JP2014031435A - Novel cyanine pigment compound, resin composition and near infrared ray cut filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a cyanine compound with less absorption in a visible range, particularly 400 nm-500 nm, and a near infrared ray cut filter (optical filter) for an image pickup device using the cyanine compound.SOLUTION: This invention provides a cyanine pigment compound represented by formula (1), a group A represents any substituent of methyl, ethyl, butoxyethyl, cyclohexylmethyl, or benzyl.

Description

  The present invention relates to a novel cyanine dye compound, a resin composition containing the same, and a near-infrared cut filter (optical filter) using the same.

  Applications of near-infrared absorbing dyes, resin compositions using the same, and near-infrared cut filters using the same include those for imaging devices such as plasma display panels and CCDs and CMOSs. A plasma display panel that is attracting attention as a large-sized thin TV or a display requires a near-infrared cut filter for blocking near-infrared rays that are inevitably generated due to its mechanism. Among them, cyanine compounds and diimonium dyes whose counter ions are hexafluoroantimonate ions are mainly used because of their excellent heat resistance.

  However, none of these dyes are satisfactory in terms of processability (solubility in coating solvents), heat resistance, light resistance, absorptance, and visible light transmittance, and compounds containing antimony are classified as deleterious substances. Therefore, in recent years, compounds that do not contain heavy metals have been desired in the industrial field where the use of heavy metals and the like is regulated, particularly in the field of electrical materials. Patent Document 4 describes compounds that do not contain heavy metals, but these compounds have insufficient solubility in solvents such as methyl ethyl ketone used for coating and the like, and compounds with better processability have improved this problem. However, it has absorption in the visible range, and therefore, as a dye compound for infrared absorption, development of a dye compound having better visible light transmittance is strongly desired.

  In addition, image sensors such as CCDs and CMOSs used in digital cameras have spectral sensitivity over the near infrared region from the visible region to near 1100 nm, whereas the human eye has a wavelength of 400 nm to 750 nm. Can feel the light. Therefore, since there is a large difference in spectral sensitivity between the image sensor and the human eye, it is necessary to provide a near-infrared cut filter that absorbs the near-infrared region in front of the image sensor to correct the visual sensitivity of the human eye. It is known.

As such a filter, for example, a glass filter in which CuO is added to a phosphate glass so as to selectively absorb near-infrared wavelengths is known as disclosed in JP-B-62-129443. This glass filter contains a large amount of P ₂ O ₅ as an essential component and contains CuO _2, and exhibits a blue-green color by forming Cu ²⁺ ions coordinated to a large number of oxygen ions in an oxidizing molten atmosphere. It has a near infrared cut characteristic.

  However, as described in Patent Document 6, when the content of CuO is increased in order to promote the near-infrared cut effect, the spectral transmittance in the wavelength region of 400 nm to 500 nm generally decreases. It is known that it tends to be green.

  In addition, when the above-described near infrared cut filter for PDP is applied to a filter of an image sensor such as a CCD or CMOS, shielding in the wavelength region of 750 nm to 850 nm necessary for correcting the sensitivity of the image sensor is not sufficient, It is known that there is a problem that it is difficult to apply as it is.

  Against this background, in recent years, near-infrared absorbing dye compounds with less visible light absorption, resin compositions using the compounds, and near-infrared cut filters, particularly those with less absorption at 400 nm to 500 nm and absorption near 750 nm to 850 nm. There is a strong demand for the development of a near-infrared cut filter for an image sensor such as a CCD or CMOS.

JP 2000-81511 A Japanese Patent Publication No. 5-37119 Japanese Patent No. 3045404 International Publication No. 2006/006573 Pamphlet JP 2008-88426 A JP 2008-303130 A

  The present invention relates to a novel cyanine dye compound, a resin composition containing the same, and a near-infrared cut filter using them. Specifically, a cyanine dye compound with little absorption in the visible region, particularly 400 nm to 500 nm and a resin composition using the same, and a near-infrared cut filter characterized by little visible region absorption, particularly a CCD or CMOS An object of the present invention is to provide a near-infrared cut filter for an image sensor.

  As a result of intensive studies, the present inventors have solved the above-mentioned problems by a specific cyanine dye compound represented by the following formula (1), a resin composition thereof, and a near-infrared filter. As a result, the present invention has been completed.

（式中、基Ａは下記式（２）〜（５）のいずれかの置換基を表す。）

（式（２）中、ｎは０〜３の整数を表す。）

（式（５）中、ｍは０〜３の整数を表す。）
（２）式（１）において、基Ａが式（２）〜（４）である（１）に記載のシアニン色素化合物、
（３）式（１）において、基Ａが式（２）である（１）に記載のシアニン色素化合物、
（４）（１）乃至（３）のいずれか一項に記載のシアニン色素化合物を含有する樹脂組成物、
（５）（４）に記載の樹脂組成物を用いた近赤外線カットフィルタ、
（６）（５）に記載の近赤外線フィルタを用いた撮像素子、
に関する。 That is, the present invention
(1) a cyanine dye compound represented by the following formula (1):

(In the formula, the group A represents a substituent of any one of the following formulas (2) to (5).)

(In formula (2), n represents an integer of 0 to 3)

(In formula (5), m represents an integer of 0 to 3.)
(2) The cyanine dye compound according to (1), wherein in the formula (1), the group A is a formula (2) to (4),
(3) The cyanine dye compound according to (1), wherein in the formula (1), the group A is the formula (2),
(4) A resin composition containing the cyanine dye compound according to any one of (1) to (3),
(5) A near-infrared cut filter using the resin composition according to (4),
(6) An imaging device using the near infrared filter according to (5),
About.

  According to the present invention, visible region absorption, particularly a cyanine dye compound that absorbs less light in the range of 400 nm to 500 nm, and a resin composition, a near-infrared cut filter characterized by low visible region absorption using them, especially CCD and CMOS It was possible to provide a near-infrared cut filter for use in an image sensor.

The present invention will be described in detail.
In the formula (1), the group A represents the formulas (2) to (5), preferably the formulas (2) to (4), and more preferably the formula (2).

  In formula (2), n represents an integer of 0 to 3, preferably 0 to 1, more preferably 0. In formula (5), m represents an integer of 0 to 3, and is preferably 3.

  Of the groups A, n, and m, a compound in which preferable ones are combined is more preferable, and a compound in which more preferable ones are combined is more preferable. The same applies to combinations of preferable and more preferable ones.

  The cyanine dye compound of the present invention represented by the above formula (1) is produced by various methods. For example, it can be produced by the following method with reference to the method described in Patent Document 3. In addition, group A, n, and m used suitably in the following formulas (AA) to (H) represent the same meaning as in the above formula (1).

An alkylating agent represented by an organic halide, dialkyl sulfate, or substituted alkyl p-toluenesulfonyl corresponding to 2,3,3-trimethylindolenine represented by the following formula (AA), which is commercially available, corresponding to group A It is converted to a derivative represented by the following formula (F) by reacting with the following formulas (B) to (E).
Where I: iodine atom, Br: bromine atom, Cl: chlorine atom, Ts: p-toluenesulfonyl group, Ms: methanesulfonyl group, Tf: trifluoromethanesulfonyl group, and Y is a general substitutable desorption. An alkylating agent having a leaving group is shown as an example, but not limited thereto.

次いで市販品として入手可能な下記式（Ｇ）で表されるグルタコンアルデヒドジアニル塩酸塩と反応させ、次いで下記式（Ｈ）で表される金属トリス（トリフルオロメタンスルホニル）メタニド、例えば、カリウム トリス（トリフルオロメタンスルホニル）メタニドと塩交換させることにより上記式（１）で表される本発明のシアニン色素化合物を得ることができる。

Next, it is reacted with a commercially available glutaconaldehyde dianil hydrochloride represented by the following formula (G), and then a metal tris (trifluoromethanesulfonyl) methanide represented by the following formula (H), for example, potassium tris The cyanine dye compound of the present invention represented by the above formula (1) can be obtained by salt exchange with (trifluoromethanesulfonyl) methanide.

  Although the specific example of the pigment | dye represented by the said Formula (1) is shown in following Table 1, this invention is not limited to these specific examples.

Table 1 Compound examples

  The cyanine dye compound of the present invention can be used as a near-infrared absorbing dye for filters, as shown in the examples below, and a resin composition using the dye compound is also included in the present invention. In addition, it can be used for an optical information recording medium.

  An infrared cut filter (optical filter) using the resin composition using the cyanine dye compound of the present invention is also included in the present invention. The infrared cut filter may be one in which the resin layer containing the cyanine dye compound of the present invention is provided on the substrate, or the substrate itself contains the cyanine dye compound of the present invention (or a cured product thereof). ). The substrate is not particularly limited as long as it can be generally used for an optical filter, but a resin material is usually used. The thickness of the layer is usually about 0.1 μm to 10 mm, but can be appropriately determined according to the purpose such as the near infrared cut rate.

  Further, the content of the cyanine dye compound to be used is appropriately determined according to the target near-infrared cut rate. Examples of the resin material to be used include polyethylene, polycycloalkane, polystyrene, polyacrylic acid, polyacrylic ester, polyvinyl acetate, polyacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and other vinyl compounds, and their Addition polymers of vinyl compounds, polymethacrylic acid, polymethacrylic acid esters, polyvinylidene chloride, polyvinylidene fluoride, poly (vinylidene fluoride), vinylidene fluoride / trifluoroethylene copolymers, vinylidene fluoride / tetrafluoroethylene copolymers, Vinyl compounds such as vinylidene cyanide / vinyl acetate copolymers or copolymers of fluorine compounds, fluorine-containing resins such as polytrifluoroethylene, polytetrafluoroethylene, and polyhexafluoropropylene, nylon 6, and nylon Polyamide 66 or the like, polyimides, polyurethanes, polypeptides, polyesters such as polyethylene terephthalate, polycarbonate, polyether polyoxymethylene or the like, epoxy resins, polyvinyl alcohol, polyvinyl butyral, and the like.

Although it does not specifically limit as a method of producing the infrared cut filter (optical filter) of this invention, For example, the following well-known method can be utilized.
1) A method of preparing a resin plate or film by kneading the cyanine dye compound of the present invention into a resin and thermoforming it,
2) A method for producing a resin plate or film by cast polymerization of the cyanine dye compound of the present invention and a resin monomer or a prepolymer of a resin monomer in the presence of a polymerization catalyst,
3) A method for producing a coating material containing the cyanine dye compound of the present invention and coating it on a transparent resin plate, a transparent film, or a transparent glass plate,
4) A method for producing a laminated resin plate, a laminated resin film, or a laminated glass plate using a composition containing the cyanine dye compound of the present invention and a resin (adhesive),
Etc.

  As the production method of 1), the processing temperature, filming (resin plate) conditions and the like are slightly different depending on the resin to be used. Usually, the cyanine dye compound of the present invention is added to the powder or pellet of the base resin, and 150 Examples thereof include a method of heating and dissolving at ˜350 ° C. and then molding to prepare a resin plate, or a method of forming a film (resin plate) with an extruder. The amount of the cyanine dye compound added varies depending on the thickness, absorption strength, visible light transmittance, etc. of the resin plate or film to be produced, but is usually about 0.01 to 30% by mass with respect to the mass of the base resin, preferably About 0.03 to 15% by mass is used.

  In the method of 2), the cyanine dye compound of the present invention and a resin monomer or a prepolymer of a resin monomer are injected into a mold in the presence of a polymerization catalyst and reacted to be cured, or poured into a mold. Solidify and mold until hard product in mold. Many resins can be molded by this method, and examples of such resins include (meth) acrylic resins, diethylene glycol bis (allyl carbonate) resins, epoxy resins, phenol-formaldehyde resins, polystyrene resins, and silicon resins. . Among them, the casting method by bulk polymerization of methyl methacrylate, which can obtain an acrylic sheet excellent in hardness, heat resistance, and chemical resistance, is preferable. As the polymerization catalyst, known radical thermal polymerization initiators can be used, for example, peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, diisopropyl peroxycarbonate, and azo compounds such as azobisisobutyronitrile. It is done. The amount used is generally from 0.01 to 5% by weight, based on the total amount of the mixture. The heating temperature in the thermal polymerization is usually 40 to 200 ° C., and the polymerization time is usually about 30 minutes to 8 hours. In addition to thermal polymerization, a method of photopolymerization by adding a photopolymerization initiator or a sensitizer can also be employed.

  Examples of the method 3) include a method in which the cyanine dye compound of the present invention is dissolved in a binder resin and a solvent to form a paint, and a method in which the cyanine dye compound is finely dispersed in the presence of the resin to form a water-based paint. In the former method, for example, aliphatic ester resin, acrylic resin, melamine resin, urethane resin, aromatic ester resin, polycarbonate resin, polyvinyl resin, aliphatic polyolefin resin, aromatic polyolefin resin, polyvinyl alcohol resin, polyvinyl modification Resins or the like or copolymer resins thereof can be used.

  As the solvent, a halogen-based, alcohol-based, ketone-based, ester-based, aliphatic hydrocarbon-based, aromatic hydrocarbon-based, ether-based solvent, or a mixed solvent thereof can be used. The concentration of the cyanine dye compound varies depending on the thickness of the coating to be produced, the absorption intensity, and the visible light transmittance, but is generally about 0.1 to 30% by mass with respect to the binder resin. The paint thus obtained can be coated on a transparent resin film, transparent resin plate, transparent glass or the like with a spin coater, bar coater, roll coater, spray or the like to obtain a near infrared absorption filter.

4) The cyanine dye compound of the present invention is applied to a known transparent adhesive for laminated glass such as silicon-based, urethane-based, acrylic-based resin, polyvinyl butyral adhesive, ethylene-vinyl acetate adhesive, and the like. Optical resin by adhering transparent resin plates to each other, resin plates and resin films, resin plates and glass, resin films to each other, resin films and glass, and glass to each other. Is made.
In addition, when kneading and mixing by each method, usual additives used for resin molding such as an ultraviolet absorber and a plasticizer may be added.

The near-infrared cut filter of the present invention may use only one or two or more of the cyanine compounds of the present invention as a near-infrared absorbing compound. However, in order to broaden the absorption wavelength range, near-infrared light other than these compounds is used. An absorbing compound may be used in combination. Examples of other near-infrared absorbing compounds that can be used in combination include metal complex compounds such as diimonium compounds, phthalocyanine compounds, and nickel dithiol complexes. When these other near infrared ray absorbing compounds that can be used in combination are cationic, the counter anion may be the same tris (halogenoalkylsulfonyl) methide anion as the cyanine compound of the present invention.
As the other near-infrared absorbing compound, a diimonium compound is particularly preferable, and a counter anion of the diimonium compound is preferably a tris (halogenoalkylsulfonyl) methide anion.

  Examples of the inorganic infrared near-absorbing compound that can be used in combination include copper, copper sulfide, copper compounds such as copper oxide, a mixture containing zinc oxide as a main component, a tungsten compound, and a mixture containing titanium oxide as a main component. Etc.

The optical filter of the present invention for absorbing near infrared rays is used not only for imaging device applications and display front plates, but also for filter films that need to cut near infrared rays, such as heat insulating films, optical products, sunglasses, etc. I can do it.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the examples. Unless otherwise specified, “part” and “%” in the text are based on mass, and the reaction temperature is the internal temperature. Among the synthesized compounds, those for which λmax (maximum absorption wavelength) was measured were described in chloroform with a UV-visible spectrophotometer UV-3150 (manufactured by Shimadzu Corporation).

[Example 1]
(Process 1)
40 parts of 2,3,3-trimethylindolenine, 70 parts of potassium carbonate and 43 parts of iodomethane were added to 50 parts of water and 50 parts of N, N-dimethylformamide, and stirred at reflux temperature for 6 hours. After cooling the obtained liquid to room temperature, liquid separation operation was performed using ethyl acetate, and magnesium sulfate was added to the organic layer to remove water. Thereafter, magnesium sulfate was filtered off and the solvent was removed under reduced pressure to obtain 45 parts of a red liquid of a compound represented by the following formula (6).

(Process 2)
To 30 parts of acetic acid and 30 parts of acetic anhydride, 3.7 parts of the compound of the formula (6) obtained in Example 1 (Step 1), 2.7 parts of glutaconaldehyde dianyl hydrochloride, tris (trifluoromethanesulfonyl) 8.5 parts of potassium methanide and 1.6 parts of sodium acetate were added and stirred at reflux temperature for 30 minutes. The obtained liquid was cooled to room temperature, poured into 200 parts of water and stirred for 30 minutes, and then the precipitated solid was collected by filtration and dried, whereby the near infrared of the present invention represented by the following formula (7) was obtained. Absorbing dye 5.0 parts (λmax: 754 nm) was obtained.

[Example 2]
In the same manner as in Example 1 except that 47 parts of iodoethane are used instead of 43 parts of iodomethane in Example 1 (Step 1), the near-infrared absorbing dye of the present invention represented by the following formula (8): 3 parts (λmax: 758 nm) were obtained.

[Example 3]
In the same manner as in Example 1 except that 82 parts of p-toluenesulfonic acid butoxyethyl ester is used instead of 43 parts of iodomethane in Example 1 (Step 1), the compound represented by the following formula (9) is used. 6.0 parts (λmax: 764 nm) of a near-infrared absorbing dye was obtained.

[Example 4]
The near infrared of the present invention represented by the following formula (10) is obtained in the same manner as in Example 1 except that 53 parts of cyclohexylmethyl bromide is used instead of 43 parts of iodomethane in Example 1 (Step 1). Absorbing dye 6.5 parts (λmax: 764 nm) was obtained.

[Example 5]
The near-infrared absorbing dye of the present invention represented by the following formula (11) in the same manner as in Example 1 except that 49 parts of benzyl bromide is used instead of 43 parts of iodomethane in Example 1 (Step 1). 6.0 parts (λmax: 764 nm) were obtained.

[Examples 6 to 10]
[Production of optical film]
Diallyl phthalate resin (manufactured by Daiso Corporation, trade name “Daiso Dup A”) was dissolved in methyl isobutyl ketone (MIBK) so as to be 30% by mass to obtain a base solution. 0.05% by mass of each of the cyanine dye compounds of the present invention [Formula (7) to Formula (11)] obtained in Examples 1 to 5 above was added to the main agent solution with respect to the total mass of the main agent solution. Thus, a coating solution in which these were dissolved was obtained. This coating solution was dropped onto a glass substrate placed on a spin coater, and the substrate surface was coated by rotating the substrate at 500 rpm for 10 seconds, and then dried at 80 ° C. for 10 minutes to obtain an optical filter. The optical filters using the cyanine dye compounds obtained in Examples 1 to 5 are referred to as Examples 6 to 10, respectively.

[Comparative Example 1]
An optical filter for comparison was produced in the same manner as in Examples 6 to 10 except that the cyanine dye compound described in Compound No. 31 of Patent Document 5 was used instead of the cyanine dye compound of the present invention obtained in each Example. did. This optical filter is referred to as Comparative Example 1. The structural formula of the compound used in Comparative Example 1 is shown in the following formula (12).

[Comparative Example 2]
Comparative optical filters were produced in the same manner as in Examples 6 to 10 except that the dye described in Compound No. 36 of Patent Document 5 was used in place of the compound of the present invention obtained in each Example. The production of this filter is referred to as Comparative Example 2. The structural formula of the compound used in Comparative Example 2 is shown in the following formula (13).

  The optical characteristics of the optical filters obtained in Examples 6 to 10 and Comparative Examples 1 and 2 were evaluated by the following methods.

  Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-3150), the transmittance of each of the optical filters of Examples 6 to 10 and Comparative Examples 1 to 2 was measured in the range of 200 to 1100 nm. Table 2 shows measured values of the transmittance (%) at the maximum absorption wavelength of the optical filters of Examples and Comparative Examples 1 and 2 and the transmittance (%) at the maximum absorption wavelength in the wavelength region of 400 nm to 500 nm. Show.

Table 2

Next, the shielding rate A2 (%) at the maximum absorption wavelength and the shielding rate A1 (%) at the maximum absorption wavelength in the wavelength region of 400 to 500 nm were calculated by the following shielding rate calculation method.
[Shielding rate (%)] = 100− [Transmissivity (%)]
Further, the ratio R of the obtained shielding rates A1 and A2 was obtained by the following calculation method.
R = (A2 / A1)
Each result is shown in Table 3.

Table 3

  It can be said that the smaller the value of A1 with respect to A2, that is, the larger the value of R, the less the visible light absorption with respect to the infrared absorption, and the near-infrared cut filter having excellent transparency in the visible light region. From the results shown in Table 3, R in Comparative Examples 1 and 2 showed a lower value than R in any of the Examples, indicating inferior results as a near-infrared cut filter.

  Since the cyanine dye compound represented by the formula (1) of the present invention, the resin composition, and the near-infrared cut filter (optical filter) obtained by these compounds are extremely excellent in the transmittance in the visible light region, particularly in the transmittance of 400 nm to 500 nm. It is very useful as an optical filter for various applications, particularly as a near-infrared cut filter (optical filter) for an image sensor such as a CCD or CMOS.

Claims (6)

A cyanine dye compound represented by the following formula (1).

(In formula (1), group A represents any one of the following formulas (2) to (5)).

(In formula (2), n represents an integer of 0 to 3)

(In formula (5), m represents an integer of 0 to 3.) The cyanine dye compound according to claim 1, wherein the group A in the formula (1) is a formula (2) to (4). The cyanine dye compound according to claim 1, wherein the group A in the formula (1) is the formula (2). The resin composition containing the cyanine dye compound as described in any one of Claims 1 thru | or 3. A near-infrared cut filter using the resin composition according to claim 4. An image pickup device using the near-infrared cut filter according to claim 5.