JP6645243B2 - Curable composition, cured film, infrared light transmitting filter, and solid-state imaging device - Google Patents

Description

  The present invention relates to a curable composition, a cured film, an infrared light transmission filter, and a solid-state imaging device, and more specifically, a curable composition suitable for forming a cured film used for an infrared light transmission filter and the like, TECHNICAL FIELD The present invention relates to a cured film formed using a conductive composition and a solid-state imaging device including the cured film.

  2. Description of the Related Art A solid-state imaging device such as a CCD image sensor or a CMOS image sensor is mounted on an imaging device such as a digital camera. These solid-state imaging devices have a very wide wavelength sensitivity from visible light recognizable by human eyes to an infrared light region having a longer wavelength. 2. Description of the Related Art Conventionally, various image pickup apparatuses have been developed using infrared light, which has a longer wavelength than visible light and is hardly scattered, and is invisible to humans and animals.

  For example, as an imaging device including an optical filter capable of sufficiently transmitting light in the infrared region, for example, a black color material such as a bisbenzofuranone-based pigment, an azomethine-based pigment, a perylene-based pigment, or an azo-based dye is contained. A specific ratio of an infrared sensor having an infrared transmission filter (Patent Document 1), a perylene black pigment, one selected from a blue colorant and a green colorant, and one selected from a yellow colorant and a red colorant There has been proposed an optical sensor including an optical filter (Patent Document 2).

JP 2014-130173 A JP 2014-130332 A

  The present inventors have studied to develop a curable composition that can sufficiently block light in the visible region, and sufficiently transmit light in the infrared region, and can form a cured film with excellent color separation. In the infrared light transmission filter described in the related art, although the transmittance of light in the infrared region is high, it has a transmission spectrum that rises gradually from the visible region to the infrared region. I found that there was room for it.

  An object of the present invention is to provide a curable composition capable of forming a cured film having excellent color separation, which achieves a high level of blocking of light in the visible region and transmission of light in the infrared region. Another object of the present invention is to provide a cured film and an infrared light transmitting filter formed from the curable composition, and a solid-state imaging device including the cured film.

  The present inventors, in a curable composition containing a colorant, a binder resin, and a polymerizable compound, by controlling the spectral characteristics in a visible region and an infrared region of a cured film formed therefrom within a specific range. It has been found that the blocking of light in the visible region and the transmission of light in the infrared region are achieved at a high level, and the color separation is enhanced.

That is, the present invention is a curable composition containing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
An object of the present invention is to provide a curable composition satisfying the following conditions (1) to (4) when a cured film having a thickness of 1.2 μm is formed.
Condition (1): The maximum light transmittance at a wavelength of 400 to 700 nm is 15% or less.
Condition (2): Minimum light transmittance at a wavelength of 850 to 1000 nm is 85% or more.
Condition (3): The wavelength at which the light transmittance becomes 50% is in the range of 700 to 800 nm.
Condition (4): The difference (λ ₂ −λ ₁ ) between the maximum wavelength λ _{1 at} which the light transmittance is 10% and the minimum wavelength λ _{2 at} which the light transmittance is 80% is within 45 nm. thing.

  The present invention also provides a cured film and an infrared light transmitting filter formed using the curable composition, and a solid-state imaging device including the infrared light transmitting filter.

The present invention further provides an infrared light transmitting filter satisfying the following conditions (1) to (4).
Condition (1): The maximum light transmittance at a wavelength of 400 to 700 nm is 15% or less.
Condition (2): Minimum light transmittance at a wavelength of 850 to 1000 nm is 85% or more.
Condition (3): The wavelength at which the light transmittance becomes 50% is in the range of 700 to 800 nm.
Condition (4): The difference (λ ₂ −λ ₁ ) between the maximum wavelength λ _{1 at} which the light transmittance is 10% and the minimum wavelength λ _{2 at} which the light transmittance is 80% is within 45 nm. thing.

  By using the curable composition of the present invention, the blocking of light in the visible region and the transmission of light in the infrared region are achieved at a high level, and a cured film having excellent color separation properties can be formed. Further, the cured film of the present invention, while sufficiently blocking light in the visible region, sufficiently transmits light in the infrared region, and has excellent color separation properties, so that it can be suitably used as an infrared light transmission filter. It is possible, and a solid-state imaging device having the cured film, for example, a game machine or a remote control of a TV, a remote control device such as an automatic door, a vehicle-mounted device such as an inter-vehicle distance detection sensor of a vehicle, a vehicle collision prevention sensor, It can be suitably used as an industrial camera, a medical near-infrared camera, a surveillance camera, a digital camera, a video camera, and the like.

1 is a schematic diagram of a solid-state imaging device according to an embodiment of the present invention. It is a top view of the solid-state imaging device concerning one embodiment of the present invention. FIG. 1 is a cross-sectional view schematically illustrating a solid-state imaging device according to an embodiment of the present invention. It is a figure which shows the transmission spectrum of the cured film (infrared light transmission film) obtained in Example 1, Comparative Example 1, and Comparative Example 2.

Hereinafter, the present invention will be described in detail.
Curable Composition The curable composition of the present invention contains (A) a colorant, (B) a binder resin, and (C) a polymerizable compound, and is cured to a thickness of 1.2 μm using the curable composition. When the film is formed, the following conditions (1) to (4) are satisfied.

Condition (1): The maximum light transmittance at a wavelength of 400 to 700 nm is 15% or less.
Condition (2): Minimum light transmittance at a wavelength of 850 to 1000 nm is 85% or more.
Condition (3): The wavelength at which the light transmittance becomes 50% is in the range of 700 to 800 nm.
Condition (4): The difference (λ ₂ −λ ₁ ) between the maximum wavelength λ _{1 at} which the light transmittance is 10% and the minimum wavelength λ _{2 at} which the light transmittance is 80% is within 45 nm. thing.

Here, in the present specification, the “maximum light transmittance at a wavelength of 400 to 700 nm” refers to the maximum value of the light transmittance at a wavelength of 400 to 700 nm in a transmission spectrum measured by a spectrophotometer. The “minimum transmittance of light at 850 to 1000 nm” refers to the minimum value of the transmittance of light at a wavelength of 850 to 1000 nm in a transmission spectrum measured by a spectrophotometer. The “wavelength at which light transmittance becomes 50%” refers to a wavelength at which light transmittance at a wavelength of 400 to 1000 nm indicates 50% in a transmission spectrum measured by a spectrophotometer. Further, the “maximum wavelength λ _{1 at} which the light transmittance becomes 10%” is the maximum value of the wavelength at which the light transmittance shows 10% in the transmission spectrum at a wavelength of 400 to 1000 nm measured by a spectrophotometer. In other words, the “minimum wavelength λ _{2 at} which the light transmittance becomes 80%” is a minimum value of a wavelength at which the light transmittance shows 80% in a transmission spectrum of a wavelength of 400 to 1000 nm measured by a spectrophotometer. Say.

  The curable composition of the present invention preferably satisfies the following conditions (1-1) to (4-1) when a cured film having a thickness of 1.2 μm is formed using the curable composition. By adopting such an aspect, in the transmission spectrum measured by the spectrophotometer, transmission of light in the visible region is further suppressed, and a spectrum shape which rises sharply from the visible region to the infrared region can be obtained. In addition, the blocking of light in the visible region and the transmission of light in the infrared region are achieved at a higher level, and the color separation can be significantly improved.

Condition (1-1): The maximum transmittance of light at a wavelength of 400 to 700 nm is preferably 13% or less, more preferably 10% or less, and even more preferably 8% or less.
Condition (2-1): The minimum light transmittance at a wavelength of 850 to 1000 nm is preferably 90% or more, and more preferably 93% or more.
Condition (3-1): The wavelength (nm) at which the light transmittance becomes 50% is preferably in the range of 750 to 800 nm.
Condition (4-1): The wavelength difference (λ ₂ −λ ₁ ) between the maximum wavelength λ _{1 at} which the light transmittance is 10% and the minimum wavelength λ _{2 at} which the light transmittance is 80% is 40 nm. Is preferably within 35 nm, and more preferably within 35 nm.

-(A) Colorant-
In the present invention, the spectrum shape of the transmission spectrum of the cured film described above is mainly characterized by the type of the colorant (A) contained in the curable composition. The colorant (A) used in the present invention is not particularly limited as long as a cured film that satisfies the above conditions (1) to (4), preferably the conditions (1-1) to (4-1) can be formed. However, it is preferable to contain the following components (a1) to (a3).

(A1) at least one colorant selected from the group consisting of a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2); (a2) a purple colorant and red At least one colorant selected from the group consisting of colorants (a3) yellow colorant

[In the formula (1), M represents a metal atom. ]

  The component (a1) is at least one selected from the group consisting of a compound having a structure represented by the formula (1) and a compound having a structure represented by the formula (2). The compound having the structure represented by the formula (1) and the compound having the structure represented by the formula (2) usually have a strong absorption band in a visible region of 600 to 700 nm, and an infrared region of 800 nm or more. Has a high transmittance, so that the visible region of 600 to 700 nm can be shielded from light without impairing the transmittance in the infrared region. In this specification, “having an absorption band” means that a maximum absorption wavelength exists in the wavelength region. Further, each of the compound having the structure represented by the formula (1) and the compound having the structure represented by the formula (2) may further have a substituent. Examples of the substituent include a halogen atom.

  In the above formula (1), the metal atom in M is preferably a divalent metal atom, for example, Be, Mg, Ca, Ba, Al, Si, Cd, Hg, Cr, Fe, Co, Ni, Cu, Examples include Zn, Ge, Pd, Cd, Sn, Pt, Pb, Sr, and Mn. Among them, Cu is preferable from the viewpoint of color separation.

As a specific example of the component (a1), for example, in a color index (CI; issued by The Society of Dyers and Colorists, the same applies hereinafter), the following color index (CI) numbers are assigned. Can be mentioned.
C. I. Pigment Blue 15, C.I. I. Pigment Blue 15: 1, C.I. I. Pigment Blue 15: 2, C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4, C.I. I. Pigment Blue 15: 6 (the above is a compound in which M is Cu in the formula (1)), C.I. I. Pigment Blue 16 (compound represented by the formula (2)).

  Above all, as the component (a1), a compound having a structure represented by the formula (1) is preferable from the viewpoint of color separation, a compound in which M is Cu in the formula (1) is more preferable, and C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4 and C.I. I. Pigment Blue 15: 6, more preferably at least one selected from the group consisting of C.I. I. Pigment Blue 15: 4 is particularly preferred.

The component (a2) is at least one selected from the group consisting of a purple colorant and a red colorant.
The purple colorant usually has an absorption band in the visible region of 500 to 600 nm, and has high transmittance in the infrared region of 800 nm or more, so that the visible region of 500 to 600 nm is not impaired without impairing the transmittance in the infrared region. Can be shielded from light.
In addition, the red colorant usually has an absorption band in the visible region of 450 to 600 nm and has high transmittance in the infrared region of 800 nm or more, without impairing the transmittance in the infrared region,
The visible region of 450 to 600 nm can be shielded from light.
Each of the purple colorant and the red colorant can use any of a pigment and a dye, and the pigment may be any of an organic pigment and an inorganic pigment. In addition, a purple colorant and a red colorant can also be used individually by 1 type or in combination of 2 or more types, respectively.

Examples of the purple colorant include purple pigments having the following color index (CI) numbers in the color index.
C. I. Pigment Violet 1, C.I. I. Pigment Violet 2, C.I. I. Pigment Violet 3, C.I. I. Pigment Violet 3: 1, C.I. I. Pigment Violet 3: 3, C.I. I. Pigment Violet 13, C.I. I. Pigment Violet 19, C.I. I. Pigment Violet 23, C.I. I. Pigment Violet 25, C.I. I. Pigment Violet 27, C.I. I. Pigment Violet 29, C.I. I. Pigment Violet 32, C.I. I. Pigment Violet 36, C.I. I. Pigment Violet 37, C.I. I. Pigment Violet 38, C.I. I. Purple pigments such as CI Pigment Violet 39;

Examples of the violet dye include those having the following color index (CI) numbers in the color index.
C. I. Basic Violet 1, C.I. C. I. Basic Violet 3, C.I. I. Triarylmethane purple dye such as Basic Violet 14;
C. I. Xanthene purple dye such as Basic Violet 11;
C. I. Basic Violet 7, C.I. I. Cyanine purple dye such as Basic Violet 16;
C. C. I. Solvent Violet 8, C.I. C. I. Solvent Violet 13, C.I. C. I. Solvent Violet 14, C.I. C. I. Solvent Violet 21, C.I. C. I. Solvent Violet 27, C.I. C. I. Solvent Violet 28, C.I. I. Anthraquinone purple dye such as Solvent Violet 36.

  Examples of the red colorant include pigments such as monoazo, disazo, monoazo lake, benzimidazolone, diketopyrrolopyrrole, condensed azo, anthraquinone, and quinacridone pigments. Examples of such a red pigment include those having the following color index (CI) numbers in the color index.

C. I. Pigment Red 1, C.I. I. Pigment Red 2, C.I. I. Pigment Red 3, C.I. I. Pigment Red 4, C.I. I. Pigment Red 5, C.I. I. Pigment Red 6, C.I. I. Pigment Red 8, C.I. I. Pigment Red 9, C.I. I. Pigment Red 12, C.I. I. Pigment Red 14, C.I. I. Pigment Red 15, C.I. I. Pigment Red 16, C.I. I. Pigment Red 17, C.I. I. Pigment Red 21, C.I. I. Pigment Red 22, C.I. I. Pigment Red 23, C.I. I. Pigment Red 31, C.I. I. Pigment Red 32, C.I. I. Pigment Red 112, C.I. I. Pigment Red 114, C.I. I. Pigment Red 146, C.I. I. Pigment Red 147, C.I. I. Pigment Red 151, C.I. I. Pigment Red 170, C.I. I. Pigment Red 184, C.I. I. Pigment Red 187, C.I. I. Pigment Red 188, C.I. I. Pigment Red 193, C.I. I. Pigment Red 210, C.I. I. Pigment Red 245, C.I. I. Pigment Red 253, C.I. I. Pigment Red 258, C.I. I. Pigment Red 266, C.I. I. Pigment Red 267, C.I. I. Pigment Red 268, C.I. I. Monoazo red pigments such as CI Pigment Red 269;
C. I. Pigment Red 37, C.I. I. Pigment Red 38, C.I. I. Disazo red pigments such as CI Pigment Red 41;
C. I. Pigment Red 48: 1, C.I. I. Pigment Red 48: 2, C.I. I. Pigment Red 48: 3, C.I. I. Pigment Red 48: 4, C.I. I. Pigment Red 49: 1, C.I. I. Pigment Red 49: 2, C.I. I. Pigment Red 50: 1, C.I. I. Pigment Red 52: 1, C.I. I. Pigment Red 52: 2, C.I. I. Pigment Red 53: 1, C.I. I. Pigment Red 53: 2, C.I. I. Pigment Red 57: 1, C.I. I. Pigment Red 58: 4, C.I. I. Pigment Red 63: 1, C.I. I. Pigment Red 63: 2, C.I. I. Pigment Red 64: 1, C.I. I. Monoazo lake red pigments such as CI Pigment Red 68;
C. I. Pigment Red 171, C.I. I. Pigment Red 175, C.I. I. Pigment red 176, C.I. I. Pigment Red 185, C.I. I. Benzimidazolone red pigments such as CI Pigment Red 208;
C. I. Pigment Red 254, C.I. I. Pigment Red 255, C.I. I. Pigment Red 264, C.I. I. Pigment Red 270, C.I. I. Diketopyrrolopyrrole red pigments such as CI Pigment Red 272;
C. I. Pigment Red 220, C.I. I. Pigment red 144, C.I. I. Pigment Red 166, C.I. I. Pigment red 214, C.I. I. Pigment Red 220, C.I. I. Pigment Red 221, C.I. I. Pigment Red 242 and other condensed azo red pigments;
C. I. Pigment Red 168, C.I. I. Pigment Red 177, C.I. I. Pigment Red 216, C.I. I. Solvent Red 149, C.I. I. Solvent Red 150, C.I. I. Solvent Red 52, C.I. I. Anthraquinone red pigments such as Solvent Red 207;
C. I. Pigment Red 122, C.I. I. Pigment Red 202, C.I. I. Pigment Red 206, C.I. I. Pigment Red 207, C.I. I. Quinacridone red pigments such as CI Pigment Red 209;

  In addition, a diketopyrrolopyrrole pigment represented by the following formula (3) can also be mentioned.

  Examples of the red dye include those having the following color index (CI) numbers in the color index.

C. I. Acid Red 37, C.I. I. Acid Red 180, C.I. I. Acid Blue 29, C.I. I. Direct Red 28, C.I. I. Direct Red 83, C.I. I. Reactive Red 17, C.I. I. Reactive Red 120, C.I. I. Disperse thread 58, C.I. I. Basic Red 18, C.I. I. Azo red dyes such as Mordant Red 7;
C. I. Anthraquinone red dyes such as Disperse Red 60;
C. I. Acid Red 52, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 289, C.I. I. Xanthene red dyes such as Acid Red 388;
C. I. Basic Red 12, C.I. I. Basic Red 13, C.I. I. Cyanine red dyes such as Basic Red 14.

As the purple colorant, C.I. I. Pigment Violet 23 and at least one selected from the group consisting of xanthene-based violet dyes. I. Pigment Violet 23 and C.I. I. At least one selected from the group consisting of basic violet 11 is more preferable. As the red colorant, a diketopyrrolopyrrole-based red pigment is preferable, and C.I. I. Pigment Red 254 and the pigment represented by the formula (3) are more preferable.
Above all, as the component (a2), C.I. I. Pigment Violet 23 and diketopyrrolopyrrole-based red pigment are preferably at least one selected from the group consisting of pigments. C. I. Pigment Violet 23 (a2-1) and a diketopyrrolopyrrole-based red pigment (a2-2) in combination. I. The content of the pigment violet 23 is preferably in excess of the content of the diketopyrrolopyrrole-based red pigment, and the mass of the pigment violet 23 (a2-1) and the diketopyrrolopyrrole-based red pigment (a2-2) The ratio (a2-1 / a2-2) is preferably from 1.1 / 1 to 5/1, and more preferably from 1.5 / 1 to 3/1.

The component (a3) is a yellow colorant. The yellow colorant usually has an absorption band in the visible region of 400 to 500 nm and has high transmittance in the infrared region of 800 nm or more, so that the visible region of 400 to 500 nm is not impaired without impairing the transmittance in the infrared region. Can be shielded from light.
As the yellow colorant, any of a pigment and a dye can be used, and the pigment may be any of an organic pigment and an inorganic pigment. In addition, a yellow colorant can also be used individually by 1 type or in combination of 2 or more types, respectively.

  Examples of the yellow colorant include anthraquinone-based, isoindolinone-based, condensed azo-based, benzimidazolone-based, monoazo-based, and disazo-based pigments. Specific examples of such yellow pigments include, for example, those having the following color index (CI) numbers in the color index.

C. I. Solvent Yellow 163, C.I. I. Pigment Yellow 24, C.I. I. Pigment Yellow 108, C.I. I. Pigment Yellow 193, C.I. I. Pigment yellow 147, C.I. I. Pigment Yellow 199, C.I. I. Anthraquinone-based yellow pigments such as CI Pigment Yellow 202;
C. I. Pigment yellow 110, C.I. I. Pigment yellow 109, C.I. I. Pigment Yellow 139, C.I. I. Pigment yellow 179, C.I. I. Isoindolinone-based yellow pigments such as CI Pigment Yellow 185;
C. I. Pigment Yellow 93, C.I. I. Pigment Yellow 94, C.I. I. Pigment Yellow 95, C.I. I. Pigment Yellow 128, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 166, C.I. I. A condensed azo yellow pigment such as CI Pigment Yellow 180;
C. I. Pigment yellow 120, C.I. I. Pigment Yellow 151, C.I. I. Pigment yellow 154, C.I. I. Pigment Yellow 156, C.I. I. Pigment yellow 175, C.I. I. Benzimidazolone yellow pigments such as CI Pigment Yellow 181;
C. I. Pigment Yellow 1, C.I. I. Pigment Yellow 2, C.I. I. Pigment Yellow 3, C.I. I. Pigment Yellow 4, C.I. I. Pigment Yellow 5, C.I. I. Pigment Yellow 6, C.I. I. Pigment Yellow 9, C.I. I. Pigment Yellow 10, C.I. I. Pigment Yellow 12, C.I. I. Pigment Yellow 61, C.I. I. Pigment yellow 62, C.I. I. Pigment Yellow 62: 1, C.I. I. Pigment Yellow 65, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment Yellow 75, C.I. I. Pigment Yellow 97, C.I. I. Pigment Yellow 100, C.I. I. Pigment Yellow 104, C.I. I. Pigment Yellow 105, C.I. I. Pigment yellow 111, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 167, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 169, C.I. I. Pigment Yellow 182, C.I. I. Monoazo yellow pigments such as CI Pigment Yellow 183;
C. I. Pigment Yellow 12, C.I. I. Pigment Yellow 13, C.I. I. Pigment Yellow 14, C.I. I. Pigment Yellow 16, C.I. I. Pigment Yellow 17, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 63, C.I. I. Pigment Yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 87, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment Yellow 152, C.I. I. Pigment yellow 170, C.I. I. Pigment Yellow 172, C.I. I. Pigment yellow 174, C.I. I. Pigment yellow 176, C.I. I. Pigment Yellow 188, C.I. I. Disazo yellow pigments such as CI Pigment Yellow 198;

  As the yellow dye, for example, those having the following color index (C.I.) numbers in the color index can be mentioned.

C. I. Acid Yellow 11, C.I. I. Direct Yellow 12, C.I. I. Reactive Yellow 2, C.I. I. Azo-based yellow dyes such as Mordant Yellow 5;
C. I. Solvent Yellow 33, C.I. I. Acid Yellow 3, C.I. I. Quinoline yellow dyes such as Disperse Yellow 64;
C. I. Acid Yellow 1, C.I. I. Nitro yellow dyes such as Disperse Yellow 42;
C. I. A methine yellow dye such as Disperse Yellow 201;
C. I. Basic Yellow 1, C.I. I. Basic Yellow 11, C.I. I. Basic Yellow 13, C.I. I. Basic Yellow 21, C.I. I. Basic Yellow 28, C.I. I. Basic Yellow 51, C.I. I. Cyanine yellow dyes such as Reactive Yellow 1.

  As the yellow colorant, an isoindolinone-based yellow pigment is preferable from the viewpoint of color separation properties. I. Pigment Yellow 139 is more preferred.

  Among the combinations of the above components (a1) to (a3), the component (a1) is particularly preferably C.I. I. Pigment Blue 15: 4, and the component (a2) is C.I. I. Pigment Violet 23, wherein the component (a3) is C.I. I. Pigment Yellow 139 (hereinafter referred to as “combination I”), wherein component (a1) is C.I. I. Pigment Blue 15: 6, the component (a2) contains a diketopyrrolopyrrole-based red pigment, and the component (a3) contains C.I. I. Pigment Yellow 139 (hereinafter, referred to as “combination II”) is preferable, and combination I is more preferable. In the case of the combination I, an embodiment in which the component (a2) further contains a diketopyrrolopyrrole-based red pigment is preferable. The diketopyrrolopyrrole red pigments in combination I and combination II include C.I. I. Pigment Red 254 and the pigment represented by the formula (3) are preferable.

  In the curable composition of the present invention, a coloring agent other than the component (a1), the component (a2) and the component (a3) may be used as long as the effects of the present invention are not impaired. As the other colorant, any of a pigment and a dye can be used, and the pigment may be any of an organic pigment and an inorganic pigment. The dye may be either an organic dye or an inorganic dye. Other colorants can be used alone or in combination of two or more.

  Examples of other colorants include organic pigments and inorganic pigments having the following color index numbers.

C. I. Pigment Orange 5, C.I. I. Pigment Orange 13, C.I. I. Pigment Orange 14, C.I. I. Pigment Orange 24, C.I. I. Pigment Orange 34, C.I. I. Pigment Orange 36, C.I. I. Pigment Orange 38, C.I. I. Pigment Orange 40, C.I. I. Pigment Orange 43, C.I. I. Pigment Orange 46, C.I. I. Pigment Orange 49, C.I. I. Pigment Orange 61, C.I. I. Pigment Orange 64, C.I. I. Pigment Orange 68, C.I. I. Pigment Orange 70, C.I. I. Pigment Orange 71, C.I. I. Pigment Orange 72, C.I. I. Pigment Orange 73, C.I. I. Orange pigments such as CI Pigment Orange 74;
C. I. Pigment Brown 23, C.I. I. Brown pigments such as Pigment Brown 25;
C. I. Pigment Black 1, C.I. I. Black pigments such as CI Pigment Black 7.

Inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, titanium black, synthetic iron black, and carbon black.

Examples of the organic dye include those having the following color index (CI) numbers.
C. I. Acid orange 7, C.I. I. Direct Orange 26, C.I. I. Reactive Black 5, C.I. I. Disperse Orange 5, C.I. I. Azo dyes such as Mordant Black 7;
C. I. Nitro dyes such as Acid Orange 3.

  In the present invention, when a pigment is used as the colorant (A), the pigment is purified and used by a recrystallization method, a reprecipitation method, a solvent washing method, a sublimation method, a vacuum heating method or a combination thereof. Is also good. If desired, the pigment may be used by modifying its particle surface with a resin. Examples of the resin that modifies the pigment particle surface include a vehicle resin described in JP-A-2001-108817 or various commercially available resins for dispersing pigments. As a method of coating the surface of the carbon black with a resin, for example, the methods described in JP-A-9-71733, JP-A-9-95625, JP-A-9-124969 and the like can be employed. The organic pigment may be used after so-called salt milling to make primary particles fine. As a method of salt milling, for example, a method disclosed in JP-A-8-179111 can be adopted. The dispersion particle size of the organic pigment measured by the dynamic light scattering method is usually 1 nm to 200 nm in view of the balance between dispersion stability and resolution.

  In the present invention, the colorant (A) can be used together with a dispersant, if desired. The dispersant is used for uniformly dissolving or dispersing the colorant in the curable composition and the colorant dispersion. Examples of the dispersant include urethane dispersants, polyethyleneimine dispersants, polyoxyethylene alkyl ether dispersants, polyoxyethylene alkylphenyl ether dispersants, polyethylene glycol diester dispersants, and sorbitan fatty acid ester dispersants. , Polyester-based dispersants, (meth) acrylic-based dispersants, and the like. As commercial products, for example, (meth) acrylic dispersants such as Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, BYK-LPN21116, BYK-LPN22102 (all manufactured by BYK (BYK)), Disperbyk-161, Disperbyk Urethane-based dispersing agents such as -162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (manufactured by Big Chemie (BYK)), Solsperse 76500 (manufactured by Lubrizol Co., Ltd.), Solsperse 24000 ( Polyethyleneimine-based dispersing agents such as Lubrizol Co., Ltd.), Azispar PB821, Azispar PB822, Azispar PB880, Azispar PB881 Above, other Ajinomoto Fine-Techno Co., Inc.) polyester dispersants such as can be used BYK-LPN21324 (Chemie (BYK) Co.). The dispersants can be used alone or in combination of two or more.

  Examples of the (meth) acrylic dispersant include, for example, JP-A-2011-232735, JP-A-2011-237969, JP-A-2012-32767, International Publication No. 2011/129078, and International Publication No. 2012. / 001945 pamphlets and the like can also be used.

  The content of the dispersant can be appropriately selected depending on the type of the dispersant, but is preferably 5 to 300 parts by mass, more preferably 10 to 200 parts by mass, and still more preferably 100 parts by mass of the colorant (A). 20 to 100 parts by mass.

  Further, in the present invention, a dispersing aid can be used together with the dispersing agent. Examples of the dispersing aid include a pigment derivative. As the pigment derivative, a pigment derivative having an acidic functional group is preferable, and examples of the acidic functional group include a sulfo group, a carboxyl group, and a phosphoric acid group. In addition, the content ratio of the dispersing aid can be appropriately selected within a range that does not impair the effects of the present invention.

It is preferable that the content ratio of the component (a1), the component (a2), and the component (a3) in the colorant (A) be the following from the viewpoint of color separation.
That is, the content ratio of the component (a1) is preferably from 20 to 70% by mass, more preferably from 25 to 50% by mass, and still more preferably from 30 to 45% by mass, based on all the colorants.
The content ratio of the component (a2) is preferably from 5 to 50% by mass, more preferably from 10 to 40% by mass, and still more preferably from 15 to 30% by mass, based on all the colorants.
The content ratio of the component (a3) is preferably from 20 to 50% by mass, more preferably from 25 to 45% by mass, and still more preferably from 30 to 40% by mass based on all the colorants.
The total amount of the component (a1), the component (a2) and the component (a3) is preferably from 80 to 100% by mass, more preferably from 90 to 100% by mass in the colorant (A) from the viewpoint of color separation. 95-100 mass% is still more preferred, and 100 mass% is even more preferred.

  (A) The content ratio of the coloring agent is preferably from 20 to 80% by mass, more preferably from 30 to 60% by mass, and more preferably from 40 to 55% by mass, in the solid content of the curable composition from the viewpoint of color separation properties. More preferred.

-(B) Binder resin-
(B) The binder resin (excluding the (meth) acrylic dispersant) is preferably alkali-soluble, and examples thereof include resins having an acidic group. Examples of the acidic group include a carboxyl group, a phenolic hydroxyl group, and a sulfo group. The resin having an acidic group is not particularly limited as long as it is a polymer having one or more acidic groups in one molecule. As a preferred embodiment, for example, a polymer having a carboxyl group (hereinafter, referred to as “ For example, an ethylenically unsaturated monomer having one or more carboxyl groups (hereinafter, also referred to as “unsaturated monomer (b1)”) and another polymer are also preferable. A copolymer with a copolymerizable ethylenically unsaturated monomer (hereinafter, also referred to as “unsaturated monomer (b2)”) can be given.

Examples of the unsaturated monomer (b1) include (meth) acrylic acid, maleic acid, maleic anhydride, succinic acid mono [2- (meth) acryloyloxyethyl], and ω-carboxypolycaprolactone mono (meth) Acrylates and p-vinylbenzoic acid can be mentioned.
The unsaturated monomers (b1) can be used alone or in combination of two or more.

As the unsaturated monomer (b2), for example,
N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, p-hydroxy-α-methylstyrene, p-vinylbenzyl glycidyl ether and 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 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, polypropylene glycol (polymerization degree 2 to 10) mono (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6] decan-8-yl (meth) acrylate, dicyclopentenyl (meth) acrylate Glycerol mono (meth) acrylate, 4-hydroxyphenyl (meth) acrylate, ethylene oxide-modified (meth) acrylate of paracumylphenol, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, 3-[( (Meth) acrylic esters such as (meth) acryloyloxymethyl] oxetane and 3-[(meth) acryloyloxymethyl] -3-ethyloxetane;

Vinyl ethers such as cyclohexyl vinyl ether, isobornyl vinyl ether, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl vinyl ether, pentacyclopentadecanyl vinyl ether, and 3- (vinyloxymethyl) -3-ethyloxetane ;
Macromonomers having a mono (meth) acryloyl group at the terminal of a polymer molecular chain, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane, can be mentioned.
The unsaturated monomers (b2) can be used alone or in combination of two or more.

  In the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2), the copolymerization ratio of the unsaturated monomer (b1) in the copolymer is preferably 5 to 50% by mass. And more preferably 10 to 40% by mass. By copolymerizing the unsaturated monomer (b1) in such a range, a curable composition having excellent alkali developability and storage stability can be obtained.

  Specific examples of the copolymer of the unsaturated monomer (b1) and the unsaturated monomer (b2) include, for example, JP-A-7-140654, JP-A-8-259876, and JP-A-10-31308. JP, JP-A-10-300922, JP-A-11-174224, JP-A-11-258415, JP-A-2000-56118, JP-A-2004-101728, and the like. Coalescence can be mentioned.

  In the present invention, for example, JP-A-5-19467, JP-A-6-230212, JP-A-7-207211, JP-A-9-325494, JP-A-11-140144, As disclosed in Japanese Unexamined Patent Publication No. 2008-181095, a carboxyl group-containing polymer having a polymerizable unsaturated bond such as a (meth) acryloyl group in a side chain can be used as the binder resin.

  The binder resin (B) in the present invention has a weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (hereinafter abbreviated as GPC) (elution solvent: tetrahydrofuran) of usually 1,000 to 100, 000, preferably 3,000 to 50,000. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) of the binder resin (B) to the number average molecular weight (Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3 0.0. Here, Mn refers to the number average molecular weight in terms of polystyrene measured by GPC (elution solvent: tetrahydrofuran). By adopting such an embodiment, the color separation properties are further enhanced, the alkali developability, the storage stability of the curable composition are improved, and the generation of deposits and coating film foreign substances can be suppressed.

  The binder resin in the present invention can be produced by a known method, and is disclosed in, for example, JP-A-2003-222717, JP-A-2006-259680, and WO2007 / 029871. The method can also control the structure, Mw, and Mw / Mn.

  In the present invention, one or more binder resins can be used in combination.

  In the present invention, the content of the binder resin (B) is usually 5 to 1,000 parts by mass, preferably 10 to 500 parts by mass, more preferably 20 to 200 parts by mass with respect to 100 parts by mass of the colorant (A). Parts, more preferably 30 to 100 parts by mass. By adopting such an embodiment, the storage stability of the alkali-developable and curable composition is improved, and the generation of deposits and coating film foreign matter can be suppressed.

-(C) Polymerizable compound-
In the present invention, a polymerizable compound refers to a compound having two or more polymerizable groups. Examples of the polymerizable group include an ethylenically unsaturated group, an oxiranyl group, an oxetanyl group, and an N-alkoxymethylamino group. In the present invention, as the polymerizable compound, a compound having two or more (meth) acryloyl groups or a compound having two or more N-alkoxymethylamino groups is preferable.

  Specific examples of the compound having two or more (meth) acryloyl groups include a polyfunctional (meth) acrylate which is a reaction product of an aliphatic polyhydroxy compound and (meth) acrylic acid, and a polyfunctional (meth) acrylate modified with caprolactone. A) an acrylate, an alkylene oxide-modified polyfunctional (meth) acrylate, a polyfunctional urethane (meth) acrylate which is a reaction product of a hydroxyl group-containing (meth) acrylate and a polyfunctional isocyanate, and a hydroxyl group-containing (meth) acrylate And a polyfunctional (meth) acrylate having a carboxyl group, which is a reaction product with a product.

  Here, examples of the aliphatic polyhydroxy compound include divalent aliphatic polyhydroxy compounds such as ethylene glycol, propylene glycol, polyethylene glycol and polypropylene glycol; and trivalent aliphatic polyhydroxy compounds such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol. And aliphatic polyhydroxy compounds having a valency or higher. Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, and glycerol diacrylate. Methacrylate and the like can be mentioned. Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, and isophorone diisocyanate. As the acid anhydride, for example, succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, dibasic acid anhydrides such as hexahydrophthalic anhydride, pyromellitic anhydride, biphenyltetracarboxylic acid Examples thereof include tetrabasic dianhydrides such as dianhydride and benzophenonetetracarboxylic dianhydride.

  Examples of the caprolactone-modified polyfunctional (meth) acrylate include compounds described in paragraphs [0015] to [0018] of JP-A-11-44955. Examples of the above-mentioned alkylene oxide-modified polyfunctional (meth) acrylate include bisphenol A di (meth) acrylate modified with at least one selected from ethylene oxide and propylene oxide, and at least one selected from ethylene oxide and propylene oxide. Modified with at least one selected from modified isocyanuric acid tri (meth) acrylate, at least one selected from ethylene oxide and propylene oxide Modified with at least one selected from trimethylolpropane tri (meth) acrylate, ethylene oxide and propylene oxide Pen modified with at least one selected from pentaerythritol tri (meth) acrylate, ethylene oxide and propylene oxide Dipentaerythritol modified with at least one selected from taerythritol tetra (meth) acrylate, ethylene oxide and propylene oxide Dipentaerythritol modified with at least one selected from penta (meth) acrylate, ethylene oxide and propylene oxide Hexa (meth) acrylate and the like can be mentioned.

  Examples of the compound having two or more N-alkoxymethylamino groups include a compound having a melamine structure, a benzoguanamine structure, and a urea structure. The melamine structure and the benzoguanamine structure refer to a chemical structure having at least one triazine ring or a phenyl-substituted triazine ring as a basic skeleton, and are a concept including melamine, benzoguanamine or a condensate thereof. 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 and the like.

Among these polymerizable compounds, a polyfunctional (meth) acrylate which is a reaction product of a trivalent or higher aliphatic polyhydroxy compound and (meth) acrylic acid, a polyfunctional (meth) acrylate modified with caprolactone, and a polyfunctional urethane (Meth) acrylate, polyfunctional (meth) acrylate having a carboxyl group, N, N, N ′, N ′, N ″, N ″ -hexa (alkoxymethyl) melamine, N, N, N ′, N ′ -Tetra (alkoxymethyl) benzoguanamine is preferred. Among the polyfunctional (meth) acrylates which are the reaction products of the trivalent or higher aliphatic polyhydroxy compound with (meth) acrylic acid, trimethylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol pentaacrylate, dipenta Among the polyfunctional (meth) acrylates having a carboxyl group, erythritol hexaacrylate has a reaction product of pentaerythritol triacrylate and succinic anhydride and a reaction product of dipentaerythritol pentaacrylate and succinic anhydride in the visible region. The point that light blocking and transmission of light in the infrared region are further enhanced, the cured film has excellent surface smoothness, and hardly causes background dirt, film residue, etc. on the unexposed portion of the substrate and the light shielding layer. Is preferred.
In the present invention, the polymerizable compound (C) can be used alone or in combination of two or more.

  From the viewpoint of the mechanical strength of the cured film, the content of the polymerizable compound (C) in the invention is preferably from 10 to 500 parts by mass, more preferably from 20 to 250 parts by mass, per 100 parts by mass of the colorant (A). More preferably, it is 30 to 100 parts by mass.

-(D) Photopolymerization initiator-
The curable composition of the present invention can contain (D) a photopolymerization initiator. Thereby, radiation sensitivity can be imparted to the curable composition. The photopolymerization initiator used in the present invention is a compound that generates an active species capable of initiating polymerization of the polymerizable compound (C) upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, an electron beam, or X-ray. .

  Such photopolymerization initiators include, for example, thioxanthone compounds, acetophenone compounds, biimidazole compounds, triazine compounds, O-acyl oxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, Examples thereof include a diazo compound and an imidosulfonate compound.

  In the present invention, one or more photopolymerization initiators can be used in combination. As the photopolymerization initiator, at least one selected from the group consisting of a thioxanthone compound, an acetophenone compound, a biimidazole compound, a triazine compound, and an O-acyl oxime compound is preferable.

  Among the preferred photopolymerization initiators in the present invention, specific examples of the thioxanthone compound include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-dichlorothioxanthone, Examples thereof include 4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone.

  Specific examples of the acetophenone compound include 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholine). Linophenyl) butan-1-one, 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one and the like can be mentioned.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole and 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 compound as a photoinitiator (D), it is preferable to use a hydrogen donor together in that a sensitivity can be improved. The term "hydrogen donor" as used herein means a compound capable of donating a hydrogen atom to a radical generated from a biimidazole compound by exposure. Examples of the hydrogen donor include mercaptan hydrogen donors such as 2-mercaptobenzothiazole and 2-mercaptobenzoxazole, and 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone. Amine hydrogen donors can be mentioned. In the present invention, the hydrogen donor can be used alone or in combination of two or more. However, it is possible to use one or more mercaptan hydrogen donors and one or more amine hydrogen donors in combination. This is preferable in that the sensitivity can be further improved.

  Specific examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, and 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -S-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) Ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxy Triazine compounds having a halomethyl group such as (tyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

  Further, specific examples of the O-acyl oxime compound include 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime), 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). As commercial products of the O-acyl oxime compound, NCI-831, NCI-930 (above, manufactured by ADEKA Corporation), DFI-020, DFI-091 (above, manufactured by Daito Chemmix) can also be used. .

  In the present invention, when a photopolymerization initiator other than a biimidazole compound such as an acetophenone compound is used, a sensitizer may be used in combination. Examples of such a sensitizer include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, and 4-dimethyl Ethyl aminobenzoate, 2-ethylhexyl 4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone, etc. Can be mentioned.

In the present invention, the content of the photopolymerization initiator (D) is preferably 0.01 to 120 parts by mass, more preferably 1 to 100 parts by mass, and preferably 5 to 100 parts by mass, per 100 parts by mass of the polymerizable compound (C). 50 parts by mass are more preferred. By adopting such an embodiment, curability and film properties can be further enhanced.
-(E) solvent-
The curable composition of the present invention contains the components (A) to (C) and optionally other components, and is usually prepared as a liquid composition by blending an organic solvent. .
As the organic solvent, components (A) to (C) constituting the curable composition and other components are dispersed or dissolved, and as long as they do not react with these components and have appropriate volatility, It can be appropriately selected and used. (E) The solvent can be used alone or in combination of two or more.

As the organic solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, dipropylene glycol Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, (poly) alkylene glycol monoalkyl ethers such as tripropylene glycol monoethyl ether;

Alkyl lactate such as methyl lactate and ethyl lactate;
(Cyclo) alkyl alcohols such as methanol, ethanol, propanol, butanol, isopropanol, isobutanol, t-butanol, octanol, 2-ethylhexanol and cyclohexanol;
Keto alcohols such as diacetone alcohol;

Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, (Poly) alkylene glycol monoalkyl ether acetates such as 3-methyl-3-methoxybutyl acetate;
Glycol ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, and tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone and 3-heptanone;

Diacetates such as propylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate;
Alkoxycarboxylic acid esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, and 3-methyl-3-methoxybutylpropionate;
Ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-butyrate Fatty acid alkyl esters such as -propyl, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Halogenated hydrocarbons such as carbon tetrachloride, trichloroethylene, chloroform, 1,1,1-trichloroethane, methylene chloride, monochlorobenzene N, N-dimethylformamide, N, N-dimethylacetamide, amides such as N-methylpyrrolidone, or Lactam and the like.

  Among these organic solvents, (poly) alkylene glycol monoalkyl ether, lactate alkyl ester, (poly) alkylene glycol monoalkyl ether acetate, glycol ether, ketone, diacetate are preferred from the viewpoints of solubility, dispersibility, coatability and the like. , Alkoxycarboxylic acid esters and fatty acid alkyl esters are preferred.

  (E) The content of the solvent is not particularly limited, but is preferably such that the total concentration of each component excluding the solvent in the curable composition is 5 to 50% by mass, and 10 to 30% by mass. Is more preferable. With such an embodiment, a curable composition having good dispersibility, stability, and applicability can be obtained.

-Additive-
The coloring composition of the present invention may contain various additives as necessary.
Examples of the additive include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); surfactants such as fluorine surfactant and silicone surfactant; vinyl trimethoxysilane , Vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl Adhesion promoters such as rimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; 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; 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) Nyl) -5-chlorobenzotriazole, an ultraviolet absorber such as alkoxybenzophenones; an aggregation inhibitor such as sodium polyacrylate; 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 Developability of mono [2- (meth) acryloyloxyethyl] succinate, mono [2- (meth) acryloyloxyethyl] phthalate, ω-carboxypolycaprolactone mono (meth) acrylate, etc. Improving agents and the like can be mentioned.

  The curable composition of the present invention is obtained by pulverizing (A) a colorant in (E) a solvent, if necessary, together with (B) a binder resin and a dispersant, for example, using a bead mill, a roll mill, or the like. A colorant dispersion is prepared by mixing and dispersing, and then (B) a binder resin, a (C) polymerizable compound, an additive, if necessary, and an additional (E) solvent. Is added and mixed.

Cured Film and Infrared Light Transmitting Filter and Production Method Thereof The cured film of the present invention is formed using the curable composition of the present invention, and has a high light-shielding property for light in the visible region and a high infrared region. (Preferably 700 to 1000 nm), it is extremely useful as an infrared light transmitting filter.

The infrared cut filter of the present invention can satisfy the following conditions (1) to (4), and it is preferable that these conditions are satisfied at a film thickness of 1.2 μm.
Condition (1): The maximum light transmittance at a wavelength of 400 to 700 nm is 15% or less.
Condition (2): Minimum light transmittance at a wavelength of 850 to 1000 nm is 85% or more.
Condition (3): The wavelength at which the light transmittance becomes 50% is in the range of 700 to 800 nm.
Condition (4): The difference (λ ₂ −λ ₁ ) between the maximum wavelength λ _{1 at} which the light transmittance is 10% and the minimum wavelength λ _{2 at} which the light transmittance is 80% is within 45 nm. thing.

  The infrared cut filter of the present invention preferably satisfies the following conditions (1-1) to (4-1), and more preferably satisfies these conditions at a film thickness of 1.2 μm. By adopting such an aspect, in the transmission spectrum measured by the spectrophotometer, transmission of light in the visible region is further suppressed, and a spectrum shape which rises sharply from the visible region to the infrared region can be obtained. In addition, the blocking of light in the visible region and the transmission of light in the infrared region are achieved at a higher level, and the color separation can be significantly improved.

Condition (1-1): The maximum transmittance of light at a wavelength of 400 to 700 nm is preferably 13% or less, more preferably 10% or less, and even more preferably 8% or less.
Condition (2-1): The minimum light transmittance at a wavelength of 850 to 1000 nm is preferably 90% or more, and more preferably 93% or more.
Condition (3-1): The wavelength (nm) at which the light transmittance becomes 50% is preferably in the range of 750 to 800 nm.
Condition (4-1): The wavelength difference (λ ₂ −λ ₁ ) between the maximum wavelength λ _{1 at} which the light transmittance is 10% and the minimum wavelength λ _{2 at} which the light transmittance is 80% is 40 nm. Is preferably within 35 nm, and more preferably within 35 nm.

  Further, the cured film and the infrared cut filter of the present invention may contain the components (a1) to (a3) as the colorant (A). The specific embodiment is as described in the curable composition described above.

The cured film and the infrared light transmitting filter of the present invention can be formed by an appropriate method. For example, using the curable composition of the present invention in a process including the following (i) to (iv): It can be manufactured by providing. Steps (i) to (iv) are preferably performed in the following order.
(I) a step of coating the curable composition of the present invention on a substrate and drying to form a coated film (ii) a step of curing the coated film (iii) a cured film obtained in step (ii) (Iv) a step of heat-treating the developed coating film

Hereinafter, each step will be sequentially described.
-Step (i)-
Step (i) is a step of applying the curable composition of the present invention on the surface of a substrate and drying it to form a coating film.
The substrate is not particularly limited, and examples thereof include glass, quartz, silicon, and resin, which can be appropriately selected. Examples of the resin material include polycarbonate, polyester, aromatic polyamide, polyamide imide, and polyimide. The substrate may be subjected to an appropriate pretreatment such as a chemical treatment with a silane coupling agent or the like, a plasma treatment, an ion plating, a sputtering, a gas phase reaction method, and a vacuum deposition, if desired.

  The method for applying the curable composition is not particularly limited, and for example, an appropriate method such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, or a bar coating method may be employed. it can. Among them, the spin coating method is preferable.

  When drying, heat treatment can be performed if necessary. For the heat treatment, known heating means such as an oven and a hot plate can be used, and the drying under reduced pressure and the drying under heating may be performed in combination. The heating conditions vary depending on the type of each component, the mixing ratio, and the like, but may be, for example, a temperature of 60 to 250 ° C. for about 30 seconds to 15 minutes.

  The film thickness of the coating film after drying is usually 0.1 to 30 μm, preferably 0.2 to 10 μm, and more preferably 0.3 to 5 μm.

-Step (ii)-
Step (ii) is a step of curing the coating film formed in step (i).
The curing treatment is not particularly limited, and can be appropriately selected depending on the purpose. For example, an exposure process, a heating process, and the like can be given. Here, in the present specification, “exposure” is a concept that includes not only light of various wavelengths but also irradiation of radiation such as electron beams and X-rays.

As a method of the exposure treatment, for example, a method of exposing a part or the whole of the surface of the formed coating film is exemplified.
Exposure is preferably performed by irradiation with radiation, and examples of the radiation include ultraviolet rays such as electron beams, KrF, ArF, g-rays, h-rays, and i-rays, and visible light, among which KrF, g-rays, and h-rays. , I-line is preferred.
Examples of the exposure method include stepper exposure and exposure using a high-pressure mercury lamp.
Exposure is preferably 5~3000mJ / cm ^2, more preferably 10 to 2000 mJ / cm ^2, more preferably 50~1000mJ / cm ^2.
The exposure apparatus is not particularly limited, and a known apparatus can be appropriately selected. For example, a UV exposure apparatus such as an ultra-high pressure mercury lamp can be used.

In addition, examples of the heat treatment include a method of heating a part or the whole of the surface of the formed coating film.
The heating temperature is preferably from 120 to 250 ° C, more preferably from 160 to 230 ° C.
The heating time is preferably from 3 minutes to 180 minutes, more preferably from 5 minutes to 120 minutes.
The heating device is not particularly limited, and a known device can be appropriately selected. Examples thereof include a dry oven, a hot plate, and an IR heater.

  The thickness of the cured film thus formed is preferably 0.1 to 10 μm, more preferably 0.3 to 5 μm, and still more preferably 0.5 to 3 μm.

-Step (iii)-
Step (iii) is a step of developing at least a part of the cured film obtained in step (ii).
As the developer, an alkaline developer is usually used. Examples of the alkaline developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, and 1,5-diazabicyclo-. An aqueous solution such as [4.3.0] -5-nonene is preferred.
An appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant can be added to the alkaline developer. After the development, it is usually washed with water.
As a developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid level) developing method, or the like can be applied. The temperature of the developer is usually room temperature, and the development is usually performed for about 10 to 300 seconds.

-Step (iv)-
Step (iv) is a step of subjecting the developed coating film to a heat treatment (post-baking).
The post-baking conditions are usually at 100 to 300 ° C. for about 1 to 60 minutes.
The thickness of the cured film thus formed is usually 0.3 to 3.0 μm, preferably 0.7 to 1.5 μm.

The obtained cured film and infrared light transmitting filter can have the following characteristics, and preferably have these characteristics at a film thickness of 1.2 μm.
(I) Maximum transmittance of light at a wavelength of 400 to 700 nm: usually 15% or less, preferably 13% or less, more preferably 10% or less, further preferably 8% or less.
(Ii) Minimum transmittance of light at a wavelength of 850 to 1000 nm: usually 85% or more, preferably 90% or more, more preferably 93% or more.
(Iii) Wavelength at which light transmittance becomes 50%: usually in the range of 700 to 800 nm, preferably in the range of 750 to 800 nm.
(Iv) wavelength difference (λ ₂ −λ ₁ ) between the maximum wavelength λ _{1 at} which the light transmittance becomes 10% and the minimum wavelength λ _{2 at} which the light transmittance becomes 80%: usually within 45 nm, preferably, It is within 40 nm, more preferably within 35 nm.

  As described above, the cured film and the infrared light transmission filter of the present invention only have sufficient transmission light in the visible region, as shown in FIG. 4, in the transmission spectrum measured by the spectrophotometer. Rather, it has a spectral shape that rises steeply from the visible region to the infrared region, and therefore has excellent color separation.

Solid-state imaging device The solid-state imaging device of the present invention includes the cured film of the present invention, and can have an appropriate structure. For example, as one embodiment, the curable composition of the present invention is used to form a cured film on a semiconductor substrate such as a CMOS substrate by the same operation as described above. Thus, a solid-state imaging device excellent in quality can be manufactured. The wavelength of the infrared light is usually 750 to 2500 nm, preferably 850 to 1000 nm.
Hereinafter, a solid-state imaging device according to an embodiment of the present invention will be described in detail with reference to the drawings. The embodiment described below is an example of the embodiment of the present invention, and the present invention is not limited to the embodiment described here.

Note that, in the drawings referred to in the present embodiment, the same portions or portions having similar functions are denoted by the same reference numerals or similar reference numerals (symbols obtained by adding a, b, etc. after the numerals), and the same is repeated. May be omitted. Further, the dimensional ratios in the drawings do not always match the actual ratios for convenience of illustration, and a part of the configuration may be omitted from the drawings.
In this specification, “up” refers to a relative position with respect to the main surface of the support substrate (the surface on which the solid-state imaging device is arranged), and the direction away from the main surface of the support substrate is “up”. It is. In the drawings of the present application, the upper side toward the paper surface is “upper”. Further, “above” includes a case where the object is in contact with the object (that is, “on”) and a case where the object is located above the object (that is, “over”). Conversely, “down” indicates a relative position with respect to the main surface of the support substrate, and the direction approaching the main surface of the support substrate is “down”. In the drawings of the present application, the lower side is “lower” toward the paper surface.

  FIG. 1 is an application example of a solid-state imaging device according to an embodiment of the present invention. Specifically, an example is shown in which the solid-state imaging device of the present embodiment is applied to a TOF (Time Of Flight) type imaging device (for example, a range image camera). Note that the imaging device described here is only a schematic diagram, and does not prevent other components from being added or deleted.

  In FIG. 1, an imaging device (camera) 10 includes a light source 11, a solid-state imaging device (image sensor) 12, a signal processing unit 13, and a main control unit 14 as basic components. The main control unit 14 is connected to the light source 11, the solid-state imaging device 12, and the signal processing unit 13, and plays a role of controlling each operation. The solid-state imaging device 12 is further connected to a signal processing unit 13, and transmits an electric signal generated by the solid-state imaging device 12 to the signal processing unit 13.

  As the light source 11, a known LED (Light Emitting Diode) that outputs infrared light can be used. The infrared light output from the light source 11 strikes the imaging object 15 and is reflected, and the reflected light enters the solid-state imaging device 12. At this time, a phase difference corresponding to the three-dimensional shape of the imaging target 15 occurs between the infrared light output from the light source 11 and the infrared light returned from the imaging target 15.

  As the solid-state imaging device 12, a CMOS image sensor or a CCD image sensor can be used. As the CMOS image sensor, any of a front-illuminated type and a back-illuminated type can be used. In the present embodiment, a highly sensitive back-illuminated CMOS image sensor is used.

  The external visible light reflected by the imaging object 15 and the infrared light output from the light source 11 are incident on a solid-state imaging device (also referred to as a photoelectric conversion element or a sensor element) in the solid-state imaging device 12 and are corresponding to the amount of light. Converted to electrical signals. The converted electric signal is digitized by an AD conversion circuit provided in the solid-state imaging device 12, and is output to the signal processing unit 13 as a digital signal. The specific structure of the solid-state imaging device 12 will be described later.

  The signal processing unit 13 receives the digital signal output from the solid-state imaging device 12, performs signal processing, and forms an image based on the imaging target 15. At this time, a digital signal based on visible light is used as information for reproducing the color and shape of the imaging target 15, and a digital signal based on infrared light is used as information for recognizing a distance to the imaging target 15. Used. These digital signals make it possible to grasp the imaging object 15 three-dimensionally.

  The main control unit 14 is an arithmetic processing unit centered on the CPU, controls the light source 11, the solid-state imaging device 12, and the signal processing unit 13, and performs other operations (not shown) based on information obtained from the signal processing unit 13. Is also controlled.

  FIG. 2 is a plan view for explaining the outline of the solid-state imaging device 12. The pixel section 17 and the terminal section 18 are arranged in the package 16. An AD conversion circuit may be provided between the pixel unit 17 and the terminal unit 18. The enlargement unit 19 shows a state where a part of the pixel unit 17 is enlarged. As shown in the enlargement section 19, the pixel section 17 includes a plurality of pixels 20 arranged in a matrix.

  FIG. 2 shows only a simple structure such as the pixel unit 17 and the terminal unit 18, but the solid-state imaging device according to the present embodiment is not limited to this. For example, the function as the signal processing unit 13 shown in FIG. 1 can be built in the solid-state imaging device 12 shown in FIG. Further, a system IC circuit having an arithmetic processing capability equivalent to that of the main control unit 14 shown in FIG. 1 and having an imaging function and an arithmetic function in one chip may be used.

  FIG. 3 is a cross-sectional view of the pixel 20 shown in FIG. 2 taken along line III-III '. 3, the first optical layer 21, the first gap 22, the microlens array 23, the second gap 24, the second optical layer 25, the third gap 26, the visible light transmitting filter ( Color filters 27a to 27c, an infrared light transmitting filter 27d, an insulator 28, photodiodes 29a to 29d, and a support substrate 30 are illustrated. The first gap 22, the second gap 24, and the third gap 26 may be secured as a space filled with air or an inert gas, or may be secured as an insulator composed of an organic insulating film or an inorganic insulating film. You may. Further, the first gap 22, the second gap 24, or the third gap 26 may not be provided. For example, the second optical layer 25 may be in contact with the visible light transmitting filters 27a to 27c, or the micro lens array 23 The second optical layer 25 may be in contact with the second optical layer 25.

  In the present specification, a pixel including the visible light transmitting filters 27a to 27c and the photodiodes 29a to 29c arranged corresponding to the visible light transmitting filters 27a to 27c is referred to as a "visible light detecting pixel", and the infrared light transmitting filter 27d and the The pixel constituted by the photodiode 29d is called an "infrared light detection pixel".

  Here, the first optical layer 21 is an optical layer that transmits at least a part of visible light and infrared light, and is, for example, a visible light having a wavelength of 400 to 700 nm and at least a part of a wavelength of 750 to 2500 nm (typically, 750-950 nm). Of course, the wavelength range to be transmitted is not limited to the range described here, and can be detected by visible light corresponding to R (red), G (green), and B (blue) light and an infrared light detection pixel described later. It is only necessary to transmit infrared light in a specific wavelength range. Such a filter having an optical characteristic transmitting two different wavelength ranges is generally called a two-wavelength bandpass filter.

  In the present embodiment, as the first optical layer 21, an optical layer in which a dielectric multilayer film is provided on a base having a transparent resin (resin having a light transmitting property) layer containing a compound having specific optical characteristics is used. . Examples of the compound having specific optical characteristics include a compound that absorbs a part of infrared light (hereinafter, referred to as “compound (X)”). The compound (X) is not particularly limited as long as it can absorb a part of infrared light. Examples of the compound (X) include a squarylium compound, a naphthalocyanine compound, a croconium compound, a hexaphyrin compound, and a cyanine compound. Can be mentioned.

  As described above, by providing the dielectric multilayer film on the substrate having the transparent resin layer containing the compound (X) that absorbs a part of infrared light, at least part of visible light and infrared light is transmitted. It can be a two-wavelength bandpass filter. At this time, the substrate may be a single layer or a multilayer. If it is a single layer, it can be a flexible substrate composed of a transparent resin layer. In the case of a multilayer, for example, a substrate in which a transparent resin layer containing a compound (X) and a curable resin is laminated on a transparent substrate such as a glass substrate or a resin substrate, or a curable resin on a transparent substrate containing a compound (X) A substrate on which a resin layer such as an overcoat layer containing a resin is laminated can be used.

  As described above, when the first optical layer 21 is made of a resin base material, it is easy to make the first optical layer 21 thinner than a general two-wavelength bandpass filter, and for example, it can be formed into a film. That is, in the case where a dielectric multilayer film is laminated on a substrate having a transparent resin layer containing the compound (X), the thickness of the first optical layer 21 is, for example, 200 μm or less, preferably 180 μm or less, Preferably it can be 150 μm or less, particularly preferably 120 μm or less.

  In the microlens array 23, the position of each microlens corresponds to the position of each pixel, and the incident light condensed by each microlens is applied to each corresponding pixel (specifically, each photodiode). Received. Since the microlens array 23 can be formed using a resin material, it can be formed on-chip. For example, an insulator may be used as the second gap 24, and the microlens array 23 may be formed by processing a resin material applied thereon. Further, a base made of resin is used as the second gap 24, and after processing the resin material applied thereon to form the microlens array 23, the base is attached to the solid-state imaging device 12. May be incorporated.

  The second optical layer 25 is an optical layer that absorbs at least a part of infrared light, and includes, for example, a compound having an absorption maximum at a wavelength of 750 to 2000 nm (hereinafter, referred to as “compound (Y)”). The compound (Y) is not particularly limited as long as it can absorb at least a part of infrared light. For example, a diiminium compound, a squarylium compound, a cyanine compound, a naphthalocyanine compound, a quaterylene compound, an aminium compound Compounds, iminium compounds, azo compounds, anthraquinone compounds, porphyrin compounds, pyrrolopyrrole compounds, oxonol compounds, croconium compounds, hexaphyrin compounds, metal dithiol compounds, copper compounds, tungsten compounds, metal borides And the like. The second optical layer 25 functions as an infrared light cut filter that absorbs a part of infrared light according to the optical characteristics of the compound (Y).

  The second optical layer 25 has an opening at a portion corresponding to the infrared light detection pixel (specifically, the photodiode 29d). That is, an opening is provided above the photodiode 29d so that the infrared light can reach the photodiode 29d as it is, so that the infrared light is not impeded. In other words, the “portion corresponding to the photodiode 29d” in the second optical layer 25 is a portion above the photodiode 29d, that is, a portion where the optical path of the infrared light toward the photodiode 29d intersects with the second optical layer 25. Point to.

  As described above, the second optical layer 25 is disposed so as to cover a portion other than the infrared light detection pixels (that is, the visible light detection pixels). This makes it possible to minimize the arrival of infrared light at the visible light detection pixels. As a result, noise components can be reduced in the visible light detection pixels, and the detection accuracy of visible light can be improved.

  A pixel group including the above-described visible light detection pixels and infrared light detection pixels is disposed below the second optical layer 25. As described above, in the present embodiment, the photodiodes 29a to 29c and the visible light transmitting filters 27a to 27c correspond to the visible light detecting pixels, respectively. The photodiode 29d and the infrared light transmitting filter 27d correspond to each other to form an infrared light detection pixel. In this specification, the photodiodes 29a to 29c are referred to as “first light receiving elements”, and the photodiode 29d is referred to as “second light receiving elements”.

  Actually, the visible light transmitting filters 27a to 27c are configured by pass filters that transmit visible light of different wavelengths. For example, the visible light transmitting filter may include a pass filter 27a that transmits green light, a pass filter 27b that transmits red light, and a pass filter 27c that transmits blue light. Therefore, the pixels corresponding to the individual colors may be referred to as green light detection pixels, red light detection pixels, and blue light detection pixels, respectively. The visible light transmitting filters 27a to 27c can be made of a resin material containing a coloring matter (pigment or dye) having absorption at a specific wavelength.

  Further, the infrared light transmission filter 27d can be suitably manufactured using the curable composition of the present invention. Further, as shown in FIG. 4, the infrared light transmission filter 27d not only sufficiently blocks transmission of light in the visible region but also transmits infrared light from the visible region in the transmission spectrum measured by the spectrophotometer. It has a spectral shape that rises steeply over the region and has the property of sufficiently blocking light in the visible region, while exhibiting the property of sufficiently transmitting light in the longer wavelength side than near the wavelength of 800 nm. It is.

  The above-described photodiodes 29a to 29d can be formed using a silicon substrate as the support substrate 30 and using a known semiconductor process on the surface of the silicon substrate. Of course, the photodiodes 29a to 29d can be formed by using a substrate of glass, ceramics, resin, or the like as the support substrate 30 and using a known thin film forming technique.

  In the present embodiment, the photodiode 29a is used as a light receiving element for receiving green light having a wavelength of 520 to 560 nm, the photodiode 29b is used as a light receiving element for receiving red light having a wavelength of 580 to 620 nm, and the photodiode 29c is used. Is used as a light receiving element for receiving blue light having a wavelength of 430 to 470 nm. As described above, in the solid-state imaging device 12 of the present embodiment, visible light incident from the outside is detected using the photodiodes 29a to 29c.

  On the other hand, the photodiode 29d functions as a light receiving element for receiving infrared light having a wavelength of 750 to 2500 nm (typically 750 to 950 nm), and the photodiode 29d detects infrared light incident from the outside. Is done.

  The solid-state imaging device 12 according to the present embodiment first filters external light by the first optical layer 21 and at least partially (visible in detail) visible light having a wavelength of 400 to 700 nm and infrared light having a wavelength of 750 to 2500 nm. 750 to 950 nm). Then, a part of the visible light and the infrared light transmitted through the first optical layer 21 enters the second optical layer 25. At this time, since an opening is provided in the second optical layer 25 above the photodiode 29d, part of the visible light and the infrared light transmitted through the first optical layer 21 is directly transmitted to the infrared light transmitting filter. 27d. In the infrared light transmission filter 27d, visible light having a wavelength of approximately 750 nm or less is absorbed (cut), and infrared light having a wavelength of 750 to 950 nm enters the photodiode 29d. Thus, the distance to the imaging object 15 can be accurately determined without being affected by noise or the like due to visible light.

  Therefore, the solid-state imaging device 12 according to the present embodiment includes, for example, a remote controller for a game machine or a television, a remote control device such as an automatic door, a vehicle-mounted device such as an inter-vehicle distance detection sensor of an automobile, a vehicle collision prevention sensor, and an industrial camera. It can be suitably used as a medical near-infrared camera, surveillance camera, digital camera, video camera and the like.

  Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

<Synthesis of dispersant>
Synthesis Example 1
Referring to Example 1 of WO2012 / 001945 pamphlet, a block composed of an A block having a repeating unit derived from dimethylaminoethyl methacrylate and a B block having a repeating unit derived from butyl methacrylate, methyl methacrylate and methacrylic acid. Copolymer (copolymerization ratio of each repeating unit is dimethylaminoethyl methacrylate / butyl methacrylate / methyl methacrylate / methacrylic acid = 22/50/23/5, Mw is 12,720, and Mw / Mn = 1.46. Is synthesized. This block copolymer is referred to as “dispersant (X-1)”.

Synthesis Example 2
With reference to Example 1 of International Publication No. 2011/129078 pamphlet, A block having a repeating unit derived from dimethylaminoethyl methacrylate, butyl methacrylate, PME-200 (Methoxy polyethylene glycol monomethacrylate, manufactured by NOF CORPORATION) And a block copolymer comprising a B block having a repeating unit derived from methacrylic acid (the copolymerization ratio of each repeating unit is dimethylaminoethyl methacrylate / butyl methacrylate / PME-200 / methacrylic acid = 22/47/26/5). And Mw is 10,000). This block copolymer is referred to as “dispersant (X-2)”.

<Synthesis of binder resin>

Synthesis Example 3
A flask equipped with a condenser and a stirrer was charged with 3 parts by mass of 2,2′-azobisisobutyronitrile and 100 parts by mass of propylene glycol monomethyl ether acetate, and subsequently 12 parts by mass of N-phenylmaleimide, 10 parts by mass of styrene, 20 parts by mass of methacrylic acid, 15 parts by mass of 2-hydroxyethyl methacrylate, 29 parts by mass of 2-ethylhexyl methacrylate, 14 parts by mass of benzyl methacrylate, and 5 parts by mass of pentaerythritol tetrakis (3-mercaptopropionate, manufactured by Sakai Chemical Industry Co., Ltd.) Was charged and replaced with nitrogen. Thereafter, the mixture was gradually stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 3 hours to carry out polymerization. Thereafter, the temperature of the reaction solution was raised to 100 ° C., and polymerization was further performed for 1 hour to obtain a solution containing a binder resin. This binder resin is referred to as “binder resin (B-1)”. The obtained binder resin (B-1) had Mw of 9,700 and Mn of 5,700.

<Preparation of colorant dispersion>
Preparation Example 1
C. I. Pigment Blue 15: 6, 45 parts by mass, C.I. I. Pigment Violet 23, 20 parts by mass of C.I. I. 35 parts by mass of CI Pigment Yellow 139, 40 parts by mass of the dispersant (X-1), 25 parts by mass of the binder resin (B-1), and 835 parts by mass of propylene glycol monomethyl ether acetate were mixed. The mixture was dispersed for 8 hours using a paint shaker to obtain Colorant Dispersion 1.

Preparation Examples 2 to 16
In Preparation Example 1, Colorant Dispersions 2 to 16 were produced in the same manner as in Preparation Example 1, except that the types and amounts of the components were changed as shown in Table 1.

In Table 1, each component is as follows.
B15: 6: C.I. I. Pigment Blue 15: 6
B15: 4: C.I. I. Pigment Blue 15: 4
V23: C.I. I. Pigment Violet 23
Y139: C.I. I. Pigment Yellow 139
R254: C.I. I. Pigment Red 254
Bk32: C.I. I. Pigment Black 32
E-1: propylene glycol monomethyl ether acetate

<Preparation and evaluation of curable composition>
Example 1
Preparation of curable composition 1000 parts by mass of colorant dispersion 1, 7 parts by mass of binder resin (B-1), KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate) 40 parts by mass), and 10 parts by mass of 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (Irgacure OXE01, manufactured by Ciba Specialty Chemicals Co., Ltd.). And 50 parts by mass of propylene glycol monomethyl ether acetate were mixed to prepare a curable composition 1.
The solid content concentration in the curable composition 1 is 20% by mass, and the content ratio of the colorant to the total solid content in the curable composition 1 is 45% by mass. Further, the content ratio of the component (a1) is 45% by mass, the content ratio of the component (a2) is 20% by mass, and the content ratio of the component (a3) is 35% by mass with respect to all the colorants.

Evaluation of Cured Film The curable composition 1 was applied on a glass substrate by spin coating, and then heated at 100 ° C. for 180 seconds to form a coating film. Thereafter, the coating film on the substrate was exposed entirely (exposure amount of 1000 mJ / cm ² at a wavelength of 365 nm). Next, after the coating film was brought into contact with an aqueous solution containing 0.05% by mass of tetramethylammonium hydroxide for 15 seconds, the coating film was washed with water. Next, the glass substrate having the coating film was heated on a hot plate at 200 ° C. for 300 seconds to obtain a glass substrate having a 1.2 μm-thick cured film.
Using the spectrophotometer (V-7300, manufactured by JASCO Corporation), the transmittance (% T) of the obtained glass substrate at a wavelength of 400 to 1000 nm was measured in increments of 1 nm. The transmittance and light-shielding property of the cured film were evaluated according to 4. Table 2 shows the evaluation results. However, the transmittance in Table 2 is a value in comparison with a glass substrate.
In addition, the film thickness was measured with a stylus type step meter (manufactured by Yamato Scientific Co., Ltd., Alpha Step IQ).

Evaluation item 1: Maximum transmittance of light at a wavelength of 400 to 700 nm (%)
Evaluation item 2: Minimum transmittance (%) of light at a wavelength of 850 to 1000 nm
Evaluation item 3: wavelength (nm) at which light transmittance becomes 50%
Evaluation item 4: wavelength difference (λ ₂ −λ ₁ ) (nm) between the maximum wavelength λ _{1 at} which the light transmittance is 10% and the minimum wavelength λ _{2 at} which the light transmittance is 80%.

Examples 2 to 6 and Comparative Examples 1 to 10
Curable compositions 2 to 16 were prepared in the same manner as in Example 1 except that the types and amounts of the components were changed as shown in Table 2. Then, evaluation was performed in the same manner as in Example 1. Table 2 shows the results. FIG. 4 shows the transmission spectrum (solid line) of the cured film obtained in Example 1, the transmission spectrum (dashed line) of the cured film obtained in Comparative Example 1, and the transmission spectrum (dotted line) of the cured film obtained in Comparative Example 2. ) Are shown.

In Table 2, each component is as follows.
C-1: KAYARAD DPHA (Nippon Kayaku Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
C-2: Monoesterified product of dipentaerythritol pentaacrylate and succinic acid, a mixture of dipentaerythritol hexaacrylate and a mixture of dipentaerythritol pentaacrylate (trade name: TO-1382, manufactured by Toagosei Co., Ltd.)
C-3: Aronix M-450 (Toa Gosei Co., Ltd., mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate)
C-4: Kayarad DPEA-12 (manufactured by Nippon Kayaku Co., Ltd., ethylene oxide-modified dipentaerythritol hexaacrylate)
D-1: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one (trade name Irgacure 369, manufactured by Ciba Specialty Chemicals)
D-2: 1,2-octanedione, 1- [4- (phenylthio) phenyl]-, 2- (O-benzoyloxime) (trade name Irgacure OXE01, manufactured by Ciba Specialty Chemicals)
D-3: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime)] (manufactured by Ciba Specialty Chemicals) Product name Irgacure OXE02)

10: Imaging equipment (camera)
11: light source 12: solid-state imaging device (image sensor)
13: signal processing unit 14: main control unit 15: imaging object 16: package 17: pixel unit 18: terminal unit 19: enlargement unit 20: pixel 21: first optical layer (two-wavelength bandpass filter)
22: first gap 23: microlens array 24: second gap 25: second optical layer (infrared cut filter)
26: third gaps 27a to 27c: visible light transmitting filter (color filter)
27d: infrared light transmitting filter 28: insulators 29a to 29d: photodiode 30: support substrate

Claims (8)

A curable composition containing (A) a colorant, (B) a binder resin, and (C) a polymerizable compound,
(A) the colorant comprises the following components (a1) to (a3);
(A1) at least one colorant selected from the group consisting of a compound having a structure represented by the following formula (1) and a compound having a structure represented by the following formula (2)
(A2) at least one colorant selected from the group consisting of a purple colorant and a red colorant
(A3) Yellow colorant
[In the formula (1), M represents a metal atom. ]
Wherein the content of the component (a1) is 20 to 70% by mass with respect to all the colorants, the content of the component (a2) is 5 to 50% by mass with respect to all the colorants, and (a3) The content ratio of the component is 24 to 50% by mass with respect to all the colorants,
A curable composition that satisfies the following conditions (1) to (4) when a cured film having a thickness of 1.2 μm is formed.
Condition (1): The maximum light transmittance at a wavelength of 400 to 700 nm is 15% or less.
Condition (2): Minimum light transmittance at a wavelength of 850 to 1000 nm is 85% or more.
Condition (3): The wavelength at which the light transmittance becomes 50% is in the range of 700 to 800 nm.
Condition (4): The difference (λ ₂ −λ ₁ ) between the maximum wavelength λ _{1 at} which the light transmittance is 10% and the minimum wavelength λ _{2 at} which the light transmittance is 80% is within 45 nm. thing. Red colorant comprises a diketopyrrolopyrrole-based red pigment, claim 1 curable composition according. The purple colorant is C.I. I. The curable composition according to claim 1 , wherein the curable composition is at least one selected from the group consisting of Pigment Violet 23 and a xanthene-based violet dye. The compound having the structure represented by the formula (1) is C.I. I. Pigment Blue 15: 3, C.I. I. Pigment Blue 15: 4 and C.I. I. The curable composition according to any one of claims 1 to 3 , which is at least one selected from the group consisting of CI Pigment Blue 15: 6. The curable composition according to any one of claims 1 to 4 , wherein the yellow colorant is an isoindoline-based yellow pigment. Cured film formed by using the curable composition according to any one of claims 1-5. IR transmission filter formed by using the curable composition according to any one of claims 1-5. A solid-state imaging device comprising the cured film according to claim 6 .