JP6958569B2 - Composition, optical film, near-infrared cut filter, image sensor - Google Patents

Description

The present invention relates to a composition containing a squarylium compound or a composition containing a croconium compound, which is preferably used for an image sensor. The present invention also relates to an optical film containing this composition, a near-infrared cut filter, and an image sensor.

In recent years, image (imaging) sensors have become sensitive in a wide wavelength range. For example, an image sensor made of silicon has a sensitivity of up to about 1100 nm. When this image sensor made of silicon is used in the visible light region of about 380 nm to 780 nm, the infrared region (near infrared region) of about 760 nm to 1100 nm, which is a wavelength outside the visible light region, affects the output. In addition, each image sensor may use a different wavelength range, and in an environment where there are multiple sensors with different wavelength ranges to use, only the specific wave range used by each sensor is input to prevent malfunction. Is required. As a means for inputting a specific wavelength range suitable for input to the image sensor, an organic compound having the ability to absorb a specific wavelength range such as near infrared rays is mixed with a constituent material in the image sensor or the imaging optical system, or a specific wavelength is used. Means for adding an optical film having an organic compound having the ability to absorb a region are known.

As a compound having a maximum wavelength in the near infrared region and little absorption in the visible light region, Patent Document 1 discloses a croconium compound for optical films having high light resistance, heat resistance and moisture resistance, and excellent color tone. Further, as a resin composition having the same performance, Patent Document 2 discloses a resin composition having at least one of a carboxylic acid ester and a phosphoric acid ester, a resin, and a squarylium compound and having excellent infrared absorption. There is.

Further, as a sensor application, Patent Document 3 includes two or more compounds selected from diimonium compounds, nickel dithiol compounds, phthalocyanine compounds, squarylium compounds, and croconium compounds as near-infrared absorbing dyes, one of which is one of them. An optical film having excellent storage stability and weather resistance, which is characterized by being a squarylium compound, has been disclosed. However, in any of the inventions, near-infrared absorption stability when irradiated with a specific wavelength for a longer period of time is higher. Sex is required.

JP-A-2007-169315 Japanese Unexamined Patent Publication No. 2015-911923 Japanese Unexamined Patent Publication No. 2007-264384

The present invention has been made in view of the above problems, and an object of the present invention is a composition contributing to an optical film having excellent near-infrared absorption stability, an optical film containing the composition, a near-infrared cut filter, and an image sensor. Is to provide.

The above object of the present invention is achieved by the following configuration.

1. 1. The compound represented by the following general formula 2 and at least one of the compounds represented by the following general formula 5 are contained, or at least two kinds of the compounds represented by the following general formula 5 are contained, and the general formula is described above. A composition containing two types of compounds, wherein the compound represented by the formula 2 is represented by the following general formula 6, and the compound represented by the general formula 5 is represented by the following general formula 7.

[In the general formula 2, A ₃ and A ₄ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A ₃ and A ₄ may further have a substituent. n is 1 or 2. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. If the molecule is not charge-neutral, it has a counter anion. ]

[In the general formula 5, A ₃ and A ₄ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A ₃ and A ₄ may further have a substituent. n is 1 or 2. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂₀ is one selected from the group consisting of an alkyl group , a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₂₀ may further have a substituent. If the molecule is not charge-neutral, it has a counter anion. ]

[In the general formula 6, each A ₁₁ and A ₂₁ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₁₁ and A ₂₁ may further have a substituent. ]

[In the general formula 7, respectively A ₃₁ and A ₄₁ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₃₁ and A ₄₁ may further have a substituent. R ₁₁ is one selected from the group consisting of an alkyl group , a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₁₁ may further have a substituent. Ctr ⁻ represents a counter anion. ]

2. The compound represented by the general formula 2 and at least one of the compounds represented by the general formula 5 are contained, or at least two of the compounds represented by the general formula 5 are contained, and the general formula is used. A composition containing two types of compounds, wherein the compound represented by the formula 2 is represented by the following general formula 8 and the compound represented by the general formula 5 is represented by the following general formula 9.

[In general formula 8, respectively A ₁₂ and A ₂₂ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₁₂ and A ₂₂ may further have a substituent. ]

[In general formula 9, each A ₃₂ and A ₄₂ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₃₂ and A ₄₂ may further have a substituent. R ₁₂ is one selected from the group consisting of an alkyl group , a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₁₂ may further have a substituent. Ctr ⁻ represents a counter anion. ]

3. 3. The composition according to claim 1 or 2, wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 500,000 ppm.

4. The composition according to claim 3 , wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 100,000 ppm.

5. The composition according to claim 4 , wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 10000 ppm.

6. The composition according to claim 5, wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 1000 ppm.

7. The composition according to claim 6 , wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 100 ppm.

8. An optical film containing the composition according to any one of claims 1 to 7.

9. A near-infrared cut filter including the optical film according to claim 8 and a dielectric multilayer film.

10. An image sensor comprising the composition according to any one of claims 1 to 7.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a composition that contributes to an optical film having excellent near-infrared absorption stability, and an optical film containing the composition.

It is a schematic diagram explaining that entropy increases by mixing A and B two components. A, B It is a figure which shows the structure of the optical film of embodiment of this invention.

Hereinafter, the present invention, its constituent elements, and modes and modes for carrying out the present invention will be described in detail. In the present application, "~" is used to mean that the numerical values described before and after the value are included as the lower limit value and the upper limit value.

In the process of examining the cause of the above problem in order to solve the above problem, the present inventor presumed as follows and came to the present invention.

According to the present inventor, the root cause of the above problems is the strength of the interaction energy of the near-infrared compound used in the optical film, and the maximum state of existence in the film changes with time. I thought it was a factor of.

As a means to solve this problem, the state change of the film can be suppressed by stabilizing the state of the film immediately after formation, that is, by increasing the free energy of Gibbs negatively.

Gibbs free energy is determined by enthalpy and entropy according to the second law of thermodynamics, but enthalpy cannot be universally improved because the chemical structure peculiar to near-infrared compounds is the dominant factor. However, since entropy is determined by the number of components and distribution, it should be possible to use it as a universal technological variable factor.

It is rational to explain this from the entropy effect.

This will be described with reference to the figures. FIG. 1 is a schematic diagram for explaining that entropy is increased by mixing two components. FIG. 1A is a mixed model of component A and component B. FIG. 1B is a mixed model of components A.

The Gibbs free energy change (ΔG) in the reaction at a constant pressure and low temperature has the following relationship with the enthalpy change (ΔH) and the entropy change (ΔS). T represents absolute temperature.
Equation (1) ΔG = ΔH−TΔS
For example, it is assumed that 2n near-infrared compounds (component A) are present in a certain film. It is assumed that the film initially contained half the number of n compounds, but later the same compound (component A) was added to make the film 2n, and the volume was doubled. At this time, since the types of compounds are the same, the amount of change in entropy is zero (FIG. 1B). On the other hand, when n compounds added later are different compounds (component B), the entropy increases because different compounds (component B) are mixed in the first compound (component A) (FIG. 1A). .. The basic principle is that this increase is the entropy effect, and the Gibbs free energy shifts to the minus side, that is, to the stable side by that amount, and as a result, the film becomes stable and the state change with time becomes small. be.

Due to the film stability due to this entropy effect, this "different compound" makes it possible to effectively suppress compound aggregation over time.

Moreover, this phenomenon can be said not only in the membrane but also in the solution of the compound. That is, it is considered that the schematic diagram of the solution in which the by-products and compounds having different substituents are completely dissolved by the solvent, that is, in the isolated and dispersed state corresponds to the right figure of FIG. 1A. The Gibbs free energy of these solutions or thin films is negatively greater than the solution or powder of a compound consisting of a single substance (corresponding to the right figure in FIG. 1B), and the fluctuation due to disturbance is small. That is, it can be interpreted that aggregation and recrystallization are less likely to occur.

Due to this effect, the dispersibility of the compound when the coating film is formed by using the solution and the variability with time of the coating film are suppressed, and the compound dispersion film close to the ideal isolated dispersion state can be formed. It is presumed that an optical filter having excellent near-infrared absorption stability can be obtained by improving the solubility in a solvent or preventing unnecessary crystal growth and obtaining a uniform film in which fluctuation with time is suppressed.

<< Composition >>
The composition according to the present invention is characterized by containing at least two kinds of compounds represented by the following general formula 2 or the following general formula 5. Preferably, at least one compound represented by the following general formula 1 and at least one compound having a structure different from that of the compound represented by the general formula 1 and represented by the following general formula 2 are preferable. Or at least one compound represented by the following general formula 3 and a compound having a structure different from that of the compound represented by the general formula 3 and represented by the following general formula 5. It is a composition containing at least one of. More preferably, one of the compounds represented by the following general formula 2 is a composition containing the compound represented by the following general formula 1, or one of the compounds represented by the following general formula 5 is the following general. It is a composition containing a compound represented by the formula 3. More preferably, the compound represented by the following general formula 2 is represented by the following general formula 6, and the compound represented by the following general formula 5 is a composition containing two kinds of compounds represented by the following general formula 7. , The compound represented by the following general formula 2 is represented by the following general formula 8, and the compound represented by the following general formula 5 is a composition containing two kinds of compounds represented by the following general formula 9.

<Compounds represented by general formulas 1 to 11>
In the present embodiment, the compounds represented by the general formulas 1 to 11 have the following characteristics.

In the following general formula 1, A ₁ and A ₂ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, and A ₁ And A ₂ may further have a substituent.

In the following general formula 2, A ₃ and A ₄ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A ₃ and A ₄ may further have a substituent. In the general formula 1 and the general formula 2, it is preferable that Q is the same. n is 1 or 2. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. If the molecule is not charge-neutral, it has a counter anion.

In the following general formula 3, A ₁ and A ₂ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group, and A ₁ and A 2 A ₂ may further have a substituent. R ₁₀ is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₁₀ may further have a substituent. good. Ctr ⁻ represents a counter anion.

In the following general formula 4, * is a connection point. X ₁ represents an oxygen atom, a sulfur atom or N-R ₄ , and R ₄ represents an alkyl group, a cycloalkyl group or an aryl group. R ₃ represents an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group or a hydrogen atom. Y ₁ and Y ₂ independently represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group, respectively.

In particular, when mixed with a resin binder having an aromatic group, R ₃ is preferably a hydrogen atom. The interaction between the hydrogen atom and the aromatic group suppresses the movement of the methine chain and significantly improves the heat resistance.

In the following general formula 5, A ₃ and A ₄ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A ₃ and A ₄ may further have a substituent. In the general formula 3 and the general formula 5, it is preferable that Q is the same. n is 1 or 2. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂₀ is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₂₀ may further have a substituent. good. If the molecule is not charge-neutral, it has a counter anion.

In the following general formula 6, each A ₁₁ and A ₂₁ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₁₁ and A ₂₁ may further have a substituent.

In the following general formula 7, respectively A ₃₁ and A ₄₁ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₃₁ and A ₄₁ may further have a substituent. R ₁₁ is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₁₁ may further have a substituent. good. Ctr ⁻ represents a counter anion.

In the following general formula 8, respectively A ₁₂ and A ₂₂ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₁₂ and A ₂₂ may further have a substituent.

In the following general formula 9, each A ₃₂ and A ₄₂ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₃₂ and A ₄₂ may further have a substituent. R ₁₂ is one selected from the group consisting of a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₁₂ may further have a substituent. good. Ctr ⁻ represents a counter anion.

In the following general formula 10, * is a connection point. A ₅ is a heterocyclic group, and A ₅ may further have a substituent. R ₂ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom.

In the following general formula 11, * is a connection point. X ₁ represents an oxygen atom, a sulfur atom or N-R ₄ , and R ₄ represents a substituted or unsubstituted alkyl group, cycloalkyl group or aryl group. R ₃ represents a substituted or unsubstituted alkyl group, cycloalkyl group, aryl group, heterocyclic group or hydrogen atom. Y ₁ and Y ₂ independently represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group, respectively. Z ₁ and Z ₂ independently represent a hydrogen atom or a substituted or unsubstituted alkyl or aryl group, respectively.

Specific examples of A ₁ , A ₂ , A ₃ , A ₄ , A ₁₁ , A ₂₁ , A ₃₁ , A ₄₁ , A ₁₂ , A ₂₂ , A ₃₂ , and A ₄₂ include linear and branched alkyl groups. Alkyl groups containing 1 to 30 carbon atoms are preferable, for example, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, n-octyl group, eicosyl group, 2-chloroethyl group, 2-cyanoethyl group. A group, a 2-ethylhexyl group and the like are preferable. As the cycloalkyl group, a cycloalkyl group having 3 to 30 carbon atoms is preferable, and for example, a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl group and the like are preferable. As the alkenyl group, an alkenyl group having 2 to 30 carbon atoms is preferable, and for example, an ethenyl group, an allyl group, a 2-pentenyl group, a 2-ethylbutenyl group and the like are preferable. As the alkynyl group, an alkynyl group having 2 to 30 carbon atoms is preferable, and for example, an ethynyl group, a 2-butynyl group and the like are preferable. As the aryl group, a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, a biphenylyl group and the like are preferable. In particular, a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenylyl group and a fluorenonyl group are preferable. Examples of the heterocyclic group include a pyridyl group, a pyrimidyl group, a frilled group, a pyrrolyl group, an imidazolyl group, a benzoimidazolyl group, a pyrazolyl group, a pyrazinyl group and a triazolyl group (for example, 1,2,4-triazole-1-yl group, 1, 2,3-Triazole-1-yl group, etc.), Oxazolyl group, benzoxazolyl group, thiazolyl group, isooxazolyl group, isothiazolyl group, frazathienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carborinyl group, diazacarbolyl group ( One of the carbon atoms constituting the carbolin ring of the carbolinyl group is replaced with a nitrogen atom), a quinoxalinyl group, a triazineyl group, a quinazolinyl group, a phthalazinyl group and the like are preferable, and a pyridyl group, a pyrimidyl group, an imidazolyl group and a pyrazolyl group are particularly preferable. , Thienyl group, quinolyl group, dibenzofuryl group, carbazolyl group, carborinyl group, diazacarbolinyl group are preferable. Above all, from the viewpoint of color, the general formula 9 and further the general formula 10 are preferable. It is more preferable to contain a heterocycle.

Specific examples of R ₁₀ , R ₂₀ , R ₁₁ , and R ₂₁ include linear and branched alkyl groups, preferably alkyl groups having 1 to 30 carbon atoms, for example, methyl group, ethyl group, and n-propyl. Groups, isopropyl groups, tert-butyl groups, n-octyl groups, eicosyl groups, 2-chloroethyl groups, 2-cyanoethyl groups, 2-ethylhexyl groups and the like are preferable. As the cycloalkyl group, a cycloalkyl group having 3 to 30 carbon atoms is preferable, and for example, a cyclohexyl group, a cyclopentyl group, a 4-n-dodecylcyclohexyl group and the like are preferable. As the alkenyl group, an alkenyl group having 2 to 30 carbon atoms is preferable, and for example, an ethenyl group, an allyl group, a 2-pentenyl group, a 2-ethylbutenyl group and the like are preferable. As the alkynyl group, an alkynyl group having 2 to 30 carbon atoms is preferable, and for example, an ethynyl group, a 2-butynyl group and the like are preferable. As the aryl group, a phenyl group, a p-chlorophenyl group, a mesityl group, a tolyl group, a xylyl group, a naphthyl group, an anthryl group, an azulenyl group, an acenaphthenyl group, a fluorenyl group, a phenanthryl group, an indenyl group, a pyrenyl group, a biphenylyl group and the like are preferable. In particular, a phenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, a biphenylyl group and a fluorenonyl group are preferable. Examples of the heterocyclic group include a pyridyl group, a pyrimidyl group, a frilled group, a pyrrolyl group, an imidazolyl group, a benzoimidazolyl group, a pyrazolyl group, a pyrazinyl group and a triazolyl group (for example, 1,2,4-triazole-1-yl group, 1, 2,3-Triazole-1-yl group, etc.), Oxazolyl group, benzoxazolyl group, thiazolyl group, isooxazolyl group, isothiazolyl group, frazathienyl group, dibenzothienyl group, indolyl group, carbazolyl group, carborinyl group, diazacarbolyl group ( One of the carbon atoms constituting the carbolin ring of the carbolinyl group is replaced with a nitrogen atom), a quinoxalinyl group, a triazineyl group, a quinazolinyl group, a phthalazinyl group and the like are preferable, and a pyridyl group, a pyrimidyl group, an imidazolyl group and a pyrazolyl group are particularly preferable. , Thienyl group, quinolyl group, dibenzofuryl group, carbazolyl group, carborinyl group, diazacarbolinyl group are preferable. The alkoxycarbonyl group is preferably a linear or branched alkoxycarbonyl group having 1 to 30 carbon atoms, for example, a methoxycarbonyl group, an ethoxycarbonyl group, an n-propoxycarbonyl group, an isopropoxycarbonyl group, or a tert-butoxycarbonyl. Groups, n-octoxycarbonyl groups and the like are preferred.

Examples of Ctr ⁻ include various inorganic anions and organic anions. Examples of the inorganic anion include halide anion, carbonate anion, hydrogen carbonate anion, sulfate anion, sulfite anion, nitrate anion, nitrite anion, sulfonic acid anion (paratoluene sulfonic acid, etc.), sulfinate anion, phosphate anion, and the like. perfluoro anion _{^{(PF 6 -, BF 4 -}} , SbF 6 -), peroxide anion include (chlorine anion, chlorite anions, hypochlorite anions, bromine anion, iodine anion, etc.) and the like .. Examples of the organic anion include a carboxylate anion (for example, an acetate anion), an alkoxy anion, an aryloxy anion, and an alkyl sulfonic acid anion (which may be fluorine-substituted, for example, methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, etc. Anions such as nonafluorobutane sulfonic acid and the like), aryl sulfonic acid anions (may have a substituent on the aryl group, for example, benzene sulfonic acid, p-toluene sulfonic acid, p-trifluoromethyl Examples thereof include anions such as sulfonic acid, pentafluorobenzene sulfonic acid and naphthalene sulfonic acid), imide anions substituted with alkyl sulfonic acid or aryl sulfonic acid (for example, bistrifluoromethyl sulfonic acid imide anion) and acetylacetone anion. .. Of these, halide anions and perfluoro anions are preferable from the viewpoint of color.

Y ₁ , Y ₂ , Z ₁ , and Z ₂ represent substituted or unsubstituted alkyl or aryl groups, and may be bonded to each other to form a ring. As the substituents of _{Y 1} , Y ₂ , Z ₁ and Z ₂ , the substituents listed in the substituents _{A 1 to} A _{5 are preferably used.} The plurality of substituents may be bonded to each other to form a ring. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a tert-butyl group, a benzyl group and the like, and examples of the aryl group include a phenyl group and a naphthyl group. From the viewpoint of compound stability, Y ₁ and Y ₂ are preferably selected from the group consisting of a substituted or unsubstituted phenyl group and a tert-butyl group.

X ₁ represents an oxygen atom, a sulfur atom or N-R ₄ , and R ₄ represents an alkyl group, a cycloalkyl group or an aryl group, and X ₁ represents an oxygen atom or a sulfur atom, especially from the viewpoint of color. Is preferable.

The resonance structure of the compound represented by the general formulas 1 to 10 of the present invention is described in the literature: Journal of Synthetic Organic Chemistry vol. 66, No. With reference to 5,2008 and Japanese Patent Application Laid-Open No. 2001-117201, for example, it is considered that the resonance structure is as shown in the following formula. Further, the exemplified compound is shown by notation A, which is synonymous with notation B.

The general formula 2 will be described in more detail by the following formula.

Further, among the above equations, those having an equilibrium state are represented by the following equations, respectively.

The general formula 5 will be described in more detail by the following formula.

The general formula 9 is specifically represented by the following formula.

Further, the general formula 10 is specifically represented by the following formula.

In the present invention, in the general formulas 1 to 3 and 5, the case where the ring formed containing Q is a four-membered ring is referred to as a squarylium compound, and the case of a five-membered ring is referred to as a croconium compound.

In the present invention, at least two compounds represented by the general formula 2 or the general formula 5 are mixed and used, and any combination may be used, but an excellent waveform is provided and the squarylium compound and the croconium compound are excellent. From the viewpoint of maintaining the visible transmittance, the composition is preferably composed of a squalylium compound represented by the general formula 1 and a squalylium compound represented by the general formula 3, or a croconium compound represented by the general formula 1 and the general. It is a composition composed of a croconium compound represented by the formula 3, and more preferably a composition composed of a squarylium compound represented by the general formula 1 and a squarylium compound represented by the general formula 3.

In the present invention, at least two compounds represented by the general formula 2 or the general formula 5 are mixed and used, but functional materials such as additives and dyes may be mixed, and the additive is preferably oxidized. It is an inhibitor, an ultraviolet absorber, and a surfactant, and the pigment is preferably a cyanine pigment, a nickel chelate, a phthalocyanine pigment, or a diimmonium pigment.

Specific examples of the compounds represented by the general formulas 1 to 11 are shown below, but the present invention is not limited thereto.

<< Optical film >>
The optical film in the present embodiment may be in any form, but in the present embodiment, the optical film includes a composition containing at least two kinds of the compounds represented by the general formula 2 and the general formula 5. The configuration may be, for example, a configuration in which a near-infrared absorbing layer formed by coating with a coating liquid containing the composition is formed on the surface of the base material (FIG. 2A), or a configuration in which the composition is mixed with a resin binder (FIG. 2A). FIG. 2B) may be used.

<Board>
The type of the substrate used in the present invention is not particularly limited to glass, plastic, etc., and may be transparent or opaque. When light is taken out from the support substrate side, the support substrate is preferably transparent. Examples of the transparent support substrate preferably used include transparent electrodes such as glass, quartz and ITO, and transparent resin films. Examples of the resin film include polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyethylene, polypropylene, cellophane, cellulose diacetate, cellulose triacetate (TAC), cellulose acetate butyrate, and cellulose acetate propionate. CAP), cellulose acetate phthalate, cellulose esters such as cellulose nitrate or derivatives thereof, polyvinylidene chloride, polyvinyl alcohol, polyethylene vinyl alcohol, syndiotactic polystyrene, polycarbonate, norbornene resin, polymethylpentene, polyether ketone, polyimide , Polyethersulfone (PES), polyphenylene sulfide, polysulfones, polyetherimide, polyetherketoneimide, polyamide, fluororesin, nylon, polymethylmethacrylate, acrylic or polyarylates, Arton (trade name: JSR) or Appel. Examples thereof include cycloolefin resins (trade name: manufactured by Mitsui Kagaku Co., Ltd.). The glass substrate is not particularly limited as long as it is a glass substrate containing a silicate as a main component, and examples thereof include a quartz glass substrate having a crystal structure. In addition, absorbent glass substrates, borosilicate glass substrates, soda glass substrates, colored glass substrates, non-alkali glass substrates, quartz glass substrates, etc., in which CuO or the like is added to fluoride-based glass or phosphate-based glass, etc. are used. However, glass substrates such as non-alkali glass substrates and low α-ray glass substrates are particularly preferable. In particular, the absorption type glass substrate is preferable because it has an absorption action in a wide range of 700 to 1200 nm in the near infrared region and has stable absorption characteristics for obliquely incident light. Examples of the opaque support substrate include a metal plate such as aluminum and stainless steel, a film or opaque resin substrate, and a ceramic substrate.

<Resin binder>
The resin used in this embodiment is not particularly limited, but a resin having excellent heat resistance is preferable. Examples of the resin having excellent heat resistance include a polyimide resin, a polyethylene naphthalate resin, a polyether sulfone resin, a polyether resin, a polycarbonate, a polyarylate, and a cyclic olefin resin. These resins may be used alone or in admixture of two or more.

In particular, a resin binder having an aromatic group is preferable because the heat resistance of the compound of the present invention is improved by interacting with the compound of the present invention.

Among them, a polyimide resin is most preferable from the viewpoint of heat resistance. Specifically, semi-alicyclic polyimide (C3450 manufactured by Mitsubishi Gas Chemical Company, etc.), aromatic polyimide (SPIXAREA HR001 manufactured by Somar Corporation, JL-20 manufactured by Shin Nihon Rika Co., Ltd., etc.), aromatic polyimide with fluorine introduced, etc. Can be mentioned.

<Additives>
Anything can be added to the resin used in the present embodiment as long as the effects of the present invention are not impaired, but other components such as antioxidants, ultraviolet absorbers and surfactants are further added. can do. Antioxidants include, for example, 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 can be mentioned.
Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone.

<Near infrared absorption layer>
In the present embodiment, the structure of the near-infrared absorbing layer is not particularly limited, but one formed by the resin binder, the additive, and the composition is preferable. In the present invention, the amount of the composition used is appropriately selected according to the desired properties, but is usually 0.01 to 10.0% by mass, preferably 0.% by mass, based on 100% by mass of the resin used in the present invention. It is 01 to 0.8% by mass, more preferably 0.01 to 5.0% by mass.
When the amount of the composition used is within the above range, a near-infrared absorbing layer having excellent near-infrared absorbing ability, transmittance and strength in the range of 430 to 580 nm can be obtained.

In the case of a resin film, the film thickness of the near-infrared absorbing layer is usually 20 to 200 μm, preferably 50 to 100 μm. When coated with spin coating or die coating, it is usually 0.1 to 20 μm, preferably 0.5 to 10 μm.
When the film thickness is within the above range, a near-infrared absorbing layer having excellent near-infrared absorbing ability, transmittance and strength in the range of 430 to 580 nm can be obtained.

<Solvent>
The solvent used in this embodiment is not particularly limited, and examples thereof include hydrocarbon solvents, more preferably aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, and halogen solvents. Can be mentioned as. Examples of the aliphatic hydrocarbon solvent include acyclic aliphatic hydrocarbon solvents such as hexane and heptane, cyclic aliphatic hydrocarbon solvents such as cyclohexane, and alcohol solvents such as methanol, ethanol, n-propanol and ethylene glycol. Examples thereof include a solvent, a ketone solvent such as acetone and methyl ethyl ketone, and an ether solvent such as diethyl ether, diisopropyl ether, tetrahydrofuran, 1,4-dioxane and ethylene glycol monomethyl ether. Examples of the aromatic hydrocarbon solvent include toluene, xylene, mesitylene, cyclohexylbenzene, isopropylbiphenyl and the like. Examples of the halogen-based solvent include methylene chloride, 1,1,2-trichloroethane, chloroform and the like. More specifically, 2-ethylhexane, sec-butyl ether, 2-pentanol, 2-methyltetrahydrofuran, 2-propylene glycol monomethyl ether, 2,3-dimethyl-1,4-dioxane, sec-butylbenzene, 2 -Methylcyclohexylbenzene and the like can be mentioned. From the viewpoint of dissolving the resin binder, methylene chloride and N-methyl-2-pyrrolidone are preferable.

<Other constituent layers>
As one of the present embodiments, the other constituent layers constituting the image sensor are not particularly limited, but for example, an image sensor support substrate, a light receiving portion, a mixed polarizing filter, a mixed color filter, and a microlens. , Dielectric multilayer film and the like. A dielectric multilayer film is preferable.

The dielectric multilayer film is formed by alternately laminating a low refractive index dielectric film and a high refractive index dielectric film. Here, the low refractive index and the high refractive index mean having a low refractive index and a high refractive index with respect to the refractive index of the adjacent layer.
A dielectric film having a high refractive index preferably has a refractive index (nd) of 1.6 or more, more preferably 2.2 to 2.5. Examples of the dielectric material having a high refractive index include Ta ₂ O ₅ , TiO ₂ , Nb ₂ O _{5, and the} like. _{Of these, TiO 2} is preferable from the viewpoint of film formation property, reproducibility in refractive index and the like, and stability.
On the other hand, the low refractive index dielectric film preferably has a refractive index (nd) of less than 1.6, more preferably 1.45 or more and less than 1.55, and even more preferably 1.45 to 1. It is .47. Examples of the low refractive index dielectric material include SiO _x N _{y and the} like. _{SiO 2} is desirable from the viewpoint of film formation reproducibility, stability, economy, and the like.
The dielectric multilayer film can be produced by using, for example, a vacuum film forming process such as a CVD method, a sputtering method, or a vacuum vapor deposition method, or a wet film forming process such as a spray method or a dip method.
In the dielectric multilayer film used in the present invention, the average transmittance of light having a wavelength of 430 to 620 nm is preferably 90% or more, more preferably 92% or more, and further 95% or more in the spectral transmittance curve at an incident angle of 0 °. preferable. Further, in the spectral transmittance curve at an incident angle of 0 °, the average transmittance of light having a wavelength of 710 to 1100 nm is preferably 10% or less, more preferably 8% or less, still more preferably 5% or less. Further, in the spectral transmittance curve at an incident angle of 0 °, it is preferable to have a wavelength having a transmittance of 50% at a wavelength of 350 to 430 nm and a wavelength having a transmittance of 50% at a wavelength of 650 to 750 nm.
For this purpose, the dielectric multilayer film preferably has 15 or more layers, more preferably 25 or more layers, and 30 or more layers as the total number of layers of the low refractive index dielectric layer and the high refractive index dielectric layer. Is even more preferable. However, as the total number of layers increases, the warp of the dielectric multilayer film increases and the overall film thickness increases. Therefore, 100 layers or less is preferable, 75 layers or less is more preferable, and 60 layers or less is further preferable. As the film thickness, it is preferable that the film thickness satisfies a preferable number of layers and is thin from the viewpoint of thinning the optical filter. The film thickness of such a dielectric multilayer film is preferably 2 to 10 μm.

<Synthesis of Exemplified Compound M-29>
Exemplified compound M-29 was synthesized by the following chemical reaction formula.

(Synthesis of Intermediate A)
28.0 g of sodium hydride and 270 mL of diethylene glycol dimethyl ether (hereinafter referred to as DME) were mixed, and reflux was performed by heating. A mixed solution of 22.8 g of benzoylacetone, 27.2 g of ethyl pivalate and 270 mL of DME was added dropwise over 30 minutes under heating under reflux. After completion of the dropping, heating and refluxing was carried out for 4 hours, and then 500 mL of DME was distilled off. The reaction was cooled with water and 30 mL of methanol was added slowly. Further, the reaction solution was cooled with ice water, 570 mL of water was added, and the mixture was stirred for 1 hour. 200 mL of ethyl acetate and 68 mL of concentrated hydrochloric acid were added in that order, and the organic layer was separated. The separated organic layer was dried over sodium sulfate, and the solvent was distilled off by concentration under reduced pressure to obtain 30 g of Intermediate A.

(Synthesis of Intermediate B)
450 mL of concentrated sulfuric acid was cooled with ice water, and a solution of Intermediate A in 60 mL of toluene was added. After stirring for 2 hours under cooling with ice water, the reaction solution was added dropwise to 5 L of water cooled with ice water. After completion of the dropping, the mixture was stirred for 2 hours under cooling with ice water, and the precipitated crystals were collected by filtration to obtain 18 g of Intermediate B.

(Synthesis of Intermediate C)
Under a nitrogen atmosphere, 10 g of Intermediate B was dissolved in 100 mL of tetrahydrofuran (hereinafter referred to as THF). 105 mL of methylmagnesium bromide (0.84 M, THF solution) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After slowly adding 1 L of saturated aqueous ammonium bromide solution, 500 mL of ethyl acetate was added, and the organic layer was separated. After drying the organic layer with sodium sulfate, the solvent was removed by concentration under reduced pressure to obtain 6.3 g of Intermediate C.

(Synthesis of Exemplified Compound M-29)
Intermediate C 6.3 g, squaric acid 1.03 g, methanol 28 mL, and pyridine 1.5 g were sequentially mixed, and the mixture was heated under reflux for 3 hours. After allowing the reaction solution to cool, the mixture was stirred under ice-water cooling for 5 hours, and the precipitated crystals were collected by filtration. The obtained crystals were purified by silica gel column chromatography to obtain 1.6 g of Exemplified Compound M-29. Further, by purification by silica gel column chromatography, 8 mg of s-5 and 16 mg of s-6, which are by-products, were obtained, respectively.

Other exemplary compounds were also synthesized using the same synthetic formulation as the exemplary compound M-29.

Exemplified compound M-35 was synthesized by the same synthetic formulation as Exemplified compound M-29 except that ethylmagnesium bromide (1M, THF solution) was used in the synthesis of intermediate C.

Exemplified compound M-113 was synthesized by the same synthetic formulation as Exemplified compound M-29 except that 4-methyl-1-octylquinoline-1-ium bromide was used instead of intermediate C.

<Synthesis of Exemplified Compound M-60>
Exemplified compound M-60 was synthesized by the following chemical reaction formula.

(Synthesis of Intermediate D)
Under ice water cooling, 8 g of 3-methyl-1-butyne was added dropwise to 69.3 mL of ethylmagnesium bromide (0.96 M, THF solution). After completion of the dropping, the mixture was stirred at room temperature for 3 hours to prepare a solution A.

4.5 g of ethyl formate was dissolved in 45 mL of THF. The mixture was cooled to −5 ° C., and the solution A was added dropwise. After completion of the dropping, the mixture was stirred at −5 ° C. for 2 hours and then further stirred at 5 ° C. for 2 hours. 20 mL of THF and 40 mL of 6M hydrochloric acid were sequentially added to the reaction solution. The reaction solution was returned to room temperature, 100 mL of ether was added, and the organic layer was separated. The organic layer was dried over magnesium sulfate, and the solvent was distilled off by concentration under reduced pressure. The residue was purified by silica gel column chromatography to obtain 5.7 g of Intermediate D.

(Synthesis of intermediate E)
5.7 g of Intermediate D was dissolved in 67 mL of toluene, 3.6 g of manganese dioxide powder was added, and the mixture was stirred at 40 ° C. for 1 hour. 3.6 g of manganese dioxide was added to the reaction solution, and the mixture was further stirred at 40 ° C. for 2 hours. Further, 3.6 g of manganese dioxide was added, and the mixture was stirred at 40 ° C. for 3 hours, and then manganese dioxide was filtered off. By distilling off the filtrate by concentration under reduced pressure, 5.3 g of Intermediate E was obtained.

(Synthesis of Intermediate F)
5.3 g of the intermediate E was dissolved in 114 mL of sodium ethoxide (0.05 M, ethanol solution), and the mixture was stirred at room temperature for 1 hour to prepare a solution B.

180 mL of sodium ethoxide (0.5 M, ethanol solution) was added to 1.9 g of sulfur, and 2.5 g of sodium borohydride was further added. The reaction solution was heated to 60 ° C. and stirred for 30 minutes, then 230 mL of ethanol was distilled off by concentration under reduced pressure, and a saturated aqueous sodium chloride solution was added to the reaction solution. 100 mL of ethyl acetate was added, the organic layer was separated, and the mixture was washed successively with saturated aqueous sodium chloride solution, water and saturated aqueous sodium chloride solution. The organic layer was dried over magnesium sulfate, and the solvent was distilled off by concentration under reduced pressure to obtain 5.1 g of Intermediate F.

(Synthesis of intermediate G)
Under a nitrogen atmosphere, 5.1 g of Intermediate F was dissolved in 30 mL of THF. 34 mL of methylmagnesium bromide (0.84 M, THF solution) was added dropwise, and the mixture was stirred at room temperature for 1 hour. After slowly adding 120 mL of a saturated aqueous ammonium bromide solution, 100 mL of ethyl acetate was added, and the organic layer was separated. After drying the organic layer with sodium sulfate, the solvent was distilled off by concentration under reduced pressure to obtain 6.2 g of Intermediate G.

(Synthesis of Exemplified Compound M-60)
6.2 g of Intermediate G, 1.5 g of croconic acid, 35 mL of methanol, and 1.68 g of pyridine were sequentially mixed, and the mixture was heated under reflux for 3 hours. After allowing the reaction solution to cool, the mixture was stirred under ice-water cooling for 5 hours, and the precipitated crystals were collected by filtration. The obtained crystals were purified by silica gel column chromatography to obtain 1.8 g of Exemplified Compound M-60. Further, by purification by silica gel column chromatography, 0.01 mg of s-17 and 0.024 g of s-18, which are by-products, were obtained.

Other exemplary compounds were also synthesized using the same synthetic formulation as the exemplary compound M-60.

<Synthesis of Exemplified Compound M-152>
Exemplified compound M-152 was synthesized by the following chemical reaction formula.

(Synthesis of Exemplified Compound M-152)
Exemplified compound M-6, 2.2 g, methylene chloride 36 mL, and dimethyl sulfate 3.0 g were sequentially mixed and heated under reflux for 6 hours. After cooling the reaction solution, sodium methoxide (28% methanol solution) was 3.8g dropwise, and stirred HBF ₄ solution was added dropwise to 1 hour After stirring at room temperature for 4 hours. Then, the organic layer was separated, dried over sodium sulfate, and then the solvent was distilled off by concentration under reduced pressure to obtain 1.5 g of Exemplified Compound M-152.

Other exemplary compounds were also synthesized using the same synthetic formulation as the exemplary compound M-152.

(Measurement of spectral absorption spectrum)
The composition is added to a polyimide resin (SPIXAREA HR001 (manufactured by Somar Co., Ltd.)) so that the resin / composition ratio is 100 parts by mass / 0.12 parts by mass, and the solid content concentration becomes 5 wt%. After diluting with N-methyl-2-pyrrolidone as described above, this was applied to a glass plate, and the solvent (to N-methyl-2-pyrrolidone) was evaporated by heating and reducing pressure on a hot plate at 90 ° C. for 1 hour. Later, it was peeled off from the glass plate to obtain a film. The spectral absorption spectrum of the produced film was measured with an ultraviolet-visible spectrophotometer V-570 (manufactured by JASCO Corporation).
Further, the composition is added to the polyimide resin A so that the resin / composition ratio is 100 parts by mass / 0.1 parts by mass, and methylene chloride and ethanol are added so that the solid content concentration is 5 wt%. After diluting with, this is applied to a glass plate, heated on a hot plate at 90 ° C. for 1 hour to evaporate the solvent (methylene chloride and ethanol), and then peeled off from the glass plate to obtain a film similar to the above. I was able to.
Here, the polyimide resin A was synthesized as follows.
A 200 mL three-necked round-bottom flask equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler was used as a reactor. Then, this reactor was filled with 88.13 g of N, N-dimethylacetamide (DMAc) while passing nitrogen, and then 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (2). , 2'-TFDB) 9.6 g was dissolved. After lowering the reaction temperature to 10 ° C., 13.32 g of 6-FDA was added thereto, and the solution was left at room temperature and stirred for 3 hours.
After the reaction was completed, 4.75 g of pyridine and 6.13 g of anhydrous acetic acid were added to the obtained polyamic acid solution, and the mixture was stirred again at 80 ° C. for 2 hours to cool at room temperature, and 1 L of methanol was stirred. Gradually put into a container in which The polyimide-based resin A of the above was obtained.

(Solubility evaluation)
The composition was dissolved in N-methyl-2-pyrrolidone so as to be 10 wt%, and allowed to stand for 24 hours to evaluate the amount of crystal precipitation (the amount of solute precipitated with respect to the total dissolved mass in the solution). ..
⊚: No crystals are precipitated ○: Precipitated crystals are less than 1% Δ: Precipitated crystals are less than 5% ×: Precipitated crystals are 5% or more

(Evaluation of near-infrared absorption stability)
The polyimide resin prepared by adding the above composition was allowed to stand at a temperature of 60 ° C. and a humidity of 90% for 600 hours as an environmental resistance test, and the spectral absorption spectrum was measured before and after that. The absorbance at the wavelength of λmax before the environmental resistance test was λ0, and the absorbance at the wavelength after the environmental resistance test was λ1, and the near-infrared absorption stability (S1) was calculated and evaluated using the following formula.
Equation S1 = λ1 / λ0 × 100

(Evaluation of the deviation of the spectral absorption spectrum of a single dye from the wavelength of λmax)
The spectral absorption spectrum of the composition was measured, the wavelength at λmax was Xnm, the spectral absorption spectrum at the time of general formula 1 alone was measured, the wavelength at λmax was Ynm, and the following formula was used to determine the single dye. The deviation (D1) of the spectral absorption spectrum from the wavelength of λmax was evaluated.
Equation D1 = | YX |

<Examples 1-27, Comparative Examples 1-9>
Each of the above compositions was prepared as shown in Table 1 below.

<Evaluation of Examples 1-27 and Comparative Examples 1-9>
Solubility and near-infrared absorption stability (S1) were evaluated for each composition. The results are summarized in Table 2 below.

<Examples 28 to 32, Comparative Examples 10 to 15>
The compositions were prepared as shown in Table 3 below.

<Evaluation of Examples 28 to 32 and Comparative Examples 10 to 15>
For each composition, the solubility and the deviation (D1) of the spectral absorption spectrum of the single dye from the wavelength of λmax were evaluated. The results are summarized in Table 4 below.

<Examples 33 to 57, Comparative Examples 16 to 24>
The compositions were prepared as shown in Table 5 below.

<Evaluation of Examples 33 to 57 and Comparative Examples 16 to 24>
Solubility and near-infrared absorption stability (S1) were evaluated for each composition. The results are summarized in Table 6 below.

<Examples 58 to 63, Comparative Examples 25 to 31>
The compositions were prepared as shown in Table 7 below.

<Evaluation of Examples 58 to 63 and Comparative Examples 25 to 31>
For each composition, the solubility and the deviation (D1) of the spectral absorption spectrum of the single dye from the wavelength of λmax were evaluated. The results are summarized in Table 8 below.

From the above, by using a composition containing at least two of the compound represented by the general formula 2 or the compound represented by the general formula 5, the solubility can be improved and a film having excellent near-infrared absorption stability can be obtained. It turns out that it can be done.

When the polyimide resin produced by adding the above composition was used as a near-infrared cut filter with reference to Japanese Patent Application Laid-Open No. 2012-103340, it functioned as a near-infrared cut filter.

It was found that the polyimide resin produced by adding the above composition has high heat resistance.

The heat resistance of the polymethyl methacrylate resin produced by adding the composition was lower than that of the polyimide resin.

Further, when the resin film produced by adding the above composition and the dielectric multilayer film are combined in the same manner as in Examples [0277] to [0291] of Patent No. 6103152, the absorption waveform is further increased. Control became possible.

Further, an IR cut filter was produced by forming a dielectric multilayer film and a polyimide thin film to which a dye was added on a glass substrate by the following method.

(Formation of a near-infrared reflective dielectric multilayer film as the first dielectric multilayer film)
A 76 mm × 76 mm × 0.214 mm borosilicate glass substrate NF-50TX (hereinafter referred to as glass substrate A) manufactured by Asahi Glass was used with Asahi Glass hydrofluoroether-based solvent Asahiclean (registered trademark) AE3000 (trade name). , Washed with an ultrasonic cleaner for 10 minutes.
Using an IAD vacuum vapor deposition apparatus, a high refractive index film and a low refractive index film are alternately formed on one main surface of the cleaned glass substrate A obtained above, starting with a high refractive index film. A near-infrared reflective dielectric multilayer film (hereinafter referred to as a dielectric multilayer film R) as a first dielectric multilayer film having a total of 40 layers (total layer thickness: 5950 nm) was formed. TiO ₂ was used as the high refractive index material, and SiO ₂ was used as the low refractive index material.

(Dielectric layer film formation)
The glass substrate A having the dielectric multilayer film R obtained above was washed again with an ultrasonic cleaner for 20 minutes using Asahi Clean (registered trademark) AE3000, a hydrofluoroether-based solvent manufactured by Asahi Glass. On the surface of the washed glass substrate A obtained above opposite to the side having the dielectric multilayer film R, a vacuum vapor deposition apparatus was used to form a 30 nm layer made of _{Al 2} O ₃ and a 170 nm _{layer made of SiO 2.} A dielectric layer composed of two layers was formed in this order. The refractive index of the formed layer made of Al ₂ O ₃ was 1.60, and the refractive index of the formed layer _{made of SiO 2 was 1.45.}

(Formation of near-infrared absorbing layer)
As the polyimide resin, the composition is mixed with a 5 wt% methylene chloride / ethanol solution of the polyimide resin A at a ratio of 1 part by mass with respect to 100 parts by mass of the polyimide resin A, and then stirred and dissolved at room temperature. A coating solution was obtained.
The obtained coating liquid is applied on the dielectric layer of the glass substrate A having the dielectric multilayer film R and the dielectric layer on both main surfaces obtained above by a spin coater, and dried by heating at 100 ° C. for 5 minutes. A near-infrared absorbing layer having a film thickness of 1 μm was formed. In this way, a laminate in which the dielectric multilayer film R, the glass substrate A, the dielectric layer, and the near-infrared absorbing layer were laminated in this order was obtained.

Further, when an image sensor was prepared by using the composition as a mixed color filter with reference to Japanese Patent Application Laid-Open No. 2016-722666, it functioned as a CMOS sensor and a CCD sensor.

1 base material, 2 near-infrared absorbing layer, 3 optical film

Claims (10)

The compound represented by the following general formula 2 and at least one of the compounds represented by the following general formula 5 are contained, or at least two kinds of the compounds represented by the following general formula 5 are contained, and the general formula is described above. A composition containing two types of compounds, wherein the compound represented by the formula 2 is represented by the following general formula 6, and the compound represented by the general formula 5 is represented by the following general formula 7.

[In the general formula 2, A ₃ and A ₄ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A ₃ and A ₄ may further have a substituent. n is 1 or 2. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. If the molecule is not charge-neutral, it has a counter anion. ]

[In the general formula 5, A ₃ and A ₄ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A ₃ and A ₄ may further have a substituent. n is 1 or 2. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂₀ is one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₂₀ may further have a substituent. If the molecule is not charge-neutral, it has a counter anion. ]

[In the general formula 6, each A ₁₁ and A ₂₁ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₁₁ and A ₂₁ may further have a substituent. ]

[In the general formula 7, respectively A ₃₁ and A ₄₁ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₃₁ and A ₄₁ may further have a substituent. R ₁₁ is one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₁₁ may further have a substituent. Ctr ⁻ represents a counter anion. ] The compound represented by the following general formula 2 and at least one of the compounds represented by the following general formula 5 are contained, or at least two kinds of the compounds represented by the following general formula 5 are contained, and the general formula is described above. A composition containing two types of compounds, wherein the compound represented by the formula 2 is represented by the following general formula 8 and the compound represented by the general formula 5 is represented by the following general formula 9.

[In the general formula 2, A ₃ and A ₄ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A ₃ and A ₄ may further have a substituent. n is 1 or 2. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. If the molecule is not charge-neutral, it has a counter anion. ]

[In the general formula 5, A ₃ and A ₄ are each independently selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, and a heterocyclic group. A ₃ and A ₄ may further have a substituent. n is 1 or 2. R ₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R ₂₀ is one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₂₀ may further have a substituent. If the molecule is not charge-neutral, it has a counter anion. ]

[In general formula 8, respectively A ₁₂ and A ₂₂ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₁₂ and A ₂₂ may further have a substituent. ]

[In general formula 9, each A ₃₂ and A ₄₂ are independently an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, is one selected from the group consisting of heterocyclic group, A ₃₂ and A ₄₂ may further have a substituent. R ₁₂ is one selected from the group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group and an alkoxycarbonyl group, and R ₁₂ may further have a substituent. Ctr ⁻ represents a counter anion. ] The composition according to claim 1 or 2, wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 500,000 ppm. The composition according to claim 3 , wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 100,000 ppm. The composition according to claim 4 , wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 10000 ppm. The composition according to claim 5, wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 1000 ppm. The composition according to claim 6 , wherein the concentration of the compound represented by the general formula 2 or the general formula 5 is 1 ppm to 100 ppm. An optical film containing the composition according to any one of claims 1 to 7. A near-infrared cut filter including the optical film according to claim 8 and a dielectric multilayer film. An image sensor comprising the composition according to any one of claims 1 to 7.

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