JPH061283B2 - Optical filter material - Google Patents

Description

TECHNICAL FIELD The present invention relates to an optical filter material that absorbs infrared rays. More specifically, the present invention relates to an optical filter material that absorbs far-red light or near-infrared light having a wavelength of 700 to 1500 nm with almost no loss of transmission of visible light.

(Prior Art) Various applications are conceivable for optical filter materials that selectively absorb far-red light or near-infrared light having a wavelength of 700 to 1500 nm, and there has been a strong demand for them, but until now, they have been suitable. I didn't get anything. The main uses of the conventional optical filter material will be described with reference to six examples.

Infrared-sensitive safelight filters for photosensitive materials In recent years, many silver halide photosensitive materials (hereinafter referred to as "sensitive materials") have been developed which have sensitivity to far-red light or near-infrared light having a wavelength of 700 nm or more. It is coming. This can be black and white or color, and can be used as a pseudo-color photograph for resource research, etc. by equipping the silver halide photographic material with infrared sensitivity, not only the normal type but also the instant type or the heat development type. Alternatively, there is a device that can be exposed by using a diode that emits light in the infrared region.

For such infrared-sensitive light-sensitive materials, a panchromatic safelight filter has been conventionally used.

Control of plant growth It has long been known that light affects the so-called morphogenesis of plant growth and differentiation such as seed germination, stem elongation, leaf development, flower bud and tuber formation. It is being studied as a morphogenic effect. In this case wavelength 660
It is known that the red light around nm and the red light around 720 to 730 nm act antagonistically with each other, and by changing the ratio of both, the timing of flowering, heading, or the degree of growth, the yield of fruits, etc. are changed. ing. All such work was done with a combination of source lamps and filters and by controlling the spectral energy distribution, making it impossible to test in large greenhouses or farms.

If a plastic film that selectively absorbs light with a wavelength of 700 nm or more can be obtained, it becomes possible to apply the above-mentioned principle to actual production situations, and it will bring great progress and benefits to institutional agriculture. For example, when a crop is covered with a near infrared absorbing film at a specific time, a wavelength of 700n
It is expected to block the light of m or more to delay the heading time and control the growth (see Katsumi Inada, "Chemical Regulation of Plants", Vol. 6, No. 1 (1971)).

Blocking heat rays Of the radiant energy of the sun, near-infrared and infrared light with a wavelength of 800 nm or more is absorbed by an object and converted into heat energy. Moreover, most of the energy distribution is concentrated in the near infrared region having a wavelength of 800 to 2000 nm. Therefore, a film that selectively absorbs near-infrared rays is extremely effective in blocking solar heat, and it is possible to suppress an increase in indoor temperature while sufficiently incorporating visible light. This can be applied to windows of houses, offices, shops, automobiles, airplanes, etc. as well as horticultural greenhouses. Especially in greenhouses, temperature control is very important, and if the temperature rises too much, the crops will be seriously damaged and eventually die. Using a near-infrared absorbing film makes it easier to control the temperature, and
It will be possible to develop new technologies such as restrained cultivation in summer.

Conventionally, as a material for blocking heat rays, a material obtained by vapor deposition of a very thin metal layer on the surface of a plastic film or a material in which an inorganic compound such as FeO is dispersed in glass has been used.

Infrared Cut Filter Harmful to Human Eye Tissue Infrared rays contained in sunlight or rays contained in rays emitted during welding have a harmful effect on human eye tissue. One of the main applications of infrared cut filters is to use them as eyeglasses to protect the human eye from such harmful infrared rays.
For example, sunglasses and protective glasses for welders.

Infrared cut filter for semiconductor light receiving element Another field in which the development of this kind of infrared absorbing plastic is most strongly demanded is the spectral sensitivity curve of the spectral sensitivity of a semiconductor light receiving element such as a silicon photodiode (hereinafter referred to as SPD). It is a field of application as an infrared cut filter of a photodetection device for approaching to.

Currently, SPD is mainly used as a light receiving element of a photodetector used in an automatic exposure meter such as a camera. FIG. 2 shows a graph of the relative luminous efficiency curve and the relative value (spectral sensitivity) of the output with respect to each wavelength of the SPD.

In order to use the SPD for the light meter, the light in the infrared region that is not felt by human eyes is cut, and the SP shown in FIG.
It is necessary to make the spectral sensitivity curve of D similar to the relative luminous efficiency curve. In particular, for light having a wavelength of 700 to 1100 nm, the output of the SPD is large, and the light in this region is invisible to the eye, which causes a malfunction of the exposure meter. Therefore, if an infrared absorbing plastic film that absorbs little in the visible region and absorbs the entire infrared region of 700 to 1100 nm can be used, the light transmittance in the visible region will be large and the output of the SPD will be large. It is clear that the performance can be improved significantly.

Conventionally, as this type of photodetector, a glass infrared cut filter using an inorganic infrared absorber has been attached to the front surface of the SPD for practical use.

Infrared cutoff filter for color solid-state image sensor In recent years, a combination of a color solid-state image sensor and a micro color filter has been widely used in VTR cameras and the like. In order to color-separate visible light having a wavelength of 400 to 700 nm,
It is necessary to block near infrared light of 700 nm or more. As an optical filter material for the purpose of blocking near-infrared rays, a multilayer interference film using an inorganic material is conventionally provided on a lens by a vapor deposition method and used, but the lens difference is large.
Therefore, if an infrared blocking layer can be provided on the color separation filter layer by a bonding method or an on-wafer method, good color reproduction can be expected without being affected by the lens difference.

It is strongly desired to develop an infrared cutoff filter material that can be incorporated in a color solid-state image pickup device using such a color image pickup tube, CCD (charge coupled device), MOSFET (insulated gate type field effect device) and the like.

On the other hand, examples of applying the metal complex as an infrared absorber include US Pat. Nos. 3,588,216 and 3,663.
No. 089, No. 3,687,862, No. 3,72
No. 4,934, No. 3,806,462, No. 3,8
50,502, 3,875,199, 3,
979,583, 4062,867, 4,
Nos. 152,332, 4,335,952, Japanese Patent Publication Nos. 46-3452 and 52-7454, and Japanese Patent Laid-Open No. 49-
No. 31748, No. 51-135886, No. 54-25
No. 060 and No. 57-21458.

(Problems to be solved by the invention) However, the above-mentioned metal complex infrared absorbers mainly have a long wave absorption maximum of 850 nm or more, and a metal complex having an absorption maximum of 800 nm or less uses an expensive metal such as platinum. It had the drawback that it could not be obtained unless it was obtained, and industrial production was difficult.

In addition, conventional organic dye-based infrared absorbers generally have little light resistance and heat resistance, and practically few have been satisfactory.

Further, the filter materials used for the above-mentioned uses also have the following drawbacks.

First, the conventional safe light filter for panchromatic used for the above-mentioned applications not only partially transmits green light with high visibility but also causes light fog to transmit a large amount of infrared light, and It was not possible to achieve the purpose as a safelight for a sensitive material.

Further, the plastic film deposited with the metal layer used for the above-mentioned applications or the glass in which FeO is dispersed strongly absorbs not only the infrared part but also the visible part, so that the internal illuminance is lowered, and especially for agriculture. It was unsuitable because it caused an absolute shortage of sunlight. In particular, for controlling the above-mentioned plant growth, the filter material has a wavelength of 700 to 750 nm.
It is necessary to selectively absorb the above-mentioned light, and a metal vapor deposition film or the like is completely unsuitable for this purpose.

In the past, many optical filter materials using organic dyes or metal complexes as infrared absorbers have been developed, but most of them have absorption maximum in the visible region below wavelength 700 nm or infrared region above wavelength 900 nm. It was Therefore, there has been a strong demand for the development of an optical filter material having a maximum absorption wavelength between 700 and 900 nm, which absorbs near-infrared rays well and transmits visible light well.

The first object of the present invention is to provide a near-infrared absorber having an absorption maximum in the wavelength range of 700 to 900 nm, and secondly, a high light transmittance in the visible region and robustness against heat and light. Another object is to provide a near-infrared absorbing optical filter material, and thirdly, to provide a particularly excellent filter material for blocking infrared rays of a silicon photodiode or a color solid-state image pickup tube.

(Means for Solving Problems) The above-mentioned various objects have been solved by an optical filter material containing at least one organometallic compound represented by the following general formula [I].

(In the formula, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an alkyl group which may have a divalent linking group between the benzene ring to be bonded and the alkyl group, Group, aryl group, cycloalkyl group or heterocyclic group, or non-metallic atomic group in which R ¹ and R ² , R ² and R ³ , or R ³ and R ⁴ are bonded to each other to form a 5- or 6-membered ring Indicates
The groups R ^{1 to} R ⁴ may be the same or different from each other. X represents an anion that neutralizes the cation in the above general formula. Although the oxidation state of the ligand of the iron complex represented by the general formula [I] used in the present invention has been discussed, as shown in the following formula, the dianion of o-phenylenediamine, o-benzosemi are believed to have a quinone diimine radical anion or o- benzoquinone diisopropyl structure of any of Min (e.g., JACS 88 5201
(1966)).

In the present specification, a complex structure is represented by using this ligand as o-benzoquinoneimine, but this is a convenient description and does not limit the oxidation state of the ligand of the present invention thereto.

The central metal and iron of the complex according to the present invention are usually considered to be divalent. The counterion of the complex ion is designed to maintain electrical neutrality as a whole, and X in the general formula [I] is usually minus divalent, for example, two monovalent anions,
1 divalent anion and 2/3 trivalent anion are represented.

The present invention will be described in more detail.

In the compound represented by the general formula [I], R ¹ ,
The halogen atom represented by R ² , R ³ and R ⁴ includes a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The alkyl group represented by R ¹ , R ² , R ³ and R ⁴ is preferably an alkyl group having 1 to 20 carbon atoms, which may be a linear alkyl group or a branched alkyl group, and may be substituted or unsubstituted. It may be any of substitution (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group,
Octyl group, decyl group, dodecyl group, hexadecyl group,
Octadecyl group).

The aryl group represented by R ¹ , R ² , R ³ and R ⁴ is preferably an aryl group having 6 to 14 carbon atoms, which may be substituted or unsubstituted (eg, phenyl group, naphthyl group). Group).

The heterocyclic group represented by R ¹ , R ² , R ³ and R ⁴ is preferably a 5-membered ring or 6-membered ring containing at least one nitrogen atom, oxygen atom or sulfur atom in the ring as a hetero atom. Yes, it may be substituted or unsubstituted (for example, furyl group, hydrofuryl group, thienyl group, pyrrolyl group, pyrrolidyl group, pyridyl group, imidazolyl group, pyrazolyl group, quinolyl group, indolyl group, oxazolyl group, thiazolyl group. Can be listed as a representative example.

The cycloalkyl group represented by R ¹ , R ² , R ³ and R ⁴ is preferably a 5-membered ring group or a 6-membered ring group, which may be substituted or unsubstituted (eg, cyclopentyl group, cyclohexyl group). Groups, cyclohexenyl groups, cyclohexadienyl groups, etc.).

The 6-membered ring formed by combining R ¹ and R ² , R ² and R ³ or R ³ and R ⁴ may be substituted or unsubstituted, or may be a condensed one. Good (eg, benzene ring, naphthalene ring, cyclohexadiene ring, isobenzothiophene ring, isobenzofuran ring, isoindoline ring, etc.).

The alkyl group, aryl group or heterocyclic group represented by R ¹ , R ² , R ³ and R ⁴ is a divalent linking group such as oxy (-O-), thio group (-S-) and amino group. ,
Oxycarbonyl group, carbonyl group, carbamoyl group,
It may be bonded to a carbon atom on the benzene ring via a sulfamoyl group, a carbonylamino group, a sulfonyl group, a carbonyloxy group or the like.

Examples of the alkyl group represented by R ¹ , R ² , R ³ and R ⁴ bonded to a carbon atom on the benzene ring via the above divalent linking group include an alkoxy group (eg, a methoxy group, Ethoxy group, propyloxy group, butoxy group, n-
Decyloxy group, n-dodecyloxy group or n-hexadecyl group), alkoxycarbonyl group (for example,
Methoxycarbonyl group, ethoxycarbonyl group, butoxycarbonyl group, n-decyloxycarbonyl group or n-hexadecyloxycarbonyl group), acyl group (for example, acetyl group, valeryl group, stearoyl group,
Acyloxy groups (eg, acetoxy group or hexadecylcarbonyloxy group) such as benzoyl group or toluoyl group, alkylamino groups (eg, N-methylamino group, N-ethylamino group, N, N-dimethylamino group, N , N-dibutylamino group, etc.), alkylcarbamoyl group (eg, butylcarbamoyl group, N, N
-Diethylcarbamoyl group, or n-dodecylcarbamoyl group), an alkylsulfamoyl group (for example,
Butylsulfamoyl group, N, N-diethylsulfamoyl group or n-dodecylsulfamoyl group), sulfonylamino group (eg, methylsulfonylamino group or butylsulfonylamino group), sulfonyl group (eg, mesyl) Group or ethanesulfonyl group) or an acylamino group (eg, acetylamino group, valerylamino group, palmitoylamino group, benzoylamino group, toluoylamino group, etc.) and the like.

Examples of the aryl group represented by R ¹ , R ² , R ³ and R ⁴ bonded to the carbon atom on the benzene ring via the above divalent linking group include aryloxy group (eg, phenoxy group or Naphthoxy group etc.), aryloxycarbonyl group (eg phenoxycarbonyl group or naphthoxycarbonyl group etc.), acyl group (eg benzoyl group or naphthoyl group etc.), anilino group (eg
Phenylamino group, N-methylanilino group or N-acetylanilino group), acyloxy group (eg, benzoyloxy group or toluoyloxy group), arylcarbamoyl group (eg, phenylcarbamoyl group), arylsulfamoyl Group (eg, phenylsulfamoyl group), arylsulfonylamino group (eg, phenylsulfonylamino group, p-tolylsulfonylamino group, etc.), arylsulfonyl group (benzenesulfonyl group, tosyl group, etc.) or acylamino group (eg, , Benzoylamino group, etc.).

The alkyl group, aryl group, heterocyclic group, cycloalkyl group or R represented by R ¹ , R ² , R ³ and R ⁴ above.
^The condensed 6-membered ring formed by combining ¹ and R ² , R ² and R ³ or R ³ and R ⁴ with each other is preferably a halogen atom (eg, fluorine atom, chlorine atom, bromine atom or iodine atom, etc.). ), Cyano group, hydroxyl group, linear or branched alkyl group (for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, heptadecyl group, Octadecyl group or methoxyethoxyethyl group), aryl group (eg, phenyl group, tolyl group, naphthyl group, chlorophenyl group, methoxyphenyl group, acetylphenyl group, etc.), alkoxy group (eg, methoxy group, ethoxy group, butoxy group, Propyloxy group or methoxyethoxy group), aryloxy group (eg, phenoxy group) , A triloxy group, a naphthoxy group or a methoxyphenoxy group), an alkoxycarbonyl group (eg, a methoxycarbonyl group, a butoxycarbonyl group or a phenoxymethoxycarbonyl group), an aryloxycarbonyl group (eg, a phenoxycarbonyl group, a triloxycarbonyl group or Methoxyphenoxyphenoxycarbonyl group etc.), acyl group (eg formyl group, acetyl group, valeryl group, stearoyl group,
Benzoyl group, toluoyl group, naphthoyl group or p-
Methoxybenzoyl group etc.), acyloxy group (eg acetoxy group or acyloxy group etc.), acylamino group (eg acetamide group, benzamide group or methoxyacetamide group etc.), anilino group (eg phenylamino group, N-methylanilino group, etc.) N-phenylanilino group or N-acetylanilino group etc.), alkylamino group (for example, n-butylamino group, N, N-diethylamino group, 4-methoxy-n-butylamino group etc.), carbamoyl group ( For example, n-butylcarbamoyl group, N, N-diethylcarbamoyl group, etc.), sulfamoyl group (for example, n-butylsulfamoyl group, N, N-diethylsulfamoyl group, n-
Dodecylsulfamoyl group or N- (4-methoxy-
n-butyl) sulfamoyl group), a sulfonylamino group (eg, methylsulfonylamino group, phenylsulfonylamino group or methoxymethylsulfonylamino group), or a sulfonyl group (eg, mesyl group,
Tosyl group or methoxymethanesulfonyl group) and the like.

Next, in the compound represented by the general formula [I], X
Represents 2 / n of n-valent anions. X is usually two monovalent
It is an ion, and as a monovalent anion, halogen (
For example Cl^-, Br^-, I^-Etc.), nitrate ion (N
O₃ ^-), Tetrafluoroborate ion (BF_Four ^-), F
Xafluorophosphate ion (PF ) Carboxy
Rate ion (eg CH₃CO₂ ^-, CF₃CO Na
), Sulfonate ion (for example,Etc.), tetraphenylborate ion (B (C₆H_Five)
_FourEtc.), etc., preferably hexafluorophosphine
Ion, sulfonate ion, tetraphenylborate
It is a rate ion.

As the anion having two or more valences represented by X, a sulfate ion (SO ₃ ^2- ), a carbonate ion (CO ₃ ^2- ), a hexafluoroaluminate ion, a hexafluoroantimonate ion, a hexafluoronickelate ion, a hexafluoro There are silicate ions.

The compound represented by the above-mentioned general formula [I] used in the present invention is, for example, a bis-ortho-phenylenediaminato iron complex obtained by heating and refluxing a ferrous salt and ortho-phenylenediamine or its salt under an inert atmosphere. It is synthesized by air oxidation at room temperature in the presence of a dehydrating agent. Then, if necessary, various anions can be obtained by anion exchange and purification.

Preferred compounds among the compounds represented by the above general formula [I] are shown in Table 1, but it goes without saying that the present invention is not limited to these exemplified compounds.

The absorption maximum (λmax, nm unit) and the molar extinction coefficient (εmax, · mol ⁻¹ · cm ⁻¹ unit) of these compounds are as follows.

In the general formula [I], the substituents R ¹ to R ⁴ affect the wavelength of the light absorption maximum of the complex, and when the electron-donating property of the substituent is increased or the number of electron-donating substituents is increased, absorption is increased. The maximum tends to shift to the long wavelength side. The type of counter anion has a great influence on the solubility of the complex. Alternatively counteranion halogen atom _{^{PF 6 -, BF 4 -,}} AlF
_{In the case of 6} ³⁻ , SbF ₆ ²⁻ , SiF ₆ ^2−, etc., the solubility in water is generally enhanced, while in the case of B (Ph) ₄ ⁻ , alkylbenzene sulfonate anion, etc., the solubility in organic solvent or organic binder is enhanced. . The lipophilic nuclear substituent of the ligand also improves the solubility in organic solvents.

The optical filter material of the present invention is a material obtained by incorporating the compound represented by the general formula [I] into an appropriate binder to form a composition or coating it on an appropriate support. The binder is not particularly limited, and organic or inorganic binders can be used as long as they exhibit an optical filter function. Examples of such a binder include polymeric materials such as plastics and inorganic materials such as glass.

Preferably, a binder that forms a film having excellent transparency and mechanical properties is used as the binder. Examples of such film-forming binders include polyesters represented by polyethylene terephthalate,
Cellulose diacetate, cellulose triacetate,
Cellulose esters such as cellulose acetate butyrate, polyolefins such as polyethylene and polypropylene, polyvinyl chloride, polyvinylidene chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl compounds such as polystyrene, acrylic addition weight such as polymethylmethacrylate. Examples thereof include known film-forming binders such as coalesce, polycarbonate composed of polycarbonate, phenolic resin, urethane resin or hydrophilic binder such as gelatin.

As a method of adding and retaining the compound of the above-mentioned general formula [I] to the above-mentioned plastic material, there is firstly a method of compounding it in a plastic sheet at the time of forming a film. That is, a compound of the formula [I] is mixed with various additives into a polymer powder or pellets, melted and extruded by a T-die method or an inflation method, or formed into a film by a calender method, whereby the compound is uniformly dispersed. A film is obtained. When a film is produced from a polymer solution by the casting method, the compound of the general formula [I] may be contained in the solution.

Second, there is a method of forming an infrared absorbing layer by coating the surface of various plastic films or glass plates manufactured by a suitable method with a polymer solution or dispersion containing the compound of the general formula [I]. is there. The binder polymer used in the coating solution is selected from those which dissolve the compound of the general formula [I] as much as possible and have excellent adhesiveness to the plastic film or glass plate serving as a support. Polymethylmethacrylate, cellulose acetate butyrate, polycarbonate and the like are suitable for this purpose. The support film may be pre-coated with a suitable undercoat in order to improve the adhesion.

The third method is to mix the compound of general formula [I] and the polymerizable monomer in the light-incident window frame of the device to be cut off infrared rays, add a suitable polymerization initiator, and add heat or light. There is a method of polymerizing and forming a filter material on a window frame with the produced polymer. In this method, the entire device can be embedded with plastics produced from a polymerizable monomer or a condensable composition such as an epoxy resin.

The fourth method is a method of depositing the compound [I] of the present invention on a suitable support. In this method, a film-forming binder layer suitable as a protective layer may be provided at a position distant from the support.

A method of using the near-infrared absorber according to the present invention in a color solid-state imaging device will be described. After forming a stripe-shaped or mosaic-shaped color separation filter layer having a plurality of predetermined spectral characteristics, a surface protective layer provided on the filter layer. To contain a near-infrared absorber, vapor deposit this absorber,
In the color separation filter layer, a visible light absorbing dye or the like and the near-infrared absorber of the present invention may be used in combination, or in a transparent intermediate layer or surface smoothing layer provided in the color separation filter having a multilayer structure. A mode in which the near-infrared absorbing agent is contained in is also possible. The filter material of the present invention is particularly effective when used in combination with a color separation filter as described in JP-A-57-58107, 59-9317 and 59-30509.

Two or more compounds represented by the above general formula [I] may be used in combination in the optical filter material of the present invention. It is also possible to use it together with a known near-infrared absorber of organic or metal complex type. In particular, when used in combination with absorbers having different absorption maximums, the absorption wavelength range can be expanded.

In the optical filter material of the present invention, in order to further improve the light resistance, the addition of an ultraviolet absorber is effective, and resorcin monobenzoate, substituted or unsubstituted benzoic acid esters such as methyl salicylate, and 2-oxy-3-methoxy. Cinnamates such as butyl cinnamate, 2,4-
Benzophenones such as dioxybenzophenone, α, β-unsaturated ketones such as dibenzalacetone, 5,7-
Coumarins such as dioxycoumarin, carbostyrils such as 1,4-dimethyl-7-oxycarbostyril,
Azoles such as 2-phenylbenzimidazole and 2- (2-hydroxyphenyl) benzotriazole are used.

In the case of a film prepared by coating the optical filter material of the present invention with a coating method, a thin plastic film can be attached to the surface of the coating layer for the purpose of protecting the coating layer, imparting drip property, and the like. For example, 0.
120-by stacking polyvinyl chloride films with a thickness of 05 mm
A laminated film is obtained by thermocompression bonding at 140 ° C.

In the optical filter material of the present invention, the general formula [I]
0.1 parts by weight of the compound represented by
.About.50 parts, preferably 0.5 to 10 parts. The optical filter material has only to have a low transmittance in the wavelength region to be cut off in view of its function so that the intended purpose can be achieved. In the case of the present invention, in the wavelength of the valley of the transmittance of about 700 to 900 nm, 10 It is important to adjust the addition amount per binder and the thickness of the filter material so that the transmittance is at most%, preferably at most 2.0%, particularly preferably at most 0.1%. Practical thickness is 0.002mm to 0.5mm
However, it is possible to design a filter having a thickness outside this range depending on the application.

According to the present invention, the maximum absorption wavelength is about 700 to 900.
A near-infrared absorbing optical filter material having a wavelength of nm can be obtained.

Further, an optical filter material having excellent fastness to heat and light can be obtained from an inexpensive complex of an iron salt, which is easy to manufacture, and a low cost optical filter material can be obtained.

Further, in the optical filter material of the present invention, the solubility in a solvent can be adjusted by appropriately selecting and combining a ligand and a counter ion of an organometallic complex infrared absorber, so that various binders can be widely adopted. Has the advantage.

The optical filter material of the present invention, as an infrared absorbing material, the above-mentioned, safelight filter for infrared-sensitive photosensitive material, control of plant growth, heat ray blocking, infrared cut filter harmful to human eye tissues, semiconductor It can be used for various applications in addition to the infrared cut filter of the light-receiving element color solid-state image sensor.

The compound according to the present invention can be applied in addition to the optical filter based on its infrared absorption property. For example, when added to the ink for an ink jet printer described in JP-A-56-135568, the reading efficiency by near infrared light can be improved, and the laser beam recording / reading described in JP-A-57-11090 can be performed. It can also be applied to media. Further, the compound of the present invention has a property of converting absorbed near-infrared light into heat, and can also be used as an infrared / heat exchange agent. Typical examples are 1) JP-A-57-14095 or 57.
-14096 can be added to the laser thermosensitive recording medium to enhance the mixed color reaction caused by the heat generated by irradiating the infrared region laser. 2) Melting by the action of heat based on laser light It can be incorporated in the resist material described in JP-A-57-40256 so that the property changes. 3) JP-A-56-1
Inclusion of a compound of the present invention in a heat-drying or thermosetting composition as described in No. 43242 can accelerate the reaction.

(Example) Next, the present invention will be described in more detail based on examples.

Reference Example 1 <Synthesis of Exemplified Compound (2)> 12.0 g of ferrous chloride (tetrahydrate) and 6.6 g of orthophenylenediamine are dispersed in 200 ml of n-propanol and refluxed for 1 hour under an argon atmosphere. The produced pale brown pisuorthophenylene dimininato iron complex was filtered under an argon atmosphere, washed with degassed ethanol and then with toluene, and dried under reduced pressure at room temperature. 4 g of the dried iron complex was taken, 48 g of molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto, 280 ml of dichloromethane and 280 ml of t-butanol were further added, and a calcium chloride tube was attached and stirred at 18 ° C. for 48 hours. To do. After completion of the reaction, the solution was filtered and the solvent of the filtrate was distilled off with a rotary evaporator at a water bath temperature of 42 ° C. The residue is methanol 80
Dissolve in a mixed solvent of 100 ml of water and 100 ml of water. In this solution,
A solution of 10 g of sodium tetraphenylborate in 200 ml of water was added dropwise with stirring at 18 ° C. Immediately a blue-green precipitate is deposited. After completion of dropping, the mixture was stirred for 1 hour and filtered. The precipitated crystals were washed with water and air dried. Acetone-dichloromethane-n-hexane (1:
(4: 2 = volume ratio) Recrystallization from a mixed solvent gave Exemplified compound (2).

Yield 2.1 g m. p. 210 ° C. Reference Example 2 <Synthesis of Exemplified Compound (12)> 12.0 g of ferrous chloride (tetrahydrate) and 8.2 g of orthophenylenediamine are dispersed in 200 ml of n-propanol and refluxed for 1 hour under an argon atmosphere. To do. The pale brown bis (3,4-dimethyl-orthophenylenediaminato) iron complex formed was quickly filtered, washed first with degassed ethanol and then with toluene and dried under vacuum at room temperature. Take 5 g of the dried iron complex, and add molecular sieve 4 to it.
48 g of A (manufactured by Wako Pure Chemical Industries, Ltd.) was added, 280 ml of dichloromethane and 280 ml of t-butanol were further added, and the mixture was stirred at 18 ° C. for 48 hours with a calcium chloride tube. After completion of the reaction, the solution was filtered and the solvent of the filtrate was distilled off with a rotary evaporator at a water bath temperature of 42 ° C. The residue is dissolved in a mixed solvent of 80 ml of methanol and 100 ml of water. A solution prepared by dissolving 10 g of sodium tetraphenylborate in 200 ml of water was added dropwise to this solvent while stirring at 18 ° C. Immediately a blue-green precipitate is deposited. After completion of the dropping, the mixture is stirred for 1 hour and filtered. The precipitated crystals were washed with water and air dried. This was recrystallized from acetone-water (1: 5 = volume ratio) to obtain Exemplified compound (12). Yield 4.1g
m. p. 193 ° C. Reference Example 3 <Synthesis of Exemplified Compound (29)> 4-Methoxyorthophenylenediamine hydrochloride 10.5
g is dissolved in 200 ml of n-propanol. While stirring at 18 ° C., 11.6 g of sodium methoxide (28% methanol solution) was added thereto, and the mixture was stirred for 30 minutes. 12.0 g of ferrous chloride (tetrahydrate) is added thereto, and the mixture is refluxed for 30 minutes. After the reaction was completed, the mixture was allowed to stand, then the supernatant was decanted under an argon atmosphere, and the solvent was immediately distilled off with a rotary evaporator (water bath temperature 50 ° C.). A reddish brown bis (4-methoxy-orthophenylenediaminato) iron complex powder is obtained. Taking 5 g of the above iron complex, 48 g of molecular sieve 4A (manufactured by Wako Pure Chemical Industries, Ltd.) was added, 280 ml of dichloromethane and 280 ml of t-butanol were further added, and a calcium chloride tube was attached at 18 ° C.
Stir for 48 hours. After completion of the reaction, the solvent of the filtrate is filtered off by rotary evaporation at a water bath temperature of 42 ° C., and the residue is dissolved in a mixed solvent of 80 ml of methanol and 100 ml of water. A solution of 10 g of sodium tetraphenylborate in 200 ml of water was added dropwise to this solution while stirring at 18 ° C. Immediately a black precipitate forms. After completion of the dropping, the mixture is stirred for 1 hour and filtered. The precipitated crystals were washed with water and air dried. This was recrystallized from a mixed solvent of acetone-water (1: 7 = volume ratio) to obtain Exemplified compound (29). Yield 2.7 g m.p. p. 230 ° C. Example 1 Three kinds of optical filter materials were prepared using the exemplified compounds synthesized in Reference Examples 1 to 3. That is, the components shown below in parts by weight, and each component are mixed and stirred well, filtered, coated on a metal support by a casting method, and peeled after film formation to obtain the desired optical Filter materials and were obtained respectively. Dry film thickness of 0.05 to 0.3m
Several types of optical filter materials were obtained which were varied between m.

Composition example TAC (cellulose triacetate) 170 parts TPP (triphenyl phosphate) 10 parts Methylene chloride 800 parts Methanol 160 parts Exemplified compound (2) 2 parts Composition example DAC (cellulose diacetate) 170 parts DEP (diethyl phthalate) 10 parts Methylene chloride 800 parts Methanol 160 parts Exemplified compound (5) 2 parts Composition example PC (polycarbonate (Mitsubishi Gas Co., E-2000)) 170 parts Methylene chloride 800 parts Exemplified compound (29) 2 parts Optical filter material and optics The concentration is shown in FIG. The thickness of this tested filter material is 0.05 m
m.

Example 2 In the same manner as in Example 1, an optical filter material containing a UV absorber and having a thickness of 0.19 mm was prepared. The composition of the casting composition is shown below.

TAC (cellulose triacetate) 170 parts TPP (triphenyl phosphate) 10 parts Methylene chloride 800 parts Methanol 160 parts Exemplified compound (2) 2 parts 2- (5-tert-butyl-2-hydroxyphenyl) benzotriazole 0.2 Part Application Example 1 Optical filter material manufactured in Example 1 (thickness 0.05
(mm) was attached to a silicon photodiode as a near-infrared cut filter, and the operation performance of the photodetector was significantly improved. Furthermore, the operational reliability did not change at all even after the forced aging test at 50 ° C.

Application Example 2 The optical filter material having a thickness of 0.19 mm manufactured in Example 1 was used as a safelight in an infrared-sensitive photosensitive manufacturing and processing field. Even after being used for one year under normal conditions, no change was observed in the absorption characteristics before use.

When the ultraviolet absorber is used in combination with the complex of the present invention, the light resistance of the filter material is remarkably improved. The light resistance of such a filter material can be measured by using the exemplary compound (2) and the ultraviolet absorber 2- (5
Table 3 shows the change with time of the optical density of the filter material under the light irradiation when -t-butyl-2-hydroxyphenyl) benzotriazole (compound (U)) was used together in a weight ratio of 10: 1. Indicated.

As can be seen from the above table, when the compound of the present invention and the ultraviolet absorber are used in combination, the light fastness of the optical filter material can be dramatically improved.

Application Example 3 A protective layer made of phosphosilicate glass and a smoothing layer having an average thickness of 5 μm and containing a near-infrared absorber as described below were provided on the surface of a CCD type solid-state image sensor.

Coating composition of smoothing layer Compound of the present invention 29: 1.5 g Diheptyl phthalate (plasticizer) ...... 3.0 cc Ethyl cellosolve acetate ...... 100 cc Next, a 0.7 micron thick dichromate gelatin photo-curable resin layer is provided on the smoothing layer, and a mosaic pattern mask ( Contact exposure was carried out by placing an exposure pattern). Next, the exposed resin layer was washed with warm water to elute and remove the uncured portion of the resin, leaving a cured resin layer composed of mosaic convex portions.

This cured resin layer was dyed with the following dye-A to prepare a colored (yellow) resin film I.

Then, a color contamination preventing layer is formed on the thus-formed colored resin film I using ethyl p-phenylenediacrylate-1,4-bis (β-hydroxyethoxy) cyclohexane, and the same as above. Then, a photocurable resin layer was formed, and the surface thereof was irradiated with light that passed through another exposure pattern to generate another mosaic-shaped cured portion on the resin layer. Then, similarly, the uncured resin portion was removed, and the cured resin layer was dyed with the following dye-B to prepare a colored (cyan) resin film II.

Finally, a micro color filter part was formed by forming a surface coating layer using ethyl p-phenylenediacrylate-1,4-bis (β-hydroxyethoxy) cyclohexane to obtain a color solid-state imaging device. A color image with good color reproducibility was reproduced on a cathode ray tube when incorporated into a CCD color camera using a lens without a near-infrared ray blocking layer and photographed.

Dye A; Color Index (C.I.)
Acid Yellow 141 Pyridinium Salt Dye B: Copper Phthalocyanine Tetrasulfonic Acid
Pyridinium cation

[Brief description of drawings]

FIG. 1 is a graph showing the optical density of the optical filter material of the present invention, and FIG. 2 is a graph showing the relative sensitivity of the human eye and the SPD relative to the wavelength of light. In FIG. 1, and were obtained in Example 1,
The optical density curves of the optical filter materials using the compounds (2), (5) and (29) are shown, respectively.

Claims (1)

[Claims] 1. An optical filter material containing at least one compound represented by the following general formula. (In the formula, R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, a halogen atom, a cyano group, a hydroxyl group, an alkyl group which may have a divalent linking group between the benzene ring to be bonded and the alkyl group, Group, aryl group, cycloalkyl group or heterocyclic group, or non-metallic atomic group in which R ¹ and R ² , R ² and R ³ , or R ³ and R ⁴ are bonded to each other to form a 5- or 6-membered ring Indicates
The groups R ^{1 to} R ⁴ may be the same or different from each other. X represents an anion that neutralizes the cation in the above general formula. )