WO2024128043A1 - カラーフィルタの製造方法および固体撮像素子の製造方法 - Google Patents
カラーフィルタの製造方法および固体撮像素子の製造方法 Download PDFInfo
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- WO2024128043A1 WO2024128043A1 PCT/JP2023/043200 JP2023043200W WO2024128043A1 WO 2024128043 A1 WO2024128043 A1 WO 2024128043A1 JP 2023043200 W JP2023043200 W JP 2023043200W WO 2024128043 A1 WO2024128043 A1 WO 2024128043A1
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- photosensitive composition
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- resin
- color filter
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Classifications
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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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
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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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
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/30—Devices specially adapted for multicolour light emission
- H10K59/38—Devices specially adapted for multicolour light emission comprising colour filters or colour changing media [CCM]
Definitions
- the present invention relates to a method for manufacturing a color filter and a solid-state imaging device.
- CCD charge-coupled device
- a color filter has pixels of multiple colors. Conventionally, pixels of each color are manufactured by forming a pattern by photolithography using a photosensitive composition containing a colorant and a resin (for example, Patent Document 1, etc.).
- the object of the present invention is therefore to provide a method for manufacturing a color filter and a method for manufacturing a solid-state imaging device that can form pixels with high colorant concentrations and good adhesion.
- the present invention provides the following: ⁇ 1> A step of applying a photosensitive composition containing a colorant and a resin onto a support to form a photosensitive composition layer; exposing the photosensitive composition layer to light in a pattern; a step of developing the exposed photosensitive composition layer with a developer to remove unexposed areas of the photosensitive composition layer to form pixels; a thinning step of heat-treating the developed pixel to reduce the film thickness of the pixel so that the colorant content of the pixel is 60% by mass or more; A method for producing a color filter comprising the steps of: ⁇ 2> The method for producing a color filter according to ⁇ 1>, wherein the content of the colorant in the total solid content of the photosensitive composition is 50 mass % or more.
- ⁇ 3> The method for producing a color filter according to ⁇ 1> or ⁇ 2>, wherein the photosensitive composition contains a resin A having a weight loss of 20% by mass or more at 245°C.
- ⁇ 4> The method for producing a color filter according to ⁇ 3>, wherein the resin A is a graft resin.
- ⁇ 5> The method for producing a color filter according to any one of ⁇ 1> to ⁇ 4>, wherein the photosensitive composition contains a polymerizable monomer and a photopolymerization initiator.
- ⁇ 6> The method for producing a color filter according to ⁇ 5>, wherein the content of the polymerizable monomer in the total solid content of the photosensitive composition is 7 mass % or less.
- ⁇ 7> The method for producing a color filter according to any one of ⁇ 1> to ⁇ 6>, wherein the weight loss of the solid content of the photosensitive composition at 245° C. is 10 to 30% by mass.
- ⁇ 8> The method for producing a color filter according to any one of ⁇ 1> to ⁇ 7>, wherein the developer is an alkaline developer.
- ⁇ 9> The method for producing a color filter according to any one of ⁇ 1> to ⁇ 8>, wherein the heat treatment in the thinning step is carried out at 180 to 260° C. for 5 minutes or longer.
- ⁇ 10> The method for producing a color filter according to ⁇ 3>, wherein the heat treatment in the thinning step is carried out at a temperature in the range of a thermal decomposition starting temperature of the resin A + 5°C to a thermal decomposition starting temperature of the resin A + 50°C for 5 minutes or longer.
- the method for producing a color filter according to any one of ⁇ 1> to ⁇ 10> which is a method for producing a color filter for a solid-state imaging device.
- ⁇ 12> A method for producing a solid-state imaging device, comprising the method for producing a color filter according to any one of ⁇ 1> to ⁇ 11>.
- the present invention provides a method for manufacturing a color filter and a method for manufacturing a solid-state imaging device that can form pixels with high colorant concentration and good adhesion.
- an "alkyl group” includes not only an alkyl group that has no substituents (unsubstituted alkyl groups) but also an alkyl group that has 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.
- Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, active rays or radiation such as electron beams.
- (meth)acrylate refers to both or either of acrylate and methacrylate
- (meth)acrylic refers to both or either of acrylic and methacrylic
- (meth)acryloyl refers to both or either of acryloyl and methacryloyl.
- Me represents a methyl group
- Et represents an ethyl group
- Bu represents a butyl group
- Pr represents a propyl group
- Ph represents a phenyl group.
- the weight average molecular weight and number average molecular weight are values calculated in terms of polystyrene measured by GPC (gel permeation chromatography).
- the total solids content refers to the total mass of all components of the composition excluding the solvent.
- the pigment means a coloring material that is difficult to dissolve in a solvent. For example, the solubility of the pigment in 100 g of water at 23° C. and 100 g of propylene glycol monomethyl ether acetate at 23° C.
- a dye means a coloring material that is easily soluble in a solvent.
- the term "process” refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the process achieves its intended effect.
- the method for producing a color filter of the present invention comprises the steps of: A step of applying a photosensitive composition containing a colorant and a resin onto a support to form a photosensitive composition layer; exposing the photosensitive composition layer to light in a pattern; a step of developing the exposed photosensitive composition layer with a developer to remove unexposed areas of the photosensitive composition layer to form pixels; a thinning step of heat-treating the developed pixel to reduce the film thickness of the pixel so that the colorant content of the pixel is 60% by mass or more;
- the present invention is characterized by comprising:
- the developed pixels are heat-treated to reduce the pixel film thickness so that the colorant content of the pixels is 60% by mass or more, and therefore the colorant content of the pixels before the thin-filming process can be reduced.
- This allows pattern formation by photolithography using a photosensitive composition with sufficient photolithographic performance that contains a large amount of materials other than colorants, such as resins, and can suppress the occurrence of peeling of pixels in exposed areas during development.
- the developed pixels are reduced in film thickness so that the colorant content of the pixels is 60% by mass or more, and therefore pixels with a high colorant concentration can be formed. Therefore, according to the present invention, pixels with a high colorant concentration can be formed with good adhesion.
- Color filter pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
- the color filter is preferably a color filter for a solid-state imaging device.
- the color filter manufacturing method of the present invention is preferably a color filter manufacturing method for a solid-state imaging device.
- Step of forming photosensitive composition layer a photosensitive composition containing a colorant and a resin is applied onto a support to form a photosensitive composition layer.
- the photosensitive composition will be described later.
- the support on which the photosensitive composition layer is formed is not particularly limited and can be appropriately selected depending on the application. Examples include a glass substrate and a silicon substrate, with a silicon substrate being preferred.
- the silicon substrate may also be formed with a charge-coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc.
- CMOS complementary metal oxide semiconductor
- the silicon substrate may also be formed with a black matrix that isolates each pixel.
- the silicon substrate may also be provided with a base layer to improve adhesion with the upper layer, prevent diffusion of substances, or flatten the substrate surface.
- the photosensitive composition can be applied by any known method.
- it can be a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, the method described in JP 2009-145395 A); various printing methods such as ejection printing such as inkjet (for example, on-demand method, piezo method, thermal method) and nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing; a transfer method using a mold or the like; and a nanoimprint method.
- ejection printing such as inkjet (for example, on-demand method, piezo method, thermal method) and nozzle jet, flexographic printing, screen printing, gravure printing, reverse offset printing, and metal mask printing
- a transfer method using a mold or the like and a nanoimprint method.
- the application method for inkjet is not particularly limited, and examples thereof include the method described in "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents -, published in February 2005 by Sumibe Techno Research" (particularly pages 115 to 133), and the methods described in JP-A-2003-262716, JP-A-2003-185831, JP-A-2003-261827, JP-A-2012-126830, and JP-A-2006-169325.
- the description of the application method of the photosensitive composition can be found in WO 2017/030174 and WO 2017/018419, the contents of which are incorporated herein by reference.
- the photosensitive composition layer formed on the support may be dried (prebaked).
- prebaking may not be performed.
- the prebaking temperature is preferably 150°C or less, more preferably 120°C or less, and even more preferably 110°C or less.
- the lower limit can be, for example, 50°C or more, and can also be 80°C or more.
- the prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, etc.
- the photosensitive composition layer formed on the support is exposed in a pattern.
- the photosensitive composition layer can be exposed in a pattern by using a stepper exposure machine or a scanner exposure machine through a mask having a predetermined mask pattern. This allows the exposed portion of the photosensitive composition layer to be cured.
- Radiation (light) that can be used for exposure includes g-line and i-line.
- Light with a wavelength of 300 nm or less (preferably light with a wavelength of 180 to 300 nm) can also be used.
- Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF line (wavelength 193 nm), with KrF line (wavelength 248 nm) being preferred.
- Long-wavelength light sources of 300 nm or more can also be used.
- Pulse exposure is an exposure method in which light is applied and paused repeatedly in short cycles (e.g., milliseconds or less).
- the irradiation amount is, for example, preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2.
- the oxygen concentration during exposure can be appropriately selected, and in addition to being performed under air, exposure may be performed under a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or under a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%).
- the exposure illuminance can be appropriately set, and can usually be selected from the range of 1000 W/m 2 to 100,000 W/m 2 (e.g., 5,000 W/m 2 , 15,000 W/m 2 , or 35,000 W/m 2 ).
- the oxygen concentration and exposure illuminance may be appropriately combined. For example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W/m 2 , and an oxygen concentration of 35% by volume and an illuminance of 20,000 W/m 2 , can be used.
- the exposed photosensitive composition layer is developed with a developer to remove the photosensitive composition layer in the unexposed areas, thereby forming pixels.
- the temperature of the developer is preferably, for example, 20 to 30°C.
- the development time is preferably 20 to 180 seconds.
- the developer may be shaken off every 60 seconds and the process of supplying new developer may be repeated several times.
- the developer may be an organic solvent, an alkaline developer, or the like, and an alkaline developer is preferably used.
- an alkaline developer an alkaline aqueous solution (alkaline developer) in which an alkaline agent is diluted with pure water is preferred.
- alkaline agent examples include organic alkaline compounds such as ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxylamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ethyltrimethylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo[5.4.0]-7-undecene, and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, and sodium metasilicate.
- organic alkaline compounds such as ammonia, ethylamine, diethyl
- 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.
- the developer may further contain a surfactant. Examples of the surfactant include those described below, and nonionic surfactants are preferred.
- the developer may be prepared as a concentrated solution and then diluted to a required concentration when used, from the viewpoint of convenience of transportation and storage. The dilution ratio is not particularly limited, but can be set in the range of, for example, 1.5 to 100 times. It is also preferred to wash (rinse) the developed layer with pure water.
- the nozzle that ejects the rinse liquid from the center of the support to the periphery of the support.
- the nozzle may be moved while gradually decreasing the moving speed of the nozzle when moving the nozzle from the center of the support to the periphery.
- the developed pixels are heat-treated to reduce the film thickness of the pixels so that the colorant content of the pixels is 60% by mass or more.
- the heat treatment in the thin film process is preferably carried out at 180-260°C for 5 minutes or more.
- the heat treatment temperature is preferably 200°C or more, more preferably 220°C or more, even more preferably 230°C or more, even more preferably 240°C or more, and particularly preferably 245°C or more.
- the heating time is preferably 10 minutes or more, more preferably 15 minutes or more.
- the upper limit of the heating time is preferably 60 minutes or less.
- the heat treatment in the thinning step is preferably performed for 5 minutes or more at a temperature in the range of from the thermal decomposition onset temperature of resin A + 5° C. to the thermal decomposition onset temperature of resin A + 50° C.
- the film thickness of the pixel can be sufficiently reduced and the occurrence of voids in the pixel can be suppressed.
- the lower limit of the heat treatment temperature is preferably the thermal decomposition onset temperature of resin A + 5°C or more, and more preferably the thermal decomposition onset temperature of resin A + 10°C or more.
- the upper limit of the heat treatment temperature is preferably the thermal decomposition onset temperature of resin A + 50°C or less, and more preferably the thermal decomposition onset temperature of resin A + 30°C or less.
- the heating time is preferably 5 minutes or more, and more preferably 15 minutes or more.
- the upper limit of the heating time is preferably 60 minutes or less.
- the thermal decomposition onset temperature of a resin refers to the temperature at which mass loss or heat absorption and heat generation associated with thermal decomposition begin to be observed when the resin is heated at a heating rate of 20° C./min in a nitrogen gas flow using a thermogravimetric analyzer (TGA).
- the colorant content of the pixel after the thin film forming step is 60% by mass or more, preferably 65% by mass or more, and more preferably 70% by mass or more.
- the colorant content of the pixel after the thinning step can be calculated by the following method.
- Colorant concentration of pixel after thin-film treatment colorant content (mass %) in the total solid content of photosensitive composition ⁇ (A2/B2)/(A1/B1)
- A2 Thickness of the pixel after the thinning process
- B1 Maximum absorbance of the film obtained using the photosensitive composition in the wavelength range of 400 to 700 nm
- B2 Maximum absorbance of the pixel after the thinning process in the wavelength range of 400 to 700 nm
- the film thickness of the pixel after the thinning process is preferably 75% or more of the film thickness of the pixel before the thinning process.
- the film thickness of the pixel after the thinning step is preferably 90% or less, and more preferably 80% or less, of the film thickness of the pixel before the thinning step, because this makes it possible to design a film with a high colorant concentration.
- the width of the pixel after the thinning process is preferably 0.3 to 0.6 ⁇ m, and more preferably 0.35 to 0.55 ⁇ m.
- the film thickness of the pixel after the thinning process is preferably 0.3 to 0.5 ⁇ m, and more preferably 0.4 to 0.5 ⁇ m.
- the photosensitive composition used in the method for producing a color filter of the present invention contains a colorant and a resin.
- the solids concentration of the photosensitive composition is preferably 5 to 30% by mass.
- the lower limit is preferably 7.5% by mass or more, and more preferably 10% by mass or more.
- the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.
- the weight loss of the solid content of the photosensitive composition at 245°C is preferably 10 to 30% by mass, because the film thickness of the pixel can be easily reduced in the thinning process and pixels with a higher colorant concentration can be obtained.
- the upper limit of the weight loss is preferably 25% by mass or less, from the viewpoint of suppressing film thickness variations between different pixels.
- the lower limit of the weight loss is preferably 15% by mass or more, because the film thickness of the pixel can be easily reduced in the thinning process and pixels with a higher colorant concentration can be obtained.
- the weight loss of the solid content of the photosensitive composition refers to the weight loss at a specific temperature when the solid content of the photosensitive composition is heated to a specific temperature.
- the weight loss of the solid content of the photosensitive composition is a value measured by the following method.
- a photosensitive composition is applied by spin coating onto a support such as a glass substrate, and heated at 100° C. for 2 minutes to form a film having a thickness of 1.0 ⁇ m.
- the film obtained is peeled off from the support and heated at a rate of 20° C./min using a thermogravimetric measuring device to measure the weight loss of the film.
- the weight loss of the film at a specific temperature is determined as the weight loss of the solid content of the photosensitive composition at a specific temperature.
- the photosensitive composition contains a colorant.
- the colorant include a yellow colorant, an orange colorant, a red colorant, a green colorant, a purple colorant, and a blue colorant.
- the colorant may be a pigment or a dye.
- the pigment may be either an inorganic pigment or an organic pigment, but is preferably an organic pigment from the viewpoints of a wide range of color variations, ease of dispersion, safety, and the like.
- a pigment derivative may be used as the colorant.
- the colorant contained in the photosensitive composition preferably contains a pigment and a pigment derivative.
- the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a colorant skeleton.
- the content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, per 100 parts by mass of the pigment. Only one type of pigment derivative may be used, or two or more types may be used in combination.
- the average primary particle diameter of the pigment and pigment derivative is preferably 1 to 200 nm.
- the lower limit is preferably 5 nm or more, more preferably 10 nm or more.
- the upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less.
- the primary particle diameter of the pigment and pigment derivative can be determined from a photograph obtained by observing the primary particles of the pigment and pigment derivative with a transmission electron microscope. Specifically, the projected area of the primary particles of the pigment is determined, and the corresponding circle equivalent diameter is calculated as the primary particle diameter of the pigment.
- the average primary particle diameter in the present invention is the arithmetic mean value of the primary particle diameters of 400 primary particles of the pigment.
- the primary particles of the pigment refer to independent particles that are not aggregated. The same applies to the average primary particle diameter of the pigment derivative.
- the crystallite size of the pigment or pigment derivative determined from the half-width of a peak derived from any crystal plane in the X-ray diffraction spectrum when CuK ⁇ radiation is used as the X-ray source, is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, even more preferably 1 to 30 nm, and particularly preferably 5 to 25 nm.
- the specific surface area of the pigment and pigment derivative is preferably 1 to 300 m 2 /g.
- the lower limit is preferably 10 m 2 /g or more, more preferably 30 m 2 /g or more.
- the upper limit is preferably 250 m 2 /g or less, more preferably 200 m 2 /g or less.
- the value of the specific surface area can be measured according to DIN 66131: determination of the specific surface area of solids by gas adsorption in accordance with the BET (Brunauer, Emmett and Teller) method.
- the pigment may be ground by milling or a mortar dry bead mill, etc., and then sieved into fine particles.
- Red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, xanthene compounds, quinacridone compounds, perylene compounds, and thioindigo compounds, with diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds being preferred, and diketopyrrolopyrrole compounds being more preferred.
- the red colorant is also preferably a pigment, and diketopyrrolopyrrole pigments are more preferred.
- red colorants include C.I. (Color Index) Pigment Red 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,
- red pigments include 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, 269, 270, 272, 279, 291, 294, 295, 296, and 297.
- red colorant a compound described in paragraph 0034 of International Publication No. 2022/085485 and a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.
- C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, and 272 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 264 are even more preferred.
- Green colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred.
- the green colorant is also preferably a pigment, with phthalocyanine pigments being more preferred.
- green colorants include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66.
- halogenated zinc phthalocyanine pigments having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms in one molecule can also be used as green colorants.
- Specific examples include the compounds described in WO 2015/118720.
- compounds described in paragraph 0029 of WO 2022/085485, aluminum phthalocyanine compounds described in JP 2020-070426 A, and diarylmethane compounds described in JP 2020-504758 A can also be used as green colorants.
- Preferred green colorants are C.I. Pigment Green 7, 36, 58, 62, and 63.
- orange colorants include orange pigments such as C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.
- Yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. Specific examples of yellow colorants include 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,
- an azobarbituric acid nickel complex having the following structure can also be used.
- the compounds described in paragraphs 0031 to 0033 of WO 2022/085485, the methine dyes described in JP 2019-073695 A, and the methine dyes described in JP 2019-073696 A can be used.
- purple colorants include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.
- blue colorants include blue pigments such as C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88.
- Aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.
- Dyes can also be used as colorants.
- any known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyrromethene dyes.
- a dye polymer can also be used as the colorant.
- the dye polymer is preferably a dye dissolved in a solvent before use.
- the dye polymer may form particles. When the dye polymer is in the form of particles, it is usually used in a state of being dispersed in a solvent.
- a particulate dye polymer can be obtained, for example, by emulsion polymerization, and examples of the compounds and manufacturing methods described in JP-A-2015-214682 include those described in JP-A-2015-214682.
- the dye polymer has two or more dye structures in one molecule, and preferably has three or more dye structures. There is no particular limit to the upper limit, but it can be 100 or less.
- the multiple dye structures in one molecule may be the same dye structure or different dye structures.
- the weight average molecular weight (Mw) of the dye polymer is preferably 2,000 to 50,000.
- the lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more.
- the upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less.
- the dye multimer may be a compound described in JP2011-213925A, JP2013-041097A, JP2015-028144A, JP2015-030742A, WO2016/031442, etc.
- triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160 As colorants, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638 A, phthalocyanine compounds described in WO 2020/174991 A, isoindoline compounds or salts thereof described in JP 2020-160279 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070 A Compounds represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by the formula 1 described in Korean Patent Publication No.
- halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649 isoindoline compounds described in JP-A-2020-180176, phenothiazine compounds described in JP-A-2021-187913, halogenated zinc phthalocyanines described in WO 2022/004261, and halogenated zinc phthalocyanines described in WO 2021/250883 can be used.
- the colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, may be used in the rod-shaped structure, or may be used in both structures.
- 10-2020-0030759 polymer dyes described in Korean Patent Publication No. 10-2020-0061793, colorants described in JP-A-2022-029701, isoindoline compounds described in WO 2022/014635, aluminum phthalocyanine compounds described in WO 2022/024926, compounds described in JP-A-2022-045895, compounds described in WO 2022/050051, compounds described in JP-A-2020-090676, compounds described in JP-A-2020-055956, compounds described in JP-A-2021-031681, compounds described in JP-A-2022-056354
- a pigment derivative can also be used as the colorant.
- pigment derivatives include compounds having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acid group or a basic group.
- the above dye structures include a quinoline dye structure, a benzimidazolone dye structure, a benzisoindole dye structure, a benzothiazole dye structure, an iminium dye structure, a squarylium dye structure, a croconium dye structure, an oxonol dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, an azo dye structure, an azomethine dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, an anthraquinone dye structure, a quinacridone dye structure, a dioxazine dye structure, a perinone dye structure, a perylene dye structure, a thiazineindigo dye structure, a thioindigo dye structure, an isoindoline dye structure, an isoindolinone dye structure, a quinophthalone dye structure, a dithiol dye structure
- Examples of the acid group possessed by the pigment derivative include a carboxy group, a sulfo group, a phosphate group, a boronic acid group, an imide acid group, and salts thereof.
- Examples of the atom or atomic group constituting the salt include an alkali metal ion (Li + , Na + , K + , etc.), an alkaline earth metal ion (Ca 2+ , Mg 2+ , etc.), an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion.
- Examples of the imide acid group include a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 , -CONHCOR X3 , or -SO 2 NHCOR X4 , more preferably a group represented by -SO 2 NHSO 2 R X1 , -CONHSO 2 R X2 , or -SO 2 NHCOR X4 , and even more preferably -SO 2 NHSO 2 R X1 or -CONHSO 2 R X2 .
- R X1 to R X4 each independently represent an alkyl group or an aryl group.
- the alkyl group and aryl group represented by R X1 to R X4 may have a substituent.
- the substituent is preferably a halogen atom, more preferably a fluorine atom.
- R X1 to R X4 each independently represent an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, more preferably an alkyl group containing a fluorine atom.
- the number of carbon atoms of the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
- the number of carbon atoms of the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6.
- Basic groups contained in pigment derivatives include amino groups, pyridinyl groups and their salts, salts of ammonium groups, and phthalimidomethyl groups.
- Atoms or atomic groups that constitute the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.
- the amino group includes a group represented by --NR.sub.x11R.sub.x12 and a cyclic amino group.
- R x11 and R x12 each independently represent a hydrogen atom, an alkyl group or an aryl group, and are preferably an alkyl group. That is, the amino group is preferably a dialkylamino group.
- the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.
- the alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.
- the alkyl group may have a substituent.
- An example of the substituent is the substituent T.
- the number of carbon atoms of the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
- the aryl group may have a substituent.
- An example of the substituent is the substituent T.
- Cyclic amino groups include pyrrolidine groups, piperidine groups, piperazine groups, and morpholine groups. These groups may further have a substituent.
- the pigment derivative may be a pigment derivative having excellent visible transparency (hereinafter, also referred to as a transparent pigment derivative).
- the maximum molar absorption coefficient ( ⁇ max) of the transparent pigment derivative in the wavelength region of 400 to 700 nm is preferably 3000 L ⁇ mol -1 ⁇ cm -1 or less, more preferably 1000 L ⁇ mol -1 ⁇ cm -1 or less, and even more preferably 100 L ⁇ mol-1 ⁇ cm -1 or less.
- the lower limit of ⁇ max is, for example, 1 L ⁇ mol - 1 ⁇ cm -1 or more, and may be 10 L ⁇ mol -1 ⁇ cm -1 or more.
- pigment derivatives include the compounds described in the Examples below, the compounds described in paragraph 0124 of WO 2022/085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, and the compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282.
- the photosensitive composition When the photosensitive composition is used as a photosensitive composition for forming green pixels of a color filter, it is preferable to use a colorant containing a green colorant, and it is more preferable to use a colorant containing a yellow colorant and a green colorant.
- the photosensitive composition When the photosensitive composition is used as a photosensitive composition for forming red pixels of a color filter, it is preferable to use a colorant containing a red colorant, and it is more preferable to use a colorant containing a yellow colorant and a red colorant.
- the photosensitive composition When the photosensitive composition is used as a photosensitive composition for forming blue pixels of a color filter, it is preferable to use a colorant containing a blue colorant, and it is more preferable to use a colorant containing a blue colorant and a purple colorant.
- the content of the colorant in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 65% by mass or less, and particularly preferably less than 60% by mass.
- the content of the pigment in the colorant is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.
- the total content of the pigment and pigment derivative in the colorant is preferably 25 to 100% by mass, more preferably 55 to 100% by mass, and even more preferably 75 to 100% by mass.
- the photosensitive composition contains a resin.
- the resin is blended, for example, for the purpose of dispersing pigments and the like in the photosensitive composition or for the purpose of a binder.
- a resin that is mainly used for dispersing pigments and the like in the photosensitive composition is also called a dispersant.
- a use of the resin is only an example, and the resin can also be used for purposes other than such a use.
- the weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000.
- the upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less.
- the lower limit is preferably 4,000 or more, and more preferably 5,000 or more.
- resins examples include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins.
- the resin there are resins described in paragraphs 0091 to 0099 of WO 2022/065215, block polyisocyanate resins described in JP 2016-222891 A, resins described in JP 2020-122052 A, resins described in JP 2020-111656 A, resins described in JP 2020-139021 A, and structural units having a ring structure in the main chain and side chains described in JP 2017-138503 A and a structural unit having a biphenyl group, the resin described in paragraphs 0199 to 0233 of JP 2020-186373 A, the alkali-soluble resin described in JP 2020-186325 A, the resin represented by formula 1 described in Korean Patent Publication No. 10-2020-0078339 A, the copolymer containing an epoxy group and an acid group described in WO 2022/030445 A, and the compound described in JP 2018-135514 A can also be used.
- the resin it is preferable to use a resin having an acid group.
- the acid group include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group.
- the acid value of the resin having acid groups is preferably 30 to 500 mgKOH/g.
- the lower limit is more preferably 40 mgKOH/g or more, and particularly preferably 50 mgKOH/g or more.
- the upper limit is more preferably 400 mgKOH/g or less, even more preferably 300 mgKOH/g or less, and particularly preferably 200 mgKOH/g or less.
- the weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000.
- the number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.
- the resin having an acid group preferably contains a repeating unit having an acid group on the side chain, and more preferably contains 5 to 70 mol% of the repeating units having an acid group on the side chain out of all the repeating units of the resin.
- the upper limit of the content of repeating units having an acid group on the side chain is preferably 50 mol% or less, and more preferably 30 mol% or less.
- the lower limit of the content of repeating units having an acid group on the side chain is preferably 10 mol% or more, and more preferably 20 mol% or more.
- the photosensitive composition also preferably contains a resin having a basic group.
- the resin having a basic group is preferably a resin containing a repeating unit having a basic group in the side chain, more preferably a copolymer having a repeating unit having a basic group in the side chain and a repeating unit not having a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in the side chain and a repeating unit not having a basic group.
- the resin having a basic group can also be used as a dispersant.
- the amine value of the resin having a basic group is preferably 5 to 300 mgKOH/g.
- the lower limit is preferably 10 mgKOH/g or more, and more preferably 20 mgKOH/g or more.
- the upper limit is preferably 200 mgKOH/g or less, and more preferably 100 mgKOH/g or less.
- resins with basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919 (all manufactured by BYK-Chemie), Solsperse 11200, 13240, 13650, 13940, 24 000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by Lubrizol Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like.
- the resin having a basic group may be a block copolymer (B) described in paragraphs 0063 to 0112 of JP 2014-219665 A, a block copolymer A1 described in paragraphs 0046 to 0076 of JP 2018-156021 A, or a vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP 2019-184763 A, the contents of which are incorporated herein by reference.
- the photosensitive composition contains both a resin having an acid group and a resin having a basic group.
- the storage stability of the photosensitive composition can be further improved.
- the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass, per 100 parts by mass of the resin having an acid group.
- a resin having an aromatic carboxy group As the resin, it is also preferable to use a resin having an aromatic carboxy group.
- the aromatic carboxy group may be included in the main chain of a repeating unit, or may be included in a side chain of the repeating unit. It is preferable that the aromatic carboxy group is included in the main chain of a repeating unit.
- an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring.
- the number of carboxy groups bonded to an aromatic ring is preferably 1 to 4, and more preferably 1 to 2.
- resins having an aromatic carboxy group include the resins described in paragraphs 0082 to 0107 of WO 2021/166858.
- the photosensitive composition preferably contains resin A (hereinafter also referred to as resin A) that has a weight loss of 20% by mass or more at 245°C.
- resin A resin A
- the film thickness of the pixel after development can be efficiently reduced by heat treatment during the thinning process, making it easier to adjust the colorant content of the pixel after the thinning process to 60% by mass or more.
- the upper limit of the weight loss of resin A at 245°C is preferably 60% by mass or less, and more preferably 50% by mass or less, from the viewpoint of the film strength after thinning.
- the lower limit of the weight loss of resin A at 245°C is preferably 30% by mass or more, and more preferably 40% by mass or more, because this allows the film thickness of the pixel to be easily reduced during the thinning process.
- the weight loss of resin A at 100°C is preferably 5% by mass or less, and more preferably 3% by mass or less.
- the weight loss of a resin refers to the weight loss at a specific temperature when the resin is heated to that temperature.
- the weight loss of a resin in this specification is a value measured using a thermogravimetric measuring device under a nitrogen gas flow at a heating rate of 20°C/min.
- Resin A has a structure such as an ester group. This structure makes it easier for the weight to decrease when heated, and can increase the amount of weight loss at 245°C.
- Resin A is preferably a graft resin because it can also be used as a dispersant for pigments.
- a graft resin is a resin having a graft chain.
- a graft chain means a polymer chain that branches off from the main chain of a repeating unit.
- the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2,000 atoms excluding hydrogen atoms, and even more preferably 60 to 500 atoms excluding hydrogen atoms.
- the graft chain preferably contains repeating units of at least one structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, more preferably contains repeating units of at least one structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, and a polystyrene structure, further preferably contains repeating units of a polyether structure or a polyester structure, and particularly preferably contains repeating units of a polyester structure because it is an excellent pigment dispersant.
- Examples of the repeating unit of the polyester structure include a repeating unit of the structure represented by formula (G-1), formula (G-4) or formula (G-5).
- Examples of the repeating unit of the polyether structure include a repeating unit of the structure represented by formula (G-2).
- Examples of the repeating unit of the poly(meth)acrylic structure include a repeating unit of the structure represented by formula (G-3).
- Examples of the repeating unit of the polystyrene structure include a repeating unit of the structure represented by formula (G-6).
- R G1 and R G2 each independently represent an alkylene group.
- the alkylene group represented by R G1 and R G2 is not particularly limited, but is preferably a linear or branched alkylene group having 1 to 20 carbon atoms, more preferably a linear or branched alkylene group having 2 to 16 carbon atoms, and even more preferably a linear or branched alkylene group having 3 to 12 carbon atoms.
- R G3 represents a hydrogen atom or a methyl group
- Q G1 represents --O-- or --NH--
- L G1 represents a single bond or a divalent linking group
- R G4 represents a hydrogen atom or a substituent.
- Examples of the divalent linking group represented by L G1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), an oxyalkylenecarbonyl group (preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these.
- an alkylene group preferably an alkylene group having 1 to 12 carbon atoms
- an alkyleneoxy group preferably an alkyleneoxy group having 1 to 12 carbon atoms
- an oxyalkylenecarbonyl group preferably an oxyalkylenecarbonyl group having 1 to 12 carbon atoms
- an arylene group preferably an arylene
- Examples of the substituent represented by R G4 include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, a heterocyclic thioether group, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a blocked isocyanate group.
- R G5 represents a hydrogen atom or a methyl group
- R G6 represents an aryl group.
- the number of carbon atoms in the aryl group represented by R G6 is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
- the aryl group represented by R G6 may have a substituent.
- substituents examples include a hydroxy group, a carboxy group, an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an alkylthioether group, an arylthioether group, a heterocyclic thioether group, an ethylenically unsaturated bond-containing group, an epoxy group, an oxetanyl group, and a blocked isocyanate group.
- the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
- the substituent may be a group represented by formula (W-1). -L w1 -R w1 ... (W-1)
- L w1 represents a single bond or a divalent linking group.
- R w1 represents 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, or an oxacycloalkyl group.
- Examples of the divalent linking group represented by L w1 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these.
- R w1 is preferably an oxacycloalkyl group.
- the oxacycloalkyl group preferably has 4 to 10 carbon atoms, more preferably 4 to 6 carbon atoms, and even more preferably 4 or 5 carbon atoms.
- the graft chain is preferably a structure represented by the following formula (G-1a), (G-2a), (G-3a), (G-4a), (G-5a) or (G-6a), and more preferably a structure represented by formula (G-1a), (G-4a) or (G-5a).
- R G1 and R G2 each represent an alkylene group
- R G3 represents a hydrogen atom or a methyl group
- Q G1 represents -O- or -NH-
- L G1 represents a single bond or a divalent linking group
- R G4 represents a hydrogen atom or a substituent
- R G5 represents a hydrogen atom or a methyl group
- R G6 represents an aryl group
- W 100 represents a hydrogen atom or a substituent
- n1 to n6 each independently represent an integer of 2 or more.
- R G1 to R G6 , Q G1 , and L G1 are synonymous with R G1 to R G6 , Q G1 , and L G1 described in formulas (G-1) to (G-6), and the preferred ranges are also the same.
- W 100 is preferably a substituent.
- substituents include the group represented by formula (W-1) above.
- n1 to n6 are each preferably an integer from 2 to 100, more preferably an integer from 2 to 80, and even more preferably an integer from 8 to 60.
- R G1 in each repeating unit may be the same or different.
- R G1 contains two or more different repeating units, the arrangement of each repeating unit is not particularly limited and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a).
- the graft chain has a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a) and contains two or more different repeating units in R G1 .
- An example of a repeating unit having a graft chain is a repeating unit represented by the following formula (A-1-2).
- X2 represents a divalent linking group
- L2 represents a single bond or a divalent linking group
- W1 represents a graft chain.
- Examples of the trivalent linking group represented by X2 include a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, a polyether linking group, and a polystyrene linking group.
- a poly(meth)acrylic linking group or a polyalkyleneimine linking group is preferable, and a poly(meth)acrylic linking group is more preferable.
- Examples of the divalent linking group represented by L2 include an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these.
- the graft chain represented by W 1 includes the graft chains described above.
- repeating unit represented by formula (A-1-2) include a repeating unit represented by the following formula (A-1-2a) and a repeating unit represented by the following formula (A-1-2b).
- R b1 to R b3 each independently represent a hydrogen atom or an alkyl group
- Q b1 represents -CO-, -COO-, -OCO-, -CONH- or a phenylene group
- L 2 represents a single bond or a divalent linking group
- W 1 represents a graft chain.
- the number of carbon atoms in the alkyl group represented by R b1 to R b3 is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1.
- Q b1 is preferably -COO- or -CONH-, and more preferably -COO-.
- R b10 and R b11 each independently represent a hydrogen atom or an alkyl group
- m2 represents an integer of 1 to 5
- L 2 represents a single bond or a divalent linking group
- W 1 represents a graft chain.
- the number of carbon atoms in the alkyl group represented by R b10 and R b11 is preferably 1 to 10, and more preferably 1 to 3.
- the weight average molecular weight of the repeating unit having a graft chain is preferably 1000 or more, more preferably 1000 to 10000, and even more preferably 1000 to 7500.
- the weight average molecular weight of the repeating unit having a graft chain is a value calculated from the weight average molecular weight of the raw material monomer used in the polymerization of the repeating unit.
- a repeating unit having a graft chain can be formed by polymerizing a macromonomer.
- a macromonomer means a polymeric compound in which a polymerizable group is introduced at the polymer end.
- the content of repeating units having graft chains in resin A is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more.
- the upper limit can be set to 100% by mass or less, and can also be set to 95% by mass or less.
- Resin A may further contain a repeating unit having an acid group.
- the acid group include the acid groups described above, and a carboxy group is preferable.
- the content of the repeating unit having an acid group in Resin A is preferably 10 to 50 mass%.
- the lower limit is preferably 15 mass% or more, and more preferably 20 mass% or more.
- the upper limit is preferably 40 mass% or less, and more preferably 30 mass% or less.
- the weight average molecular weight of resin A is preferably 5,000 to 40,000.
- the lower limit is preferably 10,000 or more, and more preferably 15,000 or more.
- the upper limit is preferably 30,000 or less, and more preferably 25,000 or less.
- the photosensitive composition preferably contains a resin as a dispersant.
- dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins).
- the term "acidic dispersant (acidic resin)” refers to a resin in which the amount of acid groups is greater than the amount of basic groups.
- the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups is 70 mol% or more when the total amount of the acid groups and the basic groups is 100 mol%.
- the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group.
- the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH/g.
- the basic dispersant refers to a resin in which the amount of basic groups is greater than the amount of acid groups.
- the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups is greater than the amount of acid groups when the total amount of the acid groups and the basic groups is 100 mol%.
- the basic group possessed by the basic dispersant is preferably an amino group.
- the resin used as the dispersant is a graft resin.
- graft resins please refer to the description in paragraphs 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
- the resin used as the dispersant is a resin having an aromatic carboxy group.
- resins having an aromatic carboxy group include those mentioned above.
- the resin used as the dispersant is preferably Resin A described above.
- the resin used as the dispersant is preferably a polyimine-based dispersant containing nitrogen atoms in at least one of the main chain and side chain.
- the polyimine-based dispersant is preferably a resin having a main chain with a partial structure having a functional group with a pKa of 14 or less, a side chain with 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and side chain.
- the basic nitrogen atom so long as it is a nitrogen atom that exhibits basicity.
- polyimine-based dispersants please refer to the description in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference.
- the resin used as the dispersant is preferably one having a structure in which multiple polymer chains are bonded to a core portion.
- resins include dendrimers (including star-shaped polymers).
- dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP2013-043962A.
- the resin used as the dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in the side chain.
- the content of the repeating unit having an ethylenically unsaturated bond-containing group in the side chain is preferably 10 mol % or more of the total repeating units of the resin, more preferably 10 to 80 mol %, and even more preferably 20 to 70 mol %.
- resins described in JP 2018-087939 A, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6,432,077 A, polyethyleneimine having a polyester side chain described in WO 2016/104803 A, block copolymers described in WO 2019/125940 A, block polymers having an acrylamide structural unit described in JP 2020-066687 A, block polymers having an acrylamide structural unit described in JP 2020-066688 A, dispersants described in WO 2016/104803 A, and the like can also be used.
- Dispersants are also available as commercially available products, and specific examples include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Lubrizol Nippon, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd.
- the products described in paragraph 0129 of JP 2012-137564 A and the products described in paragraph 0235 of JP 2017-194662 A can also be used as dispersants.
- the content of the resin in the total solid content of the photosensitive composition is preferably 5 to 30% by mass, the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more, and the upper limit is preferably 25% by mass or less, and more preferably 20% by mass or less.
- the content of the above-mentioned resin A in the total solid content of the photosensitive composition is preferably 5 to 30% by mass.
- the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.
- the upper limit is preferably 25% by mass or less, and more preferably 20% by mass or less.
- the content of the above-mentioned resin A in the resin contained in the photosensitive composition is preferably 50 to 100% by mass.
- the lower limit is preferably 75% by mass or more, and more preferably 90% by mass or more.
- the upper limit can be set to 100% by mass or less, and can be set to 95% by mass or less.
- the photosensitive composition may contain only one type of resin, or may contain two or more types. When two or more types of resins are contained, it is preferable that the total amount of the resins is within the above range.
- the photosensitive composition preferably contains a solvent.
- the solvent include organic solvents.
- the type of solvent is not particularly limited as long as the solubility of each component and the coatability of the composition are satisfied.
- the organic solvent include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, refer to paragraph 0223 of International Publication No. 2015/166779, the contents of which are incorporated herein by reference.
- ester-based solvents substituted with a cyclic alkyl group and ketone-based solvents substituted with a cyclic alkyl group can also be preferably used.
- organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, propylene glycol
- suitable ethers include diethyl ether acetate, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy
- the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons, etc. (for example, the amount can be 50 ppm (parts per million) by mass or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).
- an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, an organic solvent with a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).
- Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter.
- the filter used for filtration preferably has a pore size of 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
- the filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.
- the organic solvent may contain isomers (compounds with the same number of atoms but different structures).
- the organic solvent may contain only one type of isomer, or multiple types of isomers.
- the peroxide content in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
- the content of the solvent in the photosensitive composition is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 90% by mass.
- the photosensitive composition preferably contains a polymerizable monomer.
- the polymerizable monomer may be a compound having an ethylenically unsaturated bond-containing group.
- the ethylenically unsaturated bond-containing group may be a vinyl group, a (meth)allyl group, a (meth)acryloyl group, or the like.
- the polymerizable monomer is preferably a radical polymerizable monomer.
- the molecular weight of the polymerizable monomer is preferably 100 to 2500.
- the upper limit is preferably 2000 or less, more preferably 1500 or less.
- the lower limit is preferably 150 or more, more preferably 250 or more.
- the polymerizable monomer is preferably a compound containing 3 or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bond-containing groups.
- the polymerizable monomer is preferably a 3-15 functional (meth)acrylate compound, and more preferably a 3-6 functional (meth)acrylate compound.
- Specific examples of polymerizable monomers include the compounds described in paragraphs 0075 to 0083 of WO 2022/065215.
- Preferred polymerizable monomers include dipentaerythritol tri(meth)acrylate (commercially available product is KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product is KAYARAD D-320; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product is KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products are KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds in which the (meth)acryloyl groups are bonded via ethylene glycol and/or propylene glycol residues (e.g.,
- Examples of the polymerizable monomer include diglycerol EO (ethylene oxide) modified (meth)acrylate (commercially available product is M-460; manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (KAYARAD HDDA, manufactured by Nippon Kayaku Co., Ltd.), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.
- diglycerol EO ethylene oxide
- methacrylate commercially available product is M-460; manufactured by Toagosei Co., Ltd.
- pentaerythritol tetraacrylate NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.
- NK Oligo UA-7200 (Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (all manufactured by Taisei Fine Chemical Co., Ltd.), and Light Acrylate POB-A0 (Kyoeisha Chemical Co., Ltd.).
- the content of the polymerizable monomer in the total solid content of the photosensitive composition is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 7% by mass or less.
- the lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more.
- the photosensitive composition may contain only one type of polymerizable monomer, or may contain two or more types. When two or more types of polymerizable monomers are contained, it is preferable that the total amount thereof is within the above range.
- the photosensitive composition preferably contains a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound having photosensitivity to light rays in the ultraviolet to visible regions is preferred.
- the photopolymerization initiator is preferably a photoradical polymerization initiator.
- Photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
- halogenated hydrocarbon derivatives e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.
- acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, etc.
- the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl substituted coumarin compound, more preferably a compound selected from an oxime compound, an ⁇ -hydroxyketone compound, an ⁇ -aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.
- examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP 2014-130173 A, the compounds described in Japanese Patent No. 6301489 A, and the compounds described in MATERIAL STAGE 37 to 60p, vol. 19, No.
- hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.
- ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), Irgacure 184, Irgacure 1173, Irgacure 2959, Irgacure 127 (all manufactured by BASF), etc.
- Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc.
- Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.
- Examples of oxime compounds include the compound described in paragraph 0142 of WO 2022/085485, the compound described in Japanese Patent No. 5,430,746, the compound described in Japanese Patent No. 5,647,738, the compound represented by general formula (1) and the compounds described in paragraphs 0022 to 0024 of JP 2021-173858 A, the compound represented by general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP 2021-170089 A, and the like.
- 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, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
- an oxime compound having a fluorene ring an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound in which a substituent having a hydroxyl group is bonded to a carbazole skeleton, or a compound described in paragraphs 0143 to 0149 of WO 2022/085485 can also be used.
- oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited to these.
- the oxime compound is preferably a compound having a maximum absorption wavelength in the wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of 360 to 480 nm.
- the molar absorption coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably 1000 to 300,000, even more preferably 2000 to 300,000, and particularly preferably 5000 to 200,000.
- the molar absorption coefficient of the compound can be measured using a known method. For example, it is preferable to measure using a spectrophotometer (Varian Cary-5 spectrophotometer) at a concentration of 0.01 g/L using ethyl acetate as a solvent.
- a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used as the photopolymerization initiator.
- a photoradical polymerization initiator two or more radicals are generated from one molecule of the photoradical polymerization initiator, so good sensitivity can be obtained.
- the crystallinity is reduced and the solubility in solvents is improved, making it less likely to precipitate over time, and the stability over time of the photosensitive composition can be improved.
- Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include the compounds described in paragraph 0148 of WO 2022/065215.
- the content of the photopolymerization initiator in the total solid content of the photosensitive composition is preferably 0.1 to 30 mass%.
- the lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more.
- the upper limit is preferably 20 mass% or less, and more preferably 15 mass% or less.
- the photosensitive composition may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types of photopolymerization initiators are contained, it is preferable that the total amount thereof is within the above range.
- the photosensitive composition may contain a compound having a cyclic ether group.
- the cyclic ether group include an epoxy group and an oxetanyl group.
- the compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound).
- the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more epoxy groups are preferred.
- the epoxy compound is preferably a compound having 1 to 100 epoxy groups in one molecule.
- the upper limit of the epoxy groups contained in the epoxy compound may be, for example, 10 or less, or 5 or less.
- the lower limit of the epoxy groups contained in the epoxy compound is preferably 2 or more.
- the epoxy compound the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, 0147 to 0156 of JP-A-2014-043556, and 0085 to 0092 of JP-A-2014-089408, compounds described in JP-A-2017-179172, xanthene type epoxy resins described in JP-A-2021-195421, and xanthene type epoxy resins described in JP-A-2021-195422 can also be used.
- the epoxy compound may be a low molecular weight compound (e.g., molecular weight less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (e.g., molecular weight 1000 or more, in the case of a polymer, weight average molecular weight 1000 or more).
- the weight average molecular weight of the compound having an epoxy group is preferably 200 to 100,000, more preferably 500 to 50,000.
- the upper limit of the weight average molecular weight is more preferably 10,000 or less, particularly preferably 5,000 or less, and even more preferably 3,000 or less.
- EHPE3150 manufactured by Daicel Corporation
- EPICLON N-695 manufactured by DIC Corporation
- Marproof G-0150M G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).
- the content of the compound having a cyclic ether group in the total solid content of the photosensitive composition is preferably 0.1 to 20 mass%.
- the lower limit is preferably 0.5 mass% or more, and more preferably 1 mass% or more.
- the upper limit is preferably 15 mass% or less, and more preferably 10 mass% or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.
- the photosensitive composition may also contain a polyalkyleneimine.
- the polyalkyleneimine is used, for example, as a dispersing aid for pigments.
- the dispersing aid is a material for enhancing the dispersibility of pigments in the photosensitive composition.
- the polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine.
- the polyalkyleneimine is a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group.
- the number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2.
- the molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more.
- the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
- the molecular weight of the polyalkyleneimine is the value calculated from the structural formula.
- the molecular weight of the specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the number average molecular weight value measured by the boiling point elevation method is used.
- the number average molecular weight value measured by the viscosity method is used.
- the number average molecular weight value measured in polystyrene equivalent value by GPC (gel permeation chromatography) method is used.
- the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
- alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred.
- the polyalkyleneimine is particularly preferably polyethyleneimine.
- the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of the primary amino groups, secondary amino groups, and tertiary amino groups.
- Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
- the content of polyalkyleneimine in the total solid content of the photosensitive composition is preferably 0.1 to 5 mass%.
- the lower limit is preferably 0.2 mass% or more, more preferably 0.5 mass% or more, and even more preferably 1 mass% or more.
- the upper limit is preferably 4.5 mass% or less, more preferably 4 mass% or less, and even more preferably 3 mass% or less.
- the content of polyalkyleneimine is preferably 0.5 to 20 mass parts per 100 mass parts of pigment.
- the lower limit is preferably 0.6 mass% or more, more preferably 1 mass% or more, and even more preferably 2 mass% or more.
- the upper limit is preferably 10 mass% or less, and even more preferably 8 mass% or less. Only one type of polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.
- the photosensitive composition may contain a curing accelerator.
- the curing accelerator include a thiol compound, a methylol compound, an amine compound, a phosphonium salt compound, an amidine salt compound, an amide compound, a base generator, an isocyanate compound, an alkoxysilane compound, and an onium salt compound.
- Specific examples of the curing accelerator include the compound described in paragraph 0164 of International Publication No. 2022/085485 and the compound described in JP-A-2021-181406.
- the content of the curing accelerator in the total solid content of the photosensitive composition is preferably 0.3 to 8.9% by mass, more preferably 0.8 to 6.4% by mass.
- the photosensitive composition may contain an ultraviolet absorber.
- ultraviolet absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include the compounds described in paragraph 0179 of International Publication No. 2022/085485, the reactive triazine ultraviolet absorbers described in JP-A-2021-178918, the ultraviolet absorbers described in JP-A-2022-007884, and the compounds described in Korean Patent Publication No. 10-2022-0014454.
- the content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass.
- only one type of ultraviolet absorber may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.
- the photosensitive composition may contain a polymerization inhibitor.
- the polymerization inhibitor include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerium salts, etc.).
- p-methoxyphenol is preferred.
- the content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.0001 to 5% by mass.
- the polymerization inhibitor may be one type or two or more types. In the case of two or more types, the total amount is preferably within the above range.
- the photosensitive composition may contain a silane coupling agent.
- the silane coupling agent include silane compounds having a hydrolyzable group, and it is preferable that the silane coupling agent is a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by at least one of a hydrolysis reaction and a condensation reaction.
- Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group, and an alkoxy group is preferable. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
- examples of functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, and an amino group, a (meth)acryloyl group, and an epoxy group are preferable.
- Specific examples of the silane coupling agent include the compounds described in paragraph 0177 of International Publication No. 2022/085485 and the compounds described in JP-A-2019-183020.
- the content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.01 to 15.0% by mass, more preferably 0.05 to 10.0% by mass.
- the silane coupling agent may be one type or two or more types. In the case of two or more types, it is preferable that the total amount is within the above range.
- the photosensitive composition may contain a surfactant.
- a surfactant various surfactants such as fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone-based surfactants may be used.
- the surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant.
- Nonionic surfactants include the compounds described in paragraph 0174 of WO 2022/085485.
- Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (all manufactured by Dow Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momen Co., Ltd.).
- Examples include BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, and BYK-UV3510 (manufactured by BYK-Chemie), etc.
- silicone surfactant may also be a compound having the following structure:
- the content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001% by mass to 5.0% by mass, and more preferably 0.005% by mass to 3.0% by mass.
- the surfactant may be one type or two or more types. When two or more types are used, it is preferable that the total amount is within the above range.
- the photosensitive composition may contain an antioxidant.
- the antioxidant include phenolic compounds, phosphite compounds, and thioether compounds.
- the phenolic compound any phenolic compound known as a phenolic antioxidant may be used.
- a preferred phenolic compound a hindered phenolic compound may be used.
- a compound having a substituent at the site (ortho position) adjacent to the phenolic hydroxyl group is preferred.
- a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred.
- a compound having a phenolic group and a phosphite group in the same molecule is also preferred.
- a phosphorus-based antioxidant may also be suitably used.
- phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite.
- antioxidants include, for example, Adeka STAB AO-20, Adeka STAB AO-30, Adeka STAB AO-40, Adeka STAB AO-50, Adeka STAB AO-50F, Adeka STAB AO-60, Adeka STAB AO-60G, Adeka STAB AO-80, and Adeka STAB AO-330 (manufactured by ADEKA Corporation).
- the antioxidant may be a compound described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, a compound described in International Publication No. WO 2017/006600, a compound described in International Publication No. WO 2017/164024, or a compound described in Korean Patent Publication No. 10-2019-0059371.
- the content of the antioxidant in the total solid content of the photosensitive composition is preferably 0.01 to 20 mass %, and more preferably 0.3 to 15 mass %. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is in the above range.
- the photosensitive composition may contain, as necessary, a sensitizer, a plasticizer, and other auxiliaries (e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, fragrances, surface tension regulators, chain transfer agents, etc.).
- auxiliaries e.g., conductive particles, fillers, defoamers, flame retardants, leveling agents, peeling promoters, fragrances, surface tension regulators, chain transfer agents, etc.
- the photosensitive composition may contain a metal oxide to adjust the refractive index of the resulting film.
- the metal oxide include TiO 2 , ZrO 2 , Al 2 O 3 , and SiO 2.
- the primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm.
- the metal oxide may have a core-shell structure. In this case, the core may be hollow.
- the photosensitive composition may contain a light resistance improver.
- the light resistance improver include the compounds described in paragraph 0183 of WO 2022/085485.
- the photosensitive composition preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less.
- the free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less.
- Methods for reducing free metals and halogens in the photosensitive composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with ion-exchange resins.
- perfluoroalkylsulfonic acid and its salts may be restricted.
- the content of perfluoroalkylsulfonic acid (particularly perfluoroalkylsulfonic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts, and perfluoroalkylcarboxylic acid (particularly perfluoroalkylcarboxylic acid having 6 to 8 carbon atoms in the perfluoroalkyl group) and its salts is preferably in the range of 0.01 ppb to 1,000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, based on the total solid content of the photosensitive composition.
- the photosensitive composition may be substantially free of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts.
- a photosensitive composition that is substantially free of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts may be selected by using a compound that can be a substitute for perfluoroalkylsulfonic acid and its salts, and a compound that can be a substitute for perfluoroalkylcarboxylic acid and its salts.
- Examples of compounds that can be a substitute for regulated compounds include compounds that are excluded from regulation due to the difference in the number of carbon atoms in the perfluoroalkyl group. However, the above content does not prevent the use of perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts.
- the photosensitive composition may contain perfluoroalkylsulfonic acid and its salts, and perfluoroalkylcarboxylic acid and its salts, within the maximum allowable range.
- a solid-state imaging device can also be manufactured using the method for manufacturing a color filter of the present invention. That is, the method for manufacturing a solid-state imaging device of the present invention includes the method for manufacturing a color filter 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.
- the substrate has a plurality of photodiodes constituting the light receiving area of a solid-state imaging element (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and a transfer electrode made of polysilicon or the like, a light-shielding film on the photodiodes and the transfer electrodes with only the light receiving portion of the photodiodes open, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode, and a color filter on the device protection film.
- a solid-state imaging element such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor
- a transfer electrode made of polysilicon or the like
- the device protection film may have a light-collecting means (e.g., a microlens, etc.; the same applies below) on the device protection film and below the color filter (the side closer to the substrate), or a light-collecting means on the color filter.
- the color filter may have a structure in which each colored pixel is embedded in a space partitioned by partitions, for example in a lattice shape. In this case, it is preferable that the partitions have a lower refractive index than each colored pixel. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018/043654 A.
- an ultraviolet absorbing layer may be provided in the structure of the solid-state imaging element to improve light resistance.
- the imaging device equipped with the solid-state imaging element of the present invention can be used for digital cameras, electronic devices with imaging functions (such as mobile phones), as well as vehicle-mounted cameras and surveillance cameras.
- An image display device can also be manufactured using the color filter manufacturing method of the present invention.
- image display devices include liquid crystal display devices and organic electroluminescence (organic EL) display devices.
- the definition and details of image display devices are described in, for example, “Electronic Display Devices” (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and “Display Devices” (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989).
- Liquid crystal display devices are described in, for example, “Next Generation Liquid Crystal Display Technology” (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd.
- the image display device may have a white organic EL element.
- the white organic EL element is preferably in a tandem structure.
- the tandem structure of the organic EL element is described in JP 2003-045676 A, Akiyoshi Mikami (ed.), "The Frontline of Organic EL Technology Development - High Brightness, High Precision, Long Life, Know-How Collection", Technical Information Association, pp. 326-328, 2008, etc.
- the spectrum of white light emitted by the organic EL element preferably has strong maximum emission peaks in the blue region (430-485 nm), green region (530-580 nm), and yellow region (580-620 nm). In addition to these emission peaks, it is more preferable that the spectrum has a maximum emission peak in the red region (650-700 nm).
- the weight loss of the measurement sample was measured by using a thermogravimetric analyzer (TGA) in a nitrogen stream, by heating the sample to a predetermined temperature at a heating rate of 20° C./min.
- the weight loss of the solid content of the photosensitive composition was measured by applying the photosensitive composition onto a glass substrate by spin coating and heating at 100° C. for 2 minutes to form a film having a thickness of 1.0 ⁇ m, which was then peeled off from the glass substrate.
- ⁇ Preparation of Dispersion> The mixture of the materials listed in the table below was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm in diameter). Next, a dispersion process was carried out using a high-pressure disperser equipped with a pressure reducing mechanism, NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.), under conditions of a pressure of 2000 kg/ cm2 and a flow rate of 500 g/min. This dispersion process was repeated a total of 10 times to obtain a dispersion.
- NANO-3000-10 manufactured by Nippon BEE Co., Ltd.
- PG36 C.I. Pigment Green 36 (green pigment)
- PG58 C.I. Pigment Green 58 (green pigment)
- PR254 C.I. Pigment Red 254 (red pigment)
- PR272 C.I. Pigment Red 272 (red pigment)
- PY139 C.I. Pigment Yellow 139 (yellow pigment)
- PY150 C.I. Pigment Yellow 150 (yellow pigment)
- PY185 C.I. Pigment Yellow 185 (yellow pigment)
- PB15:6 C.I. Pigment Blue 15:6 (blue pigment)
- PV23 C.I. Pigment Violet 23 (purple pigment)
- B-1 30% by mass propylene glycol monomethyl ether acetate solution of resin having the following structure (weight average molecular weight 20,000, the number attached to the main chain is the mass ratio, and the number attached to the side chain is the number of repeating units. The weight loss at thermal decomposition starting temperatures of 170° C. and 245° C. is 40% by mass or more).
- B-2 30% by mass propylene glycol monomethyl ether acetate solution of resin having the following structure (weight average molecular weight 20,000, the number attached to the main chain is the mass ratio, and the number attached to the side chain is the number of repeating units. The weight loss at thermal decomposition starting temperatures of 170° C. and 245° C. is 40% by mass or more).
- B-3 30% by mass propylene glycol monomethyl ether acetate solution of resin having the following structure (weight average molecular weight 20,000, the weight loss at 245° C. is less than 20% by mass).
- binder A 30% by mass solution of a resin having the following structure (the numerical values attached to the main chain are molar ratios; weight average molecular weight 11,000, acid value 69.2 mgKOH/g, weight loss at 245°C less than 20% by mass) in propylene glycol monomethyl ether acetate.
- C-2 A 30% by mass solution of a resin having the following structure (the numerical values attached to the main chain are molar ratios; weight average molecular weight: 30,000; acid value: 112.8 mg KOH/g; weight loss at 245° C.: less than 20% by mass) in propylene glycol monomethyl ether acetate.
- C-3 A 30% by mass solution of a resin having the following structure (the numerical values attached to the main chain are molar ratios; weight average molecular weight 12,000, acid value 31.6 mgKOH/g, weight loss at 245°C less than 20% by mass) in propylene glycol monomethyl ether acetate.
- M-1 KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)
- M-2 NK Ester A-TMMT (manufactured by Shin-Nakamura Chemical Co., Ltd., pentaerythritol tetraacrylate)
- M-3 NK Ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd., ethoxylated dipentaerythritol polyacrylate)
- W-1 polydimethylsiloxane modified with carbinol at both ends (hydroxyl value 62 mg KOH/g)
- W-2 Compound having the following structure (weight average molecular weight: 14,000, % indicating the proportion of repeating units is mol %)
- ⁇ Pixel formation> (Examples 1 to 18)
- the film thickness of the photosensitive composition layer was measured using a stylus step gauge (DektakXT, manufactured by BRUKER).
- the absorbance of this photosensitive composition layer in the wavelength range of 400 to 700 nm was measured using a spectrophotometer (manufactured by Otsuka Electronics Co., Ltd., MCPD9800) to determine the maximum absorbance in the aforementioned range.
- the obtained photosensitive composition layer was exposed to light having a wavelength of 365 nm at an exposure illuminance of 6000 W/m2 and an exposure amount of 500 mJ/ cm2 using an i-line stepper exposure device (FPA-3000i5+, manufactured by Canon Corporation) through a mask pattern in which square unmasked portions with sides of 1.0 ⁇ m were arranged in an area of 4 mm ⁇ 3 mm.
- the glass wafer on which the exposed photosensitive composition layer was formed was placed on the horizontal rotating table of a spin-shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.), and paddle development was performed at 23° C. for 60 seconds using a developer (CD-2000, manufactured by FUJIFILM Electronic Materials Co., Ltd.).
- a spin-shower developer DW-30 type, manufactured by Chemitronics Co., Ltd.
- paddle development was performed at 23° C. for 60 seconds using a developer (CD-2000, manufactured by FUJIFILM Electronic Materials Co., Ltd.).
- pure water was supplied in the form of a shower from a spray nozzle from above the center of rotation to perform a rinsing treatment, and then the wafer was spray-dried to form a pixel (pixel 1).
- the film thickness of pixel 1 was measured using a stylus step gauge (DektakXT, manufactured by BRUKER Co., Ltd.).
- the glass wafer on which the pixel 1 was formed was subjected to a heat treatment (thinning treatment) at 245° C. for 600 seconds using a hot plate to form a pixel (pixel 2).
- the film thickness of pixel 2 was measured using a stylus step gauge (DektakXT, manufactured by BRUKER).
- the absorbance of pixel 2 in the wavelength range of 400 to 700 nm was measured using a spectrophotometer (MCPD9800, manufactured by Otsuka Electronics Co., Ltd.) to determine the maximum absorbance value in the aforementioned range.
- an undercoat layer manufactured by Fujifilm Electronic Materials Co., Ltd., CT-4000L; thickness 0.1 ⁇ m
- the obtained photosensitive composition layer was exposed to light having a wavelength of 365 nm using an i-line stepper exposure device (FPA-3000i5 +, manufactured by Canon Co., Ltd.) at an exposure illuminance of 6000 W / m 2 and an exposure amount of 500 mJ / cm 2 through a mask pattern in which square unmasked portions with sides of 1.0 ⁇ m were arranged in an area of 4 mm ⁇ 3 mm.
- the glass wafer on which the exposed photosensitive composition layer was formed was placed on the horizontal rotating table of a spin-shower developer (DW-30 type, manufactured by Chemitronics Co., Ltd.) and paddle-developed at 23° C.
- Colorant concentration of the pixel (pixel 2) after the thinning treatment was calculated using the following formula.
- Colorant concentration of pixel after thin-film treatment colorant content (mass %) in the total solid content of photosensitive composition ⁇ (A2/B2)/(A1/B1)
- B2 maximum absorbance value of pixel 2 in the wavelength range of 400 to 700 nm
- Film thickness reduction rate was calculated from the film thicknesses of pixel 1 and pixel 2.
- Film thickness reduction rate (%) ((film thickness of pixel 1 ⁇ film thickness of pixel 2)/film thickness of pixel 1) ⁇ 100 -Evaluation criteria-
- E The film thickness reduction rate was 4% or less.
- the numerical value in the colorant concentration column in the above table is the numerical value of the colorant content in the total solid content of the photosensitive composition.
- the numerical value in the polymerizable monomer content column is the numerical value of the polymerizable monomer content in the total solid content of the photosensitive composition. Note that in Comparative Example 1, since no thinning treatment was performed, the columns for pixel colorant concentration and film thickness reduction rate are marked with "-". The colorant concentration of the pixel obtained by the method of Comparative Example 1 is almost the same as the colorant concentration in the total solid content of the photosensitive composition used, so the colorant concentration of the pixel obtained by the method of Comparative Example 1 is approximately 66.8 mass%.
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Abstract
Description
<1> 着色剤と樹脂とを含む感光性組成物を支持体上に塗布して感光性組成物層を形成する工程と、
上記感光性組成物層をパターン状に露光する工程と、
露光後の感光性組成物層を現像液を用いて現像して未露光部の感光性組成物層を除去して画素を形成する工程と、
上記現像後の画素を加熱処理して、上記画素の着色剤含有量が60質量%以上となるように上記画素の膜厚を減少させる薄膜化工程と、
を含む、カラーフィルタの製造方法。
<2> 上記感光性組成物の全固形分中における着色剤の含有量が50質量%以上である、<1>に記載のカラーフィルタの製造方法。
<3> 上記感光性組成物は、245℃における重量減少量が20質量%以上の樹脂Aを含む、<1>または<2>に記載のカラーフィルタの製造方法。
<4> 上記樹脂Aは、グラフト樹脂である、<3>に記載のカラーフィルタの製造方法。
<5> 上記感光性組成物は、重合性モノマーと光重合開始剤とを含む、<1>~<4>のいずれか1つに記載のカラーフィルタの製造方法。
<6> 上記感光性組成物の全固形分中における上記重合性モノマーの含有量が7質量%以下である、<5>に記載のカラーフィルタの製造方法。
<7> 上記感光性組成物の固形分の245℃における重量減少量が10~30質量%である、<1>~<6>のいずれか1つに記載のカラーフィルタの製造方法。
<8> 上記現像液はアルカリ現像液である、<1>~<7>のいずれか1つに記載のカラーフィルタの製造方法。
<9> 上記薄膜化工程での加熱処理は、180~260℃で、5分以上行う、<1>~<8>のいずれか1つに記載のカラーフィルタの製造方法。
<10> 上記薄膜化工程での加熱処理は、上記樹脂Aの熱分解開始温度+5℃~上記樹脂Aの熱分解開始温度+50℃の範囲の温度で、5分以上行う、<3>に記載のカラーフィルタの製造方法。
<11> 固体撮像素子用のカラーフィルタの製造方法である、<1>~<10>のいずれか1つに記載のカラーフィルタの製造方法。
<12> <1>~<11>のいずれか1つに記載のカラーフィルタの製造方法を含む固体撮像素子の製造方法。
本明細書において、「~」とはそ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意味で使用される。
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、置換基を有さない基(原子団)と共に置換基を有する基(原子団)をも包含する。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。
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、水銀灯の輝線スペクトル、エキシマレーザ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、「(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、構造式中のMeはメチル基を表し、Etはエチル基を表し、Buはブチル基を表し、Prはプロピル基を表し、Phはフェニル基を表す。
本明細書において、重量平均分子量および数平均分子量は、GPC(ゲルパーミエーションクロマトグラフィ)法により測定したポリスチレン換算値である。
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総質量をいう。
本明細書において、顔料とは、溶剤に対して溶解しにくい色材を意味する。例えば、顔料は、23℃の水100gおよび23℃のプロピレングリコールモノメチルエーテルアセテート100gに対する溶解度がいずれも0.1g以下であることが好ましく、0.01g以下であることがより好ましい。
本明細書において、染料とは、溶剤に対して溶解しやすい色材を意味する。
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。
本発明のカラーフィルタの製造方法は、
着色剤と樹脂とを含む感光性組成物を支持体上に塗布して感光性組成物層を形成する工程と、
上記感光性組成物層をパターン状に露光する工程と、
露光後の感光性組成物層を現像液を用いて現像して未露光部の感光性組成物層を除去して画素を形成する工程と、
上記現像後の画素を加熱処理して、上記画素の着色剤含有量が60質量%以上となるように上記画素の膜厚を減少させる薄膜化工程と、
を含むことを特徴とする。
感光性組成物層を形成する工程では、着色剤と樹脂とを含む感光性組成物を支持体上に塗布して感光性組成物層を形成する。感光性組成物については、後述する。
露光する工程では、支持体上に形成された感光性組成物層をパターン状に露光する。例えば、感光性組成物層に対し、ステッパー露光機やスキャナ露光機などを用いて、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、パターン状に露光することができる。これにより、感光性組成物層の露光部分を硬化することができる。
画素を形成する工程では、露光後の感光性組成物層を現像液を用いて現像して未露光部の感光性組成物層を除去して画素を形成する。
薄膜化工程では、現像後の画素を加熱処理して、画素の着色剤含有量が60質量%以上となるように画素の膜厚を減少させる。
この態様において、加熱処理温度の下限は、樹脂Aの熱分解開始温度+5℃以上であることが好ましく、樹脂Aの熱分解開始温度+10℃以上であることがより好ましい。また、加熱処理温度の上限は、樹脂Aの熱分解開始温度+50℃以下であることが好ましく、樹脂Aの熱分解開始温度+30℃以下であることがより好ましい。加熱時間は、5分以上であることが好ましく、15分以上であることがより好ましい。加熱時間の上限は、60分以下であることが好ましい。
なお、本明細書において、樹脂の熱分解開始温度とは、熱重量測定装置(TGA)により、窒素気流下において、20℃/分の昇温速度で樹脂を昇温した際に、質量減少又は熱分解に伴う吸発熱が観測され始める温度のことである。
薄膜化工程後の画素の着色剤含有量は、以下の方法で算出することができる。
薄膜化処理後の画素の着色剤濃度=感光性組成物の全固形分中における着色剤の含有量(質量%)×(A2/B2)/(A1/B1)
A1:感光性組成物を用いて得られた膜の膜厚
A2:薄膜化工程後の画素の膜厚
B1:感光性組成物を用いて得られた膜の、波長400~700nmの範囲における吸光度の最大値
B2:薄膜化工程後の画素の、波長400~700nmの範囲における吸光度の最大値
薄膜化工程後の画素の膜厚は、異なる画素間の膜厚ばらつきの抑制の観点から、薄膜化工程前の画素の膜厚の75%以上であることが好ましい。
薄膜化工程後の画素の膜厚は、着色剤濃度の高い膜を設計可能であるという理由から、薄膜化工程前の画素の膜厚の90%以下であることが好ましく、80%以下であることがより好ましい。
次に、本発明のカラーフィルタの製造方法に用いられる感光性組成物について説明する。感光性組成物には、着色剤と樹脂とを含むものが用いられる。
ガラス基板などの支持体上に感光性組成物をスピンコート法で塗布し、100℃で2分間加熱して厚さ1.0μmの膜を形成し、得られた膜を支持体から剥離して、熱重量測定装置を用いて20℃/分の昇温速度で昇温して膜の重量減少量を測定する。前述の膜の特定の温度における重量減少量を、感光性組成物の固形分の特定の温度における重量減少量として求める。
感光性組成物は着色剤を含む。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、紫色着色剤および青色着色剤などが挙げられる。着色剤は、顔料であってもよく、染料であってもよい。顔料は、無機顔料または有機顔料のいずれでもよいが、カラーバリエーションの多さ、分散の容易性、安全性等の観点から有機顔料であることが好ましい。また、着色剤には顔料誘導体を用いることもできる。
感光性組成物は樹脂を含む。樹脂は、例えば、顔料などを感光性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、主に顔料などを感光性組成物中で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を目的として樹脂を使用することもできる。
LG1が表す2価の連結基としては、アルキレン基(好ましくは炭素数1~12のアルキレン基)、アルキレンオキシ基(好ましくは炭素数1~12のアルキレンオキシ基)、オキシアルキレンカルボニル基(好ましくは炭素数1~12のオキシアルキレンカルボニル基)、アリーレン基(好ましくは炭素数6~20のアリーレン基)、-NH-、-SO-、-SO2-、-CO-、-O-、-COO-、OCO-、-S-およびこれらの2以上を組み合わせてなる基が挙げられる。
RG4が表す置換基としては、ヒドロキシ基、カルボキシ基、アルキル基、アリール基、複素環基、アルコキシ基、アリールオキシ基、複素環オキシ基、アルキルチオエーテル基、アリールチオエーテル基、複素環チオエーテル基、エチレン性不飽和結合含有基、エポキシ基、オキセタニル基およびブロックイソシアネート基等が挙げられる。
-Lw1-Rw1 ・・・(W-1)
式中、Lw1は、単結合、または2価の連結基を表し、
Rw1は、アルキル基、アリール基、ヘテロアリール基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルキルチオエーテル基、アリールチオエーテル基、ヘテロアリールチオエーテル基、またはオキサシクロアルキル基を表す。
感光性組成物の全固形分中における上述した樹脂Aの含有量は、5~30質量%であることが好ましい。下限は10質量%以上であることが好ましく、15質量%以上であることがより好ましい。上限は25質量%以下であることが好ましく、20質量%以下であることがより好ましい。
感光性組成物に含まれる樹脂中における上述した樹脂Aの含有量は、50~100質量%であることが好ましい。下限は75質量%以上であることが好ましく、90質量%以上であることがより好ましい。上限は100質量%以下とすることができ、95質量%以下とすることができる。
感光性組成物は溶剤を含有することが好ましい。溶剤としては、有機溶剤が挙げられる。溶剤の種類は、各成分の溶解性や組成物の塗布性を満足すれば基本的には特に制限はない。有機溶剤としては、エステル系溶剤、ケトン系溶剤、アルコール系溶剤、アミド系溶剤、エーテル系溶剤、炭化水素系溶剤などが挙げられる。これらの詳細については、国際公開第2015/166779号の段落番号0223を参酌でき、この内容は本明細書に組み込まれる。また、環状アルキル基が置換したエステル系溶剤、環状アルキル基が置換したケトン系溶剤も好ましく用いることもできる。有機溶剤の具体例としては、ポリエチレングリコールモノメチルエーテル、ジクロロメタン、3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、3-ペンタノン、4-ヘプタノン、シクロヘキサノン、2-メチルシクロヘキサノン、3-メチルシクロヘキサノン、4-メチルシクロヘキサノン、シクロヘプタノン、シクロオクタノン、酢酸シクロヘキシル、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、プロピレングリコールモノメチルエーテルアセテート、3-メトキシ-N,N-ジメチルプロパンアミド、3-ブトキシ-N,N-ジメチルプロパンアミド、プロピレングリコールジアセテート、3-メトキシブタノール、メチルエチルケトン、ガンマブチロラクトン、スルホラン、アニソール、1,4-ジアセトキシブタン、ジエチレングリコールモノエチルエーテルアセタート、二酢酸ブタン-1,3-ジイル、ジプロピレングリコールメチルエーテルアセタート、ジアセトンアルコール(別名としてダイアセトンアルコール、4-ヒドロキシ-4-メチル-2-ペンタノン)、2-メトキシプロピルアセテート、2-メトキシ-1-プロパノール、イソプロピルアルコールなどが挙げられる。ただし有機溶剤としての芳香族炭化水素類(ベンゼン、トルエン、キシレン、エチルベンゼン等)は、環境面等の理由により低減したほうがよい場合がある(例えば、有機溶剤全量に対して、50質量ppm(parts per million)以下とすることもでき、10質量ppm以下とすることもでき、1質量ppm以下とすることもできる)。
感光性組成物は重合性モノマーを含有することが好ましい。重合性モノマーとしては、エチレン性不飽和結合含有基を有する化合物などが挙げられる。エチレン性不飽和結合含有基としては、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。重合性モノマーは、ラジカル重合性モノマーであることが好ましい。
感光性組成物は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、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、紫外線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。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。
感光性組成物は、環状エーテル基を有する化合物を含有することができる。環状エーテル基としては、エポキシ基、オキセタニル基などが挙げられる。環状エーテル基を有する化合物は、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)であることが好ましい。エポキシ化合物としては、1分子内にエポキシ基を1つ以上有する化合物が挙げられ、エポキシ基を2つ以上有する化合物が好ましい。エポキシ化合物はエポキシ基を1分子内に1~100個有する化合物であることが好ましい。エポキシ化合物に含まれる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。エポキシ化合物に含まれるエポキシ基の下限は、2個以上が好ましい。エポキシ化合物としては、特開2013-011869号公報の段落番号0034~0036、特開2014-043556号公報の段落番号0147~0156、特開2014-089408号公報の段落番号0085~0092に記載された化合物、特開2017-179172号公報に記載された化合物、特開2021-195421号公報に記載のキサンテン型エポキシ樹脂、特開2021-195422号公報に記載のキサンテン型エポキシ樹脂を用いることもできる。
感光性組成物は、ポリアルキレンイミンを含有することもできる。ポリアルキレンイミンは例えば顔料の分散助剤として用いられる。分散助剤とは、感光性組成物中において顔料の分散性を高めるための素材のことである。ポリアルキレンイミンとは、アルキレンイミンを開環重合したポリマーのことである。ポリアルキレンイミンは、1級アミノ基と、2級アミノ基と、3級アミノ基とをそれぞれ含む分岐構造を有するポリマーである。アルキレンイミンの炭素数は2~6が好ましく、2~4がより好ましく、2または3であることが更に好ましく、2であることが特に好ましい。
感光性組成物は、硬化促進剤を含んでもよい。硬化促進剤としては、チオール化合物、メチロール化合物、アミン化合物、ホスホニウム塩化合物、アミジン塩化合物、アミド化合物、塩基発生剤、イソシアネート化合物、アルコキシシラン化合物、オニウム塩化合物などが挙げられる。硬化促進剤の具体例としては、国際公開第2022/085485号の段落0164に記載の化合物、特開2021-181406号公報に記載の化合物などが挙げられる。感光性組成物の全固形分中における硬化促進剤の含有量は0.3~8.9質量%が好ましく、0.8~6.4質量%がより好ましい。
感光性組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤としては、共役ジエン化合物、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物、インドール化合物、トリアジン化合物、ジベンゾイル化合物などが挙げられる。このような化合物の具体例としては、国際公開第2022/085485号の段落番号0179に記載の化合物、特開2021-178918号公報に記載の反応性トリアジン紫外線吸収剤、特開2022-007884号公報に記載の紫外線吸収剤、韓国公開特許第10-2022-0014454号公報に記載の化合物を用いることもできる。感光性組成物の全固形分中における紫外線吸収剤の含有量は、0.01~10質量%が好ましく、0.01~5質量%がより好ましい。本発明において、紫外線吸収剤は1種のみを用いてもよく、2種以上を用いてもよい。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。
感光性組成物は、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-tert-ブチル-p-クレゾール、ピロガロール、tert-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-tert-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)が挙げられる。中でも、p-メトキシフェノールが好ましい。感光性組成物の全固形分中における重合禁止剤の含有量は、0.0001~5質量%が好ましい。重合禁止剤は、1種類のみでもよく、2種類以上でもよい。2種類以上の場合は、合計量が上記範囲となることが好ましい。
感光性組成物は、シランカップリング剤を含有することができる。シランカップリング剤としては、加水分解性基を有するシラン化合物が挙げられ、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であることが好ましい。加水分解性基とは、ケイ素原子に直結し、加水分解反応及び縮合反応の少なくともいずれか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、アルコキシ基が好ましい。すなわち、シランカップリング剤は、アルコキシシリル基を有する化合物が好ましい。また、加水分解性基以外の官能基としては、例えば、ビニル基、(メタ)アリル基、(メタ)アクリロイル基、メルカプト基、エポキシ基、オキセタニル基、アミノ基、ウレイド基、スルフィド基、イソシアネート基、フェニル基などが挙げられ、アミノ基、(メタ)アクリロイル基およびエポキシ基が好ましい。シランカップリング剤の具体例としては、国際公開第2022/085485号の段落0177に記載の化合物、特開2019-183020号公報に記載の化合物が挙げられる。感光性組成物の全固形分中におけるシランカップリング剤の含有量は、0.01~15.0質量%が好ましく、0.05~10.0質量%がより好ましい。シランカップリング剤は、1種類のみでもよく、2種類以上でもよい。2種類以上の場合は、合計量が上記範囲となることが好ましい。
感光性組成物は、界面活性剤を含有することができる。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することができる。界面活性剤はシリコーン系界面活性剤またはフッ素系界面活性剤であることが好ましい。界面活性剤については、国際公開第2015/166779号の段落番号0238~0245に記載された界面活性剤を参照することができ、この内容は本明細書に組み込まれる。
感光性組成物は、酸化防止剤を含有することができる。酸化防止剤としては、フェノール化合物、亜リン酸エステル化合物、チオエーテル化合物などが挙げられる。フェノール化合物としては、フェノール系酸化防止剤として知られる任意のフェノール化合物を使用することができる。好ましいフェノール化合物としては、ヒンダードフェノール化合物が挙げられる。フェノール性ヒドロキシ基に隣接する部位(オルト位)に置換基を有する化合物が好ましい。前述の置換基としては炭素数1~22の置換又は無置換のアルキル基が好ましい。また、酸化防止剤は、同一分子内にフェノール基と亜リン酸エステル基を有する化合物も好ましい。また、酸化防止剤は、リン系酸化防止剤も好適に使用することができる。リン系酸化防止剤としてはトリス[2-[[2,4,8,10-テトラキス(1,1-ジメチルエチル)ジベンゾ[d,f][1,3,2]ジオキサホスフェピン-6-イル]オキシ]エチル]アミン、トリス[2-[(4,6,9,11-テトラ-tert-ブチルジベンゾ[d,f][1,3,2]ジオキサホスフェピン-2-イル)オキシ]エチル]アミン、亜リン酸エチルビス(2,4-ジ-tert-ブチル-6-メチルフェニル)などが挙げられる。酸化防止剤の市販品としては、例えば、アデカスタブ AO-20、アデカスタブ AO-30、アデカスタブ AO-40、アデカスタブ AO-50、アデカスタブ AO-50F、アデカスタブ AO-60、アデカスタブ AO-60G、アデカスタブ AO-80、アデカスタブ AO-330(以上、(株)ADEKA製)などが挙げられる。また、酸化防止剤は、特許第6268967号公報の段落番号0023~0048に記載された化合物、国際公開第2017/006600号に記載された化合物、国際公開第2017/164024号に記載された化合物、韓国公開特許第10-2019-0059371号公報に記載された化合物を使用することもできる。感光性組成物の全固形分中における酸化防止剤の含有量は、0.01~20質量%であることが好ましく、0.3~15質量%であることがより好ましい。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。2種以上を用いる場合は、合計量が上記範囲となることが好ましい。
感光性組成物は、必要に応じて、増感剤、可塑剤及びその他の助剤類(例えば、導電性粒子、充填剤、消泡剤、難燃剤、レベリング剤、剥離促進剤、香料、表面張力調整剤、連鎖移動剤など)を含有してもよい。これらの成分を適宜含有させることにより、膜物性などの性質を調整することができる。これらの成分は、国際公開第2022/085485号の段落0182に記載の化合物を用いることができる。
本発明のカラーフィルタの製造方法を用いて固体撮像素子を製造することもできる。すなわち、本発明の固体撮像素子の製造方法は、上述した本発明のカラーフィルタの製造方法を含む。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。
本発明のカラーフィルタの製造方法を用いて画像表示装置を製造することもできる。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(有機EL)表示装置などが挙げられる。画像表示装置の定義や詳細については、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。画像表示装置は、白色有機EL素子を有するものであってもよい。白色有機EL素子としては、タンデム構造であることが好ましい。有機EL素子のタンデム構造については、特開2003-045676号公報、三上明義監修、「有機EL技術開発の最前線-高輝度・高精度・長寿命化・ノウハウ集-」、技術情報協会、326~328ページ、2008年などに記載されている。有機EL素子が発光する白色光のスペクトルは、青色領域(430~485nm)、緑色領域(530~580nm)及び黄色領域(580~620nm)に強い極大発光ピークを有するものが好ましい。これらの発光ピークに加え更に赤色領域(650~700nm)に極大発光ピークを有するものがより好ましい。
測定試料の重量減少量は、熱重量測定装置(TGA)を用い、窒素気流下において、20℃/分の昇温速度で所定の温度まで昇温して測定した。
感光性組成物の固形分の重量減少量については、ガラス基板上に感光性組成物をスピンコート法で塗布し、100℃で2分間加熱して形成した厚さ1.0μmの膜をガラス基板から剥離したものを測定試料として用いた。
熱重量測定装置(TGA)により、窒素気流下において、20℃/分の昇温速度で樹脂を昇温し、質量減少又は熱分解に伴う吸発熱が観測され始める温度を測定して樹脂の熱分解開始温度を求めた。
下記表に記載の素材を混合した混合液を、ビーズミル(ジルコニアビーズ0.1mm径)を用いて3時間混合および分散した。次いで、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて圧力2000kg/cm2および流量500g/minの条件の下、分散処理を行なった。この分散処理を全10回繰り返して、分散液を得た。
PG36 : C.I.ピグメントグリーン36(緑色顔料)
PG58 : C.I.ピグメントグリーン58(緑色顔料)
PR254 : C.I.ピグメントレッド254(赤色顔料)
PR272 : C.I.ピグメントレッド272(赤色顔料)
PY139 : C.I.ピグメントイエロー139(黄色顔料)
PY150 : C.I.ピグメントイエロー150(黄色顔料)
PY185 : C.I.ピグメントイエロー185(黄色顔料)
PB15:6 : C.I.ピグメントブルー15:6(青色顔料)
PV23 : C.I.ピグメントバイオレット23(紫色顔料)
Syn-1~Syn-4:下記構造の化合物
B-1:下記構造の樹脂(重量平均分子量20000主鎖に付記した数値は質量比であり、側鎖に付記した数値は繰り返し単位の数である。熱分解開始温度170℃、245℃における重量減少量は40質量%以上である)の30質量%プロピレングリコールモノメチルエーテルアセテート溶液
B-2:下記構造の樹脂(重量平均分子量20000、主鎖に付記した数値は質量比であり、側鎖に付記した数値は繰り返し単位の数である。熱分解開始温度170℃、245℃における重量減少量は40質量%以上である)の30質量%プロピレングリコールモノメチルエーテルアセテート溶液
B-3:下記構造の樹脂(重量平均分子量20000、245℃における重量減少量は20質量%未満である)の30質量%プロピレングリコールモノメチルエーテルアセテート溶液
S-1: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)
S-2:プロピレングリコールモノメチルエーテル(PGME)
S-3:シクロペンタノン
下記の表に記載の原料を混合して、感光性組成物を製造した。
分散液G-1~G-4、R-1~R-4、B-1~B-4、CG-1:上述した分散液G-1~G-4、R-1~R-4、B-1~B-4、CG-1
C-1:下記構造の樹脂(主鎖に付記した数値はモル比である。重量平均分子量11000、酸価69.2mgKOH/g、245℃における重量減少量は20質量%未満である)の30質量%プロピレングリコールモノメチルエーテルアセテート溶液
M-1:KAYARAD DPHA(日本化薬(株)製、ジペンタエリスリトールペンタアクリレートとジペンタエリスリトールヘキサアクリレートとの混合物)
M-2:NKエステルA―TMMT(新中村化学工業(株)製、ペンタエリスリトールテトラアクリレート)
M-3:NKエステルA-DPH-12E(新中村化学工業(株)製、エトキシ化ジペンタエリスリトールポリアクリレート)
I-1:下記構造の化合物
I-2:下記構造の化合物
In-1:p-メトキシフェノール
A-1:2,2-ビス(ヒドロキシメチル)-1-ブタノールノ1,2-エポキシ-4-(2-オキシラニル)シクロヘキサン付加物
W-1:両末端カルビノール変性ポリジメチルシロキサン(水酸基価62mgKOH/g)
W-2:下記構造の化合物(重量平均分子量14000、繰り返し単位の割合を示す%はモル%である。)
S-1: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)
S-2:プロピレングリコールモノメチルエーテル(PGME)
S-3:シクロペンタノン
(実施例1~18)
下記表に記載の感光性組成物を、下塗り層(富士フイルムエレクトロニクスマテリアルズ(株)製、CT-4000L;厚さ0.1μm)付き8インチ(=203.2mm)ガラスウエハ上にプリベーク後の厚さが0.5μmになるようにスピンコータを用いて塗布し、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)を行い、感光性組成物層を形成した。感光性組成物層の膜厚を触針式段差計(DektakXT、BRUKER社製)を用いて測定した。また、この感光性組成物層の波長400~700nmの範囲の吸光度を分光光度計(大塚電子社製、MCPD9800)を用いて測定し、前述の範囲における吸光度の最大値を求めた。
次いで、得られた感光性組成物層に対して、一辺1.0μmの正方形状の非マスク部が4mm×3mmの領域に配列されたマスクパターンを介して、i線ステッパー露光装置(FPA-3000i5+、Canon(株)製)を使用して波長365nmの光を6000W/m2の露光照度、500mJ/cm2の露光量で照射して露光した。
次いで、露光後の感光性組成物層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-2000、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、23℃で60秒間パドル現像した。次いで、シリコンウエハを回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行ない、その後スプレー乾燥して画素(画素1)を形成した。画素1の膜厚を触針式段差計(DektakXT、BRUKER社製)を用いて測定した。
次いで、上記画素1が形成されているガラスウエハをホットプレートを使用して245℃で600秒加熱処理(薄膜化処理)を行い、画素(画素2)を形成した。画素2の膜厚を触針式段差計(DektakXT、BRUKER社製)を用いて測定した。また、画素2の波長400~700nmの範囲の吸光度を分光光度計(大塚電子社製、MCPD9800)を用いて測定し、前述の範囲における吸光度の最大値を求めた。
感光性組成物として下記表に記載の感光性組成物を用い、かつ、薄膜化処理の加熱処理を行わない以外は、実施例と同様の操作を行い画素を形成した。
すなわち、下記表に記載の感光性組成物を、下塗り層(富士フイルムエレクトロニクスマテリアルズ(株)製、CT-4000L;厚さ0.1μm)付き8インチ(=203.2mm)ガラスウエハ上にプリベーク後の厚さが0.5μmになるようにスピンコータを用いて塗布し、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)を行い、感光性組成物層を形成した。次いで、得られた感光性組成物層に対して、一辺1.0μmの正方形状の非マスク部が4mm×3mmの領域に配列されたマスクパターンを介して、i線ステッパー露光装置(FPA-3000i5+、Canon(株)製)を使用して波長365nmの光を6000W/m2の露光照度、500mJ/cm2の露光量で照射して露光した。次いで、露光後の感光性組成物層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-2000、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、23℃で60秒間パドル現像した。次いで、シリコンウエハを回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行ない、その後スプレー乾燥して画素を形成した。
薄膜化処理後の画素(画素2)の着色剤濃度を以下の式で算出した。
薄膜化処理後の画素の着色剤濃度=感光性組成物の全固形分中における着色剤の含有量(質量%)×(A2/B2)/(A1/B1)
A1:感光性組成物層の膜厚
A2:画素2の膜厚
B1:感光性組成物層の波長400~700nmの範囲における吸光度の最大値
B2:画素2の波長400~700nmの範囲における吸光度の最大値
画素1および画素2の膜厚から膜厚減少率を算出した。
膜厚減少率(%)=((画素1の膜厚-画素2の膜厚)/画素1の膜厚)×100
-評価基準-
A:膜厚減少率が15%を超えた
B:膜厚減少率が10%を超え15%以下であった
C:膜厚減少率が7%を超え10%以下であった
D:膜厚減少率が4%を超え7%以下であった
E:膜厚減少率が4%以下であった
一辺1.0μmの画素についての剥がれ個数をカウントして密着性を評価した。画素が密着していること、および、画素のサイズについては、走査電子顕微鏡を用いて観察した。
5:剥がれ個数の割合が0%である
4:剥がれ個数の割合が0%超10%以下である
3:剥がれ個数の割合が10%超20%以下である
2:剥がれ個数の割合が20%超50%以下である
1:剥がれ個数の割合が50%超である
一方、着色剤濃度の高い感光性組成物を用いて画素を形成した比較例1においては、密着性は不十分であった。
Claims (12)
- 着色剤と樹脂とを含む感光性組成物を支持体上に塗布して感光性組成物層を形成する工程と、
前記感光性組成物層をパターン状に露光する工程と、
露光後の感光性組成物層を現像液を用いて現像して未露光部の感光性組成物層を除去して画素を形成する工程と、
前記現像後の画素を加熱処理して、前記画素の着色剤含有量が60質量%以上となるように前記画素の膜厚を減少させる薄膜化工程と、
を含む、カラーフィルタの製造方法。 - 前記感光性組成物の全固形分中における着色剤の含有量が50質量%以上である、請求項1に記載のカラーフィルタの製造方法。
- 前記感光性組成物は、245℃における重量減少量が20質量%以上の樹脂Aを含む、請求項1または2に記載のカラーフィルタの製造方法。
- 前記樹脂Aは、グラフト樹脂である、請求項3に記載のカラーフィルタの製造方法。
- 前記感光性組成物は、重合性モノマーと光重合開始剤とを含む、請求項1または2に記載のカラーフィルタの製造方法。
- 前記感光性組成物の全固形分中における前記重合性モノマーの含有量が7質量%以下である、請求項5に記載のカラーフィルタの製造方法。
- 前記感光性組成物の固形分の245℃における重量減少量が10~30質量%である、請求項1または2に記載のカラーフィルタの製造方法。
- 前記現像液はアルカリ現像液である、請求項1または2に記載のカラーフィルタの製造方法。
- 前記薄膜化工程での加熱処理は、180~260℃で、5分以上行う、請求項1または2に記載のカラーフィルタの製造方法。
- 前記薄膜化工程での加熱処理は、前記樹脂Aの熱分解開始温度+5℃~前記樹脂Aの熱分解開始温度+50℃の範囲の温度で、5分以上行う、請求項3に記載のカラーフィルタの製造方法。
- 固体撮像素子用のカラーフィルタの製造方法である、請求項1または2に記載のカラーフィルタの製造方法。
- 請求項1または2に記載のカラーフィルタの製造方法を含む固体撮像素子の製造方法。
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