KR20190132403A - Formation method of the composition for solid-state image sensors, and the infrared shielding film for solid-state image sensors - Google Patents

Abstract

The present invention provides a composition for a solid-state imaging device comprising an inorganic compound, a polymer, an organic dye, and a solvent, wherein the amine value of the polymer is 90 mgKOH / g or more and 200 mgKOH / g or less, and the solvent has a solubility parameter of 8.8 or more and 12.0 or less. Including a specific solvent, content of the said specific solvent with respect to the said whole composition for solid-state image sensors is 40 mass% or more and 90 mass% or less, The solubility of the said organic dye with respect to the said solvent in 20 degreeC, 0.1 Mpa And 2 mass% or more, the composition for solid-state image sensors.

Description

Formation method of the composition for solid-state image sensors, and the infrared shielding film for solid-state image sensors

This invention relates to the composition for solid-state image sensor, and the formation method of the infrared shielding film for solid-state image sensors.

BACKGROUND ART A video camera, a digital camera, a mobile phone having a camera function, and the like are mounted with solid-state imaging devices such as a charge-coupled device (CCD) image sensor and a complementary MOS (CMOS) image sensor. The sensitivity of the photodiode with which these solid-state image sensors are equipped extends from a visible region to an infrared region. For this reason, in a solid-state image sensor, the filter for blocking an infrared ray is provided. By this infrared cut filter, the sensitivity of the solid-state image sensor can be corrected to be close to human visibility.

The said infrared cut filter contains the organic pigment | dye and an inorganic compound as an infrared shielding agent (refer Unexamined-Japanese-Patent No. 2013-137337 and Unexamined-Japanese-Patent No. 2013-151675). An infrared cut filter is normally formed by coating the composition containing an infrared shielding agent on a board | substrate. In such an infrared cut filter, the coating film of the said composition functions as a film | membrane which shields infrared rays.

Japanese Patent Publication No. 2013-137337 Japanese Patent Publication No. 2013-151675

In the composition for solid-state image sensors, it is required to form the optical filter which has favorable visible light transmittance and infrared shielding property. In addition, the composition for a solid-state image sensor is required to have high dispersion stability and stability over time. When these are inadequate, the generation of a defect in the optical filter (infrared shielding film) to be obtained and a decrease in productivity are caused. It also affects visible light transmission and infrared shielding properties. Moreover, although the patterned infrared shielding film may be formed by exposing and developing to a coating film, in this case, it is required to have favorable patterning property in the composition for solid-state image sensors to be used.

This invention is made | formed based on the above circumstances, The objective is the solid-state imaging which can form the optical filter for solid-state imaging elements which is high in dispersion stability and aging stability, and has few defects and has favorable visible light transmittance and infrared shielding property. It is providing the composition for element and the formation method of the shielding film for solid-state image sensors using this composition for solid-state image sensors.

In order to solve the said subject, the invention made the composition for solid-state image sensors containing an inorganic compound, a polymer, an organic pigment | dye, and a solvent, The amine value of the said polymer is 90 mgKOH / g or more and 200 mgKOH / g or less, The solubility parameter contains the specific solvent of 8.8 (cal / cm <3>) ^1/2 or more and 12.0 (cal / cm <3>) ^1/2 or less, and content of the said specific solvent with respect to the said whole composition for solid-state image sensors is 40 mass% or more. It is 90 mass% or less, and the solubility of the said organic dye with respect to the said solvent in 20 degreeC and 0.1 Mpa is a composition for solid-state image sensors which is 2 mass% or more.

Another invention made in order to solve the said subject is a method of forming the infrared shielding film for solid-state image sensors which comprises the process of forming a coating film in the one surface side of a board | substrate, and forms the said coating film with the said composition for solid-state image sensors.

According to this invention, the composition for solid-state image sensors which can form the optical filter for solid-state image sensors which has high dispersion stability and time-lapse stability, has few defects, and has favorable visible light transmittance and infrared shielding property, and this composition using the composition for solid-state image sensors The formation method of the shielding film for solid-state image sensors can be provided.

EMBODIMENT OF THE INVENTION Hereinafter, the formation method of the composition for solid-state image sensors and the infrared shielding film for solid-state image sensors which concern on one Embodiment of this invention is demonstrated in detail.

<Composition for Solid-State Imaging Device>

The composition for solid-state imaging devices (henceforth simply a "composition") which concerns on one Embodiment of this invention contains an [A] inorganic compound, a [B] polymer, a [C] organic dye, and a [D] solvent. . The polymer (B) is a polymer having an amine number of 90 mgKOH / g or more and 200 mgKOH / g or less. [D] The solvent is a solvent having a solubility parameter (hereinafter also referred to as "SP value") of 8.8 (cal / cm 3) ^1/2 or more and 12.0 (cal / cm 3) ^1/2 or less (hereinafter, "[D1] Solvent. "). Content of the whole composition for solid-state image sensors of [D1] solvent is 40 mass% or more and 90 mass% or less. Moreover, the solubility of the [C] organic dye with respect to the [D] solvent in 20 degreeC and 0.1 Mpa is 2 mass% or more.

In the said composition, the dispersibility of the [A] inorganic compound improves by using the [B] polymer which has a specific amine number. Moreover, the dispersibility of the [A] inorganic compound can be improved by containing a predetermined amount of the solvent [D1] which has a specific solubility parameter. When the dispersibility of the compound [A] is high, the visible light transmittance and the infrared shielding property of the optical filter obtained are also good. In addition, by combining the highly soluble [C] organic dye and the [D] solvent, the visible light transmittance, infrared ray shielding property, and the like are further improved. Therefore, according to the said composition, the optical filter for solid-state image sensors which have high dispersion stability and time-lapse stability, few defects, and have favorable visible light transmittance and infrared shielding property can be formed.

It is preferable that the said composition further contains a [E] polymerizable compound, and it is further preferable to contain a [F] polymerization initiator. The composition may also contain other components. Hereinafter, each component is explained in full detail.

([A] inorganic compound)

The inorganic compound (A) is a component that functions as an infrared ray shielding agent. The inorganic compound (A) may be a so-called pigment. The inorganic compound (A) preferably has a maximum absorption wavelength in a range of 800 nm or more and 2,000 nm or less. The inorganic compound (A) is in particulate form, and is dispersed and present in the composition.

The inorganic compound (A) is preferably an oxide of a metal or semimetal (silicon or the like). Specifically, the inorganic oxide (A) is preferably cesium tungsten oxide, quartz, magnetite, alumina, titania, zirconia, spinel or a combination thereof. These inorganic compounds can be used individually by 1 type or in mixture of 2 or more types.

As the inorganic compound (A), cesium tungsten oxide is preferable among these. Cesium tungsten oxide is an infrared shielding agent which has high absorption (namely, high shielding against infrared rays), and low absorption with respect to infrared rays (in particular, infrared rays whose wavelength is about 800 nm or more and 1,200 nm or less). Therefore, the infrared filter can be improved, while the optical filter obtained by using cesium tungsten oxide maintains favorable visible light transmittance.

Cesium tungsten oxide can be represented by following formula (a), for example.

Cs _x WO _y ... (a)

In formula (A), it is 0.001 <= x <1.1. 2.2≤y≤3.0.

In the formula (a), when x is 0.001 or more, the infrared rays can be sufficiently shielded. 0.01 is preferable and, as for the minimum of x, 0.1 is more preferable. On the other hand, when x is 1.1 or less, generation of an impurity phase in cesium tungsten oxide can be more reliably avoided. 1 is preferable and, as for the upper limit of x, 0.5 is more preferable.

When y is 2.2 or more in said Formula (a), the chemical stability as a material can be improved more. As for the minimum of y, 2.5 is preferable. On the other hand, when y is 3.0 or less, infrared rays can be shielded sufficiently.

Specific examples of cesium tungsten oxide represented by the formula (a), and the like Cs _0.33 WO _3.

[A] The inorganic compound is preferably fine particles. As an upper limit of the average particle diameter (D50) of the inorganic compound (A), 500 nm is preferable, 200 nm is more preferable, 50 nm is more preferable, 30 nm is more preferable, 20 nm is still more preferable. Visible light transmittance can be improved more because an average particle diameter is below the said upper limit. On the other hand, from the reasons of ease of handling at the time of manufacture, etc., the average particle diameter of [A] inorganic compound is 1 nm or more normally, and 10 nm or more may be sufficient. In addition, this average particle diameter (D50) is a secondary particle diameter in the said composition.

Although an inorganic compound (A) can also be synthesize | combined by a well-known method, it can obtain as a commercial item. For example, cesium tungsten oxide is also available as a dispersion of cesium tungsten oxide fine particles such as "YMF-02" of Sumitomo Kinzoku Kozan.

As a minimum of content of the [A] inorganic compound in the total solid in the said composition, 1 mass% is preferable, 10 mass% is more preferable, 20 mass% is more preferable, 30 mass% is still more preferable Do. On the other hand, as an upper limit of this content, 70 mass% is preferable, and 60 mass% is more preferable. By making content of the (A) inorganic compound into the said range, the visible light transmittance and infrared ray shielding property of the optical filter obtained become a more favorable balance. Moreover, dispersion stability and time-lapse stability of the said composition can be made more favorable. In addition, all solid content means all components other than [D] solvent.

([B] polymer)

[B] A polymer is a component which improves dispersibility, such as an inorganic compound [A]. The polymer (B) may contain one polymer or may be a mixture of two or more polymers having the same or different amine numbers. The polymer whose amine value is 0 mgKOH / g is not contained in the [B] polymer as a mixture of several types of polymers.

The lower limit of the amine value of the polymer (B) is 90 mgKOH / g, preferably 110 mgKOH / g, and more preferably 130 mgKOH / g. In addition, the upper limit of this amine titer is 200 mgKOH / g. By using the polymer which has such an amine number, the dispersibility of [A] inorganic compound improves and the visible light transmittance and infrared shielding property of the optical filter obtained can be improved more. In addition, "amine value" is mg number of HCl and equivalent KOH which are required in order to neutralize 1g of polymer solid content. As the polymer [B], when a plurality of polymers having different amine values are mixed and used, the amine value of the polymer [B] is a weighted average value.

It is preferable that the polymer (B) is a block copolymer. As a block copolymer, the block copolymer which has the A block which has a functional group containing a nitrogen atom, and the B block which has a solvent solubility is preferable. The functional group containing the nitrogen atom of A block shows the favorable adsorption property with respect to the [A] inorganic compound. Therefore, the dispersibility of [A] inorganic compound can be improved more by using the block copolymer which has A block and B block.

It is preferable that A block has a structural unit represented by following formula (1), for example.

In formula (1), X is a bivalent coupling group. R ¹ is a hydrogen atom or a methyl group. R ² and R ³ are each independently a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, or R ² and R ³ are bonded to each other to form a ring structure with the nitrogen atom to which they are bonded; .

As the X, a methylene group, having 2 to 10 carbon atoms in the alkylene group, arylene group, -CONH-R ⁷ - there may be mentioned groups represented by (*), such as (-) group, expressed as, -COO-R ⁸ . R ⁷ and R ⁸ are each independently a methylene group, an alkylene group having 2 to 10 carbon atoms, or an alkyleneoxyalkylene group having 2 to 10 carbon atoms. (*) Represents the binding site with N. As X, group represented by -COO-R <^8> -is preferable, and as R <^8> , a C2-C6 alkylene group is preferable.

As R <^2> and R <^3> , a linear hydrocarbon group is preferable, a C1-C5 linear hydrocarbon group is more preferable, and a methyl group, an ethyl group, and a propyl group are more preferable.

As a monomer which gives the structural unit represented by said formula (1), dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, diethylaminopropyl (meth ) Acrylates and the like.

A block may contain structural units other than the structural unit represented by said formula (1). As a content rate of the A block in a block copolymer, 30 mass% or more and 70 mass% or less are preferable, for example.

It is preferable that B block has a structural unit represented by following formula (2), for example.

In formula (2), R <^4> is a C2-C4 alkylene group each independently. R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. R ⁶ is a hydrogen atom or a methyl group. n is an integer from 1 to 150.

As R ⁴ , an ethylene group and a methyl ethylene group are preferable. As R <^5> , a methyl group, an ethyl group, a propyl group, and a butyl group are preferable. 20 is preferable, as for the upper limit of n, 10 is more preferable, and 5 is still more preferable.

As a monomer which gives the structural unit represented by said Formula (2), polyethyleneglycol (n = 1-5) methyl ether (meth) acrylate, polyethyleneglycol (n = 1-5) ethyl ether (meth) acrylate, Polyethylene glycol (n = 1 to 5) propyl ether (meth) acrylate, polypropylene glycol (n = 1 to 5) methyl ether (meth) acrylate, polypropylene glycol (n = 1 to 5) ethyl ether (meth) Acrylate, polypropylene glycol (n = 1 to 5) propyl ether (meth) acrylate, and the like.

B block may contain structural units other than the structural unit represented by said formula (2). As another structural unit which the B block may contain, the structural unit derived from a (meth) acrylic acid ester is mentioned. Concretely, as a monomer which gives another structural unit, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl Hexyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, etc. are mentioned.

As a content rate of the B block in a block copolymer, 30 mass% or more and 70 mass% or less are preferable, for example.

As a minimum of the average molecular weight of the polymer [B], it is 3,000, for example, and 6,000 is preferable. In addition, as this upper limit, it is 30,000, for example, 20,000 is preferable.

The block copolymer can be synthesized by a conventionally known method. Moreover, a commercial item can also be used for a block copolymer and another [B] polymer. The polymer (B) may be a dispersant that coats at least a part of the surface of the inorganic compound [A] in the composition.

The lower limit of the content of the polymer (B) is preferably 5 parts by mass, more preferably 10 parts by mass, and even more preferably 20 parts by mass with respect to 100 parts by mass of the [A] inorganic compound. On the other hand, 200 mass parts is preferable, as for the upper limit of this content, 100 mass parts is more preferable, and 60 mass parts is more preferable.

([C] organic pigment)

The organic dye [C] is a component that functions as an infrared ray shielding agent together with the inorganic compound [A]. By using a combination of the inorganic compound (A) and the organic pigment (C), good visible light transmittance and infrared ray shielding properties can be exhibited. [C] The organic dye is dissolved in the solvent [D].

Examples of the organic pigment (C) include organic dyes and organic pigments, but are preferably organic dyes. By using an organic dye, the solubility to a solvent [D] becomes high and generation | occurrence | production of agglomerated foreign material can be suppressed more.

The solubility of the [C] organic dye in the solvent [D] at 20 ° C and 0.1 MPa is 2% by mass or more. For this reason, the said composition can obtain the optical filter which has the solubility of the [C] organic pigment | dye, high dispersion stability and stability with time, and also a few defects. The said solubility means the density | concentration (mass%) of the [C] organic dye in the solution which the maximum amount of the [C] organic dye melt | dissolved with respect to the [D] solvent, ie, saturated solution. When the solvent (D) is a mixed solvent, it is the concentration of the organic dye [C] in a saturated solution using the mixed solvent as a solvent. The solubility of this [C] organic pigment | dye can be achieved by the combination of the [C] organic pigment | dye and [D] solvent. Moreover, it does not specifically limit as an upper limit of this solubility, For example, what is necessary is just 50 mass%.

The organic dye (C) preferably has a maximum absorption wavelength in a range of 600 nm or more and 1,000 nm or less. As for the minimum of this maximum absorption wavelength, 650 nm is more preferable. On the other hand, this upper limit is more preferably 900 nm, still more preferably 850 nm. By using [C] organic pigment | dye which has such maximum absorption wavelength, the visible light transmittance and infrared shielding property of an optical filter obtained can be made more favorable.

As organic dye (C), a conventionally well-known organic pigment can be suitably selected and used in the range which satisfy | fills the said solubility. [C] As organic dyes, diiminium compounds, squarylium compounds, cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, aluminium compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pi A rolopyrrole compound, an oxonol compound, a croconium compound, a hexapyrin compound or a combination thereof can be used. [C] As the organic dye, one containing a phthalocyanine compound is preferable. The phthalocyanine compound is excellent in color tone, heat resistance, light resistance, and the like.

[C] An organic pigment can be used individually by 1 type or in combination of 2 or more types. It is preferable that the said composition contains 2 or more types of [C] organic pigment | dyes. Furthermore, it is more preferable to contain 3 or more types of [C] organic pigment | dyes. The visible light transmittance and infrared ray shielding property of the optical filter obtained by using combining multiple types of [C] organic pigment | dye can be made more favorable. On the other hand, when using several types of organic dye conventionally, dispersion stability, time-lapse stability, etc. may fall. However, according to the said composition, even if it uses multiple types of organic pigment | dye, favorable dispersion stability and time-lapse stability can be exhibited. The upper limit of the number of kinds of the [C] organic dye to be used is not particularly limited, and for example, may be 10, 5 or 3 may be used.

As a minimum of content of the [C] organic dye which occupies for the total solid in the said composition, 0.1 mass% is preferable, 0.5 mass% is more preferable, 1 mass% is further more preferable. On the other hand, as an upper limit of this content, 30 mass% is preferable, 15 mass% is more preferable, 10 mass% is further more preferable. By making content of the organic dye (C) into the said range, the visible light transmittance and infrared ray shielding property of the optical filter obtained will be a more favorable balance.

([D] solvent)

The solvent [D] is a component that functions as a dispersion medium for the inorganic compound [A] and further dissolves the [C] organic dye.

The solvent [D] includes the solvent [D1]. The solvent [D1] is a solvent having an SP value of 8.8 (cal / cm 3) ^1/2 or more and 12.0 (cal / cm 3) ^1/2 or less. As a minimum of the said SP value, 9.5 (cal / cm <3>) ^1/2 is preferable. On the other hand, 11.0 (cal / cm <3>) ^1/2 is preferable as this upper limit, and 10.5 (cal / cm <3>) ^1/2 is more preferable. By using [D1] solvent which has SP value of such a specific range, the dispersibility of [A] inorganic compound and the solubility of [C] organic dye can be improved. Here, SP value is RF Fedors, Polym. Eng. Sci. It is a value calculated | required by the following Fedors formula described in 14,147 (1974).

Expression of Fedors:

SP value (δ) = (E _v / v) _1/2 = (ΣΔe _i / ΣΔv _i ) _1/2

E _v : evaporation energy

v: molar volume

Δe _i : The evaporation energy of atoms or groups of components

Δv _i : molar volume of each atom or group of atoms

Examples of the solvent [D1] include n-propanol (SP value: 11.8), 1,2,5,6-tetrahydrobenzyl alcohol (SP value: 11.3), diethylene glycol ethyl ether (SP value: 10.9), 3-methoxybutanol (SP value: 10.9), triacetin (SP value: 10.2), propylene glycol monomethyl ether (SP value: 10.2), cyclopentanone (SP value: 10.0), γ-butyrolactone (SP Value: 9.9), cyclohexanone (SP value: 9.9), propylene glycol-n-propyl ether (SP value: 9.8), propylene glycol-n-butyl ether (SP value: 9.7), dipropylene glycol methyl ether (SP Value: 9.7), 1,4-butanediol diacetate (SP value: 9.6), 3-methoxybutyl acetate (SP value: 8.7), propylene glycol diacetate (SP value: 9.6), ethyl lactate (SP value: 9.6), ε-caprolactone (SP value: 9.6), 1,3-butylene glycol diacetate (SP value: 9.5), dipropylene glycol-n-propyl ether (SP value: 9.5), 1,6-hexane Diol diacetate (SP value: 9.5), dipropylene glycol-n-butyl ether (SP value: 9.4), tri Propylene glycol methyl ether (SP value: 9.4), tripropylene glycol-n-butyl ether (SP value: 9.3), cyclohexanol acetate (SP value: 9.2), diethylene glycol ethyl ether acetate (SP value: 9.0), Ethylene glycol methyl ether acetate (SP value: 9.0), diethylene glycol monobutyl ether acetate (SP value: 8.9), ethylene glycol monobutyl ether acetate (SP value: 8.9), toluene (SP value: 8.9), methyl acetate ( SP value: 8.8), and the like. In addition, the unit ((cal / cm <3>) ^1/2 ) of SP value is abbreviate | omitted suitably. The solvent [D1] can be used alone or in combination of two or more thereof.

The minimum of content of the solvent [D1] with respect to the said whole composition is 40 mass%, 50 mass% is preferable, 60 mass% is more preferable, 65 mass% is more preferable. By making content of a solvent [D1] more than the said minimum, the dispersibility of the [A] inorganic compound and the solubility of the [C] organic dye become higher. On the other hand, the upper limit of the content of the solvent [D1] is 90% by mass, preferably 80% by mass, and more preferably 75% by mass. By making content of a solvent [D1] below the said upper limit, sufficient amount of another component can be mix | blended, that is, by making content of the solvent [D1] into the said range, the dispersion stability and time-lapse stability of the said composition can be improved, By the said composition, the optical filter for solid-state image sensors which has few defects and has favorable visible light transmittance and infrared shielding property can be formed.

The solvent [D] may contain a solvent [D2] other than the solvent [D1]. The solvent [D2] is a solvent having an SP value of less than 8.8 (cal / cm 3) ^1/2 or more than 12.0 (cal / cm 3) ^1/2 . [D2] As the solvent, an SP value of less than 8.8 (cal / cm 3) ^1/2 or more than 12.0 (cal / cm 3) ^1/2 (poly) alkylene glycol monoalkyl ether, (cyclo) alkyl alcohol, ketoalcohol ( Poly) alkylene glycol monoalkyl ether acetate, ketone, diacetate, carboxylic acid ester, lactam, aromatic hydrocarbon and the like. For example, propylene glycol monomethyl ether acetate (SP value: 8.7) etc. are mentioned as SP value whose (poly) alkylene glycol monoalkyl ether of less than 8.8 (cal / cm <3>) ^1/2 .

As SP value of the solvent [D2], less than 8.8 (cal / cm 3) ^1/2 is preferable. Moreover, as a minimum of SP value of [D2] solvent, 7 (cal / cm <3>) ^1/2 is preferable, 8 (cal / cm <3>) ^1/2 is more preferable, 8.5 (cal / cm <3>) ^1/2 is More preferred.

As a minimum of content of the solvent [D1] in the solvent [D], 50 mass% is preferable, 70 mass% is more preferable, 80 mass% is more preferable, 90 mass% is still more preferable. The solvent [D] may be substantially composed of only the solvent [D1]. By making content of the solvent [D1] in the solvent [D] more than the said minimum, the dispersibility of the [A] inorganic compound and the solubility of the [C] organic pigment | dye become higher, and the effect of this invention is fully exhibited.

It is preferable that the solvent (D) contains the solvent which has a cyclic structure. By using a solvent having a cyclic structure, solubility and dispersibility become better. The solvent having a cyclic structure may be a solvent of [D1] or a solvent of [D2], but is preferably a solvent of [D1]. A carbocyclic ring or a heterocyclic ring may be sufficient as the said cyclic structure. In addition, the cyclic structure may be polycyclic or monocyclic. In addition, the cyclic structure may be an aromatic ring or an alicyclic ring.

As the solvent having a cyclic structure, cyclic ketones, cyclic ethers, lactones (γ-butyrolactone, ε-caprolactone and the like), lactams, aromatic hydrocarbons (toluene and the like) and combinations thereof are preferable. Among these, cyclic ketones, lactones and aromatic hydrocarbons are preferable, and cyclic ketones and lactones are more preferable.

Cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, etc. are mentioned as cyclic ketone. Among these, cyclopentanone, cyclohexanone, and cycloheptanone are preferable, and cyclopentanone and cyclohexanone are more preferable.

Tetrahydrofuran, tetrahydropyran, etc. are mentioned as cyclic ether.

As lactone, (gamma) -butyrolactone, (epsilon) -caprolactone, etc. are mentioned, and (gamma) -butyrolactone is preferable.

Examples of the lactam include pentano-4-lactam, 5-methyl-2-pyrrolidinone, hexano-6-lactam, 6-hexanelactam, and the like.

As a minimum of content of the solvent which has a cyclic structure in (D) solvent, 50 mass% is preferable, 70 mass% is more preferable, 80 mass% is more preferable, 90 mass% is still more preferable. The solvent (D) may be comprised only with the solvent which has a substantially cyclic structure. By making content of the solvent which has a cyclic structure in the solvent (D) more than the said minimum, the dispersibility of the [A] inorganic compound and the solubility of the [C] organic pigment | dye become higher, and the effect of this invention is fully exhibited.

As a minimum of solid content concentration (total concentration of each component except [D] solvent) in the said composition, 5 mass% is preferable and 10 mass% is more preferable. On the other hand, as an upper limit of this solid content concentration, 50 mass% is preferable and 40 mass% is more preferable. By making solid content concentration into the said range, dispersibility, stability, applicability | paintability, etc. become more favorable.

([E] polymerizable compound)

When the composition contains the polymerizable compound (E), good curability and the optical filter obtained can exhibit good heat resistance and the like. The polymerizable compound [E] refers to a compound having two or more polymerizable groups. As a group which can superpose | polymerize, an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, an N-alkoxy methylamino group, etc. are mentioned, for example. The polymerizable compound (E) may be a polymer or a monomer, but is preferably a monomer. As the polymerizable compound (E), a compound having two or more (meth) acryloyl groups and a compound having two or more N-alkoxymethylamino groups is preferable, and a compound having two or more (meth) acryloyl groups is more preferable. desirable. The polymerizable compound (E) can be used alone or in combination of two or more thereof.

Examples of the compound having two or more (meth) acryloyl groups include polyfunctional (meth) acrylates, caprolactone-modified polyfunctional (meth) acrylates, and alkylenes, such as reactants of aliphatic polyhydroxy compounds and (meth) acrylic acid. Reactant of polyfunctional urethane (meth) acrylate which is an oxide-modified polyfunctional (meth) acrylate, (meth) acrylate which has a hydroxyl group, and a polyfunctional isocyanate, etc., (meth) acrylate which has a hydroxyl group, and an acid anhydride The polyfunctional (meth) acrylate which has a carboxyl group which is these etc. is mentioned.

Here, as said aliphatic polyhydroxy compound, bivalent aliphatic polyhydroxy compounds, such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylol propane, pentaerythritol, and dipentaerythritol Trivalent or more aliphatic polyhydroxy compounds, such as these, are mentioned. As (meth) acrylate which has the said hydroxyl group, 2-hydroxyethyl (meth) acrylate, trimethylolpropanedi (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta, for example (Meth) acrylate, glycerol dimethacrylate, etc. are mentioned. As said polyfunctional isocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, etc. are mentioned, for example. Examples of the acid anhydride include anhydrides of dibasic acids such as succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride and hexahydro phthalic anhydride, pyromellitic anhydride, and biphenyltetracarboxylic acid. Tetrabasic dianhydrides such as dianhydride and benzophenone tetracarboxylic dianhydride;

As a specific example of a compound which has two or more (meth) acryloyl groups, For example, (omega) -carboxypolycaprolactone mono (meth) acrylate, ethylene glycol (meth) acrylate, 1, 6- hexanediol di (meth) Acrylate, 1,9-nonanediol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, bisphenoxyethanol Fluorenedi (meth) acrylate, dimethyloltricyclodecanedi (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl methacrylate, 2- (2'-vinyloxyethoxy ) Ethyl (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, di Pentaeryt Tol hexa (meth) acrylate, tri (2- (meth) acryloyloxyethyl) phosphate, ethylene oxide modified dipentaerythritol hexaacrylate, succinic acid modified pentaerythritol triacrylate, urethane (meth) acrylate compound Etc. can be mentioned.

Among the compounds having two or more (meth) acryloyl groups, polyfunctional (meth) acrylates are preferred, and polyfunctional (meth) acrylates having three to ten (meth) acryloyl groups are more preferred. Do. Specifically, trimethylol propane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol hexaacrylate are preferable.

As a compound which has two or more N-alkoxy methylamino groups, the compound etc. which have a melamine structure, a benzoguanamine structure, a urea structure, etc. are mentioned, for example. Specific examples of the compound having two or more N-alkoxymethylamino groups include N, N, N ', N', N ", N" -hexa (alkoxymethyl) melamine, N, N, N ', N'-tetra ( Alkoxymethyl) benzoguanamine, N, N, N ', N'- tetra (alkoxymethyl) glycoluril, etc. are mentioned.

As a minimum of content of the [E] polymeric compound in the total solid in the said composition, 5 mass parts is preferable, 10 mass parts is more preferable, 20 mass parts is more preferable. On the other hand, as an upper limit of this content, 60 mass% is preferable, and 50 mass% is more preferable.

([F] polymerization initiator)

[F] The polymerization initiator is a component that initiates the polymerization reaction of the [E] polymerizable compound. [F] Although a polymerization initiator, a thermal polymerization initiator, etc. are mentioned as a polymerization initiator, a photoinitiator is preferable. Thereby, photosensitive (radiation-sensitive) can be provided to the said composition. A photoinitiator means the compound which generate | occur | produces the active species which can start superposition | polymerization of [E] polymeric compound by exposure of radiation, such as visible light, an ultraviolet-ray, an ultraviolet-ray, an electron beam, and X-rays. [F] The polymerization initiator can be used 1 type or in mixture of 2 or more types.

[F] As the polymerization initiator, for example, thioxanthone compound, acetophenone compound, biimidazole compound, triazine compound, O-acyl oxime compound, onium salt compound, benzoin compound, benzophenone compound , α-diketone compounds, polynuclear quinone compounds, diazo compounds, imide sulfonate compounds, onium salt compounds and the like. Among these, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds or O-acyl oxime compounds are preferable, and O-acyl oxime compounds are more preferable.

As a thioxanthone type compound, thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2, 4- dichloro thioxanthone, 2, 4- dimethyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- diisopropyl thioxanthone, etc. are mentioned.

Examples of the acetophenone compounds include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.

As a biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetraphenyl- 1,2'-biimidazole, 2,2'-bis (2 , 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like.

In addition, when using a biimidazole type compound, using a hydrogen donor together is preferable at the point which can improve a sensitivity. The "hydrogen donor" here means the compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure. As a hydrogen donor, For example, Mercaptan-type hydrogen donors, such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole; Amine hydrogen donors, such as 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone, are mentioned.

Examples of the triazine-based compound include the compounds described in paragraphs [0063] to [0065] of JP-A-57-6096 and JP-A-2003-238898.

Examples of the O-acyl oxime compound include 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and ethanone-1- [9-ethyl-6- (2 -Methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3- Dioxolanyl) methoxybenzoyl} -9H-carbazol-3-yl] -1- (O-acetyloxime) and the like. As a commercial item of O-acyl oxime type compound, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), OXE-03, OXE-04 (above, BASF Corporation), etc. can also be used.

When a photoinitiator is used, a sensitizer can also be used together. As such a sensitizer, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylamino acetophenone, 4-dimethylamino propiophenone, for example. Ethyl 4-dimethylaminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl ) Coumarin, 4- (diethylamino) chalcone, and the like.

1 mass part is preferable with respect to 100 mass parts of [E] polymeric compounds, and, as for the minimum of content of [F] polymerization initiator, 5 mass parts is more preferable. On the other hand, as an upper limit of this content, 100 mass parts is preferable and 40 mass parts is more preferable.

(Binder resin)

The resin may further contain the binder resin. In addition, a polymer [B] is not contained in binder resin. Although it does not specifically limit as binder resin, It is preferable that it is resin which has acidic functional groups, such as a carboxyl group and a phenolic hydroxyl group. Especially, the polymer (henceforth a "carboxy group containing polymer") which has a carboxy group is preferable. As the carboxyl group-containing polymer, for example, an ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (1)") having one or more carboxyl groups and other copolymerizable ethylenically unsaturated monomer (hereinafter referred to as "unsaturated monomer (2)"). The copolymer of the above) is mentioned.

Examples of the unsaturated monomer (1) include (meth) acrylic acid, maleic acid, maleic anhydride, monosuccinic acid [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate. and p-vinyl benzoic acid.

As said unsaturated monomer (2), for example,

N-position substituted maleimide, such as N-phenylmaleimide and N-cyclohexyl maleimide,

Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether, acenaphthylene,

Methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate , Polyethylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polypropylene glycol (polymerization degree 2 to 10) methyl ether (meth) acrylate, polyethylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, poly Propylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) Ethylene oxide modified (meth) acrylate of acrylate, dicyclopentenyl (meth) acrylate, glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, paracumylphenol, glycidyl (meth ) Acrylate, 3,4- (Meth) acrylic acid esters such as epoxycyclohexylmethyl (meth) acrylate, 3-[(meth) acryloyloxymethyl] oxetane, and 3-[(meth) acryloyloxymethyl] -3-ethyloxetane ,

Cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-ylvinyl ether, pentacyclopentadedecanylvinyl ether, 3- (vinyloxymethyl) -3-ethyloxetane Vinyl ethers such as

The macromonomer which has a mono (meth) acryloyl group at the terminal of polymer molecular chains, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane, etc. are mentioned.

Moreover, as binder resin, you may use the carboxyl group-containing polymer which has a polymerizable unsaturated bond, such as a (meth) acryloyl group, in a side chain. Moreover, polysiloxane etc. can also be used as binder resin.

(additive)

The said composition may contain various additives as needed.

As an additive, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, an aggregation inhibitor, a residue improver, a developability improver, etc. are mentioned, for example.

As surfactant, a fluorine surfactant, silicone surfactant, etc. are mentioned. As content of surfactant which occupies for the total solid in the said composition, it can be 0.01 mass% or more and 5 mass% or less, for example.

Examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2 -Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimeth Oxysilane, etc. are mentioned.

As antioxidant, 2, 2- thiobis (4-methyl-6-t-butylphenol), 2, 6- di-t- butylphenol, pentaerythritol tetrakis [3- (3, 5- di-t -Butyl-4-hydroxyphenyl) propionate], 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) -propionyloxy] -1,1 -Dimethylethyl] -2,4,8,10-tetraoxa-spiro [5.5] undecane, thiodiethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate ], And the like. As content of the antioxidant which occupies for the total solid in the said composition, it can be 0.01 mass% or more and 5 mass% or less, for example.

As a ultraviolet absorber, 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxy benzophenones, etc. are mentioned.

Examples of the aggregation inhibitor include sodium polyacrylate.

As the residue improving agent, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1 , 2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol and the like.

As the developability improving agent, agents such as succinic acid mono [2- (meth) acryloyloxyethyl], phthalic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) acrylate Etc. can be mentioned.

(Production method)

It does not specifically limit as a manufacturing method of the said composition, It can manufacture by mixing each component. For example, first, a dispersion liquid containing the inorganic compound [A], the polymer [B], and the solvent [D] is prepared, and a method of adding and mixing the [C] organic dye or other components to the dispersion may be employed. Can be. At this time, you may also add a solvent [D]. A dispersion liquid or the said composition can perform a filtration process as needed and can remove a aggregate.

<Method of Forming Infrared Shielding Film for Solid-State Imaging Device>

The method for forming an infrared shielding film for solid-state imaging device according to an embodiment of the present invention,

Step of forming a coating film on one side of the substrate (Step 1)

And

The said coating film is formed with the said composition for solid-state image sensors.

The formation method is

Irradiating at least a portion of the coating film with radiation (step 2);

Process of developing the said coating film after irradiation (process 3)

It is preferable to further provide.

According to the said formation method, the optical filter for solid-state image sensors which has few defects and has favorable visible light transmittance and infrared shielding property can be formed by using the composition with high dispersion stability and time stability. Moreover, when the said formation method is equipped with the process 2 and the process 3, it has favorable patterning property.

(Step 1)

In step 1, a coating film is formed on one surface side of the substrate (support) using the composition. As said board | substrate, a glass substrate, a synthetic resin substrate, etc. are mentioned. In addition, the shape of a board | substrate is not limited to a plate. In addition, when an infrared shielding film is built into the solid-state image sensor mentioned later, the transparent substrate, microlens, a color filter, etc. which are a component of a solid-state image sensor correspond to the said board | substrate.

Formation of a coating film can be normally performed by application | coating of the said composition. As the coating, an appropriate coating method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method (slit coating method), a bar coating method, or the like can be adopted.

After coating, the coating film is formed by prebaking to evaporate the solvent. On the conditions of the heat drying in the said prebaking, it is about 70 degreeC or more and 110 degrees C or less, for example, 1 minute or more and about 10 minutes or less.

(Process 2)

In step 2, at least a part of the coating film is irradiated with radiation. As a light source of the radiation used for exposure of a coating film, lamp light sources, such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, an argon ion laser, a YAG laser, Laser light sources, such as an XeCl excimer laser and a nitrogen laser, etc. are mentioned. As the exposure light source, an ultraviolet LED can also be used. The wavelength is preferably in the range of 190 nm or more and 450 nm or less. The exposure dose of radiation is generally about 10 J / m 2 or more and 50,000 J / m 2 or less.

(Process 3)

In step 3, the coating film after irradiation with radiation is developed. As the developer, an alkaline developer or an organic solvent developer is common. In addition, after image development, water washing is carried out normally.

As the alkaline developer, for example, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide (TMAH), choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, Aqueous solutions, such as 1, 5- diazabicyclo- [4.3.0] -5-nonene, are preferable. A suitable amount of water-soluble organic solvents, such as methanol and ethanol, surfactant, etc. can also be added to alkaline developing solution.

As an organic solvent developing solution, acetone, methyl ethyl ketone, 2-octanone, 2-nonanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-hexanone, 3-hexanone, diisobutyl ketone Ketones such as methylcyclohexanone, acetophenone, methyl acetophenone, propyl acetate, butyl acetate, isobutyl acetate, amyl acetate, butenyl acetate, isoamyl acetate, propyl formate, butyl formate, isobutyl formate, and amyl formate Isoamyl formate, methyl valerate, methyl pentenate, methyl crotonate, ethyl crotonate, methyl propionate, ethyl propionate, ethyl 3-ethoxypropionate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, isobutyl lactate Amyl lactate, isoamyl lactate, methyl 2-hydroxyisobutyrate, ethyl 2-hydroxyisobutyrate, methyl benzoate, ethyl benzoate, phenyl acetate, benzyl acetate, methyl phenyl acetate, benzyl formate, form An ester such as phenylethyl, 3-phenyl-propionic acid methyl propionate, benzyl, phenyl ethyl acetate, 2-phenylethyl may be preferably used.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid buildup) developing method, and the like can be applied. Developing conditions are about 5 second or more and 300 second or less at normal temperature.

By the above development, the non-exposed part of the coating film is removed by dissolution. After that, by post-baking as necessary, an infrared shielding film patterned into a predetermined shape is obtained. On the conditions of post-baking, it is 180 degreeC or more and 280 degrees C or less, 1 minute or more and about 60 minutes or less normally.

In addition, when the said composition does not contain a [E] polymeric compound and a [F] polymerization initiator, unlike the said formation method, it is not necessary to perform hardening processes, such as exposure. In addition, development processing does not have to be performed, and in this case, the infrared shielding film which is not patterned can be formed.

As a minimum of the average film thickness of the infrared shielding film for solid-state image sensors formed in this way, it is 0.5 micrometer normally, and 1 micrometer is preferable. On the other hand, as an upper limit of this average film thickness, it is 5 micrometers normally, and 3 micrometers is preferable. When the average film thickness of an infrared shielding film is the said range, the balance of visible light transmittance and an infrared shielding property will become more favorable.

It is preferable that the said infrared shielding film is a thing comprised in a solid-state image sensor as one structural member. In this case, the infrared shielding film functions as an optical filter (infrared cut filter) by itself. The infrared shielding film is built in the solid-state image sensor, and it is preferable to obtain a large process margin. When the infrared shielding film is incorporated in the solid-state imaging device, the infrared shielding film can be disposed, for example, between the microlens outer surface side of the solid-state imaging device, between the microlens and the color filter, between the color filter and the photodiode. The infrared shielding film is preferably laminated between the microlens and the color filter or between the color filter and the photodiode.

As said optical filter, the infrared shielding film may be laminated | stacked on the surface of a transparent substrate. As said transparent substrate, glass, transparent resin, etc. are employ | adopted. As said transparent resin, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned. Such an optical filter is also used suitably as an infrared cut filter in a solid-state image sensor.

The solid-state imaging device provided with an infrared shielding film (optical filter) includes a digital still camera, a mobile phone camera, a digital video camera, a PC camera, a surveillance camera, a car camera, a portable information terminal, a personal computer, a video game, and a medical device. useful.

Example

EMBODIMENT OF THE INVENTION Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In addition, the characteristic of the polymer obtained by the synthesis example was measured by the following method.

[Weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion degree (Mw / Mn)]

Mw and Mn of the polymer were measured by gel permeation chromatography (GPC) under the following analytical conditions using a GPC column (two G2000HXL, one G3000HXL, one G4000HXL) from Tosoh Corporation.

Dispersion degree (Mw / Mn) was computed from the measurement result of Mw and Mn.

(Analysis condition)

Elution solvent: tetrahydrofuran

Flow rate: 1.0 mL / min

Sample concentration: 1.0% by mass

Sample injection volume: 100 μL

Column temperature: 40 ℃

Detector: parallax refractometer

Standard material: monodisperse polystyrene

Synthesis Example 1 (Synthesis of Organic Dye (C-1))

Using the method described in paragraphs [0020] to [0025] (Example 1) of Japanese Patent Application Laid-Open No. 05-25177, an organic dye (C-1) which is a phthalocyanine compound represented by the following formula was synthesized.

Synthesis Example 2 (Synthesis of Organic Dye (C-2))

The organic dye (C-2) which is a phthalocyanine compound represented by a following formula was synthesize | combined using the method of Unexamined-Japanese-Patent No. 2016-204536 (Example 4).

Synthesis Example 3 (Synthesis of Organic Dye (C-3))

The organic dye (C-3) which is a squarylium compound represented by a following formula was synthesize | combined using the method of Unexamined-Japanese-Patent No. 1-228960.

Synthesis Example 4 (Synthesis of Organic Dye (C-4))

The organic dye (C-4) which is a phthalocyanine compound represented by a following formula was synthesize | combined using the method of Unexamined-Japanese-Patent No. 2-138382.

In addition, the used organic pigment | dye is as follows.

Organic pigment (C-5): "FDN-002" (phthalocyanine compound) of Yamada Kagaku Kogyo Co., Ltd.

Organic pigment (C-6): "FDR-004" (phthalocyanine compound) of Yamada Kagaku Kogyo Co., Ltd.

Organic pigment (C-7): "FDN-001" (phthalocyanine compound) of Yamada Kagaku Kogyo Co., Ltd.

Synthesis Examples 5 to 7 (Synthesis of Polymers (B-1) to (B-3))

Using the method described in the literature (Macromolecules 1992, 25, p5907-5913), the polymers (B-1) to (B-3) of the monomer composition ratios (mass ratios) described in Table 1 were carried out. The polymer of the diblock structure containing the block of the monomer (DAMA) which has an adsorptive group with respect to the inorganic compound as a pigment, and the block of other components was obtained. In addition, the solution after reaction performed the methanol value using methanol, and wash | cleaned the obtained reaction solution with 7 mass% sodium hydrogencarbonate aqueous solution, and then water. Subsequently, solvent substitution was performed with propylene glycol monomethyl ether acetate (PGMEA) to obtain all the polymer solutions shown in Table 1 below in yields of 80-82 mass%. In Table 1, the amine of each obtained polymer shows Mw, Mw / Mn, and solid content. In the table, DAMA is dimethylaminoethyl methacrylate, EHMA is 2-ethylhexyl methacrylate, nBMA is normal butyl methacrylate, and PME-200 ("Blemmer" made by Nichiyu Kabushiki Kaisha) A methoxy polyethyleneglycol monomethacrylate is shown. Specifically, PME-200 is a polymer of a monomer represented by CH ₂ = C (CH ₃ ) COO (C ₂ H ₄ O) _n -CH ₃ (n ≒ 4).

Synthesis Example 8 (Synthesis of Polymer (B-8))

Except polymerizing all the monomers at once, it carried out similarly to the method of synthesis examples 5-7, and synthesize | combined the polymer (B-8) of the monomer composition ratio (mass ratio) shown in Table 1 below. Polymer (B-8) is a random copolymer.

Synthesis Example 9 (Synthesis of Cesium Tungsten Oxide Powder)

Cesium tungsten oxide (Cs _0.33 WO ₃ ) powder was synthesized using the method described in paragraph [0113] of Japanese Patent No. 4096205.

The polymer and solvent used by the manufacture example, the Example, and the comparative example are shown below.

(polymer)

B-1 to B-3: Polymers (B-1) to (B-3) of Table 1 synthesized in Synthesis Examples 5 to 7 above

B-4: `` BYK-LPN6919 '' from Big Chemisa (solid content concentration 61% by mass, amine value 120mgKOH / g)

B-5: "BYK-2001" of Big Chem Corporation (46 mass% of solid content concentration, amine value 29 mgKOH / g)

B-6: "BYK-2000" of Big Chemisa (solid content concentration 40 mass%, amine value 4 mgKOH / g)

B-7: "BYK-LPN22102" from Big Chem Corporation (solid concentration 38.5% by mass, amine number 23 mgKOH / g)

B-8: the polymer of Table 1 synthesized in Synthesis Example 8 (B-8)

(menstruum)

CPN: cyclopentanone (SP value: 10.0)

CHN: cyclohexanone (SP value: 9.9)

GBL: γ-butyrolactam (SP value: 9.9)

Tol: Toluene (SP value: 8.9)

PGMEA: Propylene glycol monomethyl ether acetate (SP value: 8.7)

Production Example 1 (Production of Dispersion Liquid (X-1))

25.00 mass parts of said cesium tungsten oxides, 13.11 mass parts of polymers (B-4), and 61.89 mass parts of cyclopentanone (CPN) as a solvent (dispersion medium) were prepared. They were filled with 2000 mass parts of 0.1 mm diameter zirconia beads, and it disperse | distributed with the paint shaker, and the dispersion liquid (X-1) of 19 nm of average particle diameters (D50) was obtained. In addition, the average particle diameter was measured by the DLS method using the light-scattering measuring apparatus ("ALV-5000" of Deutsche ALV Corporation).

Production Examples 2 to 15 (Production of Dispersions (X-2) to (X-15))

Except having used each component shown in Table 2, it carried out similarly to manufacture example 1, and obtained dispersion liquid (X-2)-(X-15), respectively. In Table 2, the average particle diameter (D50) of the particle | grains in the obtained dispersion liquid is also shown. CsWO in Table 2 shows the cesium tungsten oxide obtained in Synthesis Example 9.

Example 1

"KAYARAD DPHA" of Nippon Kayaku Co., Ltd. (Dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) as said dispersion (X-1) 50.00 mass parts, organic dye (C-1) 0.75 mass part, and a polymeric compound Mixture) 6.26 parts by mass, 1.46 parts by mass of "NCI-930" (O-acyl oxime compound) of ADEKA Corporation as a polymerization initiator, 0.02 parts by mass of "FTX-218D" (fluorine-based surfactant) from Neos as a surfactant, antioxidant As a 0.01 mass part of "Irganox1010" (phenolic antioxidant) of BASF Corporation, and 41.50 mass part of cyclopentanone (CNP) as an additional solvent were measured to the container, and it mixed with the stirrer. 200 mL of this mixture was pressure-filtered at 0.5 Mpa for 3 minutes using the 0.5 micrometer PTFE (polytetrafluoroethylene) filter, and the composition (Z-1) of Example 1 was obtained. The solubility with respect to the solvent (CPN) of the organic pigment | dye (C-1) in 20 degreeC and 0.1 Mpa was 2 mass% or more.

Here, solubility was calculated | required by the following method. First, the organic pigment | dye was added to the solvent (the addition amount at this time was made into the quantity equivalent to 10 mass% with respect to the whole solution), and after heating the obtained solution at 50 degreeC, it was left to stand at room temperature (20 degreeC) for 12 hours. . The solubility (20 degreeC) with respect to the solvent of each dye was computed based on the quantity of each organic pigment which melt | dissolved after leaving to stand.

[Examples 2 to 23, Comparative Examples 1 to 13]

Except having shown the composition of each component as shown in Tables 3-7, it carried out similarly to Example 1, and each composition (Z-2)-(Z-23), (of Examples 2-23 and Comparative Examples 1-13 Y-1) to (Y-13). In Tables 3-7, the solubility with respect to the solvent which the used organic pigment | dye used is also shown. In addition, the solvent derived from a polymer solution is also contained in each composition. The values in the table are also values taken into account.

[evaluation]

The following evaluation was performed using each obtained composition. The evaluation results are shown in Tables 3 to 7.

(Dispersion stability)

200 mL of each composition was pressure-filtered at 0.5 Mpa for 3 minutes using the 0.5 micrometer polytetrafluoroethylene (PTFE) filter. On the basis of the filtrate recovery at this time, dispersion stability (filtration, precipitation inhibition) was evaluated based on the following criteria. In the case of A or B, dispersion stability was favorable, and in the case of A, it was evaluated as especially excellent. In addition, when there are many collections of aggregates and the like and the recovery rate is less than 90% (C), the filtration becomes insufficient, and the productivity is significantly reduced.

A: more than 95%

B: 90% or more but less than 95%

C: less than 90%

The following evaluation was performed using the composition after the said filtration.

Each composition was apply | coated by the spin coat method so that it might become a predetermined | prescribed film thickness on a glass substrate. Then, the coating film was heated at 100 degreeC for 120 second, and exposure was performed so that it might become 1000mJ / cm <2> by i-line stepper. Subsequently, an infrared shielding film of 1.40-1.60 micrometers in average film thickness was produced on the glass substrate by heating at 220 degreeC for 300 second. Each average film thickness is shown to Tables 3-7. In addition, the film thickness was measured with the stylus type stepmeter ("alpha step IQ" of Yamato Chemical Co., Ltd.). Next, the transmittance | permeability in each wavelength range of the infrared shielding film produced on the said glass substrate was measured with respect to the glass substrate using the spectrophotometer ("V-7300" of Nippon Bunko Corp.). From the obtained spectrum, evaluation was performed by the following evaluation criteria.

(Visible light transmission)

The average transmittance of visible light with a wavelength of 450-550 nm was calculated. When the average transmittance is less than 70%, the sensitivity of the solid-state imaging device when used as an infrared shielding film is lowered. In addition, the following references | standards evaluated the said average transmittance | permeability.

A: more than 80%

B: 70% or more but less than 80%

C: less than 70%

(Infrared shielding 1)

The average transmittance of infrared rays with a wavelength of 700-900 nm was calculated. When the average transmittance is 20% or more, the amount of noise of the solid-state imaging element increases when used as an infrared shielding film. In addition, the following references | standards evaluated the said average transmittance | permeability.

A: less than 15%

B: 15% or more but less than 20%

C: 20% or more

(Infrared shielding 2)

About the transmittance | permeability of the infrared ray of wavelength 1200nm, it can be said that the transmittance | permeability shows the infrared shielding property favorable in practical use. The following references | standards evaluated the transmittance | permeability of wavelength 1200nm.

A: less than 10%

B: 10% or more but less than 15%

C: more than 15%

(S / N ratio)

The ratio (S / N ratio) of the average transmittance S of the said visible light region (450-550 nm) and the average transmittance N of the infrared region (700-900 nm) was taken, and the practical performance was estimated. The higher the S / N ratio, the better the performance, and when it was 5 or more, it was judged that it could be used at a practical level. The following references | standards evaluated the S / N ratio.

A: 5 or more

B: less than 5

(Defect suppression)

By the method similar to a short circuit, the cured film with a film thickness of 1 micrometer was formed. The defect density of the cured film was measured using the defect / foreign material inspection apparatus ("KLA 2351" of KLA-Tencor). It can be judged that the defect suppression property is high, so that the value of this defect density is small. In addition, a defect means the detection point whose size becomes 1 micrometer or more. Based on the said defect density, defect suppression was evaluated on the following references | standards.

A: 10 / cm 2 or less

B: more than 10 / cm 2 50 / cm 2 or less

C: greater than 50 / cm 2

(Stability over time: thickening rate)

The composition was stored at 40 ° C. for 3 days, and the viscosity before and after storage was measured. In addition, the viscosity was measured in the state which hold | maintained the coating liquid at 20 degreeC using the E-type viscosity meter (E-type viscosity meter RE-80L made by AX Sangyo Co., Ltd.). When the viscosity before storage was V1 and the viscosity after storage was set to V2, the value of (| V2-V1 | / V1) x100 was defined as thickening rate (%). Based on this thickening rate, the following references | standards evaluated. The lower the value, the better the thickening rate, and it was judged that the practicality was less than 10%.

A: less than 5%

B: 5% or more but less than 10%

C: more than 10%

(Stability over time: defects)

The composition was stored at 40 ° C. for 3 days and the number of defects was measured using the composition after storage. The measuring method and reference | standard were made similar to the evaluation of said "defect suppression."

(Patterning)

For the compositions Z-1 to Z-13, Z-17 to Z-18, Z-23, Y-1 to Y-8 and Y-10, a coating film having a film thickness of 1 µm was formed by using a spin coating method. It formed on the board | substrate. Subsequently, after heating at 100 degreeC for 120 second, 1000 mJ / cm <2> exposure was performed with i line | wire stepper through the mask which has a 50 micrometers L / S pattern. The non-exposed part was removed by immersing the board | substrate after exposure in acetone and developing. Subsequently, the infrared shielding film which has L / S pattern was produced by heating at 220 degreeC for 300 second. When observed with the optical microscope, it confirmed that the L / S pattern of 50 micrometers of line widths was formed.

For compositions Z-14 to Z-16, Z-19 to Z-22, and Y-9, an infrared shielding film was produced in the same manner except that the developer was replaced with a 2.38% TMAH solution. When observed with the optical microscope, it confirmed that the 50 micrometers L / S pattern was formed.

As shown in Tables 3 to 7, it is understood that the compositions Z-1 to Z-23 of Examples 1 to 23 have high dispersion stability and stability over time, and also have good patterning properties. Moreover, it turns out that the infrared shielding film (optical filter) obtained by these compositions has few defects, and has both favorable visible light transmittance and infrared shielding property.

The composition for solid-state image sensors of this invention can be used suitably as formation materials, such as an optical filter of a solid-state image sensor, More specifically, an infrared filter.

Claims (11)

In the composition for solid-state imaging devices containing an inorganic compound, a polymer, an organic dye and a solvent,
The amine value of the said polymer is 90 mgKOH / g or more and 200 mgKOH / g or less,
The solvent comprises a specific solvent having a solubility parameter of 8.8 (cal / cm 3) ^1/2 or more and 12.0 (cal / cm 3) ^1/2 or less,
Content with respect to the said whole composition for solid-state image sensors of the said specific solvent is 40 mass% or more and 90 mass% or less,
The composition for solid-state imaging elements whose solubility of the said organic dye with respect to the said solvent in 20 degreeC and 0.1 Mpa is 2 mass% or more. The composition for a solid-state imaging device according to claim 1, comprising two or more kinds of the organic dyes. The composition for solid-state imaging devices according to claim 1 or 2, wherein the solvent comprises a solvent having a cyclic structure. The composition for a solid-state imaging device according to claim 3, wherein the solvent having a cyclic structure is a cyclic ketone, a cyclic ether, a lactone, a lactam, an aromatic hydrocarbon, or a combination thereof. The composition for solid-state image sensors according to any one of claims 1 to 4, wherein the organic dye has a maximum absorption wavelength in a range of 600 nm to 1,000 nm. The organic pigment according to any one of claims 1 to 5, wherein the organic pigment is a diiminium compound, a squarylium compound, a cyanine compound, a phthalocyanine compound, a naphthalocyanine compound, a quaterylene compound, an aluminum compound, or an iminium compound. Azo compound, anthraquinone compound, porphyrin compound, pyrrolopyrrole compound, oxonol compound, croconium compound, hexapyrin compound or a combination thereof. The composition for solid-state imaging devices according to any one of claims 1 to 6, wherein the polymer is a block copolymer having a block having a functional group containing a nitrogen atom and a block having a solvent resistance. The composition for solid-state imaging devices according to any one of claims 1 to 7, wherein the inorganic compound is cesium tungsten oxide, quartz, magnetite, alumina, titania, zirconia, spinel, or a combination thereof. The composition for solid-state image sensors according to any one of claims 1 to 8, further comprising a polymerizable compound. Process of forming coating film on one side of substrate
And
The formation method of the infrared shielding film for solid-state image sensors which forms the said coating film with the composition for solid-state image sensors as described in any one of Claims 1-9. The method of claim 10, further comprising irradiating at least a portion of the coating film with radiation;
Process of developing the said coating film after irradiation
The formation method of the infrared shielding film for solid-state image sensors further equipped.