) of preferably from 110 ° C to 380 ° C, more preferably from 110 ° C to 370 ° C, even more preferably from 120 ° C to 360 ° C. Further, when the glass transition temperature of the resin is 140 ° C or higher, a film which can be vapor-deposited at a higher temperature to form a dielectric multilayer film can be obtained, which is particularly preferable.

Regarding the transparent resin, in the case of forming a resin sheet having a thickness of 0.1 mm of the resin, the total light transmittance of the resin sheet can be used (Japanese Industrial Standard) (Japanese Industrial Standards, JIS) K7105) is preferably a resin of 75% to 95%, more preferably 78% to 95%, and particularly preferably 80% to 95%. When a resin having a total light transmittance of such a range is used, the obtained substrate exhibits excellent transparency as an optical film.

The polystyrene-equivalent weight average molecular weight (Mw) of the transparent resin measured by Gel Permeation Chromatography (GPC) is usually 15,000 to 350,000, preferably 30,000 to 250,000; and the number average molecular weight (Mn) ) is usually 10,000 to 150,000, preferably 20,000 to 100,000.

Examples of the transparent resin include a cyclic olefin resin, an aromatic polyether resin, a polyamidene resin, a fluorene polycarbonate resin, a fluorene polyester resin, a polycarbonate resin, and a polyamine. Polyamide resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyparaphenylene resin, polyamidoximine resin, polyethylene naphthalate , PEN) resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin, and sesquiterpene oxide resin.

"Ring olefin resin"

The cyclic olefin-based 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 ). And a resin obtained by hydrogenating the resin.

[Chemistry 9]

In the formula (X ₀ ), R ^x1 to R ^x4 each independently represent an atom or a group selected from the following (i') to (ix'), and k ^x , m ^x and p ^x each independently represent 0 or A positive integer.

(i') hydrogen atom

(ii') halogen atom

(iii') trialkyldecylalkyl

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

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

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

(vii') an alkylene group formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^{x4 to} each other (wherein R ^x1 to R ^x4 not participating in the bonding are independently represented from the above (i' ) an atom or group in ~(vi')

(viii') a monocyclic or polycyclic hydrocarbon ring or a heterocyclic ring formed by bonding R ^x1 and R ^x2 or R ^x3 and R ^{x4 to} each other (wherein R ^x1 to R ^x4 not participating in the bonding are independently Representing an atom or group selected from the group (i') to (vi')

(ix') a monocyclic hydrocarbon ring or a heterocyclic ring formed by bonding R ^x2 and R ^{x3 to} each other (wherein R ^x1 and R ^x4 which do not participate in the bonding are independently represented from the above (i') An atom or group in ~(vi')

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 a single bond formed by bonding R ^y1 and R ^{y2 to} each other. A cyclic or polycyclic alicyclic hydrocarbon, an aromatic hydrocarbon or a heterocyclic ring, k ^y and p ^y each independently represent 0 or a positive integer.

"Aromatic Polyether Resin"

The aromatic polyether-based resin preferably contains 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).

In the formula (1), 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.

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), and Y represents 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, and g and h each independently represent an integer of 0 to 4, and m represents 0 or 1. Wherein, when m is 0, R ⁷ is not a cyano group.

In addition, the aromatic polyether-based resin preferably further contains at least one structure 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). unit.

In the formula (3), R ⁵ and R ⁶ each independently represent a monovalent organic group having 1 to 12 carbon atoms, and Z represents a single bond, -O-, -S-, -SO ₂ -, >C=O, - CONH-, -COO- or a divalent organic group having 1 to 12 carbon atoms, and e and f each independently represent an integer of 0 to 4, and n represents 0 or 1.

In the formula (4), 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), 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).

Polyimide Resin

The polyimine-based resin is not particularly limited as long as it is a polymer compound containing a quinone bond in the repeating unit. For example, JP-A-2006-199945 or JP-A-2008-163107 can be used. The method described in the synthesis.

"茀 polycarbonate resin"

The fluorene-based polycarbonate resin is not particularly limited as long as it is a polycarbonate resin containing a fluorene moiety, and can be synthesized, for example, by the method described in JP-A-2008-163194.

"茀 polyester resin"

The oxime-based polyester resin is not particularly limited as long as it is a polyester resin containing a ruthenium moiety, and can be synthesized, for example, by the method described in JP-A-2010-285505 or JP-A-2011-197450. .

Fluorinated Aromatic Polymer Resins

The fluorinated aromatic polymer-based resin is not particularly limited as long as it contains an aromatic ring having at least one fluorine and has an ether bond, a ketone bond, a hydrazone bond, a guanamine bond, a quinone bond, and an ester bond. The polymer of the repeating unit of at least one of the bonds in the group may be synthesized, for example, by the method described in JP-A-2008-181121.

"commercial goods"

Commercially available products of the transparent resin include the following commercial products. Commercial products of the cyclic olefin resin include Arton manufactured by Japan Synthetic Rubber (JSR) Co., Ltd., Zeonor manufactured by Japan Zeon Japan Co., Ltd., and Mitsui Chemicals Co., Ltd. APEL, TOPAS manufactured by Polyplastics Co., Ltd., etc. A commercially available product of a polyether oxime resin is Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd., and the like. Commercially available products of the polyimine-based resin include Neoprim L manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. A commercially available product of a polycarbonate resin is, for example, Pureace manufactured by Teijin Co., Ltd. Commercial products of the fluorene-based polycarbonate resin include Iupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. Commercially available products of 茀 polyester resin include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Wait. Commercially available products of the acrylic resin include Acryviewa manufactured by Nippon Shokubai Co., Ltd., and the like. A commercially available product of a sesquioxane-based resin is, for example, Silplus manufactured by Nippon Steel Chemical Co., Ltd.

<Other ingredients>

The resin substrate may further contain a near-infrared absorbing dye other than the antioxidant, the near ultraviolet ray absorbing agent, the compound (A), and the near infrared absorbing dye (X), within a range that does not impair the effects of the present invention (hereinafter, It is called "other near infrared absorbing pigment"), an additive such as a fluorescent matting agent and a metal complex compound. In the case where a resin substrate is produced by casting molding described later, the addition of a leveling agent or an antifoaming agent can facilitate the production of a resin substrate. These other components may be used alone or in combination of two or more.

The antioxidant may, for example, be 2,6-di-t-butyl-4-methylphenol, 2,2'-dioxy-3,3'-di-t-butyl-5,5' - dimethyldiphenylmethane and tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane.

Examples of the near-ultraviolet absorber include an azomethylene-based compound, an anthraquinone-based compound, a benzotriazole-based compound, and a triazine-based compound.

Examples of the other near-infrared absorbing dye include a dithiol-based dye, a diimonium-based dye, a porphyrin-based dye, and a croconium-based dye. The structure of these dyes is not particularly limited, and those generally known can be used as long as the effects of the present invention are not impaired.

Further, these additives may be mixed with a resin or the like in the production of a resin substrate, or may be added at the time of resin production. In addition, the amount added is based on the desired characteristics. Suitably, it is usually -0.01 parts by weight to 5.0 parts by weight, preferably 0.05 parts by weight to 2.0 parts by weight, based on 100 parts by weight of the resin.

<Method for Producing Resin Substrate>

The resin substrate can be formed, for example, by melt molding or cast molding, and can be produced by a method of applying a coating agent such as an antireflection agent, a hard coating agent, and/or an antistatic agent after molding, if necessary.

Melt Forming

The resin substrate can be produced by a method of melt-molding particles obtained by melt-kneading a resin and a near-infrared absorbing dye, and a method of melt-molding a resin composition containing a resin and a near-infrared absorbing dye. Or a method of melt-molding particles obtained by removing a solvent from a resin composition containing a near-infrared absorbing dye, a resin, and a solvent. Examples of the melt molding method include injection molding, melt extrusion molding, and blow molding.

Casting

The resin substrate can also be produced by casting a resin composition containing a near-infrared absorbing dye, a resin, and a solvent onto a suitable substrate and removing the solvent; and containing the near-infrared absorbing pigment and resin. A method in which a curable resin composition is applied onto a suitable substrate, dried, and hardened.

Examples of the substrate include a glass plate, a steel band, an steel drum, and a transparent resin film (for example, a polyester film or a cyclic olefin resin film).

The resin substrate can be obtained by peeling off from the substrate, and the product of the substrate and the coating film can be removed without peeling off from the substrate as long as the effect of the present invention is not impaired. The layer body is used as the resin substrate.

Further, a resin substrate may be directly formed on the optical component by a method of applying the resin composition to an optical component such as a glass plate, a quartz or a transparent plastic, and drying the solvent; or coating A method of hardening and drying the curable resin composition, and the like.

The amount of residual solvent in the resin substrate obtained by the above method is preferably as small as possible. Specifically, the amount of the residual solvent is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight or less based on the weight of the resin substrate. When the amount of the residual solvent is within the above range, deformation or deformation is not easily changed, and a resin substrate which can easily exhibit a desired function can be obtained.

[Near Infrared Reflective Film]

The near-infrared reflecting film constituting the optical filter of the present invention is a film having the ability to reflect near-infrared rays. In the present invention, the near-infrared reflective film may be provided on one surface of the resin substrate or on both surfaces. When it is provided on one surface, it is excellent in manufacturing cost or ease of manufacture, and when it is provided on both surfaces, a filter having high strength and warp is unlikely to be obtained. When the filter is applied to the use of a solid-state imaging device, it is preferable that the warpage of the filter is small. Therefore, it is preferable to provide the near-infrared reflective film on both surfaces of the resin substrate.

Examples of the near-infrared reflective film include an aluminum deposited film, a noble metal thin film, and a resin film in which metal oxide fine particles containing indium oxide as a main component and a small amount of tin oxide are dispersed, and a high refractive index material layer and a low refractive index material layer are alternated. A dielectric multilayer film laminated. In the near-infrared reflective film, it is more preferable to have a high refractive index material layer A dielectric multilayer film in which a layer of a low refractive index material is alternately laminated.

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 of usually 1.7 to 2.5 is selected. Examples of such a material include titanium oxide, zirconium oxide, antimony pentoxide, antimony pentoxide, antimony oxide, antimony oxide, zinc oxide, zinc sulfide, or indium oxide or the like as a main component and a small amount (for example, relative to the main component). From 0% by weight to 10% by weight, titanium oxide, tin oxide, and/or cerium oxide are contained.

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 of usually 1.2 to 1.6 is selected. Examples of such a material include cerium oxide, aluminum oxide, cerium fluoride, magnesium fluoride, and sodium aluminum hexafluoride.

The method of laminating the high refractive index material layer and the low refractive index material is not particularly limited as long as the dielectric multilayer film in which the materials are laminated is formed. For example, a high refractive index material can be formed directly on a resin substrate by a chemical vapor deposition (CVD) method, a sputtering method, a vacuum deposition method, an ion assist evaporation method, or an ion plating method. A dielectric multilayer film in which a layer and a low refractive index material layer are alternately laminated.

Generally, when the near-infrared wavelength to be blocked is set to λ (nm), the thickness of each layer of the high refractive index material layer and the low refractive index material layer is preferably 0.1 λ to 0.5 λ. The value of λ (nm) is, for example, 700 nm to 1400 nm, preferably 750 nm to 1300 nm. When the thickness is in this range, the optical film thickness calculated from the product of λ/4 versus the refractive index (n) and the film thickness (d) (n×d) and the high refractive index material layer and the low refractive index material layer are The thickness of each layer becomes approximately the same value, depending on the optical properties of reflection and refraction Sexual relationships have a tendency to easily control the blocking and transmission of specific wavelengths.

The total number of layers of the high refractive index material layer and the low refractive index material layer of the dielectric multilayer film is preferably 5 to 60 layers, more preferably 10 to 50 layers, in the entire filter.

[Other functional films]

In the optical filter of the present invention, an antireflection film, a hard coat film, and an anti-reflection film are appropriately provided between a resin substrate and a near-infrared reflective film such as a dielectric multilayer film, etc., within a range that does not impair the effects of the present invention. A functional film such as an electrostatic film improves the surface hardness of a resin substrate or a near-infrared reflective film, improves chemical resistance, and is resistant to static electricity and damage.

In order to improve the adhesion between the resin substrate and the functional film and/or the near-infrared reflective film, or the adhesion between the functional film and the near-infrared reflective film, the surface of the resin substrate or the functional film may be subjected to corona treatment or plasma treatment. Wait for surface treatment.

[The characteristics of the filter, etc.]

The optical filter of the present invention has the resin substrate. Therefore, the optical filter of the present invention is excellent in transmittance characteristics and is not restricted in use. Further, since the compound (A) contained in the resin substrate has maximum absorption at a wavelength of from 700 nm to 800 nm, it is possible to efficiently absorb near-infrared light, and by combining with the near-infrared reflecting film, low incident angle dependency can be obtained. Filter.

By using the resin substrate as a filter such as a near-infrared cut filter, it is possible to obtain a value of a wavelength at which the transmittance is 50% when measured in the vertical direction of the optical film in the range of 560 nm to 800 nm. Xa), a value of a wavelength at which the transmittance is 50% when measured at an angle of 30° with respect to the vertical direction of the optical film The absolute value of the difference of (Xb) is small, and the value (Za) of the wavelength at which the transmittance is 10% from the vertical direction of the optical film in the region of the wavelength of 560 nm to 800 nm, and the vertical from the optical film. When the angle is 30°, the absolute value of the difference (Zb) of the wavelength at which the transmittance is 10% becomes small, and the incident angle dependence of the absorption wavelength becomes small, and the viewing angle is wide even near the edge of the transmission wavelength range. Filter. In the optical filter of the present invention, the absolute value of the difference between (Xa) and (Xb) is preferably less than 20 nm, more preferably less than 15 nm, still more preferably less than 10 nm, and the absolute difference between (Za) and (Zb) The value is preferably 18 nm or less, and particularly preferably 15 nm or less.

When the filter is used for a solid-state image sensor, it is preferred that the visible light transmittance is high. In particular, in recent years, high image quality has been strongly demanded in camera modules, and in order to improve image sensitivity or color reproducibility, it is necessary to increase the transmittance on the short-wavelength side of wavelengths of 430 nm to 460 nm. Specifically, the average transmittance of the wavelength of 430 nm to 460 nm is preferably 81% or more, more preferably 83% or more, and particularly preferably 85% or more. Further, it is preferable that the average transmittance of the wavelength of 461 nm to 580 nm is also high, preferably 85% or more, more preferably 88% or more, and still more preferably 90% or more. When the average transmittance in each wavelength range is within this range, excellent imaging sensitivity and color reproducibility can be achieved when used as a solid-state imaging device.

In the case where the filter is used for a solid-state image sensor, it is preferable that the transmittance in the near-infrared wavelength range is low. In particular, it is known that the solid-state imaging device has a high light-receiving sensitivity in a region having a wavelength of 800 nm to 1000 nm, and by reducing the transmittance in the wavelength range, the camera image and the human eye can be effectively corrected in visibility, and excellent color can be achieved. Reproducibility. The average transmittance of the wavelength of 800 nm to 1000 nm is preferably 15% or less, and further preferably 10% or less, and particularly preferably 5% or less. When the average transmittance of the wavelength of 800 nm to 1000 nm is within this range, the near-infrared rays can be sufficiently cut off, and excellent color reproducibility can be achieved, which is preferable.

[Use of filter]

The filter of the present invention has a wide viewing angle and an excellent near-infrared cut-off function. Therefore, it is effectively used as a photographic sensitivity correction for a solid-state imaging device such as a CCD or a CMOS image sensor of a camera module. It is especially effective for digital still cameras, mobile phone cameras, digital cameras, personal computer cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, mobile information terminals, video game consoles, and portable games. Machine, fingerprint authentication system device, digital music player, etc. Further, it is also effective as a hot wire cut filter or the like attached to a glass plate or the like of an automobile or a building.

[Solid camera]

The solid-state imaging device of the present invention includes the optical filter of the present invention. Here, the solid-state imaging device refers to an image sensor including a solid-state imaging device such as a CCD or a CMOS image sensor, and is specifically a digital still camera, a mobile phone camera, a digital camera, or the like. For example, the camera module of the present invention is provided with the filter of the present invention.

[Examples]

Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited by the examples. In addition, "parts" means "parts by weight" unless otherwise specified. Moreover, the measuring method of each physical property value and the evaluation method of physical property are as follows.

<molecular weight>

The molecular weight of the resin is measured by the method of the following (a) or (b) in consideration of the solubility of each resin in a solvent.

(a) Using a gel permeation chromatography (GPC) apparatus manufactured by WATERS (150C type, column: H-type column manufactured by Tosoh Corporation, developing solvent: o-dichlorobenzene), measurement standard The polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn).

(b) Using a GPC apparatus manufactured by Tosoh Corporation (HLC-8220 type, column: TSKgelα-M, developing solvent: tetrahydrofuran (THF)), measuring the weight average molecular weight (Mw) and quantity in terms of standard polystyrene Average molecular weight (Mn).

In the resin synthesized in the resin synthesis example 3 to be described later, the measurement of the molecular weight by the above method was not carried out, and the measurement of the logarithmic viscosity by the following method (c) was carried out.

(c) A part of the polyimine resin solution is poured into anhydrous methanol to precipitate a polyimine resin, which is filtered and separated from the unreacted monomer. 0.1 g of polyimine obtained by vacuum drying at 80 ° C for 12 hours was dissolved in 20 mL of N-methyl-2-pyrrolidone using a Cannon-Fenske viscometer. The logarithmic viscosity (μ) at 30 ° C was obtained by the following formula.

μ={ln(t _s /t ₀ )}/C

t ₀ : the flow time of the solvent

t _s : the flow time of the thin polymer solution

C: 0.5g/dL

<glass transition temperature (Tg)>

Using a differential scanning calorimeter (DSC6200) manufactured by SII-Nanotechnologies Co., Ltd., the temperature was measured at a rate of 20 ° C per minute under a nitrogen stream.

<Spectral transmittance>

The maximum absorption wavelength and the transmittance of the maximum absorption wavelength of the resin substrate, the transmittance of each wavelength range of the filter, and (Xa), (Xb), (Za), and (Zb) are Hitachi High-Tech (Hitachi High- Spectrophotometer (U-4100) manufactured by the company).

Here, the transmittance of the case where the measurement was performed from the vertical direction of the optical filter was measured for light that was transmitted perpendicularly to the filter as shown in FIG. 1(a). Further, the reflectance in the case of measuring at an angle of 30° with respect to the vertical direction of the filter is measured for light transmitted at an angle of 30° with respect to the vertical direction of the filter as shown in Fig. 1(b). .

Further, in addition to the measurement (Xb) or (Zb), the transmittance is measured using the spectrophotometer under the condition that light is incident perpendicularly to the substrate and the filter. In the case of measuring (Xb) or (Zb), the transmittance is measured using the spectrophotometer under the condition that light is incident at an angle of 30° with respect to the vertical direction of the filter.

<Evaluation of Light Resistance of Near Infrared Absorbing Pigments>

The resin substrate was exposed to an indoor fluorescent lamp (illuminance of 1000 lux) for 500 hours, and the light resistance (ambient light resistance) of the near-infrared absorbing pigment contained in the resin was evaluated. The absorbance change before and after exposure of the fluorescent lamp according to the wavelength at which the absorption strength of the resin substrate is the highest (hereinafter referred to as "λa"; when the resin substrate has a plurality of maximum absorption, λa is the wavelength at which the absorption intensity is the highest). The color residual ratio (%) was calculated to evaluate the light resistance. The residual ratio of the pigment after exposure to the fluorescent lamp for 500 hours is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more.

[Synthesis example]

The compound (A), the squaraine-based compound, the phthalocyanine-based compound, and the cyanine compound used in the following examples were synthesized by a generally known method. For example, Japanese Patent No. 3366697, Japanese Patent No. 2846091, Japanese Patent No. 2864475, Japanese Patent No. 3703869, Japanese Patent Laid-Open No. Hei 60-228448, and Japanese Patent No. Japanese Patent Laid-Open No. Hei 1-128960, Japanese Patent Laid-Open No. Hei No. 1-228960, Japanese Patent No. 4,081,149, Japanese Patent Laid-Open No. SHO-63-124054, "Phthadium-Chemistry and Function" (IPC, 1997), The method described in JP-A-2007-169315, JP-A-2009-108267, JP-A-2010-241873, Japanese Patent No. 3699464, and Japanese Patent No. 4,746,631.

<Resin Synthesis Example 1>

8-methyl-8-methoxycarbonyltetracyclo [4.4.0.1 ^2,5 .1 ^7,10 ]dodecene represented by the following formula (a) (hereinafter also referred to as "DNM") 100 parts, 18 parts of 1-hexene (molecular weight modifier), and 300 parts of toluene (solvent for ring-opening polymerization reaction) were added to a reaction vessel substituted with nitrogen, and the solution was heated to 80 °C. Then, 0.2 parts of a toluene solution (0.6 mol/L) of triethylaluminum as a polymerization catalyst, and a toluene solution of methanol-modified tungsten hexachloride (concentration: 0.025 mol/L) were added to the solution in the reaction vessel. 0.9 parts, the solution was heated and stirred at 80 ° C for 3 hours, thereby performing ring-opening polymerization to obtain a ring-opening polymer solution. The polymerization conversion ratio of this polymerization reaction was 97%.

1,000 parts of the thus obtained ring-opening polymer solution was placed in an autoclave, and 0.12 part of RuHCl(CO)[P(C ₆ H ₅ ) ₃ ] ₃ was added to the ring-opening polymer solution at a hydrogen pressure of The hydrogenation reaction was carried out by heating and stirring for 3 hours at 100 kg/cm ² and a reaction temperature of 165 °C. After cooling the obtained reaction solution (hydrogenated polymer solution), the hydrogen pressure was released. This reaction solution was poured into a large amount of methanol, and the coagulum was separated and recovered, and dried to obtain a hydrogenated polymer (hereinafter also referred to as "resin A"). The obtained 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 °C.

<Resin Synthesis Example 2>

2,6-difluorobenzonitrile 35.12 g (0.253 mol), 9,9-bis(4-hydroxyphenyl)phosphonium 87.60 g (0.250 mol), potassium carbonate 41.46 g (0.300 mol) were added to a 3 L four-necked flask. ), N,N-dimethylacetamide (hereinafter also referred to as "DMAc") 443 g and toluene 111 g. Then, a four-necked flask was equipped with a thermometer, a stirrer, a three-way cock with a nitrogen introduction tube, a Dean-stark tube, and a condenser. Then, after the inside of the flask was purged with nitrogen, the resulting solution was reacted at 140 ° C for 3 hours, and the generated water was removed from the Dean-stark tube at any time. When the formation of water was not confirmed, the temperature was gradually raised to 160 ° C, and the temperature was maintained to carry out a reaction for 6 hours. After cooling to room temperature (25 ° C), the formed salt was removed by a filter paper, and the filtrate was poured into methanol to be reprecipitated, and the filtrate (residue) was separated by filtration. The obtained filtrate was vacuum dried at 60 ° C overnight to obtain a white powder (hereinafter also referred to as "resin B") (yield 95%). The obtained resin B 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.

<Resin Synthesis Example 3>

In a 500 mL five-necked flask equipped with a thermometer, a stirrer, a nitrogen introduction tube, a dropping funnel with a side tube, a Dean-Stark tube, and a condenser tube, 1,4-double (4-) was added under a nitrogen stream. 27.66 g (0.08 mol) of amino-α,α-dimethylbenzyl)benzene and 7.38 g (0.02 mol) of 4,4′-bis(4-aminophenoxy)biphenyl to dissolve In γ-butyrolactone 68.65 g and N,N-dimethylacetamide 17.16 g. The resulting solution was cooled to 5 ° C using an ice water bath, and while maintaining the temperature, 22.62 g (0.1 mol) of 1,2,4,5-cyclohexanetetracarboxylic dianhydride was added in one portion and as a quinone imine. Catalyst triethylamine 0.50 g (0.005 mol). After the completion of the addition, the temperature was raised to 180 ° C, and the distillate was distilled off at any time, and refluxed for 6 hours. After completion of the reaction, the mixture was air-cooled to an internal temperature of 100 ° C, and then diluted with 143.6 g of N,N-dimethylacetamide, and cooled while stirring to obtain a polyimide resin having a solid concentration of 20% by weight. The solution was 264.16 g. A part of the polyimine resin solution was poured into 1 L of methanol to precipitate a polyimine. After the filter-separated polyimine was washed with methanol, it was dried in a vacuum dryer at 100 ° C for 24 hours to obtain a white powder (hereinafter also referred to as "resin C"). The infrared (Infrared, IR) spectrum of the obtained resin C was measured, and as a result, absorption of 1704 cm ^-1 and 1770 cm ^-1 peculiar to the quinone imine group was observed. The glass transition temperature (Tg) of the resin C was 310 ° C, and the logarithmic viscosity was measured and found to be 0.87.

<Resin Synthesis Example 4>

9,9-bis(4-(2-hydroxyethoxy)phenyl)phosphonium 9.167 kg (20.90 mol), bisphenol A 4.585 kg (20.084 mol), diphenyl carbonate 9.000 kg (42.01 mol) And 0.02066 kg (2.459 × 10 ^-4 mol) of sodium hydrogencarbonate were placed in a 50 L reactor equipped with a stirrer and a distillation apparatus, and heated to 215 ° C for 1 hour under a nitrogen atmosphere at 760 Torr. Stir. Thereafter, the degree of pressure reduction was adjusted to 150 Torr over 15 minutes, and the mixture was kept at 215 ° C and 150 Torr for 20 minutes to carry out a transesterification reaction. Further, the temperature was raised to 240 ° C at a rate of 37.5 ° C / Hr, and the temperature was maintained at 240 ° C and 150 Torr for 10 minutes, adjusted to 120 Torr for 10 minutes, and maintained at 240 ° C and 120 Torr for 70 minutes, and further adjusted to 10 minutes. 100 Torr, kept at 240 ° C, 100 Torr for 10 minutes. Thereafter, the mixture was adjusted to 1 Torr or less in 40 minutes, and stirred at 240 ° C for 1 minute or less to carry out a polymerization reaction. After the completion of the reaction, nitrogen gas was introduced into the reactor to be pressurized, and the produced polycarbonate resin (hereinafter also referred to as "resin D") was taken out while being pelletized. The obtained resin D had a weight average molecular weight of 41,000 and a glass transition temperature (Tg) of 152 °C.

<Resin Synthesis Example 5>

9,9-bis{4-(2-hydroxyethoxy)-3,5-dimethylphenyl}fluorene 0.8 mol, ethylene glycol 2.2 mol and isophthalic acid were added to the reactor. The ester was 1.0 mol, and was slowly heated and melted while stirring to carry out a transesterification reaction. Then, while adding cerium oxide 20 × 10 ^-4 mol, the ethylene glycol was removed while gradually raising the temperature and reducing the pressure until it reached 290 ° C and 1 Torr or less. Thereafter, the contents were taken out from the reactor to obtain pellets of a polyester resin (hereinafter also referred to as "resin E"). The obtained resin E had a number average molecular weight of 40,000 and a glass transition temperature of 145 °C.

<Resin Synthesis Example 6>

Add 4,4'-bis(2,3,4,5,6-pentafluorobenzylidene) diphenyl ether (BPDE) 16.74 to a reactor equipped with a thermometer, a condenser, a gas introduction tube and a stirrer. Parts: 9,0.5 parts of 9,9-bis(4-hydroxyphenyl)fluorene (HF), 4.34 parts of potassium carbonate, and 90 parts of DMAc. The mixture was warmed to 80 ° C and allowed to react for 8 hours. After completion of the reaction, the reaction solution was vigorously stirred by a blender, and added to a 1% aqueous acetic acid solution. The precipitated reaction product was separated by filtration, washed with distilled water and methanol, and then dried under reduced pressure to obtain a fluorinated polyether ketone (hereinafter also referred to as "resin F"). The obtained resin F had a number average molecular weight of 71,000 and a glass transition temperature (Tg) of 242 °C.

[Example 1]

100 parts by weight of the resin A obtained in the resin synthesis example 1 and the compound (a-12) described in the above Table 1 as the compound (A) (the maximum absorption wavelength in dichloromethane was 736 nm) was added to the container. 0.06 parts by weight and methylene chloride were used to obtain a solution having a resin concentration of 20% by weight. Then, the obtained solution was cast on a smooth glass plate, dried at 20 ° C for 8 hours, and then peeled off from the glass plate. The peeled coating film was further dried at 100 ° C for 8 hours under reduced pressure to obtain a substrate having a thickness of 0.1 mm, a longitudinal length of 60 mm, and a lateral length of 60 mm.

The spectral transmittance of the substrate was measured, and the maximum absorption wavelength of the resin substrate, the transmittance at the maximum absorption wavelength, and the residual ratio of the dye after the light resistance test were determined and found to be 736 nm, 2%, and 100%, respectively. The results are shown in Table 2.

Then, a multilayer vapor-deposited film of near-infrared rays was formed on one surface of the obtained substrate at a vapor deposition temperature of 100 ° C [cerium oxide (SiO ₂ ; film thickness: 83 nm to 199 nm) layer and titanium oxide (TiO ₂ ; film thickness: 101 nm). ~125nm) layer is alternately laminated, the number of layers is 20], and a multilayer vapor-deposited film reflecting near-infrared rays is formed on the other surface of the substrate at a vapor deposition temperature of 100 ° C [SiO ₂ (film thickness 77 nm to 189 nm) The layer was formed by alternately laminating layers of titanium oxide (TiO ₂ ; film thickness: 84 nm to 118 nm), and the number of layers was 26], and a filter having a thickness of 0.105 mm was obtained. The spectral transmittance of the filter was measured, and the optical characteristics in each wavelength range were evaluated.

The average value of the transmittance at a wavelength of 430 nm to 460 nm is 87%, the average value of the transmittance at a wavelength of 461 nm to 580 nm is 91%, and the average value of the transmittance at a wavelength of 800 nm to 1000 nm is 1% or less, and the absolute value |Xa-Xb| 5nm, |Za-Zb | is 12nm. The results are shown in Table 2.

[Example 2] to [Example 17] and [Comparative Example 1] to [Comparative Example 5]

In the same manner as in Example 1, except that the transparent resin, the near-infrared absorbing dye, the solvent, and the film drying conditions shown in Table 2 were used, a filter having a thickness of 0.105 mm was produced. The evaluation results are shown in Table 2. Further, in Table 2, the number of parts of the resin added was 100 parts by weight, and the concentration of the resin solution was 20% by weight. Further, the various compounds used in the examples and comparative examples are as follows.

<Transparent Resin>

Resin A: cyclic olefin resin (resin synthesis example 1)

Resin B: Aromatic polyether resin (Resin Synthesis Example 2)

Resin C: Polyimine resin (Resin Synthesis Example 3)

Resin D: 茀 polycarbonate resin (Resin Synthesis Example 4)

Resin E: 茀 polyester resin (Resin Synthesis Example 5)

Resin F: fluorinated polyether ketone (Resin Synthesis Example 6)

Resin G: a cyclic olefin resin "Zeonor 1420R" (manufactured by Zeon Japan Co., Ltd.)

Resin H: Cyclic olefin resin "APEL #6015" (manufactured by Mitsui Chemicals Co., Ltd.)

Resin I: polycarbonate resin "Pureace" (manufactured by Teijin Co., Ltd.)

Resin J: Polyether oxime resin "Sumilite FS-1300" (made by Sumitomo Bakelite (share))

Resin K: Heat-resistant acrylic resin "Acryviewa" (manufactured by Nippon Shokubai Co., Ltd.)

<Near infrared absorbing pigment>

Compound (A)

Compound (a-8): Compound (a-8) described in Table 1 above (maximum absorption wavelength in dichloromethane is 735 nm)

Compound (a-11): Compound (a-11) described in Table 1 above (maximum absorption wavelength in dichloromethane is 707 nm)

Compound (a-12): Compound (a-12) described in Table 1 above (maximum absorption wavelength in dichloromethane is 736 nm)

"Near infrared absorption pigment (X)"

Compound (X-1): a squaraine-based compound represented by the following formula (X-1) (maximum absorption wavelength in dichloromethane is 670 nm)

Compound (X-2): a squaraine-based compound represented by the following formula (X-2) (maximum absorption wavelength in dichloromethane is 698 nm)

[化17]

Compound (X-3): a cyanine compound represented by the following formula (X-3) (maximum absorption wavelength in dichloromethane is 681 nm)

Compound (X-4): a phthalocyanine-based compound represented by the following formula (X-4) (maximum absorption wavelength in dichloromethane is 698 nm)

Compound (X-5): a phthalocyanine compound represented by the following formula (X-5) (maximum absorption wavelength in dichloromethane is 733 nm)

Compound (X-6): a cyanine compound represented by the following formula (X-6) (maximum absorption wavelength in dichloromethane is 760 nm)

Compound (X-7): a phthalocyanine compound represented by the following formula (X-7) (maximum absorption wavelength in dichloromethane is 681 nm)

[化22]

<solvent>

Solvent (1): dichloromethane

Solvent (2): N,N-dimethylacetamide

Solvent (3): ethyl acetate / toluene (weight ratio: 5/5)

Solvent (4): cyclohexane / xylene (weight ratio: 7/3)

Solvent (5): cyclohexane / dichloromethane (weight ratio: 99/1)

Solvent (6): N-methyl-2-pyrrolidone

The film drying conditions of the examples and comparative examples in Table 2 are as follows. Further, the coating film was peeled off from the glass plate before drying under reduced pressure.

<film drying conditions>

Condition (1): 20 ° C / 8 hr → reduced pressure, 100 ° C / 8 hr

Condition (2): 60 ° C / 8 hr → 80 ° C / 8 hr → reduced pressure, 140 ° C / 8 hr

Condition (3): 60 ° C / 8 hr → 80 ° C / 8 hr → reduced pressure, 100 ° C / 24 hr

Condition (4): 40 ° C / 4 hr → 60 ° C / 4 hr → reduced pressure, 100 ° C / 8 hr

[Industrial availability]

The optical filter of the present invention can be preferably used for a digital still camera, a mobile phone camera, a digital camera, a personal computer camera, a surveillance camera, a car camera, a television, an in-vehicle device for a car navigation system, a mobile information terminal, Video game consoles, portable game consoles, devices for fingerprint authentication systems, digital music players, and the like. Further, it can be preferably used as a hot wire cut filter or the like attached to a glass plate or the like of an automobile, a building or the like.

1‧‧‧ Filter

2‧‧‧Spectrophotometer

3‧‧‧Light

Claims (8)

A filter comprising: a transparent resin substrate comprising a compound (A) represented by the following formula (I); and a near-infrared reflective film formed on at least one surface of the substrate, [In the formula (I), M represents 2 hydrogen atoms, 2 monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom; a plurality of R _a independent represents L ^1, a plurality of R _b independently represent a hydrogen atom, a halogen atom, L ¹ or -SO ^₂ -L _2; L ¹ represented by the following L ^a, L ^b or L ^c, L ² represented by the following L ^a, L ^b , L ^c , L ^d or L ^e ; (L ^a ) aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ); carbon number 3 to 14 An alicyclic hydrocarbon group (L ^d ) having an aromatic hydrocarbon group of 6 to 14 carbon atoms (L ^e ), a heterocyclic group having 3 to 14 carbon atoms, and the L ^a to L ^e may further have a carbon number of 1 to 12 An aliphatic hydrocarbon group, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms, and carbon At least one substituent L] in the group consisting of 1 to 12 alkoxy groups. The filter according to claim 1, wherein in the formula (I), M is a divalent transition metal belonging to Group 4 to Group 12 of the periodic table and the fourth to fifth periods, a trivalent or tetravalent metal halide or a tetravalent metal oxide; R _{a is} independently an alkyl group having 1 to 10 carbon atoms, a fluorine-substituted alkyl group having 1 to 6 carbon atoms, a cyclopentyl group or a cyclohexyl group. R _{b is} independently a hydrogen atom, a fluorine atom, an alkyl group having 1 to 10 carbon atoms, a cyclopentyl group, a cyclohexyl group or -SO ₂ -L ² ; L ² is an alkyl group having 1 to 6 carbon atoms, and a carbon number of 6 An aromatic hydrocarbon group of ~12 or a heterocyclic group of 3 to 6 carbon atoms. The filter according to the first or second aspect of the invention, wherein the transparent resin constituting the transparent resin substrate is selected from the group consisting of a cyclic olefin resin, an aromatic polyether resin, and a polyamidene. Resin, fluorene polycarbonate resin, fluorene polyester resin, polycarbonate resin, polyamine resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyparaphenyl resin, Polyamidoximine resin, polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin, and sesquiterpene At least one resin selected from the group consisting of oxyalkylene resins. The filter according to claim 1 or 2, wherein the near-infrared reflective film is formed on both sides of the substrate. The filter according to claim 1 or 2, which is used for a solid-state imaging device. A solid-state imaging device comprising the optical filter according to any one of claims 1 to 5. A camera module comprising the filter according to any one of claims 1 to 5. A resin composition comprising a compound (A) represented by the following formula (I), and a cyclic olefin resin, an aromatic polyether resin, a polyamidene resin, a fluorene polycarbonate resin,茀 polyester resin, polycarbonate resin, polyamine resin, polyarylate resin, polyfluorene resin, polyether oxime resin, polyparaphenylene resin, polyamidoximine resin, a group consisting of polyethylene naphthalate resin, fluorinated aromatic polymer resin, (modified) acrylic resin, epoxy resin, allyl ester resin, and sesquiterpene oxide resin At least one resin; [In the formula (I), M represents 2 hydrogen atoms, 2 monovalent metal atoms, a divalent metal atom, or a substituted metal atom containing a trivalent or tetravalent metal atom; a plurality of R _a independent represents L ^1, a plurality of R _b independently represent a hydrogen atom, a halogen atom, L ¹ or -SO ^₂ -L _2; L ¹ represented by the following L ^a, L ^b or L ^c, L ² represented by the following L ^a, L ^b , L ^c , L ^d or L ^e ; (L ^a ) aliphatic hydrocarbon group having 1 to 12 carbon atoms (L ^b ) halogen-substituted alkyl group having 1 to 12 carbon atoms (L ^c ); carbon number 3 to 14 An alicyclic hydrocarbon group (L ^d ) having an aromatic hydrocarbon group of 6 to 14 carbon atoms (L ^e ), a heterocyclic group having 3 to 14 carbon atoms, and the L ^a to L ^e may further have a carbon number of 1 to 12 An aliphatic hydrocarbon group, a halogen-substituted alkyl group having 1 to 12 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, a heterocyclic group having 3 to 14 carbon atoms, and carbon At least one substituent L] in the group consisting of 1 to 12 alkoxy groups.