WO2019039172A1 - 構造体、構造体の製造方法、吸収層形成用組成物、固体撮像素子および画像表示装置 - Google Patents
構造体、構造体の製造方法、吸収層形成用組成物、固体撮像素子および画像表示装置 Download PDFInfo
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- WO2019039172A1 WO2019039172A1 PCT/JP2018/027737 JP2018027737W WO2019039172A1 WO 2019039172 A1 WO2019039172 A1 WO 2019039172A1 JP 2018027737 W JP2018027737 W JP 2018027737W WO 2019039172 A1 WO2019039172 A1 WO 2019039172A1
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- H—ELECTRICITY
- H04—ELECTRIC COMMUNICATION TECHNIQUE
- H04N—PICTORIAL COMMUNICATION, e.g. TELEVISION
- H04N23/00—Cameras or camera modules comprising electronic image sensors; Control thereof
- H04N23/10—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths
- H04N23/12—Cameras or camera modules comprising electronic image sensors; Control thereof for generating image signals from different wavelengths with one sensor only
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
- H10F39/011—Manufacture or treatment of image sensors covered by group H10F39/12
- H10F39/024—Manufacture or treatment of image sensors covered by group H10F39/12 of coatings or optical elements
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
- H10F39/10—Integrated devices
- H10F39/12—Image sensors
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
- H10F39/80—Constructional details of image sensors
- H10F39/802—Geometry or disposition of elements in pixels, e.g. address-lines or gate electrodes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/14—Monoazo compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/24—Disazo or polyazo compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
- C09B57/04—Isoindoline dyes
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- H10F39/00—Integrated devices, or assemblies of multiple devices, comprising at least one element covered by group H10F30/00, e.g. radiation detectors comprising photodiode arrays
- H10F39/80—Constructional details of image sensors
- H10F39/805—Coatings
- H10F39/8053—Colour filters
Definitions
- the present invention relates to a structure, a method of manufacturing a structure, a composition for forming an absorption layer, a solid-state imaging device, and an image display device.
- a color filter has pixels containing a colorant.
- color degradation may occur.
- attempts have been made to improve the light resistance of the color filter by providing a layer containing an ultraviolet absorber on the light incident side of the color filter (see Patent Documents 1 to 7).
- an object of the present invention is to provide a structure having a color filter excellent in light resistance. Another object of the present invention is to provide a method for producing a structure having a color filter excellent in light resistance, a composition for forming an absorption layer used in the above structure, a solid-state imaging device and an image display device including the above structure. .
- the present invention is as follows.
- a color filter having two or more different types of pixels An absorbing layer comprising a yellow colorant and at least one selected from colorants having a maximum absorption wavelength in the range of 400 to 500 nm;
- the structure which has an absorption layer in the optical path of at least 1 type of pixel among the pixels of a color filter, and on the incident side of the light to a pixel.
- the ultraviolet light absorber is at least one selected from a benzotriazole compound, a benzophenone compound and a triazine compound.
- ⁇ 4> The structure according to any one of ⁇ 1> to ⁇ 3>, wherein the absorption layer contains at least one selected from an azo compound and an isoindoline compound.
- ⁇ 5> The structure according to any one of ⁇ 1> to ⁇ 3>, including at least one selected from color index pigment yellow 139, color index pigment yellow 150, and color index pigment yellow 185. .
- ⁇ 6> The color filter according to any one of ⁇ 1> to ⁇ 5>, including at least one type of colored pixel selected from a green pixel and a red pixel, and having an absorption layer on the light path of the colored pixel. Structure.
- the color filter includes green pixels, red pixels and blue pixels, In any one of ⁇ 1> to ⁇ 5>, an absorption layer is provided on the light path of at least one pixel selected from a green pixel and a red pixel, and no absorption layer is provided on the light path of the blue pixel.
- Structure of. The structure as described in ⁇ 7> in which an ⁇ 8> green pixel contains a halogenated zinc phthalocyanine pigment.
- the structure as described in ⁇ 7> or ⁇ 8> which has an absorption layer on the optical path of a ⁇ 9> green pixel and a red pixel.
- a film thickness of the ⁇ 11> absorption layer is 0.1 to 1 times a film thickness of a pixel provided on the light path of the absorption layer.
- the ⁇ 12> color filter further includes at least one pixel selected from a transparent pixel and a pixel of the infrared transmission layer.
- the ⁇ 13> absorption layer is obtained by curing a composition containing a yellow colorant and at least one colorant selected from colorants having a maximum absorption wavelength in the wavelength range of 400 to 500 nm, and a curable compound.
- a method for producing a structure comprising the steps of forming a color filter and forming an absorption layer,
- the color filter has two or more different types of pixels,
- the absorbing layer contains at least one selected from a yellow colorant and a colorant having a maximum absorption wavelength in the range of 400 to 500 nm.
- the structure has an absorption layer on the light path of at least one of the pixels of the color filter on the light incident side of the pixel,
- the step of forming the absorption layer includes the step of applying a composition for forming an absorption layer containing a yellow colorant and at least one selected from colorants having a maximum absorption wavelength in the range of 400 to 500 nm. Production method.
- the manufacturing method of the structure as described in ⁇ 15> which apply
- the manufacturing method of the structure as described in ⁇ 15> or ⁇ 16> which the process of forming a ⁇ 17> absorption layer further includes the process of forming a pattern.
- a composition for forming an absorption layer of a structure having an absorption layer on the light path of at least one of the pixels of the color filter and on the light incident side of the pixels A composition for forming an absorption layer, which comprises a yellow colorant and at least one selected from colorants having a maximum absorption wavelength in the range of 400 to 500 nm.
- a solid-state imaging device having the structure according to any one of ⁇ 1> to ⁇ 14>.
- An image display apparatus having the structure according to any one of ⁇ 1> to ⁇ 14>.
- a structure having a color filter excellent in light resistance can be provided. Further, it is possible to provide a method of manufacturing a structure having a color filter excellent in light resistance, a composition for forming an absorption layer used in the above-mentioned structure, a solid-state imaging device and an image display device including the above-mentioned structure. .
- 1 is a schematic view showing an embodiment of a structure of the present invention.
- 1 is a schematic view showing an embodiment of a structure of the present invention.
- 1 is a schematic view showing an embodiment of a structure of the present invention.
- 1 is a schematic view showing an embodiment of a structure of the present invention.
- 1 is a schematic view showing an embodiment of a structure of the present invention.
- 1 is a schematic view showing an embodiment of a structure of the present invention.
- 1 is a schematic view showing an embodiment of a structure of the present invention.
- 1 is a schematic view showing an embodiment of a structure of the present invention.
- the notations not describing substitution and non-substitution include those having no substituent and those having a substituent.
- the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
- a bright line spectrum of a mercury lamp generally, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), actinic rays such as X-rays, electron beams and the like can be mentioned.
- EUV light extreme ultraviolet rays
- a numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit value and the upper limit value.
- total solids refers to the total mass of all components of the composition excluding the solvent.
- infrared light refers to light (electromagnetic wave) having a wavelength of 700 to 2500 nm.
- (meth) acrylate represents both or either of acrylate and methacrylate
- (meth) acryl represents both or either of acrylic and methacryl
- Allyl represents both or any of allyl and methallyl
- (meth) acryloyl represents both or any of acryloyl and methacryloyl.
- the term "process” is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).
- the structure of the present invention comprises a color filter having two or more different types of pixels; An absorbing layer comprising a yellow colorant and at least one selected from colorants having a maximum absorption wavelength in the range of 400 to 500 nm; It is characterized in that an absorption layer is provided on the light path of at least one of the pixels of the color filter and on the light incident side to the aforementioned pixels.
- the yellow colorant and the maximum absorption in the wavelength range of 400 to 500 nm are on the light path of at least one of the pixels of the color filter and on the light incident side to the aforementioned pixels.
- the absorption layer containing at least one selected from coloring agents having wavelengths it is possible to effectively absorb light in the vicinity of the ultraviolet region among light in the visible region by the absorption layer.
- the light resistance of the color filter can be enhanced, and the fluctuation of the spectral characteristics of the color filter after the light resistance test can be effectively suppressed.
- the moisture resistance of the color filter can be improved, and the fluctuation of the spectral characteristics can be effectively suppressed even after the moisture resistance test. It is presumed that the reason why such an effect is obtained is that the penetration of water into the color filter can be effectively suppressed by providing the above-mentioned absorption layer.
- the structure of the present invention include the following aspects 1 and 2. According to these aspects, the light resistance of the color filter can be improved without affecting the hue of the pixel of the color filter. Furthermore, the ability to cut off unnecessary absorption can also improve the color separation performance of the pixel.
- the color filter includes green pixels, red pixels and blue pixels, The aspect which has an absorption layer in the optical path of at least one pixel selected from a green pixel and a red pixel, and does not have an absorption layer in the optical path of a blue pixel.
- an absorption layer may be provided on the light path of at least one of the green pixel and the red pixel. It is preferable to have an absorption layer, and more preferable to have an absorption layer on the light path of both the green pixel and the red pixel.
- the green pixel tends to be low in light resistance, and it is likely that the color separation is caused by light irradiation and the green spectrum tends to fluctuate, but the hue of the green pixel is impaired by providing an absorption layer on the light path of the green pixel. Without, it is possible to improve the light resistance.
- the color filter further includes a blue pixel, it is preferable that the absorption path is not provided on the light path of the blue pixel.
- the second aspect it is preferable to have an absorption layer on the light path of the green pixel, and more preferable to have an absorption layer on the light path of both the green pixel and the red pixel.
- the film thickness of the absorption layer is preferably 0.001 to 2 times the film thickness of the pixel provided on the light path of the absorption layer, and more preferably 0.01 to 2 times. More preferably, it is 0.1 to 1 time.
- the color filter may further include a transparent pixel and / or a pixel of the infrared transmission layer (hereinafter, also referred to as another pixel).
- the absorption layer may not be provided on the light path of the other pixels, but the absorption layer is also provided on the light paths of the other pixels from the viewpoint of light resistance Is preferably provided.
- the absorbing layer preferably further contains an ultraviolet absorber. According to this aspect, the light resistance of the color filter can be more significantly improved.
- the pixel of the color filter and the absorption layer be in contact with each other. According to this aspect, the moisture resistance of the color filter can be more significantly improved.
- the structure of the present invention will be described in detail.
- the structure of the present invention comprises a color filter having two or more different types of pixels.
- the color filter is preferably formed on a support.
- the support is not particularly limited.
- a substrate silicon wafer, silicon carbide wafer, silicon nitride wafer, sapphire wafer, glass wafer or the like
- a subbing layer may be provided to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to planarize the surface.
- the color filter has two or more different types of pixels.
- the color filter used in the present invention preferably has at least one type of colored pixel.
- Examples of colored pixels include green pixels, red pixels, blue pixels, cyan pixels, magenta pixels, and yellow pixels, and preferably include at least one selected from green pixels and red pixels.
- the colored pixels can be formed using a composition for forming a colored pixel including a coloring agent described later.
- the green pixel used in the present invention preferably contains a phthalocyanine pigment, and more preferably contains a halogenated zinc phthalocyanine pigment. The composition for forming colored pixels will be described later.
- the light resistance may be improved by increasing the oxygen concentration of the pixels.
- the thickness of a film such as an antireflective film formed between the open air and the structure of the present invention can be reduced, or the aforementioned film can be made discontinuous There are methods such as making the density of the film sparse.
- the coloring pixel may contain only one coloring agent, and may contain two or more coloring agents.
- the green pixels may contain only a green colorant as a colorant described later, and may further contain a yellow colorant as well as the green colorant. By incorporating a yellow colorant in the green pixels, color separation characteristics with other colors can be enhanced.
- the red pixel may contain only a red colorant as a colorant to be described later, and may further contain a yellow colorant as a red colorant. By incorporating a yellow colorant in the red pixel, color separation characteristics with other colors can be enhanced.
- the absorbing layer can enhance the color separation characteristics of the green pixel, and the yellow coloring agent on the green pixel The same effect as in the case of containing.
- the color separation characteristics of the red pixel can be enhanced by the absorption layer even if the red pixel does not contain the yellow colorant. The same effect as in the case where the yellow colorant is contained in the red pixel can be expected.
- films of two or more layers may be laminated to adjust the desired spectral characteristics.
- a film containing the green colorant and a film containing the yellow colorant are laminated to adjust the desired spectral characteristics.
- the color filter may include at least one type of pixel selected from a transparent pixel and a pixel of the infrared transmission layer.
- the minimum value of transmittance in the wavelength range of 400 to 600 nm is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more.
- a transparent pixel can be formed using the composition for transparent pixel formation mentioned later.
- the pixel of the infrared transmission layer is not particularly limited as long as it is a pixel having a spectral characteristic that shields visible light and transmits at least a part of infrared light.
- the pixels of the infrared ray transmitting layer can be formed using a composition for forming an infrared ray transmitting layer described later.
- the pixel of the infrared ray transmitting layer for example, a pixel having any one of the following spectral characteristics (1) to (4) can be mentioned.
- the maximum value of the light transmittance in the thickness direction in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the light transmittance in the thickness direction Pixels whose minimum value in the wavelength range of 800 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this pixel, light in the wavelength range of 400 to 640 nm can be blocked and light in excess of the wavelength of 670 nm can be transmitted.
- the maximum value of light transmittance in the thickness direction in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and light transmittance in the thickness direction Pixels whose minimum value in the wavelength range of 900 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this pixel, light in the wavelength range of 400 to 750 nm can be blocked and light in excess of the wavelength of 850 nm can be transmitted.
- the maximum value of light transmittance in the thickness direction in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and light transmittance in the thickness direction Pixels whose minimum value in the wavelength range of 1000 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this pixel, light in the wavelength range of 400 to 830 nm can be blocked and light in excess of the wavelength of 940 nm can be transmitted.
- the maximum value of light transmittance in the thickness direction in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and light transmittance in the thickness direction Pixels whose minimum value in the wavelength range of 1100 to 1300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). According to this pixel, light in the wavelength range of 400 to 950 nm can be blocked and light in excess of the wavelength of 1040 nm can be transmitted.
- the color filter may be one having two or more different types of pixels, and examples thereof include the following aspects (1) to (3).
- the colored pixels in the embodiments (1) and (2) preferably include at least one selected from a green pixel and a red pixel, and more preferably include at least a green pixel, a red pixel, and a blue pixel. It is preferable that the coloring pixel in the aspect of said (3) is a green pixel or a red pixel.
- each pixel of the color filter is not particularly limited. For example, 100 micrometers or less are preferable, 15 micrometers or less are more preferable, 5 micrometers or less are more preferable, and 1 micrometer or less is especially preferable.
- the thickness of each pixel may be different, but is preferably substantially the same. Further, it is preferable that the height difference between the top surfaces of the pixels be substantially the same.
- the structure of the present invention is a yellow colorant and a maximum absorption wavelength in the wavelength range of 400 to 500 nm on the light path of at least one of the pixels of the color filter and on the light incident side to the above-mentioned pixels. It has the absorption layer containing at least 1 sort (s) chosen from the coloring agent to have.
- the yellow colorant and the colorant having a maximum absorption wavelength in the wavelength range of 400 to 500 nm are also referred to as a colorant Y.
- the absorption layer may be provided on the light incident side of the pixel of the color filter.
- that the absorbing layer is provided on the light incident side of the pixel of the color filter means, for example, when the color filter is formed on the support, the absorbing layer is the support for the color filter. It is preferable to be provided on the opposite side.
- an absorbing layer 20 may be provided on the surface of the color filter 10, and as shown in FIGS. 2 and 3, a microlens provided on the light incident side to the color filter 10.
- the absorbing layer 20 may be provided on the surface of the planarizing layer 30 or 30.
- the absorption layer 20 is a light to the color filter 10 such as the surface of the condenser lens 50 (see FIG. 4), the surface of the infrared cut filter 60 (see FIG. 5), and the surface of the sealing glass 70 (see FIG. 6). It may be provided on the other member provided on the incident side of.
- the absorbing layer 20 is provided on the surface of the color filter 10 (that is, an aspect in which the pixel of the color filter and the absorbing layer are in contact). According to this aspect, the moisture resistance of the color filter can be more significantly improved.
- the condenser lens 50 and the infrared cut filter 60 are drawn away from the flattening layer 40 in FIGS. 4 and 5, the condenser lens 50 and the infrared cut filter 60 and the flattening layer 40 are illustrated. Between the above and the other, some members may be provided depending on the application.
- reference numeral 1 denotes a support.
- the color filter 10 has the pixels 11 to 13, and the absorption layer 20 is provided on the light path of the pixels 11 to 13 of the color filter.
- the absorption layer 20 may be provided on the light path of at least one pixel, and the absorption layer 20 may not be provided on all the light paths of the pixels 11 to 13.
- the absorption layer 20 is provided only in the surface of the incident side of the light of the condensing lens 50, it may be provided only in the surface of the injection
- the absorption layer may be provided on the light path of at least one of the pixels of the color filter.
- the absorption layer may have a pattern or may be a film having no pattern (flat film).
- an absorption layer does not have a pattern, the case where an absorption layer is provided in the optical path of all the pixels of a color filter etc. are mentioned. Further, in the case where the hue of the pixel of the color filter is affected by the absorption layer, it is preferable that the absorption layer is not provided on the light path of these pixels.
- pixels of the type that exerts an influence on hue by the absorption layer include colored pixels of hue having a transmission region in the wavelength range of 400 to 500 nm, such as blue pixels, cyan pixels, magenta pixels, etc. .
- FIG. 7 has a color filter 10a formed of a red pixel 11a, a green pixel 12a and a blue pixel 13a on the support 1.
- the absorbing layer 21 is a red pixel It is preferable to have it on the light path of at least one pixel of 11a and the green pixel 12a, and not to have it on the light path of the blue pixel 13a.
- FIG. 7 has a color filter 10a formed of a red pixel 11a, a green pixel 12a and a blue pixel 13a on the support 1.
- the absorbing layer 21 is a red pixel It is preferable to have it on the light path of at least one pixel of 11a and the green pixel 12a, and not to have it on the light path of the blue pixel 13a.
- the absorption layer 21 is provided on the light path of both the red pixel 11a and the green pixel 12a, but the absorption layer 21 is provided only on the light path of one of the red pixel 11a and the green pixel 12a. It can also be an aspect.
- the total thickness of the absorption layer and the pixels provided with the absorption layer is set to the absorption layer.
- the height of the upper surface of the absorption layer may be adjusted to be substantially the same as the height of the upper surface of the pixel not provided with the absorption layer by adjusting the thickness to be substantially the same as the thickness of the non-pixel.
- the structure shown in FIG. 8 includes, on the support 1, a color filter formed of a red pixel 11b, a green pixel 12b, and a blue pixel 13b. And the absorption layer 22 is provided only on the optical path of the green pixel 12a.
- the total thickness of the green pixel 12b and the absorption layer 22, the thickness of the red pixel 11b, and the thickness of the blue pixel 13b are substantially the same, and the heights of the upper surfaces of the absorption layer 22, the red pixel 11b and the blue pixel 13b are high. It is almost equal.
- the coloring agent Y used for an absorption layer may be either a pigment or a dye, but is preferably a pigment because it is easy to obtain more excellent light resistance and moisture resistance.
- the average particle diameter of the pigment is preferably 0.01 to 0.1 ⁇ m, and more preferably 0.01 to 0.05 ⁇ m.
- the pigment means an insoluble dye compound which is hardly soluble in a solvent.
- a dye refers to a dye compound that dissolves in a solvent.
- the pigment used in the present invention preferably has, for example, an amount dissolved in 100 g of propylene glycol monomethyl ether acetate at 25 ° C.
- the content is more preferably 05 g or less, further preferably 0.01 g or less.
- at least one of the amount dissolved in 100 g of propylene glycol monomethyl ether acetate at 25 ° C. and the amount dissolved in 100 g of water at 25 ° C. preferably exceeds 0.1 g. Is more preferably 5 g or more.
- the colorant Y preferably has a pigment content of 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and substantially only the pigment Is particularly preferred.
- the case where the colorant Y is substantially only a pigment means that the content of the pigment in the colorant Y is 99% by mass or more, and preferably 99.5% by mass or more. It is more preferable that it is 99.9 mass% or more, and it is especially preferable that the coloring agent Y is comprised only with a pigment.
- the colorant Y is preferably at least one selected from an azo compound and an isoindoline compound, more preferably an azo compound, and still more preferably an azo compound having a barbituric acid structure.
- the colorant Y preferably has a maximum absorption wavelength in the range of 450 to 500 nm, and more preferably has a maximum absorption wavelength in the range of 450 to 460 nm.
- colorant Y examples include Color Index (C.I.) Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20 , 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74 , 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 16 , And yellow pigments such as 169,170,171,172,173,174,175,176,177,179,180,181,
- colorant Y compounds having a structure represented by the following formulas (Y1) to (Y4) can also be used.
- R 1 to R 13 each independently represent a hydrogen atom or a substituent, and adjacent groups among R 1 to R 8 may combine to form a ring. However, at least one pair of two adjacent groups of R 1 to R 8 combine to form an aromatic ring.
- R 205 and R 208 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group
- R 201 to R 204 , R 206 and R 207 each independently represent hydrogen represents an atom or a substituent
- Y 1 is a nitrogen atom or -CR Y1 - represents
- Y 2 is a sulfur atom or -NR Y2 - represents
- R Y1 and R Y2 are each independently a hydrogen atom, an alkyl
- X represents a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion or an anion having a boron atom.
- R 301 , R 311 and R 310 each independently represent a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group
- R 302 to R 305 and R 306 to R 309 each independently represent Represents a hydrogen atom or a substituent
- X represents a bis (sulfonyl) imide anion, a tris (sulfonyl) methide anion or an anion having a boron atom.
- R 401 and R 402 each independently represent SO 2 R 403 or COR 403 ;
- R 403 represents an alkyl group, an aryl group or a heteroaryl group.
- coloring agent Y a quinophthalone compound described in paragraph 0011 to 0034 of JP-A-2013-54339, a quinophthalone compound described in paragraph 0013 to 0058 of JP-A 2014-26228, or the like may be used. .
- the absorbing layer preferably contains 30 to 99% by mass of the colorant Y.
- the upper limit is preferably 95% by mass or less, more preferably 90% by mass or less, and still more preferably 85% by mass or less.
- the lower limit is preferably 40% by mass or more, more preferably 45% by mass or more, and still more preferably 50% by mass or more.
- the absorbing layer may contain only one type of colorant Y, or may contain two or more types. When two or more colorants Y are contained, the total amount thereof is preferably in the above range.
- 50% by mass or more of the colorant Y contained in the absorbing layer is at least one selected from an azo compound and an isoindoline compound (preferably an azo compound, more preferably an azo compound having a barbituric acid structure) Is more preferably 70% by mass or more, still more preferably 90% by mass or more.
- 50% by mass or more of the colorant Y contained in the absorbing layer is C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150 and C.I. I. It is preferable that it is at least 1 sort (s) selected from pigment yellow 185 (preferably CI pigment yellow 150), More preferably, it is 70 mass% or more, More preferably, it is 90 mass% or more.
- the absorbing layer preferably contains substantially no colorant other than the colorant Y. According to this aspect, it is possible to improve the light resistance of the color filter without affecting the hue of the pixel of the color filter.
- the absorbing layer substantially does not contain a colorant other than the colorant Y
- the content of the colorant other than the colorant Y is 1 part by mass or less with respect to 100 parts by mass of the colorant Y It is more preferable that it is 0.5 mass part or less, It is still more preferable that it is 0.1 mass part or less, It is especially preferable not to contain.
- the absorbing layer preferably further contains a UV absorber. According to this aspect, not only the light in the vicinity of the ultraviolet region but also the light in the ultraviolet region can be absorbed by the absorption layer among the light in the visible region, so that the light resistance of the color filter can be significantly improved. it can.
- the ultraviolet absorber is preferably a compound having a maximum absorption wavelength in the range of 300 to 380 nm, and more preferably a compound having a maximum absorption wavelength in the range of 320 to 380 nm.
- the molar absorption coefficient of the ultraviolet absorber at a wavelength of 365 nm is preferably 5000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, more preferably 10000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more, and 30000 L ⁇ mol More preferably, it is ⁇ 1 ⁇ cm ⁇ 1 or more.
- the upper limit is preferably, for example, 100000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
- UV absorber conjugated diene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, triazine compounds, benzodithiazole compounds, and the like can be used.
- at least one selected from benzotriazole compounds, benzophenone compounds and triazine compounds is preferable, and triazine compounds are more preferable.
- the conjugated diene compound is preferably a compound represented by the following formula (UV-1).
- R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms, and R 1 and R 2 represent They may be the same as or different from each other, but do not simultaneously represent a hydrogen atom.
- R 1 and R 2 may form a cyclic amino group together with the nitrogen atom to which R 1 and R 2 are bonded. Examples of the cyclic amino group include piperidino group, morpholino group, pyrrolidino group, hexahydroazepino group, piperazino group and the like.
- R 1 and R 2 are preferably independently an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 5 carbon atoms.
- R 3 and R 4 represent an electron withdrawing group.
- R 3 and R 4 are preferably an acyl group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group or a sulfamoyl group, and an acyl group or a carbamoyl group.
- Groups, alkyloxycarbonyl groups, aryloxycarbonyl groups, cyano groups, alkylsulfonyl groups, arylsulfonyl groups, sulfonyloxy groups and sulfamoyl groups are preferable.
- R 3 and R 4 may be bonded to each other to form a cyclic electron withdrawing group.
- bonds and forms the 6-membered ring containing two carbonyl groups can be mentioned, for example.
- At least one of the above R 1 , R 2 , R 3 and R 4 may be in the form of a polymer derived from a monomer bonded to a vinyl group via a linking group. It may be a copolymer with another monomer.
- UV-1 ultraviolet absorber
- UV503 made by Daito Chemical Co., Ltd.
- UV-2 methyldibenzoyl compound
- R 101 and R 102 each independently represent a substituent, and m1 and m2 each independently represent 0 to 4.
- the substituent represented by R 101 and R 102 is a halogen atom, cyano group, nitro group, alkyl group, aryl group, heteroaryl group, alkoxy group, aryloxy group, heteroaryloxy group, alkylthio group, arylthio group, heteroarylthio , -NR U1 R U2 , -COR U3 , -COOR U4 , -OCOR U5 , -NHCOR U6 , -CONR U7 R U8 , -NHCONR U9 R U10 , -NHCOOR U11 , -SO 2 R U12 , -SO 2 OR U13, include -NHSO 2 R U14 or -SO 2 NR U15 R U16.
- R U1 to R U16 each independently represent a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.
- the substituents represented by R 101 and R 102 are preferably each independently an alkyl group or an alkoxy group.
- the carbon number of the alkyl group is preferably 1 to 20, and more preferably 1 to 10.
- the alkyl group may be linear, branched or cyclic, preferably linear or branched, and more preferably branched.
- the carbon number of the alkoxy group is preferably 1 to 20, and more preferably 1 to 10.
- the alkoxy group is preferably linear or branched, more preferably branched.
- UV-2 a combination in which one of R 101 and R 102 is an alkyl group and the other is an alkoxy group is preferable.
- M1 and m2 each independently represent 0 to 4.
- Each of m1 and m2 is preferably independently 0 to 2, more preferably 0 to 1, and particularly preferably 1.
- UV-2 Specific examples of the compound represented by the formula (UV-2) include avobenzone and the like.
- TINUVIN PS TINUVIN 99-2, TINUVIN 109, TINUVIN 328, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 171, TINUVIN 1130 (manufactured by BASF Corporation) and the like.
- benzotriazole compound MYUA series (Chemical Industry Daily, February 1, 2016) manufactured by Miyoshi Yushi may be used.
- TINUVIN 400 As a triazine compound, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, TINUVIN 479 (above, BASF Corporation make) etc. are mentioned.
- benzophenone compounds include 2-hydroxy-4-n-octoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone.
- Commercially available products include Yubinal A, Yubinal 3049, Yubinal 3050 (manufactured by BASF AG), and the like.
- the coumarin compounds include coumarin-4, 4-hydroxycoumarin, 7-hydroxycoumarin and the like.
- the absorbing layer preferably contains 0.1 to 90% by mass of an ultraviolet absorber.
- the upper limit is more preferably 50% by mass or less, still more preferably 30% by mass or less, and still more preferably 20% by mass or less.
- the lower limit is more preferably 1% by mass or more, still more preferably 3% by mass or more, and still more preferably 5% by mass or more.
- the absorbing layer preferably contains 0.1 to 200 parts by mass of an ultraviolet absorber with respect to 100 parts by mass of the colorant Y.
- the upper limit is more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, and still more preferably 30 parts by mass or less.
- the lower limit is more preferably 1 part by mass or more, further preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more. If the ratio between the colorant Y and the ultraviolet light absorber is in the above range, an effect of effectively shielding light in the vicinity of the ultraviolet region to further enhance the light resistance of the pixel can be expected.
- the absorption layer may contain only one type of ultraviolet absorber, or may contain two or more types. When 2 or more types of ultraviolet absorbers are contained, it is preferable that the total amount of them is the said range.
- the absorbing layer can be formed using the composition for forming an absorbing layer containing the colorant Y.
- an absorption layer is a thing obtained by hardening the composition for absorption layer formation containing the coloring agent Y and a curable compound. It is also preferable that the composition for forming an absorption layer further contains a UV absorber. Details of the composition for forming an absorbent layer will be described later.
- the thickness of the absorbing layer is preferably 0.001 to 10 ⁇ m.
- the upper limit is more preferably 5 ⁇ m or less, still more preferably 1 ⁇ m or less, and still more preferably 0.5 ⁇ m or less.
- the lower limit is preferably 0.01 ⁇ m or more, more preferably 0.05 ⁇ m or more, and still more preferably 0.1 ⁇ m or more.
- the absorption layer preferably has a minimum transmittance of 60% or more, more preferably 70% or more, and still more preferably 80% or more in a wavelength range of more than 500 nm and 700 nm or less.
- the absorption layer has a transmittance of 10% in at least a part of a wavelength range of 400 nm to 500 nm (preferably, at least a part of a wavelength range of 400 nm to 450 nm, more preferably a full range of wavelength of 400 nm to 450 nm). It is preferable that it is the following, It is more preferable that it is 5% or less, It is still more preferable that it is 1% or less.
- the absorption layer has a transmittance of 10% in at least part of a wavelength range of 300 nm to less than 400 nm (preferably at least a portion of the wavelength range of 300 nm to less than 400 nm, more preferably the entire range of wavelength of 300 nm to less than 400 nm). It is preferable that it is the following, It is more preferable that it is 5% or less, It is still more preferable that it is 1% or less.
- the structure of the present invention may further have a layer or member such as a flattening layer, a microlens, a condenser lens, an infrared cut filter, sealing glass, etc., in addition to the color filter and the above-described absorption layer.
- a layer or member such as a flattening layer, a microlens, a condenser lens, an infrared cut filter, sealing glass, etc.
- a layer or member such as a flattening layer, a microlens, a condenser lens, an infrared cut filter, sealing glass, etc.
- the structure of the present invention can be incorporated into a solid-state imaging device or an image display device (for example, a liquid crystal display device or an organic electroluminescence (organic EL) display device).
- a solid-state imaging device for example, a liquid crystal display device or an organic electroluminescence (organic EL) display device.
- an image display device for example, a liquid crystal display device or an organic electroluminescence (organic EL) display device.
- composition for absorbent Layer Formation Next, the composition for formation of the absorption layer of the structure of this invention (composition for absorption layer formation) is demonstrated.
- the composition for forming an absorption layer contains a yellow colorant and at least one kind (colorant Y) selected from colorants having a maximum absorption wavelength in the range of wavelength 400 to 500 nm. Details and preferable ranges of the yellow colorant and the colorant having the maximum absorption wavelength in the range of 400 to 500 nm are the same as the contents described in the section of the above-mentioned absorption layer.
- the content of the colorant Y is preferably 30 to 99% by mass with respect to the total solid content of the composition for forming an absorption layer.
- the upper limit is more preferably 95% by mass or less, still more preferably 90% by mass or less, and still more preferably 85% by mass or less.
- the lower limit is more preferably 40% by mass or more, still more preferably 45% by mass or more, and still more preferably 50% by mass or more.
- the composition for forming an absorbent layer may contain only one type of colorant Y or may contain two or more types. When two or more colorants Y are contained, the total amount thereof is preferably in the above range.
- the composition for forming an absorbent layer preferably contains substantially no colorant other than the colorant Y. According to this aspect, it is possible to improve the light resistance of the color filter without affecting the hue of the pixel of the color filter.
- the content of the colorant other than the colorant Y is 1 part by mass with respect to 100 parts by mass of the colorant Y It is preferable that it is the following, It is more preferable that it is 0.5 mass part or less, It is still more preferable that it is 0.1 mass part or less, It is especially preferable not to contain.
- the composition for absorber layer formation further contains an ultraviolet absorber in addition to the colorant Y. According to this aspect, the light resistance of the color filter can be more significantly improved.
- the details and the preferable range of the ultraviolet absorber are the same as the contents described in the section of the above-mentioned absorption layer.
- the content of the ultraviolet light absorber is preferably 0.1 to 90% by mass with respect to the total solid content of the composition for forming an absorption layer.
- the upper limit is more preferably 50% by mass or less, still more preferably 30% by mass or less, and still more preferably 20% by mass or less.
- the lower limit is more preferably 1% by mass or more, still more preferably 3% by mass or more, and still more preferably 5% by mass or more.
- the composition for forming an absorption layer preferably contains 0.1 to 200 parts by mass of an ultraviolet absorber with respect to 100 parts by mass of the colorant Y.
- the upper limit is more preferably 100 parts by mass or less, still more preferably 50 parts by mass or less, and still more preferably 30 parts by mass or less.
- the lower limit is more preferably 1 part by mass or more, further preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more.
- the composition for forming an absorption layer may contain only one type of ultraviolet absorber, or may contain two or more types. When 2 or more types of ultraviolet absorbers are contained, it is preferable that the total amount of them is the said range.
- the composition for forming an absorbent layer preferably further contains a curable compound.
- a curable compound known compounds which can be crosslinked by a radical, an acid or heat can be used.
- examples of the curable compound include a compound having an ethylenically unsaturated bond group, a compound having an epoxy group, and the like, and a compound having an ethylenically unsaturated bond group is preferable.
- an ethylenically unsaturated bond group a vinyl group, a (meth) allyl group, a (meth) acryloyl group etc. are mentioned.
- the compound having an ethylenically unsaturated bond group is preferably a polymerizable compound, and more preferably a radically polymerizable compound.
- the content of the curable compound is preferably 1 to 60% by mass with respect to the total solid content of the composition for forming an absorbent layer.
- the lower limit is, for example, preferably 5% by mass or more, and more preferably 10% by mass or more.
- the upper limit is, for example, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
- the curable compounds may be used alone or in combination of two or more. When 2 or more types are used together, it is preferable that the total amount of them becomes the said range.
- the compound having an ethylenically unsaturated bond group may be any of chemical forms such as monomers, prepolymers, oligomers and the like, but monomers are preferred.
- the molecular weight of the compound having an ethylenically unsaturated bonding group is preferably 100 to 3,000.
- the upper limit is more preferably 2000 or less, still more preferably 1500 or less.
- the lower limit is more preferably 150 or more, and still more preferably 250 or more.
- the compound having an ethylenically unsaturated bonding group is preferably a compound containing 3 or more ethylenically unsaturated bonding groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bonding groups, and ethylene More preferably, the compound contains 3 to 6 unsaturated unsaturated bonding groups.
- the compound having an ethylenically unsaturated bond group is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
- NK ester A-DPH-12E Shin-Nakamura Chemical Co., Ltd. product, and these (meth) acryloyl groups are linked via ethylene glycol and / or propylene glycol residue Compounds of the structure (eg, Available from mer Inc., SR454, SR499) is preferred. These oligomer types can also be used.
- NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD RP-1040, DPCA-20 manufactured by Nippon Kayaku Co., Ltd.
- DPCA-20 manufactured by Nippon Kayaku Co., Ltd.
- trimethylolpropane tri (meth) acrylate trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy
- a trifunctional (meth) acrylate compound such as modified tri (meth) acrylate or pentaerythritol tri (meth) acrylate.
- Commercially available products of trifunctional (meth) acrylate compounds include Alonics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
- M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.
- a compound further having an acid group can also be used.
- an acid group a carboxyl group, a sulfo group, a phosphoric acid group etc. are mentioned, A carboxyl group is preferable.
- Commercially available products of the compound having an acid group include ALONIX M-510, M-520, ALONIX TO-2349 (manufactured by Toagosei Co., Ltd.), and the like.
- the preferred acid value of the compound having an ethylenically unsaturated bonding group is 0.1 to 40 mg KOH / g, more preferably 5 to 30 mg KOH / g It is.
- the compound having an ethylenically unsaturated bond group is a compound further having a caprolactone structure.
- Compounds having a caprolactone structure are commercially available, for example, as KAYARAD DPCA series from Nippon Kayaku Co., Ltd., and include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.
- a compound having an ethylenically unsaturated bond group a compound having an ethylenically unsaturated bond group and an alkyleneoxy group can also be used.
- a compound having an ethylenically unsaturated bond group and an alkyleneoxy group a compound having an ethylenically unsaturated bond group and an ethyleneoxy group and / or a propyleneoxy group is preferable, and the ethylenically unsaturated bond group and the ethyleneoxy group are preferable.
- SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, having three isobutylene oxy groups
- KAYARAD TPA-330 which is a trifunctional (meth) acrylate.
- the content of the compound having an ethylenically unsaturated bond group is equal to the total solid content of the composition for forming an absorbent layer.
- 1 to 60% by mass is preferable.
- the lower limit is, for example, preferably 5% by mass or more, and more preferably 10% by mass or more.
- the upper limit is, for example, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
- the compound having an ethylenically unsaturated bond group may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that these sum totals become the said range.
- the compound having an epoxy group (hereinafter also referred to as an epoxy compound) is preferably a compound having 1 to 100 epoxy groups in one molecule.
- the lower limit of the epoxy group is more preferably 2 or more.
- the upper limit of the epoxy group may be, for example, 10 or less, or 5 or less.
- the epoxy compound may be a low molecular weight compound (for example, having a molecular weight of less than 1000) or a macromolecular compound (for example, having a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more).
- the weight average molecular weight of the epoxy compound is preferably 200 to 100,000, and more preferably 500 to 50,000.
- the upper limit of the weight average molecular weight is more preferably 10000 or less, still more preferably 5000 or less, and still more preferably 3000 or less.
- Paragraph No. 0034 of Unexamined-Japanese-Patent No. 2013-011869, Paragraph No. 0147-0156 of Unexamined-Japanese-Patent No. 2014-043556, Paragraph No. 0085-0092 of Unexamined-Japanese-Patent No. 2014-089408 Compounds can also be used. The contents of these are incorporated herein.
- the content of the epoxy compound is preferably 0.1 to 60% by mass with respect to the total solid content of the composition for forming an absorption layer.
- the lower limit is, for example, preferably 1% by mass or more, and more preferably 3% by mass or more.
- the upper limit is, for example, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
- the epoxy compounds may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that those sum totals become said range.
- the composition for forming an absorption layer contains a polymerizable compound as a curable compound, it is preferable to further contain a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited as long as it has the ability to initiate the polymerization of the polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet region to the visible region are preferred. In addition, it may be a compound which produces an active radical by causing an action with a photoexcited sensitizer.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- a halogenated hydrocarbon derivative for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.
- an acylphosphine compound for example, a hexaarylbiimidazole, an oxime compound, an organic peroxide, Thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxy ketone compounds, ⁇ -amino ketone compounds and the like
- an organic peroxide for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.
- an acylphosphine compound for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.
- an acylphosphine compound for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.
- the photopolymerization initiator is a trihalomethyl triazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxy ketone compound, an ⁇ -amino ketone compound, an acyl phosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triaryl imidazole from the viewpoint of exposure sensitivity.
- Dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyl oxadiazole compounds and 3-aryl substituted coumarin compounds are preferred, and oxime compounds, ⁇ -hydroxy ketone compounds, ⁇ -hydroxy ketone compounds More preferred are compounds selected from amino ketone compounds and acyl phosphine compounds, and more preferred are oxime compounds.
- the description of paragraph Nos. 0065 to 0111 of JP-A-2014-130173 and paragraph Nos. 0274 to 0306 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification. .
- Examples of commercially available ⁇ -hydroxy ketone compounds include IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (manufactured by BASF Corporation) and the like.
- Examples of commercially available ⁇ -amino ketone compounds include IRGACURE-907, IRGACURE-369, IRGACURE-379, and IRGACURE-379EG (manufactured by BASF Corporation).
- Examples of commercially available products of acyl phosphine compounds include IRGACURE-819, DAROCUR-TPO (all manufactured by BASF Corp.) and the like.
- Examples of the oxime compound include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, the compounds described in JP-A-2006-342166, and the like.
- C. S. Perkin II (1979, pp. 1653-1660) a compound described in J. Am. C. S. A compound described in Perkin II (1979, pp. 156-162), a compound described in Journal of Photopolymer Science and Technology (1995, pp.
- oxime compound examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-Acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxycarbonyloxy And imino-1-phenylpropan-1-one and the like.
- IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03 and IRGACURE-OXE04 are also suitably used.
- TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (made by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), Adeka ARKules NCI-930 And Adeka Optomer N-1919 (photopolymerization initiator 2 of JP 2012-14052 A) (all manufactured by ADEKA Co., Ltd.).
- oxime compounds other than those described above compounds described in JP-T-2009-519904, in which an oxime is linked to the N-position of a carbazole ring, and compounds described in US Pat. No. 7,626,957, in which a hetero substituent is introduced in the benzophenone moiety
- compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site, a ketoxime compound described in WO2009 / 131189, the same triazine skeleton and oxime skeleton.
- an oxime compound having a fluorene ring can also be used as a photopolymerization initiator.
- the oxime compound having a fluorene ring compounds described in JP-A-2014-137466 can be mentioned. This content is incorporated herein.
- an oxime compound having a benzofuran skeleton can also be used as a photopolymerization initiator.
- Specific examples thereof include the compounds OE-01 to OE-75 described in International Publication WO 2015/036910.
- an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used as a photopolymerization initiator.
- an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring
- the compound described in International Publication WO 2013/083505 can be mentioned.
- an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. And the like (C-3) and the like. This content is incorporated herein.
- an oxime compound having a nitro group can be used as a photopolymerization initiator.
- the oxime compound having a nitro group is also preferably a dimer.
- specific examples of the oxime compound having a nitro group compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and patent 4223071 Compounds described in Paragraph Nos. 0007 to 0025 of the gazette, Adeka Arkles NCI-831 (manufactured by ADEKA Co., Ltd.), and the like.
- oxime compounds preferably used in the present invention are shown below, but the present invention is not limited thereto.
- the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 nm to 500 nm, and more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 nm to 480 nm. Moreover, the oxime compound is preferably a compound having a high absorbance at 365 nm and 405 nm.
- the molar absorption coefficient of the oxime compound at 365 nm or 405 nm is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, and 5,000 to 200, Particularly preferred is 000.
- the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure at a concentration of 0.01 g / L using an ethyl acetate solvent with a UV-visible spectrophotometer (Cary-5 spectrophotometer manufactured by Varian).
- a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator.
- a photopolymerization initiator paragraph Nos. 0417 to 0412 of JP-A-2010-527339, JP-A-2011-524436, International Publication WO2015 / 004565, JP-A-2016-532675.
- the content of the photopolymerization initiator is preferably 1 to 20% by mass with respect to the total solid content of the composition for forming an absorption layer.
- the lower limit is, for example, preferably 3% by mass or more, and more preferably 5% by mass or more.
- the upper limit is, for example, more preferably 15% by mass or less and still more preferably 10% by mass or less.
- the composition for forming an absorbent layer may contain only one type of photopolymerization initiator, or may contain two or more types. When 2 or more types of photoinitiators are included, it is preferable that the total amount of them becomes said range.
- the composition for forming an absorbent layer preferably contains a resin.
- the resin is blended, for example, in applications of dispersing particles such as pigments in a composition and applications of a binder.
- grains, such as a pigment is also called a dispersing agent.
- such an application of the resin is an example, and can be used for purposes other than such an application.
- the content of the resin is preferably 1 to 60% by mass with respect to the total solid content of the composition for forming an absorbent layer.
- the lower limit is, for example, preferably 5% by mass or more, and more preferably 10% by mass or more.
- the upper limit is, for example, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
- the composition for absorption layer formation contains a dispersing agent as resin.
- the dispersant includes an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acidic dispersant (acidic resin) when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, the resin in which the amount of acid groups occupies 70 mol% or more is preferable, Resins consisting only of acid groups are more preferred.
- the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant is preferably 5 to 105 mg KOH / g.
- a basic dispersing agent represents resin whose quantity of a basic group is larger than the quantity of an acidic radical.
- resin when the total amount of the quantity of an acidic radical and the quantity of a basic group is made into 100 mol%, resin whose quantity of a basic group exceeds 50 mol% is preferable.
- the basic group possessed by the basic dispersant is preferably an amino group.
- polymer dispersing agents eg, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) Acrylic copolymers, naphthalene sulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanolamines and the like.
- polymer dispersing agents eg, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) Acrylic copolymers, naphthalene sulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanolamines and the like.
- Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures.
- the polymeric dispersant adsorbs to the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal modified polymer, a graft polymer, and a block polymer having an anchor site on the pigment surface can be mentioned as a preferable structure.
- dispersants described in paragraphs 0028 to 0124 of JP-A-2011-070156 and dispersants described in JP-A-2007-277514 are preferably used. The contents of these are incorporated herein.
- a resin containing a repeating unit having a graft chain in a side chain (hereinafter, also referred to as a graft resin).
- a graft resin means a polymer chain which branches and extends from the main chain of the repeating unit.
- the length of the graft chain is not particularly limited, but as the graft chain becomes longer, the steric repulsion effect becomes higher, and the dispersibility of the pigment etc. can be enhanced.
- the number of atoms excluding hydrogen atoms is preferably 40 to 10,000, and the number of atoms excluding hydrogen atoms is more preferably 50 to 2,000, and the number of atoms excluding hydrogen atoms is 60 to 60 More preferably, it is 500.
- the graft chain preferably includes at least one structure selected from polyester chains, polyether chains, poly (meth) acrylic chains, polyurethane chains, polyurea chains and polyamide chains, and polyester chains, polyether chains and poly (meta It is more preferable to include at least one structure selected from acryl chains, and it is further preferable to include a polyester chain.
- the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
- substituents include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group and the like.
- a group having a steric repulsion effect is preferable, and an alkyl group having 5 to 24 carbon atoms or an alkoxy group is preferable.
- the alkyl group and the alkoxy group may be linear, branched or cyclic, and linear or branched is preferable.
- graft resin Details of the graft resin can be referred to the description of Paragraph Nos. 0025 to 0094 of JP-A-2012-255128, the contents of which are incorporated herein. Further, specific examples of the graft resin include the resins described in paragraph Nos. 0072 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein.
- an oligoimine resin containing a nitrogen atom in at least one of the main chain and the side chain can be used as the resin.
- the oligoimine resin is at least selected from poly (lower alkyleneimine) -based repeating units, polyallylamine-based repeating units, polydiallylamine-based repeating units, metaxylenediamine-epichlorohydrin polycondensate-based repeating units, and polyvinylamine-based repeating units. It is preferable to include one kind of repeating unit having a nitrogen atom.
- a commercial product can also be used as resin as a dispersing agent.
- the product described in paragraph No. 0129 of JP 2012-137564 A can also be used as a dispersant.
- Disperbyk-111 manufactured by BYK Chemie
- the resin demonstrated as the said dispersing agent can also be used for uses other than a dispersing agent.
- it can also be used as a binder.
- the content of the dispersant is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the pigment.
- the lower limit is more preferably 5 parts by mass or more, and still more preferably 10 parts by mass or more.
- the upper limit is more preferably 150 parts by mass or less, and still more preferably 100 parts by mass or less.
- the composition for absorption layer formation can contain alkali-soluble resin as resin.
- alkali-soluble resin can also be used as a dispersing agent or a binder.
- the alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali dissolution.
- the group promoting alkali dissolution include, for example, a carboxyl group, a phosphate group, a sulfo group, a phenolic hydroxyl group and the like, with a carboxyl group being preferable.
- the type of the acid group possessed by the alkali-soluble resin may be only one type, or two or more types.
- the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 100,000.
- the number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 to 20,000.
- the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin. From the viewpoint of control of developability, acrylic resins, acrylamide resins and acrylic / acrylamide copolymer resins are preferred.
- the alkali-soluble resin is preferably a polymer having a carboxyl group in a side chain.
- a copolymer having a repeating unit derived from a monomer such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinylbenzoic acid, partially esterified maleic acid examples thereof include alkali-soluble phenol resins such as novolac resins, acid cellulose derivatives having a carboxyl group in a side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group.
- copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin.
- Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like.
- alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc.
- Examples of the vinyl compound include styrene, ⁇ -methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like.
- N-substituted maleimide monomers such as N-phenyl maleimide, N-cyclohexyl maleimide and the like described in JP-A-10-300922 can be mentioned.
- These other monomers copolymerizable with (meth) acrylic acid may be only one type or two or more types.
- benzyl (meth) acrylate / (meth) acrylic acid copolymer As an alkali soluble resin, benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate
- a multicomponent copolymer composed of / (meth) acrylic acid / other monomers can be preferably used.
- Methacrylic acid copolymer 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used. Further, as a commercial product, for example, FF-426 (manufactured by Fujikura Kasei Co., Ltd.) can also be used.
- the alkali-soluble resin can also be an alkali-soluble resin having a polymerizable group.
- the polymerizable group include (meth) allyl group and (meth) acryloyl group.
- the alkali-soluble resin having a polymerizable group an alkali-soluble resin having a polymerizable group in a side chain is useful.
- Commercial products of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264.
- KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (both manufactured by Daicel Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UBC Co., Ltd.), Acrylice RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), DP-1305 (manufactured by Fuji Fine Chemicals Co., Ltd.), and the like.
- Cyclomer P series for example, ACA 230 AA
- Plaxcel CF 200 series both manufactured by Daicel Co., Ltd.
- Ebecryl 3800 manufactured by Daicel UBC Co., Ltd.
- Acrylice RD-F8 manufactured by Nippon Shokubai Co., Ltd.
- DP-1305 manufactured by Fuji Fine Chemicals Co., Ltd.
- the alkali-soluble resin comprises at least one compound selected from a compound represented by the following formula (ED1) and a compound represented by formula (1) in JP-A-2010-168539 (hereinafter referred to as “ether dimer It is also preferable to include a polymer formed by polymerizing a monomer component including “sometimes referred to as
- R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
- the ether dimer may be only one type, or two or more types.
- a polymer formed by polymerizing a monomer component containing an ether dimer for example, a polymer of the following structure can be mentioned.
- the alkali-soluble resin may contain a repeating unit derived from a compound represented by the following formula (X).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkylene group having 2 to 10 carbon atoms
- R 3 has a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring.
- Represents an alkyl group of n represents an integer of 1 to 15.
- the carbon number of the alkylene group of R 2 is preferably 2 to 3.
- the carbon number of the alkyl group of R 3 is preferably 1 to 10.
- the alkyl group of R 3 may contain a benzene ring. Examples of the alkyl group containing a benzene ring represented by R 3 include benzyl and 2-phenyl (iso) propyl.
- the alkali-soluble resin can be referred to the description in paragraphs 0558 to 0571 of JP 2012-208494 A (paragraph 0685 to 0700 in the corresponding US Patent Application Publication 2012/0235099), the contents of which are incorporated herein by reference. Incorporated into the book.
- Binder resin described and binder resin used in Examples Binder resin described in paragraphs 0022 to 0032 of JP 2012-137531 A and binder resin used in Examples, JP 2013-024934 Binder resins described in paragraphs 0132 to 0143 of the gazette and binder resins used in the examples, binder resins described in paragraphs 0092 to 0098 of JP 2011-242752 A and binders used in the examples Resin, JP 2012-032770 It is also possible to use a binder resin described in paragraphs 0030 to 0072 of the broadcast. The contents of these are incorporated herein.
- the acid value of the alkali-soluble resin is preferably 30 to 500 mg KOH / g.
- the lower limit is more preferably 50 mg KOH / g or more, and still more preferably 70 mg KOH / g or more.
- the upper limit is preferably 400 mg KOH / g or less, more preferably 200 mg KOH / g or less, still more preferably 150 mg KOH / g or less, and particularly preferably 120 mg KOH / g or less.
- the content of the alkali-soluble resin is preferably 1 to 60% by mass with respect to the total solid content of the composition for forming an absorbent layer.
- the lower limit is, for example, preferably 5% by mass or more, and more preferably 10% by mass or more.
- the upper limit is, for example, more preferably 50% by mass or less, and still more preferably 40% by mass or less.
- the composition for forming an absorbent layer can contain a resin (also referred to as another resin) other than the resin described in the section of the dispersant and the alkali-soluble resin described above as the resin.
- a resin also referred to as another resin
- resin for example, (meth) acrylic resin, (meth) acrylamide resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyphenylene resin, polyarylene ether Phosphine oxide resin, polyimide resin, polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, etc. may be mentioned.
- the other resins may be used singly or in combination of two or more of these resins.
- the resin the resins described in JP-A-2017-57265, JP-A-2017-32685, JP-A-2017-075248, and JP-A-2017-066240 can also be used. , The contents of which are incorporated herein.
- the composition for forming an absorption layer can contain a pigment derivative.
- the pigment derivative include compounds having a structure in which a part of a chromophore is substituted with an acid group, a basic group or a phthalimidomethyl group.
- the chromophores constituting the pigment derivative include quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, perinone compound Skeletons, perylene skeletons, thioindigo skeletons, isoindoline skeletons, isoindolinone skeletons, quinophthalone skeletons, threne skeletons, metal complex skeletons, etc., and quinoline skeletons, benzimidazolone skeletons, diketo A pyrrolopyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferable, and an azo skeleton and a
- the composition for forming an absorption layer contains a pigment derivative
- the content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment.
- the pigment derivative may use only 1 type and may use 2 or more types together. When two or more pigment derivatives are contained, the total amount thereof is preferably in the above range.
- the composition for forming an absorbent layer preferably contains a solvent.
- the solvent is preferably an organic solvent.
- the solvent is not particularly limited as long as the solubility of each component and the coatability of the composition for forming an absorbent layer are satisfied.
- esters for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkyl oxyacetate alkylate (Eg, methyl alkyl oxyacetate, ethyl alkyl oxyacetate, butyl alkyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate,
- 2-alkyloxypropionic acid alkyl esters eg methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate etc.
- ethers for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like can be mentioned.
- ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
- Preferred examples of the aromatic hydrocarbons include toluene and xylene. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene etc.) as a solvent due to environmental reasons etc. (For example, 50 mass ppm (parts per part of the total amount of organic solvent) or less, 10 mass ppm or less, or 1 mass ppm or less).
- the organic solvents may be used alone or in combination of two or more.
- methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate is particularly preferable.
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
- an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content.
- the metal content of the organic solvent is preferably 10 parts by weight or less (parts per billion).
- the metal content of the organic solvent may be of the mass ppt (parts per trillion) level, and such a high purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Journal, 2015) November 13).
- the content of the solvent is preferably such that the total solid content of the composition for forming an absorbent layer is 5 to 80% by mass.
- the lower limit is more preferably 10% by mass or more. 60 mass% or less is more preferable, 50 mass% or less is further more preferable, and 40 mass% or less is still more preferable.
- the composition for absorption layer formation does not contain an environmental regulation substance substantially from a viewpoint of environmental regulation.
- not containing the environmental regulation substance substantially means that the content of the environmental regulation substance in the composition for forming an absorption layer is 50 mass ppm or less, and is 30 mass ppm or less Is preferable, 10 mass ppm or less is more preferable, and 1 mass ppm or less is particularly preferable.
- the environmental control substance include benzene; alkyl benzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene and the like.
- distillation methods may be carried out at the stage of the raw material, the stage of the product obtained by reacting the raw material (for example, the resin solution after polymerization or the polyfunctional monomer solution), or the stage of the composition prepared by mixing these compounds. Stages are also possible.
- the composition for forming an absorbent layer preferably contains a surfactant.
- a surfactant various surfactants such as fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, silicone surfactants can be used to further improve the coating property. Fluorinated surfactants are preferred because they can be used.
- the liquid properties when prepared as a coating liquid can be improved, and the uniformity of the coating thickness can be further improved. That is, in the case of forming a film using a coating solution to which a composition for forming an absorbent layer containing a fluorine-based surfactant is applied, the interfacial tension on the surface of the coated film is reduced, and the uniformity of drying is improved. Do. For this reason, film formation with few coating nonuniformity can be performed more suitably.
- the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- the fluorine-based surfactant having a fluorine content in the above range is effective in terms of uniformity of the thickness of the coating film and liquid saving property, and the solubility in the composition for forming an absorption layer is also good. .
- fluorine-based surfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, R44, R437, F475, F479, F482, F554, F780, EXP, MFS-330 (for example, As mentioned above, DIC Corporation product, Florard FC430, FC431, FC171 (above, Sumitomo 3M Corporation product), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068 SC-381, SC-383, S-393, KH-40 (all, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (all, manufactured by OMNOVA) and the like.
- MFS-330 for example, As mentioned above, DIC Corporation product, Florard FC430, FC431, FC171 (above, Sumitomo 3M Corporation product), Surflon S-382, SC-101, SC
- fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, and compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used.
- a block polymer can also be used as the fluorine-based surfactant, and specific examples include the compounds described in JP-A-2011-89090.
- the fluorine-based surfactant preferably has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the portion of the functional group containing a fluorine atom is cleaved when heat is applied to volatilize the fluorine atom is also preferable. It can be used.
- a fluorochemical surfactant Megafuck DS series (Chemical Chemical Daily, February 22, 2016) manufactured by DIC Corporation (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS -21 may be mentioned, and these may be used.
- a fluorine-based surfactant a repeating unit derived from a (meth) acrylate compound having a fluorine atom, and an alkyleneoxy group (preferably an ethyleneoxy group or a propyleneoxy group) having 2 or more (preferably 5 or more) (meta).
- an alkyleneoxy group preferably an ethyleneoxy group or a propyleneoxy group
- metal metal
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
- % indicating the proportion of repeating units is mol%.
- the weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, for example, 14,000.
- a fluorine-based surfactant a fluorine-containing polymer having a group having an ethylenically unsaturated bond in the side chain can also be used. Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965. Examples of commercially available products include Megafac RS-101, RS-102, RS-718-K, RS-72-K and the like manufactured by DIC Corporation.
- nonionic surfactants glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company), Tetronics 304, 701, 704, 901, 904, 150R1 (BA).
- BA nonionic surfactants
- organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid (co) polymer polyflow No. 1 is used. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.
- anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co., Ltd.), and the like.
- silicone type surfactant for example, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (more than Toray Dow Corning ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, Momentive Performance Materials Inc.), KP341, KF6001, KF6002 (above, Shin-Etsu Silicone Co., Ltd.) , BYK 307, BYK 323, BYK 330 (above, manufactured by Big Chemie Co., Ltd.), and the like.
- the content of the surfactant is preferably 0.001 to 2.0% by mass with respect to the total solid content of the composition for forming an absorbent layer.
- the lower limit is, for example, more preferably 0.005% by mass or more.
- the upper limit is, for example, more preferably 1.0% by mass or less. Only one surfactant may be used, or two or more surfactants may be combined. When two or more surfactants are contained, the total amount thereof is preferably in the above range.
- the composition for absorber layer formation can contain a silane coupling agent.
- the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group is a substituent which is directly bonded to a silicon atom and can form a siloxane bond by hydrolysis reaction and / or condensation reaction.
- a hydrolysable group a halogen atom, an alkoxy group, an acyloxy group etc. are mentioned, for example.
- the silane coupling agent is at least one selected from vinyl, epoxy, (meth) allyl, (meth) acryloyl, amino, isocyanurate, ureido, mercapto, sulfide, and isocyanate groups. Silane compounds having the following groups and an alkoxy group are preferred.
- silane coupling agent examples include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-602), N- ⁇ -aminoethyl- ⁇ -aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-602), ⁇ -aminopropyltrimethoxysilane (Shin-Etsu Chemical Co., Ltd.) Product, KBM-903), ⁇ -aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacryloxypropyl trimethoxysilane (Shin-Etsu Chemical Co.,
- the content of the silane coupling agent is preferably 0.001 to 20% by mass with respect to the total solid content of the composition for forming an absorbent layer, and 0. 01 to 10% by mass is more preferable, and 0.1 to 5% by mass is particularly preferable.
- the composition for forming an absorbent layer may contain only one type of silane coupling agent, or may contain two or more types. When 2 or more types of silane coupling agents are contained, it is preferable that the total amount of them becomes the said range.
- the composition for absorbent layer formation can contain a polymerization inhibitor.
- a polymerization inhibitor hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts etc.) and the like.
- the content of the polymerization inhibitor is preferably 0.01 to 5% by mass with respect to the total solid content of the composition for forming an absorbent layer.
- the composition for formation of an absorbent layer may contain only one type of polymerization inhibitor, or may contain two or more types. When it contains two or more types, it is preferable that the total amount of them becomes the said range.
- additives such as a filler, an adhesion promoter, an antioxidant, a latent antioxidant and the like can be blended, if necessary.
- these additives include the additives described in paragraphs [0155] to [0156] of JP-A-2004-295116, the contents of which are incorporated herein.
- the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph 0042 of JP-A-2011-90147), a thioether compound or the like can be used.
- Adekastab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60G, AO-60, AO-80, AO-A manufactured by ADEKA Co., Ltd.) 330).
- the polyfunctional hindered amine antioxidant described in international publication WO 2017/006600 can also be used as antioxidant.
- One type of antioxidant may be used or two or more types may be used.
- a latent antioxidant is a compound in which a site that functions as an antioxidant is protected by a protecting group, and is heated at 100 to 250 ° C. or at 80 to 200 ° C. in the presence of an acid / base catalyst.
- the latent antioxidant include compounds described in International Publication WO 2014/021023, International Publication WO 2017/030005, and Japanese Unexamined Patent Publication No. 2017-008219.
- Examples of commercially available products include Adeka ARKRUZ GPA-5001 (manufactured by ADEKA Co., Ltd.) and the like.
- composition for forming colored pixels a composition (composition for forming colored pixels) that can be preferably used for forming colored pixels in a color filter will be described.
- the composition for forming colored pixels preferably contains a colorant.
- colorants include chromatic colorants such as yellow colorants, orange colorants, red colorants, green colorants, purple colorants and blue colorants.
- the colorant may be a pigment or a dye.
- I. Pigment green 7, 10, 36, 37, 58, 59 above, green pigment
- a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in the molecule, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms. Can also be used. Specific examples include the compounds described in International Publication WO 2015/118720.
- the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue coloring agent.
- Specific examples thereof include compounds described in Paragraph Nos. 0022 to 0030 of JP-A-2012-247591 and Paragraph No. 0047 of JP-A-2011-157478.
- the compound mentioned by the coloring agent Y mentioned above can also be used as a yellow coloring agent.
- Examples of the dye include, for example, JP-A 64-90403, JP-A 64-91102, JP-A 1-94301, JP-A 6-11614, US Pat. Dyes disclosed in JP-A-3-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828 and the like can be mentioned.
- pyrazole azo compounds When classified as chemical structures, pyrazole azo compounds, pyrromethene compounds, anilino azo compounds, triarylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be mentioned.
- the dye multimer is preferably a dye used by being dissolved in a solvent, but may form particles.
- the dye polymer is a particle, the dye polymer is dispersed in a solvent or the like.
- the pigment multimer in a particulate state can be obtained, for example, by emulsion polymerization.
- examples of the pigment multimer in the particle state include compounds described in JP-A-2015-214682.
- compounds described in JP 2011-213925 A, JP 2013-041097 A, JP 2015-028144 A, JP 2015-030742 A, etc. can also be used as a dye polymer. .
- the content of the coloring agent is preferably 20% by mass or more, more preferably 30% by mass or more, and still more preferably 40% by mass or more, with respect to the total solid content of the composition for forming colored pixels.
- the above is even more preferable, 60 mass% or more is still more preferable, and 65 mass% or more is particularly preferable.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less.
- the colorant contained in the composition for forming colored pixels may be one type, or two or more types. When two or more colorants are contained, the total amount is preferably in the above range.
- the composition for forming a colored pixel further includes a resin, a curable compound, a photopolymerization initiator, a pigment derivative, a solvent, a surfactant, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a filler, an adhesion promoter, Additives such as antioxidants and latent antioxidants may be included.
- a resin a curable compound, a photopolymerization initiator, a pigment derivative, a solvent, a surfactant, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a filler, an adhesion promoter, Additives such as antioxidants and latent antioxidants may be included.
- Additives such as antioxidants and latent antioxidants may be included.
- composition for transparent pixel formation which can be preferably used for formation of the transparent pixel in a color filter is explained.
- the composition for forming a transparent pixel preferably contains a resin.
- a resin the above-mentioned material used for the composition for absorption layer formation mentioned above is mentioned, A preferable range is also the same. Further, the preferable content of the resin is also the same as the content in the composition for forming an absorbent layer.
- the composition for forming an absorption layer further comprises at least one selected from Ti, Zr, Sn, Sb, Cu, Fe, Mn, Pb, Cd, As, Cr, Hg, Zn, Al, Mg, Si, P and S.
- the content of the inorganic particles is preferably 20 to 70% by mass with respect to the total solid content of the composition for forming an absorption layer. As for a minimum, 25 mass% or more is more preferable, and 30 mass% or more is further more preferable. As for the upper limit, 65 mass% or less is more preferable, and 60 mass% or less is still more preferable.
- the composition for forming a transparent pixel further includes a curable compound, a photopolymerization initiator, a solvent, a surfactant, a silane coupling agent, a polymerization inhibitor, an ultraviolet light absorber, a filler, an adhesion promoter, an antioxidant, and a latent Additives such as antioxidants may be included.
- a curable compound a photopolymerization initiator, a solvent, a surfactant, a silane coupling agent, a polymerization inhibitor, an ultraviolet light absorber, a filler, an adhesion promoter, an antioxidant, and a latent Additives such as antioxidants may be included.
- composition for infrared rays transmission layer formation which can be preferably used for formation of the pixel of the infrared rays transmission layer in the structure of the present invention is explained.
- a / B which is the ratio of the minimum value A of absorbance in the wavelength range of 400 to 640 nm to the maximum value B of absorbance in the range of wavelength 1100 to 1300 nm, is 5 or more
- it is 7.5 or more, more preferably 15 or more, and still more preferably 30 or more.
- the condition of the absorbance can suitably achieve the condition of the absorbance, for example, by adjusting the type of the light shielding material described later and the content thereof.
- the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
- a ⁇ -log (T ⁇ / 100) (1)
- a ⁇ is the absorbance at wavelength ⁇
- T ⁇ is the transmittance (%) at wavelength ⁇ .
- the value of absorbance may be a value measured in the state of a solution, or may be a value of a film formed using a composition for forming an infrared transmitting layer.
- a composition for forming an infrared ray transmitting layer is applied on a glass substrate by a method such as spin coating so that the thickness of the film after drying becomes a predetermined thickness. It is preferable to measure using a membrane prepared by drying at 100 ° C. for 120 seconds using The thickness of the film can be measured on a substrate having a film using a stylus profilometer (DEKTAK150 manufactured by ULVAC, Inc.).
- the absorbance can be measured using a conventionally known spectrophotometer.
- the measurement conditions of the absorbance are not particularly limited, under the conditions adjusted so that the minimum value A of the absorbance in the wavelength range of 400 to 640 nm is 0.1 to 3.0, the absorbance in the wavelength range of 1100 to 1300 nm It is preferable to measure the maximum value B. The measurement error can be further reduced by measuring the absorbance under such conditions.
- the method of adjusting the minimum value A of the absorbance in the wavelength range of 400 to 640 nm to be 0.1 to 3.0 is not particularly limited. For example, in the case of measuring the absorbance in the state of a solution, there is a method of adjusting the optical path length of the sample cell. Moreover, when measuring a light absorbency in the state of a film
- the composition for forming an infrared transmitting layer preferably contains a light shielding material.
- the light shielding material is preferably a coloring material that absorbs light in the violet to red wavelength region.
- the light blocking material is preferably a color material that blocks light in a wavelength range of 400 to 640 nm.
- the light blocking material is preferably a color material that transmits light of a wavelength of 1100 to 1300 nm.
- the light blocking material preferably satisfies at least one of the following requirements (1) and (2).
- the light blocking material preferably has an A / B ratio of 4.5 or more, which is, for example, the ratio of the minimum value A of the absorbance in the wavelength range of 400 to 640 nm to the maximum value B of the absorbance in the range of wavelength 1100 to 1300 nm. .
- the above characteristics may be satisfied by one kind of material, or may be satisfied by a combination of plural materials.
- the organic type black coloring agent may satisfy
- the above-mentioned spectral characteristics may be satisfied by a combination of an organic black colorant and a chromatic colorant.
- the light shielding material preferably contains two or more selected from red colorants, blue colorants, yellow colorants, purple colorants and green colorants. That is, the light shielding material preferably forms a black color by a combination of two or more types of colorants selected from red colorants, blue colorants, yellow colorants, purple colorants and green colorants. Examples of preferable combinations include the following. (1) An embodiment containing a red colorant and a blue colorant. (2) An embodiment containing a red colorant, a blue colorant and a yellow colorant. (3) An embodiment containing a red coloring agent, a blue coloring agent, a yellow coloring agent and a purple coloring agent.
- An embodiment containing a red coloring agent, a blue coloring agent, a yellow coloring agent, a purple coloring agent and a green coloring agent An embodiment containing a red colorant, a blue colorant, a yellow colorant and a green colorant. (6) An embodiment containing a red colorant, a blue colorant and a green colorant. (7) An embodiment containing a yellow colorant and a purple colorant.
- the mass ratio of red colorant, blue colorant, yellow colorant, purple colorant and green colorant is red colorant: blue colorant: yellow colorant: purple colorant: green colorant
- the agent is 10 to 80: 20 to 80: 5 to 40: 5 to 40, and it is 10 to 60:30 to 80: 5 to 30: 5 to 30: 5 to 30. More preferably, it is 10 to 40:40 to 80: 5 to 20: 5 to 20: 5 to 20.
- the ratio is preferably 80: 5 to 40: 5 to 40, more preferably 10 to 60:30 to 80: 5 to 30: 5 to 30, and further preferably 10 to 40:40 to 80: 5 to 20: 5. It is more preferable that the value is 20.
- C.I. I. Pigment yellow 139, 150 and 185 are preferred, and C.I. I. Pigment yellow 139, 150 is more preferable, and C.I. I. Pigment yellow 139 is more preferable.
- a blue coloring agent C.I. I. Pigment blue 15: 6 is preferable.
- a purple coloring agent C.I. I. Pigment Violet 23 is preferred.
- a red coloring agent C.I. I. Pigment red 122, 177, 224, 254, and C.I. I. Pigment red 122, 177, 254 are more preferable, C.I. I. Pigment red 254 is more preferred.
- As a green coloring agent C.I. I. Pigment green 7, 36, 58, 59 are preferred.
- an organic black colorant When using an organic black colorant as a light shielding material, it is preferable to use it in combination with a chromatic colorant.
- a chromatic colorant By using an organic black colorant and a chromatic colorant in combination, excellent spectral characteristics are easily obtained.
- the chromatic colorant used in combination with the organic black colorant include red colorants, blue colorants, purple colorants and the like, and red colorants and blue colorants are preferable. These may be used alone or in combination of two or more.
- the mixing ratio of the chromatic coloring agent to the organic black coloring agent is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, with respect to 100 parts by mass of the organic black coloring agent. preferable.
- the content of the pigment in the light shielding material is preferably 95% by mass or more, more preferably 97% by mass or more, and still more preferably 99% by mass or more based on the total amount of the light shielding material.
- the content of the light shielding material is preferably 5 to 60% by mass with respect to the total solid content of the composition for forming an infrared transmitting layer. 9 mass% or more is preferable, and, as for a lower limit, 13 mass% or more is more preferable. 50 mass% or less is preferable, and, as for the upper limit, 40 mass% or less is more preferable.
- the composition for forming an infrared transmitting layer may further contain an infrared absorber.
- the infrared ray absorbing agent has a role of limiting the transmitted light (infrared ray) to a longer wavelength side.
- the infrared absorber a compound having a maximum absorption wavelength in the infrared region (preferably in the range of wavelength 700 to 1300 nm, more preferably in the range of wavelength 700 to 1000 nm) can be preferably used.
- pyrrolopyrrole compounds As an infrared absorber, pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, piromethene compounds, azomethine
- At least one selected from a compound, an anthraquinone compound and a dibenzofuranone compound is preferable, and at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound and a diimonium compound is more preferable, and a pyrrolopyrrole compound More preferably, at least one selected from cyanine compounds and squarylium compounds Pyrrolo pyrrole compounds are particularly
- pyrrolopyrrole compounds compounds described in paragraphs 0016 to 0058 of JP 2009-263614 A, compounds described in paragraphs 0037 to 0052 of JP 2011-68731 A, WO 2015/166873 No. 0010-0033, and the like, the contents of which are incorporated herein.
- squarylium compounds compounds described in paragraphs 0044 to 0049 of JP 2011-208101 A, compounds described in paragraphs 0060 to 0061 of Patent No.
- diimmonium compounds include the compounds described in JP-A-2008-528706, the contents of which are incorporated herein.
- phthalocyanine compound include the compounds described in paragraph 0093 of JP 2012-77153 A, the oxytitanium phthalocyanine described in JP 2006-343631 A, paragraph 0013 of JP 2013-195480 A, and the like.
- the compounds described in 0029 are included, the contents of which are incorporated herein.
- naphthalocyanine compounds include the compounds described in paragraph 0093 of JP-A-2012-77153, the contents of which are incorporated herein.
- the infrared absorbing compound a compound described in JP-A-2016-146619 can also be used, and the contents thereof are incorporated in the present specification.
- the content of the infrared absorbing agent is preferably 1 to 30% by mass with respect to the total solid content of the composition for forming an infrared transmitting layer. 20 mass% or less is more preferable, and, as for an upper limit, 10 mass% or less is still more preferable. The lower limit is more preferably 3% by mass or more, further preferably 5% by mass or more. Further, the total amount of the infrared ray absorbing agent and the light shielding material is preferably 10 to 70% by mass of the total solid content of the composition for forming an infrared ray transmitting layer.
- the content of the infrared absorber in the total amount of the infrared absorber and the light shielding material is preferably 5 to 40% by mass.
- the upper limit is more preferably 30% by mass or less, and still more preferably 25% by mass or less.
- 10 mass% or more is more preferable, and 15 mass% or more is still more preferable.
- the composition for forming an infrared ray transmitting layer further includes a resin, a curable compound, a photopolymerization initiator, a pigment derivative, a solvent, a surfactant, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a filler, and an adhesion promoter. And additives such as antioxidants and latent antioxidants.
- a resin a curable compound, a photopolymerization initiator, a pigment derivative, a solvent, a surfactant, a silane coupling agent, a polymerization inhibitor, an ultraviolet absorber, a filler, and an adhesion promoter.
- additives such as antioxidants and latent antioxidants.
- ⁇ Containment container of composition> There is no limitation in particular as a storage container of each composition mentioned above, A well-known storage container can be used.
- a storage container a multi-layered bottle in which the inner wall of the container is made of a resin of six types and six layers and a bottle in which a seven types of resin of six types are formed for the purpose of suppressing mixing of impurities into raw materials and compositions. It is also preferred to use.
- a container for example, the container described in JP-A-2015-123351 can be mentioned.
- compositions mentioned above can mix and prepare the above-mentioned ingredient.
- all the components may be simultaneously dissolved or dispersed in a solvent to prepare the composition, or, if necessary, two or more solutions or dispersions in which the respective components are appropriately blended in advance.
- the composition may be prepared by mixing it at the time of use (at the time of application).
- the composition contains particles such as pigments
- mechanical force used to disperse the particles includes compression, squeezing, impact, shearing, cavitation and the like.
- Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like.
- a bead having a small diameter, treatment under conditions in which the pulverizing efficiency is enhanced by increasing the packing ratio of beads, or the like.
- the process of dispersing particles and the dispersing machine are the dispersion technology and industrial application centering on "Dispersion Technology Complete, Information Technology Co., Ltd. issued July 15, 2005" and "suspension (solid / liquid dispersion system)" The process and the dispersing machine described in Paragraph No.
- JP-A-2015-157893 published on October 10, 1978
- the particles may be subjected to a refinement process in a salt milling step.
- the materials, equipment, processing conditions and the like used in the salt milling step can be referred to, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-04629.
- the composition is preferably filtered with a filter for the purpose of removing foreign matter and reducing defects.
- a filter if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular.
- a fluorocarbon resin such as polytetrafluoroethylene (PTFE), a polyamide-based resin such as nylon (for example, nylon-6, nylon-6, 6), or a polyolefin resin such as polyethylene or polypropylene (PP)
- Filters made of materials such as polyolefin resins of Among these materials, polypropylene (including high density polypropylene) and nylon are preferable.
- the pore diameter of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, and more preferably about 0.05 to 0.5 ⁇ m. If the pore diameter of the filter is in the above range, fine foreign particles can be reliably removed. It is also preferable to use a fibrous filter medium.
- the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like. Specifically, filter cartridges of SBP type series (SBP 008 and the like), TPR type series (TPR 002, TPR 005 and the like), and SHPX type series (SHPX 003 and the like) manufactured by Loki Techno, Inc. can be mentioned.
- filters different filters (eg, a first filter, a second filter, etc.) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above.
- the pore size here can refer to the nominal value of the filter manufacturer. As a commercially available filter, for example, it is selected from various filters provided by Nippon Pall Co., Ltd. (DFA4201 NXEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (old Japan Microlith Co., Ltd.) or Kitz Micro Filter Co., Ltd. can do.
- the second filter can be made of the same material as the first filter.
- the filtration with the first filter may be performed only on the dispersion liquid, and after mixing other components, the filtration may be performed with the second filter.
- the method for producing a structure of the present invention includes the steps of forming a color filter and forming an absorption layer,
- the color filter has two or more different types of pixels,
- the absorbing layer contains at least one selected from a yellow colorant and a colorant having a maximum absorption wavelength in the range of 400 to 500 nm.
- the structure has an absorption layer on the light path of at least one of the pixels of the color filter and on the light incident side of the aforementioned pixels,
- the step of forming the absorbing layer includes the step of applying a composition for forming an absorbing layer containing a yellow colorant and at least one selected from colorants having a maximum absorption wavelength in the range of 400 to 500 nm.
- the absorption layer is preferably formed after forming a color filter. That is, it is preferable to perform the process of forming an absorption layer after performing the process of forming a color filter. Each step will be described in detail below.
- the step of forming a color filter is a step of applying a composition for forming each pixel of the color filter to form a composition layer for forming a pixel, and for the composition layer for forming a pixel by photolithography or dry etching. And b) forming a pattern.
- a composition for pixel formation the composition for colored pixel formation mentioned above, the composition for transparent pixel formation, and the composition for infrared rays transmission layer formation are used. It is preferable to form at least one type of pixel using a composition for forming a colored pixel.
- the pattern formation method by the photolithography method includes a step of exposing the composition layer for forming a pattern in a pattern (exposure step) and a step of developing and removing the composition layer for forming a pixel in an unexposed area to form a pattern It is preferable to include (developing step).
- a pattern formation method by the dry etching method a step of curing the composition layer for pixel formation to form a cured product layer, a step of forming a photoresist layer patterned on the cured product layer, and patterning And the step of dry-etching the cured product layer using the photoresist layer as a mask using an etching gas.
- exposure step a step of developing and removing the composition layer for forming a pixel in an unexposed area to form a pattern
- developing step As a pattern formation method by the dry etching method, a step of curing the composition layer for pixel formation to form a cured product layer, a step of forming a photoresist layer
- Step of forming a composition layer for forming a pixel it is preferable to form the composition for forming a pixel on the support.
- a support body there is no limitation in particular as a support body, According to a use, it can select suitably.
- a substrate silicon wafer, silicon carbide wafer, silicon nitride wafer, sapphire wafer, glass wafer or the like
- a subbing layer may be provided to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to planarize the surface.
- composition layer for forming a pixel various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing can be used.
- the composition layer for forming a pixel may be dried (prebaked). In the case of forming a pattern by a low temperature process, the prebaking may not be performed.
- the prebaking temperature is preferably 150 ° C. or less, more preferably 120 ° C. or less, and still more preferably 110 ° C. or less.
- the lower limit may be, for example, 50 ° C. or more, and may be 80 ° C. or more.
- the pre-bake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven or the like.
- the composition layer for pixel formation is exposed in a pattern (exposure step).
- pattern exposure can be performed by exposing the composition layer for forming a pixel with an exposure device such as a stepper through a mask having a predetermined mask pattern. Thereby, the exposed portion can be cured.
- radiation which can be used at the time of exposure, ultraviolet rays such as g-line and i-line are preferably used (particularly preferably i-line).
- Irradiation dose (exposure dose) for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
- the oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed under the atmosphere, for example, under a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially It may be exposed with no oxygen, and may be exposed under a high oxygen atmosphere (for example, 22% by volume, 30% by volume, or 50% by volume) in which the oxygen concentration exceeds 21% by volume.
- the exposure intensity is can be set appropriately, usually 1000W / m 2 ⁇ 100000W / m 2 ( e.g., 5000W / m 2, 15000W / m 2, or, 35000W / m 2) selected from the range of Can.
- Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
- the unexposed area is removed by development to form a pattern.
- the development and removal of the unexposed area can be carried out using a developer.
- the composition layer for pixel formation of the unexposed part in an exposure process elutes to a developing solution, and only the photocured part remains.
- a developing solution an alkaline developing solution (alkaline aqueous solution) which does not damage the solid-state imaging device or circuit of the base is desirable.
- the temperature of the developing solution is preferably, for example, 20 to 30.degree.
- the development time is preferably 20 to 180 seconds.
- the process of shaking off the developer every 60 seconds and further supplying the developer anew may be repeated several times.
- alkaline agent used for a developing solution for example, ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide Tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0]- Organic alkaline compounds such as 7-undecene, sodium hydroxide, potassium hydroxide, sodium carbonate, hydrogen carbonate Thorium, sodium silicate, and inorganic alkaline compound such as sodium metasilicate.
- the alkaline agent is preferably a compound having a large molecular weight in terms of the environment and safety.
- an alkaline aqueous solution obtained by diluting such an alkaline agent with pure water is preferably used.
- the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
- a surfactant may be contained in the developer and used.
- surfactant the surfactant mentioned above is mentioned and nonionic surfactant is preferable.
- the developer may be prepared once as a concentrate and diluted to a concentration required for use, from the viewpoint of transportation and storage convenience.
- the dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times.
- Post-baking is a post-development heat treatment to complete film curing.
- the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable.
- the post-baking film preferably has a Young's modulus of 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
- the support on which the cured film is formed includes an organic electroluminescent (organic EL) element, an image sensor having a photoelectric conversion film made of an organic material, and the like
- the post-baking temperature is 150 ° C. or less Is preferably 120 ° C.
- Post-baking is performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulating dryer), high frequency heater or the like so that the film (cured film) after development becomes the above conditions. It can be carried out.
- a heating means such as a hot plate, convection oven (hot air circulating dryer), high frequency heater or the like so that the film (cured film) after development becomes the above conditions. It can be carried out.
- a heating means such as a hot plate, convection oven (hot air circulating dryer), high frequency heater or the like
- the curability is increased, the weather resistance may be improved.
- Examples of the method of enhancing the curability of the pixel include ultraviolet curing, heat treatment in a nitrogen atmosphere, and further heat treatment after post-baking, or a combination thereof.
- the composition layer for forming a pixel formed by applying the composition layer for forming a pixel on a support or the like is cured to form a cured product layer, and then the cured product layer is formed.
- the photoresist layer patterned on the substrate may be formed, and then, the cured photoresist layer may be dry etched using an etching gas with the patterned photoresist layer as a mask.
- the photoresist layer is preferably formed by applying a positive or negative radiation sensitive composition on the cured product layer and drying it to form a photoresist layer.
- a positive type radiation sensitive composition is preferably used as a radiation sensitive composition used for formation of a photoresist layer.
- a positive type radiation sensitive composition radiation sensitive to radiations such as ultraviolet rays (g rays, h rays, i rays), far ultraviolet rays including KrF rays, ArF rays and the like, electron beams, ion beams and X rays Sex compositions are preferred.
- the above-mentioned positive type radiation sensitive composition is preferably a radiation sensitive composition that is sensitive to KrF rays, ArF rays, i rays, and X rays, and a radiation sensitive composition that is sensitive to KrF rays from the viewpoint of microfabrication Is more preferred.
- the positive photosensitive resin composition positive resist compositions described in JP-A-2009-237173 and JP-A-2010-134283 are suitably used.
- the exposure step of the radiation sensitive composition is preferably performed by KrF ray, ArF ray, i ray, X ray or the like, more preferably by KrF ray, ArF ray, X ray or the like It is further preferable to carry out with KrF radiation.
- a color filter having two or more different types of pixels can be manufactured by sequentially repeating the above-described steps for each type of pixel.
- each pixel preferably has high flatness.
- the surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and still more preferably 15 nm or less.
- the surface roughness can be measured, for example, using an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco.
- the contact angle of water on the pixel can be set to a preferable value as appropriate, but is typically in the range of 50 to 110 °.
- the contact angle can be measured, for example, using a contact angle meter CV-DT ⁇ A type (manufactured by Kyowa Interface Science Co., Ltd.).
- the volume resistance value of each pixel be high.
- the volume resistivity of the pixel is preferably 10 9 ⁇ ⁇ cm or more, and more preferably 10 11 ⁇ ⁇ cm or more.
- the upper limit is not limited, for example, 10 14 ⁇ ⁇ cm or less is preferable.
- the volume resistance value of the pixel can be measured, for example, using an ultra-high resistance meter 5410 (manufactured by Advantest Corporation).
- An absorption layer includes the process of apply
- various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing can be used.
- the absorption layer may be provided on the light incident side of the pixel of the color filter. Therefore, the composition for forming the absorption layer may be applied to the surface of the color filter, and various layers and members provided on the light path of the pixel of the color filter on the light incident side to this pixel (for example, May be applied to the surface of a flat layer, a microlens, a condenser lens, an infrared cut filter, a sealing glass). Among them, it is preferable to apply the composition for forming an absorption layer on the surface of the color filter because it is easier to improve the moisture resistance of the color filter.
- the composition layer formed by applying the composition for forming an absorbent layer may be dried (prebaked). 150 degrees C or less is preferable, 120 degrees C or less is more preferable, and 110 degrees C or less is still more preferable.
- the lower limit may be, for example, 50 ° C. or more, and may be 80 ° C. or more.
- the pre-bake time is preferably 10 seconds to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Drying can be performed on a hot plate, an oven or the like.
- the curing treatment includes a heat curing treatment and a light curing treatment.
- a thermosetting process and a photocuring process can also be used together.
- the heat curing temperature is preferably, for example, 180 to 260 ° C. 250 degrees C or less is preferable, and, as for the upper limit of thermosetting temperature, 240 degrees C or less is more preferable. 190 degreeC or more is preferable and, as for the minimum of thermosetting temperature, 200 degreeC or more is more preferable.
- the heat curing time is preferably 60 to 600 seconds.
- the upper limit of the heat curing time is preferably 300 seconds or less, and more preferably 180 seconds or less.
- the lower limit of the heat curing time is preferably 80 seconds or more, and more preferably 100 seconds or more.
- the heat curing treatment can be performed using a hot plate, an oven or the like.
- radiation which can be used at the time of photocuring, ultraviolet rays, such as g line and i line, are preferable, and i line is more preferable.
- Irradiation dose exposure dose
- the oxygen concentration in photocuring can be selected appropriately.
- the step of forming the absorbing layer may further include the step of forming a pattern.
- the color filter includes pixels of a type in which the hue is influenced by the absorption layer, it is preferable to perform patterning so that no absorption layer is provided on the light path of these pixels.
- the types of pixels affected by the absorption layer include the pixels described above.
- the step of forming a pattern is preferably performed before the above-mentioned curing treatment step or in place of the above-mentioned curing treatment.
- a pattern formation method using a photolithography method is preferable.
- the detail of the pattern formation method using the photolithographic method it is synonymous with the method mentioned above, and its preferable range is also the same.
- the solid-state imaging device of the present invention includes the structure of the present invention described above.
- the configuration of the solid-state imaging device is not particularly limited as long as it functions as a solid-state imaging device, and examples thereof include the following configurations.
- a plurality of photodiodes constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.), transfer electrodes made of polysilicon etc.
- the color filter may have a structure in which a cured film forming each pixel is embedded in a space partitioned in a grid shape by partition walls.
- the partition walls in this case preferably have a low refractive index for each pixel.
- an imaging device having such a structure devices described in JP 2012-227478 A and JP 2014-179577 A can be mentioned.
- the imaging device provided with the solid-state imaging device according to the present invention can be used not only for digital cameras and electronic devices (such as mobile phones) having an imaging function, but also for in-vehicle cameras and surveillance cameras.
- An image display apparatus of the present invention includes the structure of the present invention described above.
- Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device.
- Examples of the image display device include a liquid crystal display device and an organic electroluminescence display device.
- the liquid crystal display device is described, for example, in “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, published by Industry Research Association, 1994)”.
- composition 1 for forming an absorbent layer Pigment dispersion Y-1 ... 62.6 parts by mass Resin 1 ... 1.5 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compound 2 ... 1.9 parts by mass Silane cup Ring agent 1 ⁇ 1.8 parts by weight Photopolymerization initiator 1 ⁇ ⁇ ⁇ 0.9 parts by weight Surfactant 1 ⁇ ⁇ ⁇ 4.2 parts by weight Ultraviolet absorber 1 ⁇ ⁇ ⁇ 1.4 parts by weight Polymerization prohibited Agent (p-methoxyphenol) ... 0.001 part by mass PGMEA ... 23.4 parts by mass
- composition for Absorbent Layer Formation 2 Pigment dispersion Y-2 ... 58.1 parts by mass Resin 1 ... 1.5 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compound 2 ... 1.9 parts by mass Silane cup Ring agent 1 ⁇ 1.8 parts by weight Photopolymerization initiator 1 ⁇ ⁇ ⁇ 0.9 parts by weight Surfactant 1 ⁇ ⁇ ⁇ 4.2 parts by weight Ultraviolet absorber 1 ⁇ ⁇ ⁇ 1.4 parts by weight Polymerization prohibited Agent (p-methoxyphenol) ... 0.001 part by mass PGMEA ... 20.7 parts by mass
- composition 3 for forming an absorbent layer Pigment dispersion Y-3 ... 58.1 parts by mass Resin 1 ... 1.5 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compound 2 ... 1.9 parts by mass Silane cup Ring agent 1 ⁇ 1.8 parts by weight Photopolymerization initiator 1 ⁇ ⁇ ⁇ 0.9 parts by weight Surfactant 1 ⁇ ⁇ ⁇ 4.2 parts by weight Ultraviolet absorber 1 ⁇ ⁇ ⁇ 1.4 parts by weight Polymerization prohibited Agent (p-methoxyphenol) ... 0.001 part by mass PGMEA ... 20.7 parts by mass
- composition 5 for forming an absorbent layer Pigment dispersion Y-2 ... 58.1 parts by mass Resin 1 ... 1.5 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compound 2 ... 1.9 parts by mass Silane cup Ring agent 1 ⁇ 1.8 parts by mass Photopolymerization initiator 1 ⁇ ⁇ ⁇ 0.9 parts by mass Surfactant 1 ⁇ ⁇ ⁇ 4.2 parts by mass Ultraviolet absorber 2 ⁇ ⁇ ⁇ 5.0 parts by mass Polymerization inhibition Agent (p-methoxyphenol) ... 0.001 part by mass PGMEA ... 20.7 parts by mass
- composition 6 for forming an absorbent layer Pigment dispersion Y-3 ... 58.1 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compounds 2 ... 1.9 parts by mass Silane coupling agent 1 ... 1.8 parts by mass Parts
- composition 7 for forming an absorbent layer
- Dye solution Y-1 ... 62.6 parts by mass Resin 1 ... 1.5 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compound 2 ... 1.9 parts by mass Silane coupling Agent 1: ... 1.8 parts by mass Photopolymerization initiator 1 ... ... 0.9 parts by mass Surfactant 1: ... 4.2 parts by mass UV absorber 1 ... ... 1.4 parts by mass Polymerization inhibitor (P-methoxyphenol): 0.001 part by mass PGMEA: 23.4 parts by mass
- composition 9 for forming an absorbent layer Pigment dispersion Y-1 ... 62.6 parts by mass Resin 1 ... 2.9 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compound 2 ... 1.9 parts by mass Silane cup Ring agent 1 ... 1.8 parts by mass Photopolymerization initiator 1 ... 0.9 parts by mass Surfactant 1 ... 4.2 parts by mass Polymerization inhibitor (p-methoxyphenol) ... 0. 001 parts by mass PGMEA: 23.4 parts by mass
- composition 10 for forming an absorbent layer Pigment dispersion Y-1 ... 71.4 parts by mass Resin 1 ... 3.2 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compound 2 ... 1.9 parts by mass Silane cup Ring agent 1 ⁇ 1.8 parts by weight Photopolymerization initiator 1 ⁇ ⁇ ⁇ 0.9 parts by weight Surfactant 1 ⁇ ⁇ ⁇ 4.2 parts by weight Ultraviolet absorber 1 ⁇ ⁇ ⁇ 1.4 parts by weight Polymerization prohibited Agent (p-methoxyphenol) ... 0.001 part by mass PGMEA ... 13.0 parts by mass
- composition 11 for forming an absorbent layer Pigment dispersion Y-1 ... 71.4 parts by mass Resin 1 ... 3.2 parts by mass Polymerizable compound 1 ... 2.2 parts by mass Polymerizable compound 2 ... 1.9 parts by mass Silane cup Ring agent 1 ⁇ 1.8 parts by weight Photopolymerization initiator 1 ⁇ ⁇ ⁇ 0.9 parts by weight Surfactant 1 ⁇ ⁇ ⁇ 4.2 parts by weight Ultraviolet absorber 2 ⁇ ⁇ ⁇ 1.4 parts by weight Polymerization prohibited Agent (p-methoxyphenol) ... 0.001 part by mass PGMEA ... 13.0 parts by mass
- Polymerizable compound 1 56 mass% PGMEA solution of a mixture of compounds of the following structure (mixture of left side compound and right side compound in molar ratio 7: 3) -Polymerizable compound 2: 65 mass% PGMEA solution of the compound of the following structure
- Silane coupling agent 1 10% by weight PGMEA solution of a compound of the following structure (in the following structural formula, Et is an ethyl group)
- -Ultraviolet absorber 1 compound of the following structure
- UV absorber 2 Tinuvin 477 (manufactured by BASF, triazine compound)
- Dye solution Y-1 C.I. I.
- composition for forming colored pixels The following raw materials were mixed and stirred, followed by filtration through a nylon filter with a pore size of 0.45 ⁇ m (manufactured by Nippon Pall Co., Ltd.) to prepare a composition for forming a pixel of each color.
- Red pigment dispersion 51.7 parts by mass
- Resin 11 0.6 parts by mass
- Polymerizable compound 11 0.6 parts by mass
- Photopolymerization initiator 11 0.3 parts by mass Surfactant 11 ... 4.2 parts by mass PGMEA ... 42.6 parts by mass
- Green pigment dispersion 1 ... 73.7 parts by mass Resin 11 ... 0.3 parts by mass Polymerizable compound 12 ... 1.2 parts by mass Photopolymerization initiator 11 ... 0.6 parts by mass Surface activity Agent 11 ⁇ ⁇ ⁇ 4.2 parts by weight UV absorber 11 ⁇ ⁇ ⁇ 0.5 parts by weight PGMEA ⁇ ⁇ 19.5 parts by weight
- Green pigment dispersion 2 ... 73.7 parts by mass Resin 11 ... 0.3 parts by mass Polymerizable compound 12 ... 1.2 parts by mass Photopolymerization initiator 11 ... 0.6 parts by mass Surface activity Agent 11 ⁇ ⁇ ⁇ 4.2 parts by weight UV absorber 11 ⁇ ⁇ ⁇ 0.5 parts by weight PGMEA ⁇ ⁇ 19.5 parts by weight
- Green pigment dispersion 3 ... 73.7 parts by mass Resin 11 ... 0.3 parts by mass Polymerizable compound 12 ... 1.2 parts by mass Photopolymerization initiator 11 ... 0.6 parts by mass Surface activity Agent 11 ⁇ ⁇ ⁇ 4.2 parts by weight UV absorber 11 ⁇ ⁇ ⁇ 0.5 parts by weight PGMEA ⁇ ⁇ 19.5 parts by weight
- Green pixel formation compositions 4 to 7 were obtained in the same manner as in the green pixel formation composition 1 except that the green pigment dispersion liquid 1 was replaced with green pigment dispersion solutions 4 to 7.
- compositions 8 to 11 for forming green pixels Compositions 8 to 11 for forming a green pixel were obtained in the same manner as the composition 1 for forming a green pixel except that the green pigment dispersion 1 was replaced with green pigment dispersions 8 to 11.
- compositions 12 to 15 for forming green pixels Compositions 12 to 15 for forming a green pixel were obtained in the same manner as the composition 1 for forming a green pixel except that 0.5 parts by mass of the ultraviolet absorber 11 was changed to the additives 12 to 15, respectively.
- compositions 16 to 27 for forming green pixels Green pixel formation compositions 16 to 27 were obtained in the same manner as in the green pixel formation composition 1 except that 1.2 parts by mass of the polymerizable compound 12 was changed to polymerizable compounds 16 to 27, respectively.
- Green pixel formation compositions 16 to 27 were obtained in the same manner as in the green pixel formation composition 1 except that 0.3 parts by mass of the resin 11 was changed to the resins 28 to 34, respectively.
- the raw materials used for the composition for pixel formation of each color are as follows. Red pigment dispersion C.I. I. Pigment red 254, 9.6 parts by mass, C.I. I. Pigment yellow 139, 6.8 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 79.3 parts by mass of PGMEA were added to a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours using 3 mm diameter).
- dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a red pigment dispersion.
- Green pigment dispersion 1 C. I. Pigment green 58 and 6.4 parts by mass of C.I. I. Pigment Yellow 185, 5.2 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA were added to a bead mill (zirconia beads 0. Mix and disperse for 3 hours using 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a green pigment dispersion 1.
- Green pigment dispersion 2 C I. Pigment green 58, 5.2 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA were added to a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours using 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a green pigment dispersion liquid 2.
- a dispersing agent Dispersing agent
- Green pigment dispersion 3 C I. Pigment green 36, 5.2 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 83.1 parts by mass of PGMEA were added to a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours using 3 mm diameter). Thereafter, dispersion treatment was performed at a flow rate of 500 g / min5 under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a green pigment dispersion liquid 3.
- a dispersing agent Dispersing agent
- Green pigment dispersion 4 to 7 C I.
- the pigment dispersion was treated in the same manner as in the green pigment dispersion 1 except that 5.3 parts by mass of pigment yellow 185 was replaced with the following compounds 1 to 4, to obtain green pigment dispersions 4 to 7.
- Green pigment dispersion 8 to 11 Except that 5.2 parts by mass of the dispersant (Disperbyk-161, manufactured by BYK Chemie) was replaced with the following pigment dispersants 1 to 4 (the solid content was adjusted to be the same part by mass), the Green pigment dispersion 1 and The same process was carried out to obtain Green pigment dispersions 8 to 11.
- the reaction vessel is heated to 80 ° C., 12 parts of 3-mercapto-1,2-propanediol are added, and 0.2 parts by mass of 2,2′-azobisisobutyronitrile is divided into 20 parts.
- pigment dispersant 1 having a weight average molecular weight of 9,500 and an acid value of 45 mg KOH / g per solid content.
- pigment dispersant 2 having an acid value of 80 mg KOH / g per solid content and a weight average molecular weight of 7800.
- a mixed solution of 2.4 parts by mass of CI Pigment Violet 23, 5.5 parts by mass of a dispersing agent (Disperbyk-161, manufactured by BYK Chemie), and 82.4 parts by mass of PGMEA was used as a bead mill (zirconia beads 0. 2). Mix and disperse for 3 hours using 3 mm diameter). Thereafter, dispersion treatment was carried out at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism. This dispersion process was repeated 10 times to obtain a blue pigment dispersion.
- Polymerizable compound 11 compound of the following structure
- Polymerizable compound 12 mixture of compounds of the following structure (mixture in which the molar ratio of the left compound and the right compound is 7: 3)
- Polymerizable compound 13 Alonics M-305 (55 to 63% by mass of triacrylate, manufactured by Toagosei Co., Ltd.)
- Polymerizable compound 16 2-cyano-3-phenylacrylic acid
- Polymerizable compound 17 4-cyanophenyl methacrylate
- Polymerizable compound 18 3-chloro-2-hydroxypropyl methacrylate
- Polymerizable compound 19 3- Chloro-2-hydroxypropyl acrylate ⁇
- Polymerizable compound 20 3-bromo-2-hydroxypropyl methacrylate
- Polymerizable compound 21 3-bromo-2-hydroxypropyl acrylate
- Polymerizable compound 22 3-fluoro-2-hydroxy Propyl methacrylate
- Polymerizable compound 23 3-fluoro-2-hydroxypropyl
- Photopolymerization initiator 11 IRGACURE-OXE01 (manufactured by BASF)
- Photopolymerization initiator 12 compound of the following structure
- Additive 12 LA-63P (manufactured by ADEKA Co., Ltd.)
- Additive 13 Tinuvin 622 (manufactured by BASF)
- Additive 14 2-Nitrophenyl methacrylate
- Additive 15 p-nitrophenol
- Resin 11 the above resin 1
- Resin 28 70 parts by mass of cyclohexanone is put in a reaction vessel, and heated to 80 ° C. while injecting nitrogen gas into the vessel, 12.3 parts by mass of benzyl methacrylate, 4.6 parts by mass of 2-hydroxyethyl methacrylate, methacrylic acid 5 at the same temperature .3 parts by mass, a mixture of 7.4 parts by mass of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd., Alonix M110) as a photopolymerizable monomer, and 0.8 parts by mass of azobisisobutyro nitrile for 2 hours
- the polymerization reaction was carried out dropwise over After completion of the dropwise addition, the reaction is further carried out at 80 ° C.
- Resin 29 70 parts by mass of cyclohexanone is put in a reaction vessel, and heated to 80 ° C. while injecting nitrogen gas into the vessel, 12.3 parts by mass of benzyl methacrylate, 4.6 parts by mass of 2-hydroxyethyl methacrylate, methacrylic acid 5 at the same temperature A mixture of 3 parts by mass and 0.4 parts by mass of azobisisobutyronitrile was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, reaction was further carried out at 80 ° C.
- Resin 30 Maleimide group-containing photoreactive acrylic polymer (Alonics UVT-302, manufactured by Toagosei Co., Ltd.)
- Resin 31 70 parts by mass of cyclohexanone is put in a reaction vessel, and heated to 80 ° C. while injecting nitrogen gas into the vessel, and 50 parts by mass of cyclohexylmaleimide as N-substituted maleimide at the same temperature, 15 parts by mass of hydroxyethyl methacrylate, methacryl A mixture of 12 parts by mass of an acid, 23 parts by mass of methyl methacrylate, and 0.4 parts by mass of azobisisobutyronitrile was added dropwise over 2 hours to carry out a polymerization reaction. After completion of the dropwise addition, the reaction is further carried out at 80 ° C.
- ⁇ Resin 32 In a reaction vessel, 70 parts by mass of cyclohexanone are charged, and the vessel is heated to 80 ° C. while injecting nitrogen gas into the vessel to obtain N- (4-phenyl)-(N-substituted norbornene-5,6-dicarboximide at the same temperature. 50 parts by mass of 5-norbornene-2,3-dicarboximide, 15 parts by mass of hydroxyethyl methacrylate, 12 parts by mass of methacrylic acid, 23 parts by mass of methyl methacrylate, 0.4 parts by mass of azobisisobutyronitrile The polymerization reaction was carried out dropwise over 2 hours. After completion of the dropwise addition, the reaction is further carried out at 80 ° C.
- Resin 33 70 parts by mass of cyclohexanone is put in a reaction vessel, and heated to 80 ° C. while injecting nitrogen gas into the vessel, 12.3 parts by mass of benzyl methacrylate, 4.6 parts by mass of 2-hydroxyethyl methacrylate, methacrylic acid 5 at the same temperature .3 parts by mass, (b) a mixture of 7.4 parts by mass of paracumylphenol ethylene oxide modified acrylate (Toho Gosei Co., Ltd., Alonix M110) as a photopolymerizable monomer, and 0.4 parts by mass of azobisisobutyronitrile The polymerization reaction was carried out dropwise over 2 hours.
- Resin 34 70 parts by mass of cyclohexanone is put in a reaction vessel, and heated to 80 ° C. while injecting nitrogen gas into the vessel, 12.3 parts by mass of benzyl methacrylate, 4.6 parts by mass of 2-hydroxyethyl methacrylate, methacrylic acid 5 at the same temperature .3 parts by mass, a mixture of 7.4 parts by mass of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd., Alonix M110) as a photopolymerizable monomer, and 0.8 parts by mass of azobisisobutyro nitrile for 2 hours
- the polymerization reaction was carried out dropwise over After completion of the dropwise addition, the reaction is further carried out at 80 ° C.
- Example 1 for forming a green pixel is applied on a glass wafer using a spin coater so that the film thickness after drying is 0.6 ⁇ m, and heat treatment (pre-baking) is performed for 120 seconds using a hot plate at 100 ° C. went. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon (Ltd.)), 50mJ / cm 2 steps to 50 ⁇ 1500mJ / cm 2 using a photomask having a Bayer pattern of 1.1 ⁇ m angle is formed The exposure was performed to determine the optimum exposure amount for resolving the square pixel pattern, and the exposure was performed with this optimum exposure amount.
- FPA-3000i5 + manufactured by Canon (Ltd.)
- the glass wafer on which the exposed coating film is formed is placed on the horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and the developing solution (CD-2060, Paddle development was performed at 23 ° C. for 60 seconds using Fujifilm Electronics Materials Co., Ltd.).
- rinse treatment was performed with pure water, and spin drying was performed thereafter.
- heat treatment post bake was performed for 300 seconds using a hot plate at 200 ° C. to form a green colored pattern (green pixels) on the glass wafer.
- composition for forming a red pixel and the composition for forming a blue pixel pattern formation is performed in the same process to form a red pixel and a blue pixel sequentially, and a color having a green pixel, a red pixel and a blue pixel Formed a filter.
- the composition for forming an absorption layer shown in the following table is coated on the surface of this color filter using a spin coater so that the film thickness after drying is 0.5 ⁇ m, and heated for 120 seconds using a hot plate at 100 ° C. The treatment (prebake) was performed.
- This structure is a structure in which an absorption layer is provided on the light path of the pixels (green and red pixels) of the color filter and on the light incident side to these pixels.
- the film thickness of each of the green pixel, the red pixel, and the blue pixel was 0.6 ⁇ m
- the film thickness of the absorption layer was 0.5 ⁇ m.
- Example 13 to 18 instead of the composition 1 for forming a green pixel, the composition 2 for forming a green pixel was applied on a glass wafer using a spin coater so that the film thickness after drying was 0.4 ⁇ m. Pattern formation was performed in the same process as in the above to form green pixels. Subsequently, using the composition for forming a red pixel and the composition for forming a blue pixel, pattern formation is performed in the same process to sequentially form red pixels and blue pixels, and a color filter having green pixels, red pixels and blue pixels Formed.
- the compositions 1 to 6 for absorbing layer formation shown in the following table are applied using a spin coater so that the film thickness after drying becomes 0.1 ⁇ m, and a hot plate at 100 ° C. Heat treatment (pre-baking) was performed for 120 seconds. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.), exposure was performed using a photomask at an exposure amount of 1000 mJ / cm 2 . Thereafter, the glass wafer on which the exposed coating film is formed is placed on the horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and the developing solution (CD-2060, Paddle development was performed at 23 ° C.
- DW-30 type manufactured by Chemitronics
- This structure is a structure in which an absorption layer is provided on the light path of the pixels (green pixels) of the color filter and on the light incident side to these pixels.
- the thickness of the green pixel was 0.4 ⁇ m
- the thickness of each of the red pixel and the blue pixel was 0.5 ⁇ m
- the thickness of the absorption layer was 0.1 ⁇ m.
- Example 19 to 24 instead of the composition 1 for forming a green pixel, the composition 3 for forming a green pixel was applied on a glass wafer using a spin coater so that the film thickness after drying was 0.48 ⁇ m. Pattern formation was performed in the same process as in the above to form green pixels. Subsequently, using the composition for forming a red pixel and the composition for forming a blue pixel, pattern formation is performed in the same process to sequentially form red pixels and blue pixels, and a color filter having green pixels, red pixels and blue pixels Formed.
- the compositions 1 to 6 for absorbing layer formation shown in the following table are applied using a spin coater so that the film thickness after drying is 0.12 ⁇ m, and a hot plate at 100 ° C. Heat treatment (pre-baking) was performed for 120 seconds. Then, using an i-line stepper exposure apparatus FPA-3000i5 + (Canon Co., Ltd.), exposure was performed using a photomask at an exposure amount of 1000 mJ / cm 2 . Thereafter, the glass wafer on which the exposed coating film is formed is placed on the horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and the developing solution (CD-2060, Paddle development was performed at 23 ° C.
- DW-30 type manufactured by Chemitronics
- This structure is a structure in which an absorption layer is provided on the light path of the pixels (green pixels) of the color filter and on the light incident side to these pixels.
- the thickness of the green pixel was 0.48 ⁇ m
- the thickness of each of the red pixel and the blue pixel was 0.6 ⁇ m
- the thickness of the absorption layer was 0.12 ⁇ m.
- Examples 25 to 55 Structures were formed in the same manner as in Example 1 except that the green pixel forming compositions 4 to 34 were used instead of the green pixel forming composition 1.
- Comparative example 9 In the same manner as in Examples 1 to 12, Comparative Composition 1 was applied to the surface of a color filter to form a film, whereby a structure was produced.
- This structure is a structure having a film formed using the comparative composition 1 on the light path of the pixels (green and red pixels) of the color filter and on the light incident side to these pixels.
- the amount of change in transmittance ( ⁇ T%) compared is the amount of change in the wavelength where the amount of change in transmittance is the largest in the wavelength range of 400 to 700 nm (
- the Green composition indicates a composition for forming a green pixel.
- the structures of the examples were excellent in light resistance. Furthermore, the moisture resistance was also excellent. On the other hand, the structure of the comparative example was inferior in light resistance.
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Abstract
Description
<1> 2種以上の異なる種類の画素を有するカラーフィルタと、
黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層と、を有し、
吸収層を、カラーフィルタの画素のうち少なくとも1種の画素の光路上であって画素への光の入射側に有する、構造体。
<2> 吸収層は更に紫外線吸収剤を含む、<1>に記載の構造体。
<3> 紫外線吸収剤は、ベンゾトリアゾール化合物、ベンゾフェノン化合物およびトリアジン化合物から選ばれる少なくとも1種である、<2>に記載の構造体。
<4> 吸収層は、アゾ化合物およびイソインドリン化合物から選ばれる少なくとも1種を含む、<1>~<3>のいずれか1つに記載の構造体。
<5> 吸収層は、カラーインデックスピグメントイエロー139、カラーインデックスピグメントイエロー150およびカラーインデックスピグメントイエロー185から選ばれる少なくとも1種を含む、<1>~<3>のいずれか1つに記載の構造体。
<6> カラーフィルタは、緑色画素および赤色画素から選ばれる少なくとも1種の着色画素を含み、着色画素の光路上に吸収層を有する、<1>~<5>のいずれか1つに記載の構造体。
<7> カラーフィルタは、緑色画素、赤色画素および青色画素を含み、
緑色画素および赤色画素から選ばれる少なくとも一方の画素の光路上に吸収層を有し、青色画素の光路上には吸収層を有さない、<1>~<5>のいずれか1つに記載の構造体。
<8> 緑色画素は、ハロゲン化亜鉛フタロシアニン顔料を含有する、<7>に記載の構造体。
<9> 緑色画素および赤色画素の光路上に吸収層を有する、<7>または<8>に記載の構造体。
<10> 吸収層の膜厚は、吸収層の光路上に有する画素の膜厚の0.001~2倍である、<6>~<9>のいずれか1つに記載の構造体。
<11> 吸収層の膜厚は、吸収層の光路上に有する画素の膜厚の0.1~1倍である、<6>~<9>のいずれか1つに記載の構造体。
<12> カラーフィルタは、更に、透明画素および赤外線透過層の画素から選ばれる少なくとも1種の画素を含む、<6>~<11>のいずれか1つに記載の構造体。
<13> 吸収層は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種と、硬化性化合物とを含む組成物を硬化して得られたものである、<1>~<12>のいずれか1つに記載の構造体。
<14> カラーフィルタの画素と吸収層とが接している、<1>~<13>のいずれか1つに記載の構造体。
<15> カラーフィルタを形成する工程と、吸収層を形成する工程とを含む、構造体の製造方法であって、
カラーフィルタは、2種以上の異なる種類の画素を有し、
吸収層は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含み、
構造体は、吸収層を、カラーフィルタの画素のうち少なくとも1種の画素の光路上であって画素への光の入射側に有し、
吸収層を形成する工程は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層形成用組成物を塗布する工程を含む、構造体の製造方法。
<16> カラーフィルタの表面に吸収層形成用組成物を塗布する、<15>に記載の構造体の製造方法。
<17> 吸収層を形成する工程は、更にパターンを形成する工程を含む、<15>または<16>に記載の構造体の製造方法。
<18> 2種以上の異なる種類の画素を有するカラーフィルタと、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層と、を有し、吸収層を、カラーフィルタの画素のうち少なくとも1種の画素の光路上であって画素への光の入射側に有する構造体の、吸収層の形成用の組成物であって、
黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層形成用組成物。
<19> 更に紫外線吸収剤を含む、<18>に記載の吸収層形成用組成物。
<20> 紫外線吸収剤は、ベンゾトリアゾール化合物、ベンゾフェノン化合物およびトリアジン化合物から選ばれる少なくとも1種である、<19>に記載の吸収層形成用組成物。
<21> <1>~<14>のいずれか1つに記載の構造体を有する固体撮像素子。
<22> <1>~<14>のいずれか1つに記載の構造体を有する画像表示装置。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の合計質量をいう。
本明細書において、赤外線は、波長700~2500nmの光(電磁波)をいう。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アリル」は、アリルおよびメタリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィ(GPC)により測定したポリスチレン換算値として定義される。
本発明の構造体は、2種以上の異なる種類の画素を有するカラーフィルタと、
黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層と、を有し、
吸収層を、カラーフィルタの画素のうち少なくとも1種の画素の光路上であって前述の画素への光の入射側に有することを特徴とする。
(態様1)カラーフィルタが、緑色画素および赤色画素から選ばれる少なくとも1種の着色画素を含み、この着色画素の光路上に吸収層を有する態様。
(態様2)カラーフィルタが、緑色画素、赤色画素および青色画素を含み、
緑色画素および赤色画素から選ばれる少なくとも一方の画素の光路上に吸収層を有し、青色画素の光路上には吸収層を有さない態様。
上記態様1、2において、カラーフィルタは、更に、透明画素および/または赤外線透過層の画素(以下、他の画素ともいう)を含んでいてもよい。カラーフィルタが、更に、上記の他の画素を含む場合、他の画素の光路上には吸収層が設けられていなくてもよいが、耐光性の観点から他の画素の光路上にも吸収層が設けられていることが好ましい。
以下、本発明の構造体について詳細に説明する。
本発明の構造体は、2種以上の異なる種類の画素を有するカラーフィルタを有する。本発明の構造体において、カラーフィルタは、支持体上に形成されていることが好ましい。支持体としては特に限定はない。固体撮像素子などの各種電子デバイスなどで使用されている基板(シリコンウエハ、炭化ケイ素ウエハ、窒化ケイ素ウエハ、サファイアウエハ、ガラスウエハなど)を用いることができる。また、これらの基板上には、必要により、上部の層との密着改良、物質の拡散防止あるいは表面の平坦化のために下塗り層が設けられていてもよい。
(1):厚み方向における光の透過率の、波長400~640nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、厚み方向における光の透過率の、波長800~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である画素。この画素によれば、波長400~640nmの範囲の光を遮光して、波長670nmを超える光を透過させることができる。
(2):厚み方向における光の透過率の、波長400~750nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、厚み方向における光の透過率の、波長900~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である画素。この画素によれば、波長400~750nmの範囲の光を遮光して、波長850nmを超える光を透過させることができる。
(3):厚み方向における光の透過率の、波長400~830nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、厚み方向における光の透過率の、波長1000~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である画素。この画素によれば、波長400~830nmの範囲の光を遮光して、波長940nmを超える光を透過させることができる。
(4):厚み方向における光の透過率の、波長400~950nmの範囲における最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、厚み方向における光の透過率の、波長1100~1300nmの範囲における最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)である画素。この画素によれば、波長400~950nmの範囲の光を遮光して、波長1040nmを超える光を透過させることができる。
(1)2種(2色)以上の異なる色相の着色画素のみで構成された態様。
(2)2種(2色)以上の異なる色相の着色画素と、透明画素および/または赤外線透過層の画素とで構成された態様。
(3)1種(1色)のみの着色画素と、透明画素および/または赤外線透過層の画素とで構成された態様。
上記(3)の態様における着色画素は、緑色画素または赤色画素であることが好ましい。
本発明の構造体は、カラーフィルタの画素のうち少なくとも1種の画素の光路上であって前述の画素への光の入射側に、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層を有する。以下、黄色着色剤と、波長400~500nmの範囲に極大吸収波長を有する着色剤とをあわせて、着色剤Yともいう。
式(Y2)において、R205およびR208は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、R201~R204、R206およびR207は、それぞれ独立に、水素原子または置換基を表し、Y1は、窒素原子または-CRY1-を表し、Y2は、硫黄原子または-NRY2-を表し、RY1およびRY2は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、Xは、ビス(スルホニル)イミドアニオン、トリス(スルホニル)メチドアニオンまたはホウ素原子を有するアニオンを表す。
式(Y3)において、R301、R311およびR310は、それぞれ独立に、水素原子、アルキル基、アリール基またはヘテロアリール基を表し、R302~R305、R306~R309は、それぞれ独立に、水素原子または置換基を表し、Xは、ビス(スルホニル)イミドアニオン、トリス(スルホニル)メチドアニオンまたはホウ素原子を有するアニオンを表す。
式(Y4)において、R401およびR402は、それぞれ独立に、SO2R403またはCOR403を表す;R403は、アルキル基、アリール基またはヘテロアリール基を表す。
また、本発明の構造体において、吸収層に含まれる着色剤Yの50質量%以上がC.I.ピグメントイエロー139、C.I.ピグメントイエロー150およびC.I.ピグメントイエロー185から選ばれる少なくとも1種(好ましくはC.I.ピグメントイエロー150)であることが好ましく、より好ましくは70質量%以上であり、更に好ましくは90質量%以上である。
R1及びR2は、R1及びR2が結合する窒素原子とともに、環状アミノ基を形成していてもよい。環状アミノ基としては、例えば、ピペリジノ基、モルホリノ基、ピロリジノ基、ヘキサヒドロアゼピノ基、ピペラジノ基等が挙げられる。
R1及びR2は、各々独立に、炭素原子数1~20のアルキル基が好ましく、炭素原子数1~10のアルキル基がより好ましく、炭素原子数1~5のアルキル基が更に好ましい。
R3及びR4は、電子求引性基を表す。R3及びR4は、アシル基、カルバモイル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、シアノ基、ニトロ基、アルキルスルホニル基、アリールスルホニル基、スルホニルオキシ基、スルファモイル基が好ましく、アシル基、カルバモイル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、シアノ基、アルキルスルホニル基、アリールスルホニル基、スルホニルオキシ基、スルファモイル基が好ましい。また、R3及びR4は、互いに結合して環状の電子求引性基を形成してもよい。R3およびR4が互いに結合して形成する環状の電子求引性基としては、例えば、2個のカルボニル基を含む6員環を挙げることができる。
上記のR1、R2、R3、及びR4の少なくとも1つは、連結基を介して、ビニル基と結合したモノマーより導かれるポリマーの形になっていてもよい。他のモノマーとの共重合体であっても良い。
ベンゾフェノン化合物としては、2-ヒドロキシ-4-n-オクトキシベンゾフェノン、2,2’,4,4’-テトラヒドロキシベンゾフェノンなどが挙げられる。市販品としては、ユビナールA、ユビナール3049、ユビナール3050(以上、BASF社製)などが挙げられる。
クマリン化合物としては、例えば、クマリン-4、4-ヒドロキシクマリン、7-ヒドロキシクマリンなどが挙げられる。
また、吸収層は、着色剤Yの100質量部に対して紫外線吸収剤を0.1~200質量部含有することが好ましい。上限は、100質量部以下であることがより好ましく、50質量部以下であることが更に好ましく、30質量部以下であることが更により好ましい。下限は、1質量部以上であることがより好ましく、5質量部以上であることが更に好ましく、10質量部以上であることが更により好ましい。着色剤Yと紫外線吸収剤との割合が上記範囲であれば、紫外領域近傍の光を効率的に遮光して画素の耐光性をより高めるという効果が期待できる。
吸収層は、紫外線吸収剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。紫外線吸収剤を2種以上含む場合はそれらの合計量が上記範囲であることが好ましい。
また、吸収層は、波長400nm以上500nm以下の範囲の少なくとも一部(好ましくは波長400nm以上450nm以下の範囲の少なくとも一部、より好ましくは波長400nm以上450nm以下の全範囲)における透過率が10%以下であることが好ましく、5%以下であることがより好ましく、1%以下であることが更に好ましい。
また、吸収層は、波長300nm以上400nm未満の範囲の少なくとも一部(好ましくは波長300nm以上400nm未満の範囲の少なくとも一部、より好ましくは波長300nm以上400nm未満の全範囲)における透過率が10%以下であることが好ましく、5%以下であることがより好ましく、1%以下であることが更に好ましい。
次に、本発明の構造体の吸収層の形成用の組成物(吸収層形成用組成物)について説明する。
吸収層形成用組成物は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種(着色剤Y)を含む。黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤の詳細および好ましい範囲については、上述した吸収層の欄で説明した内容と同様である。
吸収層形成用組成物は、着色剤Y以外の着色剤を実質的に含まないことが好ましい。この態様によれば、カラーフィルタの画素の色相に影響を与えることなく、カラーフィルタの耐光性を向上させることができる。吸収層形成用組成物が着色剤Y以外の着色剤を実質的に含まない場合とは、着色剤Y以外の着色剤の含有量が、着色剤Yの100質量部に対して、1質量部以下であることが好ましく、0.5質量部以下であることがより好ましく、0.1質量部以下であることが更に好ましく、含有しないことが特に好ましい。
吸収層形成用組成物は、着色剤Yの他にさらに紫外線吸収剤を含むことが好ましい。この態様によれば、カラーフィルタの耐光性をより顕著に向上させることができる。紫外線吸収剤の詳細および好ましい範囲については、上述した吸収層の欄で説明した内容と同様である。
また、吸収層形成用組成物は着色剤Yの100質量部に対して紫外線吸収剤を0.1~200質量部含有することが好ましい。上限は、100質量部以下であることがより好ましく、50質量部以下であることが更に好ましく、30質量部以下であることが更により好ましい。下限は、1質量部以上であることがより好ましく、5質量部以上であることが更に好ましく、10質量部以上であることが更により好ましい。
吸収層形成用組成物は、紫外線吸収剤を1種のみ含んでいてもよく、2種以上含んでいてもよい。紫外線吸収剤を2種以上含む場合はそれらの合計量が上記範囲であることが好ましい。
吸収層形成用組成物は、更に硬化性化合物を含むことが好ましい。この態様によれば、カラーフィルタの耐光性や耐湿性をより効果的に向上させることができる。硬化性化合物としては、ラジカル、酸、熱により架橋可能な公知の化合物を用いることができる。本発明において、硬化性化合物は、例えば、エチレン性不飽和結合基を有する化合物、エポキシ基を有する化合物などが挙げられ、エチレン性不飽和結合基を有する化合物であることが好ましい。エチレン性不飽和結合基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。エチレン性不飽和結合基を有する化合物としては、重合性化合物であることが好ましく、ラジカル重合性化合物であることがより好ましい。
エチレン性不飽和結合基を有する化合物としては、モノマー、プレポリマー、オリゴマーなどの化学的形態のいずれであってもよいが、モノマーが好ましい。エチレン性不飽和結合基を有する化合物の分子量は、100~3000が好ましい。上限は、2000以下がより好ましく、1500以下が更に好ましい。下限は、150以上がより好ましく、250以上が更に好ましい。
また、エチレン性不飽和結合基を有する化合物としては、特開2017-48367号公報、特許第6057891号公報、特許第6031807号公報に記載されている化合物を用いることもできる。
また、エチレン性不飽和結合基を有する化合物としては、8UH-1006、8UH-1012(以上、大成ファインケミカル(株)製)、ライトアクリレートPOB-A0(共栄社化学(株)製)などを用いることも好ましい。
エポキシ基を有する化合物(以下、エポキシ化合物ともいう)は、エポキシ基を1分子内に1~100個有する化合物であることが好ましい。エポキシ基の下限は、2個以上がより好ましい。エポキシ基の上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。
吸収層形成用組成物は、硬化性化合物として重合性化合物を含有する場合、更に光重合開始剤を含有することが好ましい。光重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外領域から可視領域の光線に対して感光性を有する化合物が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する化合物であってもよい。光重合開始剤は光ラジカル重合開始剤であることが好ましい。
吸収層形成用組成物は、樹脂を含むことが好ましい。樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料などの粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で使用することもできる。
吸収層形成用組成物は樹脂として分散剤を含むことが好ましい。分散剤は、酸性分散剤(酸性樹脂)、塩基性分散剤(塩基性樹脂)が挙げられる。ここで、酸性分散剤(酸性樹脂)とは、酸基の量が塩基性基の量よりも多い樹脂を表す。酸性分散剤(酸性樹脂)としては、酸基の量と塩基性基の量の合計量を100モル%としたときに、酸基の量が70モル%以上を占める樹脂が好ましく、実質的に酸基のみからなる樹脂がより好ましい。酸性分散剤(酸性樹脂)が有する酸基は、カルボキシル基が好ましい。酸性分散剤(酸性樹脂)の酸価は、5~105mgKOH/gが好ましい。また、塩基性分散剤(塩基性樹脂)とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤(塩基性樹脂)としては、酸基の量と塩基性基の量の合計量を100モル%としたときに、塩基性基の量が50モル%を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基が好ましい。
吸収層形成用組成物は、樹脂としてアルカリ可溶性樹脂を含有することができる。なお、アルカリ可溶性樹脂は、分散剤やバインダーとして用いることもできる。
式(X)において、R1は、水素原子またはメチル基を表し、R2は炭素数2~10のアルキレン基を表し、R3は、水素原子またはベンゼン環を含んでもよい炭素数1~20のアルキル基を表す。nは1~15の整数を表す。
吸収層形成用組成物は、樹脂として上述した分散剤やアルカリ可溶性樹脂の欄で説明した樹脂以外の樹脂(その他の樹脂ともいう)を含有することができる。その他の樹脂としては、例えば、(メタ)アクリル樹脂、(メタ)アクリルアミド樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、シロキサン樹脂などが挙げられる。他の樹脂は、これらの樹脂から1種を単独で使用してもよく、2種以上を混合して使用してもよい。また、本発明では、樹脂として、特開2017-57265号公報、特開2017-32685号公報、特開2017-075248号公報、特開2017-066240号公報に記載された樹脂を用いることもでき、これらの内容は本明細書に組み込まれる。
吸収層形成用組成物は、顔料誘導体を含有することができる。顔料誘導体としては、発色団の一部分を、酸基、塩基性基またはフタルイミドメチル基で置換した構造を有する化合物が挙げられる。顔料誘導体を構成する発色団としては、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、フタロシアニン系骨格、アンスラキノン系骨格、キナクリドン系骨格、ジオキサジン系骨格、ペリノン系骨格、ペリレン系骨格、チオインジゴ系骨格、イソインドリン系骨格、イソインドリノン系骨格、キノフタロン系骨格、スレン系骨格、金属錯体系骨格等が挙げられ、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、キノフタロン系骨格、イソインドリン系骨格およびフタロシアニン系骨格が好ましく、アゾ系骨格およびベンゾイミダゾロン系骨格がより好ましい。顔料誘導体が有する酸基としては、スルホ基、カルボキシル基が好ましく、スルホ基がより好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、三級アミノ基がより好ましい。顔料誘導体の具体例としては、特開2011-252065号公報の段落番号0162~0183の記載を参酌でき、この内容は本明細書に組み込まれる。
吸収層形成用組成物が顔料誘導体を含有する場合、顔料誘導体の含有量は、顔料100質量部に対し、1~30質量部が好ましく、3~20質量部がさらに好ましい。顔料誘導体は、1種のみを用いてもよいし、2種以上を併用してもよい。顔料誘導体を2種以上含む場合はそれらの合計量が上記範囲であることが好ましい。
吸収層形成用組成物は、溶剤を含有することが好ましい。溶剤は有機溶剤が好ましい。溶剤は、各成分の溶解性や吸収層形成用組成物の塗布性を満足すれば特に制限はない。
吸収層形成用組成物は、界面活性剤を含有することが好ましい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用でき、塗布性をより向上できるという理由からフッ素系界面活性剤が好ましい。
上記の化合物の重量平均分子量は、好ましくは3,000~50,000であり、例えば、14,000である。
吸収層形成用組成物は、シランカップリング剤を含有することができる。本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、ケイ素原子に直結し、加水分解反応および/または縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられる。
吸収層形成用組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン塩(アンモニウム塩、第一セリウム塩等)等が挙げられる。
吸収層形成用組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、吸収層形成用組成物の全固形分に対して、0.01~5質量%が好ましい。吸収層形成用組成物は、重合禁止剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、それらの合計量が上記範囲となることが好ましい。
吸収層形成用組成物には、必要に応じて、各種添加剤、例えば、充填剤、密着促進剤、酸化防止剤、潜在酸化防止剤等を配合することができる。これらの添加剤としては、特開2004-295116号公報の段落番号0155~0156に記載の添加剤を挙げることができ、この内容は本明細書に組み込まれる。また、酸化防止剤としては、例えばフェノール化合物、リン系化合物(例えば特開2011-90147号公報の段落番号0042に記載の化合物)、チオエーテル化合物などを用いることができる。市販品としては、例えば(株)ADEKA製のアデカスタブシリーズ(AO-20、AO-30、AO-40、AO-50、AO-50F、AO-60、AO-60G、AO-80、AO-330など)が挙げられる。また、酸化防止剤として、国際公開WO2017/006600号公報に記載された多官能ヒンダードアミン酸化防止剤を用いることもできる。酸化防止剤は1種のみを用いてもよく、2種以上を用いてもよい。また、潜在酸化防止剤としては、酸化防止剤として機能する部位が保護基で保護された化合物であって、100~250℃で加熱するか、又は酸/塩基触媒存在下で80~200℃で加熱することにより保護基が脱離して酸化防止剤として機能する化合物が挙げられる。潜在酸化防止剤としては国際公開WO2014/021023号公報、国際公開WO2017/030005号公報、特開2017-008219号公報に記載された化合物が挙げられる。市販品としては、アデカアークルズGPA-5001((株)ADEKA製)等が挙げられる。
次に、カラーフィルタにおける着色画素の形成に好ましく用いることができる組成物(着色画素形成用組成物)について説明する。着色画素形成用組成物は、着色剤を含むことが好ましい。着色剤としては、黄色着色剤、オレンジ色着色剤、赤色着色剤、緑色着色剤、紫色着色剤、青色着色剤などの有彩色着色剤が挙げられる。着色剤は、顔料であってもよく、染料であってもよい。
カラーインデックス(C.I.)ピグメントイエロー1、2、3、4、5、6、10、11、12、13、14、15、16、17、18、20、24、31、32、34、35、35:1、36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、127、128、129、137、138、139、147、148、150、151、152、153、154、155、156、161、162、164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、188、193、194、199、213、214(以上、黄色顔料);
C.I.ピグメントオレンジ2、5、13、16、17:1、31、34、36、38、43、46、48、49、51、52、55、59、60、61、62、64、71、73(以上、オレンジ色顔料);
C.I.ピグメントレッド1、2、3、4、5、6、7、9、10、14、17、22、23、31、38、41、48:1、48:2、48:3、48:4、49、49:1、49:2、52:1、52:2、53:1、57:1、60:1、63:1、66、67、81:1、81:2、81:3、83、88、90、105、112、119、122、123、144、146、149、150、155、166、168、169、170、171、172、175、176、177、178、179、184、185、187、188、190、200、202、206、207、208、209、210、216、220、224、226、242、246、254、255、264、270、272、279(以上、赤色顔料);
C.I.ピグメントグリーン7、10、36、37、58、59(以上、緑色顔料);
C.I.ピグメントバイオレット1、19、23、27、32、37、42、58、59(以上、紫色顔料);
C.I.ピグメントブルー1、2、15、15:1、15:2、15:3、15:4、15:6、16、22、60、64、66、79、80(以上、青色顔料)。
次に、カラーフィルタにおける透明画素の形成に好ましく用いることができる組成物(透明画素形成用組成物)について説明する。透明画素形成用組成物は、樹脂を含有することが好ましい。樹脂としては、上述した吸収層形成用組成物に用いられる前述の材料が挙げられ、好ましい範囲も同様である。また、樹脂の好ましい含有量についても吸収層形成用組成物における含有量と同様である。吸収層形成用組成物は、更に、Ti、Zr、Sn、Sb、Cu、Fe、Mn、Pb、Cd、As、Cr、Hg、Zn、Al、Mg、Si、PおよびSから選択される少なくとも一種の元素を含む酸化物の粒子(無機粒子ともいう)を含有することもできる。前述の無機粒子を含有する場合、無機粒子の含有量は、吸収層形成用組成物の全固形分に対して、20~70質量%であることが好ましい。下限は、25質量%以上がより好ましく、30質量%以上がさらに好ましい。上限は、65質量%以下がより好ましく、60質量%以下が更に好ましい。透明画素形成用組成物は、更に、硬化性化合物、光重合開始剤、溶剤、界面活性剤、シランカップリング剤、重合禁止剤、紫外線吸収剤、充填剤、密着促進剤、酸化防止剤、潜在酸化防止剤などの添加剤を含んでいてもよい。これらの詳細については、上述した吸収層形成用組成物に用いられる前述の材料が挙げられ、好ましい範囲も同様である。また、これらの材料の好ましい含有量についても吸収層形成用組成物における含有量と同様である。
次に、本発明の構造体における赤外線透過層の画素の形成に好ましく用いることができる組成物(赤外線透過層形成用組成物)について説明する。赤外線透過層形成用組成物は、波長400~640nmの範囲における吸光度の最小値Aと、波長1100~1300nmの範囲における吸光度の最大値Bとの比であるA/Bが5以上であることが好ましく、7.5以上であることが好ましく、15以上であることがより好ましく、30以上であることが更に好ましい。
Aλ=-log(Tλ/100) ・・・(1)
Aλは、波長λにおける吸光度であり、Tλは、波長λにおける透過率(%)である。
本発明において、吸光度の値は、溶液の状態で測定した値であってもよく、赤外線透過層形成用組成物を用いて製膜した膜での値であってもよい。膜の状態で吸光度を測定する場合は、ガラス基板上にスピンコート等の方法により、乾燥後の膜の厚さが所定の厚さとなるように赤外線透過層形成用組成物を塗布し、ホットプレートを用いて100℃、120秒間乾燥して調製した膜を用いて測定することが好ましい。膜の厚さは、膜を有する基板について、触針式表面形状測定器(ULVAC社製 DEKTAK150)を用いて測定することができる。
(1):2種類以上の有彩色着色剤を含み、2種以上の有彩色着色剤の組み合わせで黒色を形成している。
(2):有機系黒色着色剤を含む。(2)の態様において、更に有彩色着色剤を含有することも好ましい。
(1)赤色着色剤と青色着色剤とを含有する態様。
(2)赤色着色剤と青色着色剤と黄色着色剤とを含有する態様。
(3)赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤とを含有する態様。
(4)赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤と緑色着色剤とを含有する態様。
(5)赤色着色剤と青色着色剤と黄色着色剤と緑色着色剤とを含有する態様。
(6)赤色着色剤と青色着色剤と緑色着色剤とを含有する態様。
(7)黄色着色剤と紫色着色剤とを含有する態様。
上記(2)の態様において、赤色着色剤と青色着色剤と黄色着色剤の質量比は、赤色着色剤:青色着色剤:黄色着色剤=10~80:20~80:10~40であることが好ましく、10~60:30~80:10~30であることがより好ましく、10~40:40~80:10~20であることが更に好ましい。
上記(3)の態様において、赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤との質量比は、赤色着色剤:青色着色剤:黄色着色剤:紫色着色剤=10~80:20~80:5~40:5~40であることが好ましく、10~60:30~80:5~30:5~30であることがより好ましく、10~40:40~80:5~20:5~20であることが更に好ましい。
上記(4)の態様において、赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤と緑色着色剤の質量比は、赤色着色剤:青色着色剤:黄色着色剤:紫色着色剤:緑色着色剤=10~80:20~80:5~40:5~40:5~40であることが好ましく、10~60:30~80:5~30:5~30:5~30であることがより好ましく、10~40:40~80:5~20:5~20:5~20であることが更に好ましい。
上記(5)の態様において、赤色着色剤と青色着色剤と黄色着色剤と緑色着色剤の質量比は、赤色着色剤:青色着色剤:黄色着色剤:緑色着色剤=10~80:20~80:5~40:5~40であることが好ましく、10~60:30~80:5~30:5~30であることがより好ましく、10~40:40~80:5~20:5~20であることが更に好ましい。
上記(6)の態様において、赤色着色剤と青色着色剤と緑色着色剤の質量比は、赤色着色剤:青色着色剤:緑色着色剤=10~80:20~80:10~40であることが好ましく、10~60:30~80:10~30であることがより好ましく、10~40:40~80:10~20であることが更に好ましい。
上記(7)の態様において、黄色着色剤と紫色着色剤の質量比は、黄色着色剤:紫色着色剤=10~50:40~80であることが好ましく、20~40:50~70であることがより好ましく、30~40:60~70であることが更に好ましい。
上述した各組成物の収容容器としては、特に限定はなく、公知の収容容器を用いることができる。また、収納容器として、原材料や組成物中への不純物混入を抑制することを目的に、容器内壁を6種6層の樹脂で構成する多層ボトルや6種の樹脂を7層構造にしたボトルを使用することも好ましい。このような容器としては例えば特開2015-123351号公報に記載の容器が挙げられる。
上述した各組成物は、前述の成分を混合して調製できる。組成物の調製に際しては、全成分を同時に溶剤に溶解または分散して組成物を調製してもよいし、必要に応じては、各成分を適宜配合した2つ以上の溶液または分散液をあらかじめ調製し、使用時(塗布時)にこれらを混合して組成物として調製してもよい。
フィルタの孔径は、0.01~7.0μm程度が適しており、好ましくは0.01~3.0μm程度であり、更に好ましくは0.05~0.5μm程度である。フィルタの孔径が上記範囲であれば、微細な異物を確実に除去できる。また、ファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えばポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられる。具体的には、ロキテクノ社製のSBPタイプシリーズ(SBP008など)、TPRタイプシリーズ(TPR002、TPR005など)、SHPXタイプシリーズ(SHPX003など)のフィルタカートリッジが挙げられる。
次に、本発明の構造体の製造方法について説明する。本発明の構造体の製造方法は、カラーフィルタを形成する工程と、吸収層を形成する工程とを含み、
カラーフィルタは、2種以上の異なる種類の画素を有し、
吸収層は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含み、
構造体は、吸収層を、カラーフィルタの画素のうち少なくとも1種の画素の光路上であって前述の画素への光の入射側に有し、
吸収層を形成する工程は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層形成用組成物を塗布する工程を含む。
本発明の構造体の製造方法において、吸収層は、カラーフィルタを形成した後、形成することが好ましい。すなわち、カラーフィルタを形成する工程を行った後、吸収層を形成する工程を行うことが好ましい。以下、各工程について詳細に説明する。
カラーフィルタを形成する工程は、カラーフィルタの各画素形成用組成物を塗布して画素形成用組成物層を形成する工程と、フォトリソグラフィ法またはドライエッチング法により、画素形成用組成物層に対してパターンを形成する工程と、を含むことが好ましい。画素形成用組成物としては、上述した着色画素形成用組成物、透明画素形成用組成物、赤外線透過層形成用組成物が用いられる。少なくとも1種の画素は、着色画素形成用組成物を用いて形成することが好ましい。フォトリソグラフィ法でのパターン形成方法は、画素形成用組成物層に対しパターン状に露光する工程(露光工程)と、未露光部の画素形成用組成物層を現像除去してパターンを形成する工程(現像工程)と、を含むことが好ましい。ドライエッチング法でのパターン形成方法としては、画素形成用組成物層を硬化して硬化物層を形成する工程と、この硬化物層上にパターニングされたフォトレジスト層を形成する工程と、パターニングされたフォトレジスト層をマスクとして硬化物層に対してエッチングガスを用いてドライエッチングする工程とを含むことが好ましい。以下、各工程について説明する。
画素形成用組成物層を形成する工程では、支持体上に画素形成用組成物を形成することが好ましい。支持体としては、特に限定は無く、用途に応じて適宜選択できる。固体撮像素子などの各種電子デバイスなどで使用されている基板(シリコンウエハ、炭化ケイ素ウエハ、窒化ケイ素ウエハ、サファイアウエハ、ガラスウエハなど)を用いることができる。また、これらの基板上には、必要により、上部の層との密着改良、物質の拡散防止あるいは表面の平坦化のために下塗り層が設けられていてもよい。
[露光工程]
次に、画素形成用組成物層をパターン状に露光する(露光工程)。例えば、画素形成用組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。露光に際して用いることができる放射線(光)としては、g線、i線等の紫外線が好ましく(特に好ましくはi線)用いられる。照射量(露光量)は、例えば、0.03~2.5J/cm2が好ましく、0.05~1.0J/cm2がより好ましい。露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が19体積%以下の低酸素雰囲気下(例えば、15体積%、5体積%、または、実質的に無酸素)で露光してもよく、酸素濃度が21体積%を超える高酸素雰囲気下(例えば、22体積%、30体積%、または、50体積%)で露光してもよい。また、露光照度は適宜設定することが可能であり、通常1000W/m2~100000W/m2(例えば、5000W/m2、15000W/m2、または、35000W/m2)の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度10体積%で照度10000W/m2、酸素濃度35体積%で照度20000W/m2などとすることができる。
次に、未露光部を現像除去してパターンを形成する。未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の画素形成用組成物層が現像液に溶出し、光硬化した部分だけが残る。現像液としては、下地の固体撮像素子や回路などにダメージを与えない、アルカリ現像液(アルカリ性水溶液)が望ましい。現像液の温度は、例えば、20~30℃が好ましい。現像時間は、20~180秒が好ましい。また、残渣除去性を向上するため、現像液を60秒ごとに振り切り、更に新たに現像液を供給する工程を数回繰り返してもよい。
ドライエッチング法でのパターン形成は、画素形成用組成物層を支持体上などに塗布して形成した画素形成用組成物層を硬化して硬化物層を形成し、次いで、この硬化物層上にパターニングされたフォトレジスト層を形成し、次いで、パターニングされたフォトレジスト層をマスクとして硬化物層に対してエッチングガスを用いてドライエッチングするなどの方法で行うことができる。フォトレジスト層は、硬化物層上にポジ型またはネガ型の感放射線性組成物を塗布し、これを乾燥させることによりフォトレジスト層を形成することが好ましい。フォトレジスト層の形成に用いる感放射線性組成物としては、ポジ型の感放射線性組成物が好ましく用いられる。ポジ型の感放射線性組成物としては、紫外線(g線、h線、i線)、KrF線、ArF線等を含む遠紫外線、電子線、イオンビームおよびX線等の放射線に感応する感放射線性組成物が好ましい。上述のポジ型の感放射線性組成物は、KrF線、ArF線、i線、X線に感応する感放射線性組成物が好ましく、微細加工性の観点からKrF線に感応する感放射線性組成物がより好ましい。ポジ型の感光性樹脂組成物としては、特開2009-237173号公報や特開2010-134283号公報に記載のポジ型レジスト組成物が好適に用いられる。フォトレジスト層の形成において、感放射線性組成物の露光工程は、KrF線、ArF線、i線、X線などで行うことが好ましく、KrF線、ArF線、X線などで行うことがより好ましく、KrF線で行うことが更に好ましい。
また、画素上の水の接触角は適宜好ましい値に設定することができるが、典型的には、50~110°の範囲である。接触角は、例えば接触角計CV-DT・A型(協和界面科学(株)製)を用いて測定できる。
次に、吸収層を形成する工程について説明する。吸収層は、上述した吸収層形成用組成物を塗布する工程と含む。吸収層形成用組成物の塗布方法としては、スリット塗布、インクジェット法、回転塗布、流延塗布、ロール塗布、スクリーン印刷法等の各種の方法を用いることができる。
本発明の固体撮像素子は、上述した本発明の構造体を含む。固体撮像素子の構成としては、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。
本発明の画像表示装置は、上述した本発明の構造体を含む。画像表示装置としては、液晶表示装置や有機エレクトロルミネッセンス表示装置などが挙げられる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス(佐々木 昭夫著、(株)工業調査会 1990年発行)」、「ディスプレイデバイス(伊吹 順章著、産業図書(株)平成元年発行)」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術(内田 龍男編集、(株)工業調査会 1994年発行)」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
[顔料分散液の調製]
以下に示す原料を攪拌および混合した後、ビーズミルにより3時間混合および分散して各顔料分散液を調製した。
C.I.ピグメントイエロー150・・・11.3質量部
分散樹脂1・・・8.4質量部
プロピレングリコールモノメチルエーテル アセテート(PGMEA)・・・68.3質量部
シクロヘキサノン・・・12.0質量部
C.I.ピグメントイエロー185・・・12.4質量部
分散樹脂1・・・3.8質量部
PGMEA・・・83.7質量部
C.I.ピグメントイエロー139・・・12.4質量部
分散樹脂1・・・3.8質量部
PGMEA・・・83.7質量部
以下に示す原料を攪拌および混合して各吸収層形成用組成物を調製した。
顔料分散液Y-1・・・62.6質量部
樹脂1・・・1.5質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤1・・・1.4質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・23.4質量部
顔料分散液Y-2・・・58.1質量部
樹脂1・・・1.5質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤1・・・1.4質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・20.7質量部
顔料分散液Y-3・・・58.1質量部
樹脂1・・・1.5質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤1・・・1.4質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・20.7質量部
顔料分散液Y-1・・・62.6質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤2・・・4.8質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・23.4質量部
顔料分散液Y-2・・・58.1質量部
樹脂1・・・1.5質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤2・・・5.0質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・20.7質量部
顔料分散液Y-3・・・58.1質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤2・・・10.2質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・20.7質量部
染料溶液Y-1・・・62.6質量部
樹脂1・・・1.5質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤1・・・1.4質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・23.4質量部
染料溶液Y-2・・・62.6質量部
樹脂1・・・1.5質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤1・・・1.4質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・23.4質量部
顔料分散液Y-1・・・62.6質量部
樹脂1・・・2.9質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・23.4質量部
顔料分散液Y-1・・・71.4質量部
樹脂1・・・3.2質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤1・・・1.4重量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・13.0質量部
顔料分散液Y-1・・・71.4質量部
樹脂1・・・3.2質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤2・・・1.4重量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・13.0質量部
顔料分散液Y-1・・・85.7質量部
樹脂1・・・0.9質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・2.4質量部
樹脂1・・・30質量部
重合性化合物1・・・2.2質量部
重合性化合物2・・・1.9質量部
シランカップリング剤1・・・1.8質量部
光重合開始剤1・・・0.9質量部
界面活性剤1・・・4.2質量部
紫外線吸収剤2・・・5質量部
重合禁止剤(p-メトキシフェノール)・・・0.001質量部
PGMEA・・・54質量部
・光重合開始剤1:IRGACURE-OXE01(BASF社製)
・界面活性剤1:下記化合物(Mw=14000)の1質量%PGMEA溶液。下記の式中、繰り返し単位の割合を示す%はモル%である。
・重合性化合物1:下記構造の化合物の混合物(左側化合物と右側化合物とのモル比が7:3の混合物)の56質量%PGMEA溶液
・重合性化合物2:下記構造の化合物の65質量%PGMEA溶液
・シランカップリング剤1:下記構造の化合物の10質量%PGMEA溶液(以下の構造式中、Etはエチル基である)
・紫外線吸収剤1:下記構造の化合物
・紫外線吸収剤2:Tinuvin477(BASF製、トリアジン化合物)
・染料溶液Y-1:C.I.ソルベントイエロー162の11.3質量部をPGMEA(プロピレングリコールモノメチルエーテルアセテート)の90質量部に溶解させた溶液。
・染料溶液Y-2:下記黄色染料Aの11.3質量部をテトラヒドロフランの90質量部に溶解させた溶液。
黄色染料A:下記構造の化合物
以下に示す原料を混合し、撹拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して各色の画素形成用組成物を調製した。
Red顔料分散液・・・51.7質量部
樹脂11・・・0.6質量部
重合性化合物11・・・0.6質量部
光重合開始剤11・・・0.3質量部
界面活性剤11・・・4.2質量部
PGMEA・・・42.6質量部
Green顔料分散液1・・・73.7質量部
樹脂11・・・0.3質量部
重合性化合物12・・・1.2質量部
光重合開始剤11・・・0.6質量部
界面活性剤11・・・4.2質量部
紫外線吸収剤11・・・0.5質量部
PGMEA・・・19.5質量部
Green顔料分散液2・・・73.7質量部
樹脂11・・・0.3質量部
重合性化合物12・・・1.2質量部
光重合開始剤11・・・0.6質量部
界面活性剤11・・・4.2質量部
紫外線吸収剤11・・・0.5質量部
PGMEA・・・19.5質量部
Green顔料分散液3・・・73.7質量部
樹脂11・・・0.3質量部
重合性化合物12・・・1.2質量部
光重合開始剤11・・・0.6質量部
界面活性剤11・・・4.2質量部
紫外線吸収剤11・・・0.5質量部
PGMEA・・・19.5質量部
Green顔料分散液1をGreen顔料分散液4~7に置き換えた以外は緑色画素形成用組成物1と同様にして緑色画素形成用組成物4~7を得た。
Green顔料分散液1をGreen顔料分散液8~11に置き換えた以外は緑色画素形成用組成物1と同様にして緑色画素形成用組成物8~11を得た。
紫外線吸収剤11の0.5質量部を、それぞれ添加剤12~15に変えた以外は緑色画素形成用組成物1と同様にして緑色画素形成用組成物12~15を得た。
重合性化合物12の1.2質量部を、それぞれ重合性化合物16~27に変えた以外は緑色画素形成用組成物1と同様にして緑色画素形成用組成物16~27を得た。
樹脂11の0.3質量部を、それぞれ樹脂28~34に変えた以外は緑色画素形成用組成物1と同様にして緑色画素形成用組成物16~27を得た。
Blue顔料分散液・・・44.9質量部
樹脂11・・・2.1質量部
重合性化合物11・・・1.5質量部
重合性化合物13・・・0.7質量部
光重合開始剤12・・・0.8質量部
界面活性剤11・・・4.2質量部
PGMEA・・・45.8質量部
・Red顔料分散液
C.I.ピグメントレッド254の9.6質量部と、C.I.ピグメントイエロー139の4.3質量部と、分散剤(Disperbyk-161、BYKChemie社製)の6.8質量部と、PGMEAの79.3質量部とからなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)を用いて3時間混合および分散した。その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、Red顔料分散液を得た。
C.I.ピグメントグリーン58の6.4質量部と、C.I.ピグメントイエロー185の5.3質量部と、分散剤(Disperbyk-161、BYKChemie社製)の5.2質量部と、PGMEAの83.1質量部とからなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)を用いて3時間混合および分散した。その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、Green顔料分散液1を得た。
C.I.ピグメントグリーン58の11.7質量部と、分散剤(Disperbyk-161、BYKChemie社製)の5.2質量部と、PGMEAの83.1質量部とからなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)を用いて3時間混合および分散した。その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、Green顔料分散液2を得た。
C.I.ピグメントグリーン36の11.7質量部と、分散剤(Disperbyk-161、BYKChemie社製)の5.2質量部と、PGMEAの83.1質量部とからなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)を用いて3時間混合および分散した。その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/min5として分散処理を行なった。この分散処理を10回繰り返し、Green顔料分散液3を得た。
分散剤(Disperbyk-161、BYKChemie社製)の5.2質量部を下記顔料分散剤1~4に置き換えた(固形分が同じ質量部となるように調整した)以外はGreen顔料分散液1と同様の処理を行いGreen顔料分散液8~11を得た。
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽に、1段目の合成として、メチルメタクリレート100質量部、n-ブチルアクリレート100質量部、N-置換マレイミドとしてシクロへキシルマレイミド50質量部、プロピレングリコールモノメチルエーテルアセテート40質量部を仕込み、窒素ガスで置換した。反応容器内を80℃に加熱して、3-メルカプト-1,2-プロパンジオール12部を添加した後、2,2’-アゾビスイソブチロニトリル0.2質量部を20回に分けて30分ごとに加え、80℃のまま12時間反応し、固形分測定により95%が反応したことを確認した。
次に、2段目の合成として、ピロメリット酸無水物30質量部、プロピレングリコールモノメチルエーテルアセテート160質量部、触媒として1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン0.40質量部を追加し、120℃で7時間反応させた。98%以上の酸無水物がハーフエステル化していることを滴定で確認し反応を終了した。反応終了後、不揮発分が40重量%になるようにプロピレングリコールモノメチルエーテルアセテートを添加して調製し、固形分当たりの酸価45mgKOH/g、重量平均分子量9500の顔料分散剤1を得た。
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽に、1段目の合成として、メチルメタクリレート100質量部、n-ブチルアクリレート100質量部、N-置換マレイミドとしてN-フェニルマレイミド35質量部、プロピレングリコールモノメチルエーテルアセテート40質量部を仕込み、窒素ガスで置換した。反応容器内を80℃に加熱して、3-メルカプト-1,2-プロパンジオール12質量部を添加した後、2,2’-アゾビスイソブチロニトリル0.2質量部を20回に分けて30分ごとに加え、80℃のまま12時間反応し、固形分測定により95%が反応したことを確認した。
次に、2段目の合成として、ピロメリット酸無水物30質量部、プロピレングリコールモノメチルエーテルアセテート160質量部、触媒として1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン0.40質量部を追加し、120℃で7時間反応させた。98%以上の酸無水物がハーフエステル化していることを滴定で確認し反応を終了した。反応終了後、不揮発分が40質量%になるようにプロピレングリコールモノメチルエーテルアセテートを添加して調製し、固形分当たりの酸価80mgKOH/g、重量平均分子量7800の顔料分散剤2を得た。
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽に、1段目の合成として、ジアリルイソフタレート100質量部、n-ブチルアクリレート100質量部、プロピレングリコールモノメチルエーテルアセテート40質量部を仕込み、窒素ガスで置換した。反応容器内を80℃に加熱して、3-メルカプト-1,2-プロパンジオール12質量部を添加した後、2,2'-アゾビスイソブチロニトリル0.2質量部を20回に分けて30分ごとに加え、80℃のまま12時間反応し、固形分測定により95%が反応したことを確認した。
次に、2段目の合成として、ピロメリット酸無水物30質量部、プロピレングリコールモノメチルエーテルアセテート160質量部、触媒として1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン0.40質量部を追加し、120℃で7時間反応させた。98%以上の酸無水物がハーフエステル化していることを滴定で確認し反応を終了した。反応終了後、不揮発分が40質量%になるようにプロピレングリコールモノメチルエーテルアセテートを添加して調製し、固形分当たりの酸価45mgKOH/g、重量平均分子量10000の顔料分散剤3を得た。
ガス導入管、コンデンサー、攪拌翼、及び温度計を備え付けた反応槽に、1段目の合成として、ジアリルオルソフタレート100質量部、n-ブチルアクリレート100質量部、プロピレングリコールモノメチルエーテルアセテート40質量部を仕込み、窒素ガスで置換した。反応容器内を80℃に加熱して、3-メルカプト-1,2-プロパンジオール12質量部を添加した後、2,2'-アゾビスイソブチロニトリル0.2質量部を20回に分けて30分ごとに加え、80℃のまま12時間反応し、固形分測定により95%が反応したことを確認した。
次に、2段目の合成として、ピロメリット酸無水物30質量部、プロピレングリコールモノメチルエーテルアセテート160質量部、触媒として1,8-ジアザビシクロ-[5.4.0]-7-ウンデセン0.40質量部を追加し、120℃で7時間反応させた。98%以上の酸無水物がハーフエステル化していることを滴定で確認し反応を終了した。反応終了後、不揮発分が40質量%になるようにプロピレングリコールモノメチルエーテルアセテートを添加して調製し、固形分当たりの酸価45mgKOH/g、重量平均分子量9800の顔料分散剤4を得た。
C.I.ピグメントイエローブルー15:6の9.7質量部と、C.I.ピグメントバイオレット23の2.4質量部と、分散剤(Disperbyk-161、BYKChemie社製)の5.5質量部と、PGMEAの82.4質量部とからなる混合液を、ビーズミル(ジルコニアビーズ0.3mm径)を用いて3時間混合および分散した。その後さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、Blue顔料分散液を得た。
・重合性化合物12:下記構造の化合物の混合物(左側化合物と右側化合物とのモル比が7:3の混合物)
・重合性化合物13:アロニックスM-305(トリアクリレートが55~63質量%、東亞合成(株)製)
・重合性化合物16:2-シアノ-3-フェニルアクリル酸
・重合性化合物17:メタクリル酸4-シアノフェニル
・重合性化合物18:3-クロロ-2-ヒドロキシプロピルメタクリレート
・重合性化合物19:3-クロロ-2-ヒドロキシプロピルアクリレート
・重合性化合物20:3-ブロモ-2-ヒドロキシプロピルメタクリレート
・重合性化合物21:3-ブロモ-2-ヒドロキシプロピルアクリレート
・重合性化合物22:3-フルオロ-2-ヒドロキシプロピルメタクリレート
・重合性化合物23:3-フルオロ-2-ヒドロキシプロピルアクリレート
・重合性化合物24:3-クロロプロピルメタクリレート
・重合性化合物25:N-アクリロイルオキシエチルヘキサヒドロフタルイミド(アロニックスM140、東亞合成(株)製)
・重合性化合物26:マレイミドアクリレート(アロニックスM145、東亞合成(株)製)
・重合性化合物27:1,4-ビス(マレイミド)ブタン
・添加剤13:Tinuvin622(BASF社製)
・添加剤14:メタクリル酸2-ニトロフェニル
・添加剤15:p-ニトロフェノール
反応容器にシクロヘキサノン70質量部を入れ、容器に窒素ガスを注入しながら80℃に加熱して、同温度でベンジルメタクリレート12.3質量部、2-ヒドロキシエチルメタクリレート4.6質量部、メタクリル酸5.3質量部、光重合性モノマーとしてパラクミルフェノールエチレンオキサイド変性アクリレート(東亞合成(株)製、アロニックスM110)7.4質量部、アゾビスイソブチロニトリル0.8質量部の混合物を2時間かけて滴下して重合反応を行った。滴下終了後、さらに80℃で3時間反応させた後、メタクリル酸4-シアノフェニル4.0質量部をシクロヘキサノン20質量部に溶解させたものを添加し、さらに80℃で2時間反応を続けて、非感光性透明樹脂共重合体溶液を得た。室温まで冷却した後、不揮発分が20質量%になるようにシクロヘキサノンを添加して樹脂28を得た。得られた樹脂28の質量平均分子量は15000であった。
反応容器にシクロヘキサノン70質量部を入れ、容器に窒素ガスを注入しながら80℃に加熱して、同温度でベンジルメタクリレート12.3質量部、2-ヒドロキシエチルメタクリレート4.6質量部、メタクリル酸5.3質量部、アゾビスイソブチロニトリル0.4質量部の混合物を2時間かけて滴下して重合反応を行った。滴下終了後、さらに80℃で3時間反応させた後、3-クロロ-2-ヒドロキシプロピルメタクリレート7.4質量部、アゾビスイソブチロニトリル0.2質量部をシクロヘキサノン10質量部に溶解させたものを添加し、さらに80℃で1時間反応を続けて、非感光性透明樹脂共重合体溶液を得た。室温まで冷却した後、非感光性透明樹脂溶液約2gをサンプリングして180℃、20分加熱乾燥して不揮発分を測定し、先に合成した非感光性透明樹脂溶液に不揮発分が20質量%になるようにシクロヘキサノンを添加して樹脂29を得た。得られた樹脂29の質量平均分子量は15000であった。
反応容器にシクロヘキサノン70質量部を入れ、容器に窒素ガスを注入しながら80℃に加熱して、同温度でN-置換マレイミドとしてシクロへキシルマレイミド50質量部と、ヒドロキシエチルメタクリレート15質量部、メタクリル酸12質量部と、メチルメタクリレート23質量部、アゾビスイソブチロニトリル0.4質量部の混合物を2時間かけて滴下して重合反応を行った。滴下終了後、さらに80℃で3時間反応させた後、アゾビスイソブチロニトリル0.2質量部をシクロヘキサノン10質量部に溶解させたものを添加し、さらに80℃で1時間反応を続けて、非感光性透明樹脂共重合体溶液を得た。室温まで冷却した後、非感光性透明樹脂溶液約2gをサンプリングして180℃、20分加熱乾燥して不揮発分を測定し、先に合成した非感光性透明樹脂溶液に不揮発分が20質量%になるようにシクロヘキサノンを添加して樹脂31を得た。得られた樹脂31の質量平均分子量は14000であった。
反応容器にシクロヘキサノン70質量部を入れ、容器に窒素ガスを注入しながら80℃に加熱して、同温度でN-置換ノルボルネン-5,6-ジカルボキシイミドとしてN-(4-フェニル)-(5-ノルボルネン-2,3-ジカルボキシイミド)50質量部と、ヒドロキシエチルメタクリレート15質量部、メタクリル酸12質量部と、メチルメタクリレート23質量部、アゾビスイソブチロニトリル0.4質量部の混合物を2時間かけて滴下して重合反応を行った。滴下終了後、さらに80℃で3時間反応させた後、アゾビスイソブチロニトリル0.2質量部をシクロヘキサノン10質量部に溶解させたものを添加し、さらに80℃で1時間反応を続けて、非感光性透明樹脂共重合体溶液を得た。室温まで冷却した後、非感光性透明樹脂溶液約2gをサンプリングして180℃、20分加熱乾燥して不揮発分を測定し、先に合成した非感光性透明樹脂溶液に不揮発分が20質量%になるようにシクロヘキサノンを添加して樹脂32を得た。得られた樹脂32の質量平均分子量は20000であった。
反応容器にシクロヘキサノン70質量部を入れ、容器に窒素ガスを注入しながら80℃に加熱して、同温度でベンジルメタクリレート12.3質量部、2-ヒドロキシエチルメタクリレート4.6質量部、メタクリル酸5.3質量部、(b)光重合性モノマーとしてパラクミルフェノールエチレンオキサイド変性アクリレート(東亞合成(株)製、アロニックスM110)7.4質量部、アゾビスイソブチロニトリル0.4質量部の混合物を2時間かけて滴下して重合反応を行った。滴下終了後、さらに80℃で3時間反応させた後、アゾビスイソブチロニトリル0.2質量部をシクロヘキサノン10質量部に溶解させたものを添加し、さらに80℃で1時間反応を続けて、非感光性透明樹脂共重合体溶液を得た。室温まで冷却した後、非感光性透明樹脂溶液約2gをサンプリングして180℃、20分加熱乾燥して不揮発分を測定し、先に合成した非感光性透明樹脂溶液に不揮発分が20質量%になるようにシクロヘキサノンを添加して樹脂33を得た。得られた樹脂33の質量平均分子量は20000であった。
反応容器にシクロヘキサノン70質量部を入れ、容器に窒素ガスを注入しながら80℃に加熱して、同温度でベンジルメタクリレート12.3質量部、2-ヒドロキシエチルメタクリレート4.6質量部、メタクリル酸5.3質量部、光重合性モノマーとしてパラクミルフェノールエチレンオキサイド変性アクリレート(東亞合成(株)製、アロニックスM110)7.4質量部、アゾビスイソブチロニトリル0.8質量部の混合物を2時間かけて滴下して重合反応を行った。滴下終了後、さらに80℃で3時間反応させた後、メタクリル酸4-ニトロフェニル4.0質量部をシクロヘキサノン20質量部に溶解させたものを添加し、さらに80℃で2時間反応を続けて、非感光性透明樹脂共重合体溶液を得た。室温まで冷却した後、不揮発分が20質量%になるようにシクロヘキサノンを添加して樹脂34を得た。得られた樹脂34の質量平均分子量は15000であった。
(実施例1~12)
緑色画素形成用組成物1を、ガラスウエハ上に乾燥後の膜厚が0.6μmになるようにスピンコーターを用いて塗布し、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行った。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、1.1μm角のベイヤーパターンが形成されるフォトマスクを用いて50~1500mJ/cm2まで50mJ/cm2ステップで露光を行うことで、上記正方形ピクセルパターンを解像する最適露光量を決定し、この最適露光量にて露光を行った。
その後、露光された塗布膜が形成されているガラスウエハをスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、現像液(CD-2060、富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行った。次いで、純水でリンス処理を行い、その後スピン乾燥を行った。次いで、200℃のホットプレートを用いて300秒間加熱処理(ポストベーク)を行い、ガラスウエハ上に緑色の着色パターン(緑色画素)を形成した。
同様に、赤色画素形成用組成物、青色画素形成用組成物を用い、同様のプロセスでパターン形成を行い、赤色画素、青色画素を順次形成して、緑色画素、赤色画素および青色画素を有するカラーフィルタを形成した。
このカラーフィルタの表面に、下記表に示す吸収層形成用組成物を乾燥後の膜厚が0.5μmになるようにスピンコーターを用いて塗布し、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行った。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、フォトマスクを用いて1000mJ/cm2の露光量で露光を行った。その後、露光された塗布膜が形成されているガラスウエハをスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、現像液(CD-2060、富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行った。次いで、純水でリンス処理を行い、その後スピン乾燥を行った。次いで、200℃のホットプレートを用いて300秒間加熱処理(ポストベーク)を行い、カラーフィルタの緑色画素および赤色画素上に吸収層を形成した。この構造体は、カラーフィルタの画素(緑色画素および赤色画素)の光路上であってこれらの画素への光の入射側に吸収層が設けられた構造体である。この構造体は、緑色画素、赤色画素および青色画素の膜厚がそれぞれ0.6μmであり、吸収層の膜厚が0.5μmであった。
緑色画素形成用組成物1のかわりに緑色画素形成用組成物2を、ガラスウエハ上に乾燥後の膜厚が0.4μmになるようにスピンコーターを用いて塗布した以外は実施例1~12と同様のプロセスでパターン形成を行い緑色画素を形成した。次いで、赤色画素形成用組成物、青色画素形成用組成物を用い、同様のプロセスでパターン形成を行い、赤色画素、青色画素を順次形成して、緑色画素、赤色画素および青色画素を有するカラーフィルタを形成した。
このカラーフィルタの表面に、下記表に示す吸収層形成用組成物1~6を乾燥後の膜厚が0.1μmになるようにスピンコーターを用いて塗布し、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行った。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、フォトマスクを用いて1000mJ/cm2の露光量で露光を行った。その後、露光された塗布膜が形成されているガラスウエハをスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、現像液(CD-2060、富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行った。次いで、純水でリンス処理を行い、その後スピン乾燥を行った。次いで、200℃のホットプレートを用いて300秒間加熱処理(ポストベーク)を行い、カラーフィルタの緑色画素上に吸収層を形成した。この構造体は、カラーフィルタの画素(緑色画素)の光路上であってこれらの画素への光の入射側に吸収層が設けられた構造体である。この構造体は、緑色画素の膜厚が0.4μmであり、赤色画素および青色画素の膜厚がそれぞれ0.5μmであり、吸収層の膜厚が0.1μmであった。
緑色画素形成用組成物1のかわりに緑色画素形成用組成物3を、ガラスウエハ上に乾燥後の膜厚が0.48μmになるようにスピンコーターを用いて塗布した以外は実施例1~12と同様のプロセスでパターン形成を行い緑色画素を形成した。次いで、赤色画素形成用組成物、青色画素形成用組成物を用い、同様のプロセスでパターン形成を行い、赤色画素、青色画素を順次形成して、緑色画素、赤色画素および青色画素を有するカラーフィルタを形成した。
このカラーフィルタの表面に、下記表に示す吸収層形成用組成物1~6を乾燥後の膜厚が0.12μmになるようにスピンコーターを用いて塗布し、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行った。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、フォトマスクを用いて1000mJ/cm2の露光量で露光を行った。その後、露光された塗布膜が形成されているガラスウエハをスピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、現像液(CD-2060、富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行った。次いで、純水でリンス処理を行い、その後スピン乾燥を行った。次いで、200℃のホットプレートを用いて300秒間加熱処理(ポストベーク)を行い、カラーフィルタの緑色画素上に吸収層を形成した。この構造体は、カラーフィルタの画素(緑色画素)の光路上であってこれらの画素への光の入射側に吸収層が設けられた構造体である。この構造体は、緑色画素の膜厚が0.48μmであり、赤色画素および青色画素の膜厚がそれぞれ0.6μmであり、吸収層の膜厚が0.12μmであった。
(実施例25~55)
緑色画素形成用組成物1のかわりに緑色画素形成用組成物4~34を用いた以外は実施例1と同様にして構造体を形成した。
カラーフィルタを形成したガラスウエハの、カラーフィルタとは反対側の面に吸収層形成用組成物1~8を用いて、それぞれ実施例1~8と同様の方法で吸収層を形成して構造体を製造した。この構造体は、カラーフィルタの画素(緑色画素および赤色画素)の光路上であってこれらの画素からの光の射出側に吸収層が設けられた構造体である。
実施例1~12と同様にして比較組成物1をカラーフィルタの表面に塗布して膜を形成して構造体を製造した。この構造体は、カラーフィルタの画素(緑色画素および赤色画素)の光路上であってこれらの画素への光の入射側に比較組成物1を用いて形成された膜を有する構造体である。
(耐光性)
上記の構造体に対し、スーパーキセノンウェーザーメーターSX75(スガ試験機製)を用いて照度10万luxで1500時間光を照射して耐光性試験を行った。なお、実施例1~55、比較例9の構造体については、吸収層側(比較例9については比較組成物1を用いて形成された膜側)から光を照射した。また、比較例1~8の構造体については、カラーフィルタ側から光を照射した。
耐光性試験の後、各画素の透過率の変化量(ΔT%)を測定し、以下の基準により耐光性の評価を行った。なお、比較した透過率の変化量(ΔT%)は、波長が400~700nmの範囲において、最も透過率の変化量が大きい波長についての変化量(|耐光性試験前の透過率(%)-耐光性試験後の透過率(%)|)である。
<評価基準>
5: ΔT%≦10
4: 10<ΔT%≦20
3: 20<ΔT%≦30
2: 30<ΔT%≦40
1: 40<ΔT%
上記の構造体に対し、HASTEST MODEL304R8(HIRAYAMA製)を用いて温度110℃/湿度85%の条件で250時間耐湿試験を行った。耐湿性試験の後、各画素の透過率の変化量(ΔT%)を測定し、以下の基準により耐湿性の評価を行った。なお、比較した透過率の変化量(ΔT%)は、波長が400~700nmの範囲において、最も透過率の変化量が大きい波長についての変化量(|耐湿性試験前の透過率(%)-耐湿性試験後の透過率(%)|)である。
<評価基準>
5: ΔT%≦1
4: 1<ΔT%≦2
3: 2<ΔT%≦3
2: 3<ΔT%≦4
1: 4<ΔT%
上記表に示すように実施例の構造体は、耐光性に優れていた。更には耐湿性も優れていた。これに対し比較例の構造体は、耐光性が劣っていた。
10、10a:カラーフィルタ
11~13:画素
11a、11b:赤色画素
12a、12b:緑色画素
13a、13b:青色画素
20、21、22:吸収層
30:マイクロレンズ
40:平坦化層
50:集光レンズ
60:赤外線カットフィルタ
70:封止ガラス
Claims (22)
- 2種以上の異なる種類の画素を有するカラーフィルタと、
黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層と、を有し、
前記吸収層を、前記カラーフィルタの画素のうち少なくとも1種の画素の光路上であって前記画素への光の入射側に有する、構造体。 - 前記吸収層は更に紫外線吸収剤を含む、請求項1に記載の構造体。
- 前記紫外線吸収剤は、ベンゾトリアゾール化合物、ベンゾフェノン化合物およびトリアジン化合物から選ばれる少なくとも1種である、請求項2に記載の構造体。
- 前記吸収層は、アゾ化合物およびイソインドリン化合物から選ばれる少なくとも1種を含む、請求項1~3のいずれか1項に記載の構造体。
- 前記吸収層は、カラーインデックスピグメントイエロー139、カラーインデックスピグメントイエロー150およびカラーインデックスピグメントイエロー185から選ばれる少なくとも1種を含む、請求項1~3のいずれか1項に記載の構造体。
- 前記カラーフィルタは、緑色画素および赤色画素から選ばれる少なくとも1種の着色画素を含み、前記着色画素の光路上に前記吸収層を有する、請求項1~5のいずれか1項に記載の構造体。
- 前記カラーフィルタは、緑色画素、赤色画素および青色画素を含み、
前記緑色画素および前記赤色画素から選ばれる少なくとも一方の画素の光路上に前記吸収層を有し、前記青色画素の光路上には前記吸収層を有さない、請求項1~5のいずれか1項に記載の構造体。 - 前記緑色画素は、ハロゲン化亜鉛フタロシアニン顔料を含有する、請求項7に記載の構造体。
- 前記緑色画素および前記赤色画素の光路上に前記吸収層を有する、請求項7または8に記載の構造体。
- 前記吸収層の膜厚は、前記吸収層の光路上に有する前記画素の膜厚の0.001~2倍である、請求項6~9のいずれか1項に記載の構造体。
- 前記吸収層の膜厚は、前記吸収層の光路上に有する前記画素の膜厚の0.1~1倍である、請求項6~9のいずれか1項に記載の構造体。
- 前記カラーフィルタは、更に、透明画素および赤外線透過層の画素から選ばれる少なくとも1種の画素を含む、請求項6~11のいずれか1項に記載の構造体。
- 前記吸収層は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種と、硬化性化合物とを含む組成物を硬化して得られたものである、請求項1~12のいずれか1項に記載の構造体。
- 前記カラーフィルタの画素と前記吸収層とが接している、請求項1~13のいずれか1項に記載の構造体。
- カラーフィルタを形成する工程と、吸収層を形成する工程とを含む、構造体の製造方法であって、
前記カラーフィルタは、2種以上の異なる種類の画素を有し、
前記吸収層は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含み、
前記構造体は、前記吸収層を、前記カラーフィルタの画素のうち少なくとも1種の画素の光路上であって前記画素への光の入射側に有し、
前記吸収層を形成する工程は、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層形成用組成物を塗布する工程を含む、構造体の製造方法。 - 前記カラーフィルタの表面に前記吸収層形成用組成物を塗布する、請求項15に記載の構造体の製造方法。
- 前記吸収層を形成する工程は、更にパターンを形成する工程を含む、請求項15または16に記載の構造体の製造方法。
- 2種以上の異なる種類の画素を有するカラーフィルタと、黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層と、を有し、前記吸収層を、前記カラーフィルタの画素のうち少なくとも1種の画素の光路上であって前記画素への光の入射側に有する構造体の、前記吸収層の形成用の組成物であって、
黄色着色剤および波長400~500nmの範囲に極大吸収波長を有する着色剤から選ばれる少なくとも1種を含む吸収層形成用組成物。 - 更に紫外線吸収剤を含む、請求項18に記載の吸収層形成用組成物。
- 前記紫外線吸収剤は、ベンゾトリアゾール化合物、ベンゾフェノン化合物およびトリアジン化合物から選ばれる少なくとも1種である、請求項19に記載の吸収層形成用組成物。
- 請求項1~14のいずれか1項に記載の構造体を有する固体撮像素子。
- 請求項1~14のいずれか1項に記載の構造体を有する画像表示装置。
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2021006132A1 (ja) * | 2019-07-09 | 2021-01-14 | ||
| JPWO2021039410A1 (ja) * | 2019-08-27 | 2021-03-04 | ||
| WO2021106670A1 (ja) * | 2019-11-26 | 2021-06-03 | 富士フイルム株式会社 | 固体撮像素子 |
| WO2021251309A1 (ja) | 2020-06-12 | 2021-12-16 | 富士フイルム株式会社 | 半導体膜、半導体膜の製造方法、光検出素子およびイメージセンサ |
| WO2022080046A1 (ja) * | 2020-10-13 | 2022-04-21 | 富士フイルム株式会社 | 着色組成物、膜、カラーフィルタ、光センサおよび表示装置 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI883186B (zh) * | 2020-05-12 | 2025-05-11 | 日商富士軟片股份有限公司 | 洋紅色感光性樹脂組成物、膜、濾色器、固體攝像元件及圖像顯示裝置 |
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003294932A (ja) * | 2002-04-03 | 2003-10-15 | Dainippon Printing Co Ltd | カラーフィルタ |
| JP2006078766A (ja) * | 2004-09-09 | 2006-03-23 | Toppan Printing Co Ltd | カラー固体撮像素子及びそのカラーフィルター |
| JP2006313974A (ja) * | 2005-05-06 | 2006-11-16 | Toppan Printing Co Ltd | 受光素子 |
| JP2009152314A (ja) * | 2007-12-19 | 2009-07-09 | Toppan Printing Co Ltd | イメージセンサーおよびその製造方法 |
| JP2009152315A (ja) * | 2007-12-19 | 2009-07-09 | Toppan Printing Co Ltd | イメージセンサーおよびその製造方法 |
| JP2011176182A (ja) * | 2010-02-25 | 2011-09-08 | Toppan Printing Co Ltd | イメージセンサー及びその製造方法 |
| JP2016075886A (ja) * | 2014-10-06 | 2016-05-12 | 采▲ぎょく▼科技股▲ふん▼有限公司VisEra Technologies Company Limited | スタックフィルターとそれを含むイメージセンサー |
| JP2017167389A (ja) * | 2016-03-17 | 2017-09-21 | 凸版印刷株式会社 | カラーフィルタおよび液晶表示装置 |
| JP2017203810A (ja) * | 2016-05-09 | 2017-11-16 | 日本化薬株式会社 | 有機エレクトロルミネッセンスディスプレイ用カラーフィルタに含有される光吸収層、及びそれを用いたシート |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6383703A (ja) | 1986-09-29 | 1988-04-14 | Matsushita Electronics Corp | カラ−フイルタ |
| JPH0381122A (ja) | 1989-08-24 | 1991-04-05 | Shin Kobe Electric Mach Co Ltd | 熱硬化性樹脂金属箔張り積層板の製造法 |
| JP3130601B2 (ja) | 1991-11-12 | 2001-01-31 | 九州日本電気株式会社 | 固体撮像素子用光学カラーフィルター及びその製造方法並びに固体撮像素子 |
| JP4357625B2 (ja) | 1999-03-30 | 2009-11-04 | 大日本印刷株式会社 | カラーフィルタおよびその製造方法 |
| JP2001118967A (ja) | 1999-10-19 | 2001-04-27 | Sanyo Electric Co Ltd | 固体撮像素子のパッケージ構造 |
| JP4882182B2 (ja) | 2001-08-08 | 2012-02-22 | 凸版印刷株式会社 | 固体撮像素子 |
| CN100505277C (zh) * | 2004-06-30 | 2009-06-24 | 凸版印刷株式会社 | 摄像元件 |
| JP2008046584A (ja) * | 2006-07-19 | 2008-02-28 | Fujifilm Corp | カラーフィルタの製造方法 |
| JP4991479B2 (ja) * | 2006-10-27 | 2012-08-01 | 大阪瓦斯株式会社 | 光学フィルム及びその製造方法 |
| JP5602448B2 (ja) * | 2009-03-26 | 2014-10-08 | 富士フイルム株式会社 | 顔料分散液、着色硬化性組成物、カラーフィルタ、及びカラーフィルタの製造方法 |
| KR101081122B1 (ko) | 2009-10-28 | 2011-11-07 | 엘지이노텍 주식회사 | 태양전지 및 이의 제조방법 |
| JP5791874B2 (ja) * | 2010-03-31 | 2015-10-07 | 富士フイルム株式会社 | 着色組成物、インクジェット用インク、カラーフィルタ及びその製造方法、固体撮像素子、並びに表示装置 |
| JP5834448B2 (ja) * | 2011-03-31 | 2015-12-24 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物およびカラーフィルタ |
| JP6099213B2 (ja) * | 2014-02-07 | 2017-03-29 | Dic株式会社 | カラーフィルタ用緑色顔料およびカラーフィルタ |
| TWI723994B (zh) * | 2015-05-22 | 2021-04-11 | 日商富士軟片股份有限公司 | 著色組成物、膜、彩色濾光片、圖案形成方法、彩色濾光片的製造方法、固體攝像元件及紅外線感測器 |
| CN106967043B (zh) * | 2015-10-29 | 2020-03-17 | 三星Sdi株式会社 | 化合物、聚合物、着色剂、感光性树脂组成物、感光性树脂层以及彩色滤光片 |
| JP2017092302A (ja) | 2015-11-12 | 2017-05-25 | 凸版印刷株式会社 | 固体撮像素子および固体撮像素子の製造方法 |
-
2018
- 2018-07-24 KR KR1020197035878A patent/KR102354075B1/ko active Active
- 2018-07-24 JP JP2019538008A patent/JP7011662B2/ja active Active
- 2018-07-24 WO PCT/JP2018/027737 patent/WO2019039172A1/ja not_active Ceased
- 2018-08-06 TW TW107127271A patent/TWI810200B/zh active
-
2019
- 2019-12-11 US US16/710,629 patent/US11152413B2/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003294932A (ja) * | 2002-04-03 | 2003-10-15 | Dainippon Printing Co Ltd | カラーフィルタ |
| JP2006078766A (ja) * | 2004-09-09 | 2006-03-23 | Toppan Printing Co Ltd | カラー固体撮像素子及びそのカラーフィルター |
| JP2006313974A (ja) * | 2005-05-06 | 2006-11-16 | Toppan Printing Co Ltd | 受光素子 |
| JP2009152314A (ja) * | 2007-12-19 | 2009-07-09 | Toppan Printing Co Ltd | イメージセンサーおよびその製造方法 |
| JP2009152315A (ja) * | 2007-12-19 | 2009-07-09 | Toppan Printing Co Ltd | イメージセンサーおよびその製造方法 |
| JP2011176182A (ja) * | 2010-02-25 | 2011-09-08 | Toppan Printing Co Ltd | イメージセンサー及びその製造方法 |
| JP2016075886A (ja) * | 2014-10-06 | 2016-05-12 | 采▲ぎょく▼科技股▲ふん▼有限公司VisEra Technologies Company Limited | スタックフィルターとそれを含むイメージセンサー |
| JP2017167389A (ja) * | 2016-03-17 | 2017-09-21 | 凸版印刷株式会社 | カラーフィルタおよび液晶表示装置 |
| JP2017203810A (ja) * | 2016-05-09 | 2017-11-16 | 日本化薬株式会社 | 有機エレクトロルミネッセンスディスプレイ用カラーフィルタに含有される光吸収層、及びそれを用いたシート |
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| WO2021006132A1 (ja) * | 2019-07-09 | 2021-01-14 | 富士フイルム株式会社 | カラーフィルタ、固体撮像素子および画像表示装置 |
| US12111487B2 (en) | 2019-07-09 | 2024-10-08 | Fujifilm Corporation | Color filter, solid-state imaging element, and image display device |
| JP7185780B2 (ja) | 2019-07-09 | 2022-12-07 | 富士フイルム株式会社 | カラーフィルタ、固体撮像素子および画像表示装置 |
| US12421340B2 (en) | 2019-08-27 | 2025-09-23 | Fujifilm Corporation | Curable composition, cured product, color filter, solid-state imaging element, and image display device |
| JPWO2021039410A1 (ja) * | 2019-08-27 | 2021-03-04 | ||
| JPWO2021106670A1 (ja) * | 2019-11-26 | 2021-06-03 | ||
| JP7454592B2 (ja) | 2019-11-26 | 2024-03-22 | 富士フイルム株式会社 | 固体撮像素子 |
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| WO2021106670A1 (ja) * | 2019-11-26 | 2021-06-03 | 富士フイルム株式会社 | 固体撮像素子 |
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| WO2021251309A1 (ja) | 2020-06-12 | 2021-12-16 | 富士フイルム株式会社 | 半導体膜、半導体膜の製造方法、光検出素子およびイメージセンサ |
| JPWO2022080046A1 (ja) * | 2020-10-13 | 2022-04-21 | ||
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Also Published As
| Publication number | Publication date |
|---|---|
| JPWO2019039172A1 (ja) | 2020-07-27 |
| TW201912729A (zh) | 2019-04-01 |
| JP7011662B2 (ja) | 2022-01-26 |
| US20200119071A1 (en) | 2020-04-16 |
| KR20190139316A (ko) | 2019-12-17 |
| KR102354075B1 (ko) | 2022-01-24 |
| TWI810200B (zh) | 2023-08-01 |
| US11152413B2 (en) | 2021-10-19 |
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