WO2019181724A1 - 感光性組成物、膜、パターンの形成方法、カラーフィルタ、固体撮像素子、および、画像表示装置 - Google Patents
感光性組成物、膜、パターンの形成方法、カラーフィルタ、固体撮像素子、および、画像表示装置 Download PDFInfo
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- WO2019181724A1 WO2019181724A1 PCT/JP2019/010520 JP2019010520W WO2019181724A1 WO 2019181724 A1 WO2019181724 A1 WO 2019181724A1 JP 2019010520 W JP2019010520 W JP 2019010520W WO 2019181724 A1 WO2019181724 A1 WO 2019181724A1
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 150000008027 tertiary esters Chemical group 0.000 description 1
- 125000003718 tetrahydrofuranyl group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000004001 thioalkyl group Chemical group 0.000 description 1
- 125000005000 thioaryl group Chemical group 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical group S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002088 tosyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1C([H])([H])[H])S(*)(=O)=O 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
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- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/208—Filters for use with infrared or ultraviolet radiation, e.g. for separating visible light from infrared and/or ultraviolet radiation
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
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- 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
-
- 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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- 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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0382—Macromolecular compounds which are rendered insoluble or differentially wettable the macromolecular compound being present in a chemically amplified negative photoresist composition
-
- 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
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
-
- 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
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- 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
-
- 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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/325—Non-aqueous compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
Definitions
- the present invention relates to a photosensitive composition. More specifically, the present invention relates to a photosensitive composition used for forming a negative pattern by developing with a developer containing an organic solvent. The present invention also relates to a film, a pattern forming method, a color filter, a solid-state imaging device, and an image display device using the above-described photosensitive composition.
- CCD charge coupled device
- a film containing a color material such as a color filter is manufactured by patterning by performing exposure and development using a photosensitive composition containing a color material, for example (see Patent Documents 1 and 2).
- a photosensitive composition used for the production of a film containing a color material such as a color filter may be used after being stored for a long period of time.
- the photosensitive composition may be stored in a low temperature environment of 5 ° C. or less, for example.
- the formed pattern has good rectangularity and light leakage (crosstalk) to other adjacent films is small.
- an object of the present invention is to provide a photosensitive composition that can form a pattern with good rectangularity and suppressed light leakage to other adjacent films even after the photosensitive composition has been stored for a long period of time.
- Another object of the present invention is to provide a film, a pattern forming method, a color filter, a solid-state imaging device, and an image display device.
- the present invention provides the following.
- a photosensitive composition used to form a negative pattern by developing with a developer containing an organic solvent A photosensitive composition comprising a coloring material, a resin whose solubility in an organic solvent is lowered by the action of an acid, and a photoacid generator.
- ⁇ 3> The content of the resin according to ⁇ 1> or ⁇ 2>, wherein the content of the resin whose solubility in an organic solvent is reduced by the action of an acid in the total amount of the resin contained in the photosensitive composition is 40% by mass or more.
- Composition. ⁇ 6> The resin whose solubility in an organic solvent is lowered by the action of an acid has a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid, and any one of ⁇ 1> to ⁇ 5> The photosensitive composition as described in one.
- Rn and Ar may be bonded to each other to form a ring.
- ⁇ 11> The photosensitive composition according to any one of ⁇ 1> to ⁇ 10>, wherein the content of the radical polymerizable monomer in the total solid content of the photosensitive composition is 5% by mass or less.
- ⁇ 12> A film obtained from the photosensitive composition according to any one of ⁇ 1> to ⁇ 11>.
- ⁇ 13> a step of forming a photosensitive composition layer on a support using the photosensitive composition according to any one of ⁇ 1> to ⁇ 11>; Irradiating the photosensitive composition layer with light and exposing it in a pattern; and Removing the photosensitive composition layer in the unexposed area using a developer containing an organic solvent, and developing the pattern.
- ⁇ 14> After forming the first pixel using the pattern forming method according to ⁇ 13>, A method for producing a color filter, wherein the second pixel is formed in the missing portion of the first pixel by using the pattern forming method according to ⁇ 13>.
- ⁇ 16> A solid-state imaging device having the film according to ⁇ 12>.
- ⁇ 17> An image display device having the film according to ⁇ 12>.
- the present invention it is possible to provide a photosensitive composition capable of forming a pattern having good rectangularity and suppressing light leakage to other adjacent films even after the photosensitive composition has been stored for a long period of time. it can.
- membrane using the above-mentioned photosensitive composition, the formation method of a pattern, a color filter, a solid-state image sensor, and an image display apparatus can be provided.
- ⁇ is used to mean that the numerical values described before and after it are included as a lower limit and an upper limit.
- the notation in which neither substitution nor substitution is described includes a group (atomic group) having a substituent together with a group (atomic group) having no substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams.
- the light used for exposure include an emission line spectrum of a mercury lamp, actinic rays or radiation such as far ultraviolet rays, extreme ultraviolet rays (EUV light) typified by excimer laser, X-rays, and electron beams.
- EUV light extreme ultraviolet rays
- (meth) acrylate” represents both and / or acrylate and methacrylate
- (meth) acryl” represents both and / or acrylic and “(meth) acrylic”.
- Acryloyl represents both and / or acryloyl and methacryloyl.
- the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by Tosoh Corporation).
- GPC measurement solvent: tetrahydrofuran
- flow rate sample injection amount
- column TSK gel Multipore HXL-M manufactured by Tosoh Corporation
- column temperature 40 ° C.
- flow rate 1.0 mL / min
- detector differential refractive index It is defined as a polystyrene equivalent value by a detector (Refractive Index Detector).
- the total solid content refers to the total mass of components obtained by removing the solvent from all components of the composition.
- the term “process” is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
- the photosensitive composition of the present invention is a photosensitive composition used to form a negative pattern by developing with a developer containing an organic solvent, It contains a colorant, a resin whose solubility in an organic solvent is lowered by the action of an acid, and a photoacid generator.
- the photosensitive composition of the present invention is applied to, for example, a photosensitive composition on a support to form a photosensitive composition layer, and the photosensitive composition layer is exposed in a pattern, thereby exposing the exposed portion.
- the solubility of the above resin in the organic solvent can be effectively reduced by the action of the acid generated from the photoacid generator, and the solubility in the organic solvent can be reduced between the exposed portion and the unexposed portion. You can make a difference.
- the photosensitive composition layer after the exposure is developed using a developer containing an organic solvent, whereby the photosensitive composition layer in the unexposed area is removed by the developer, and the photosensitive composition layer in the exposed area is removed. Remains as a pattern (negative pattern). For this reason, a pattern with good rectangularity can be formed.
- a negative pattern is formed using a conventional negative photocurable photosensitive composition
- the thickness of the pattern obtained is not particularly changed after exposure, but in the case of the photosensitive composition of the present case, By heat-treating the pattern after development, the resin contained in the pattern after development is decomposed, so that the pattern thickness can be made thinner than that immediately after exposure, and a pattern with a smaller thickness can be formed. .
- the resin whose solubility in an organic solvent is reduced by the action of an acid is a resin having a structure in which a polar group described later is protected by a group (leaving group) that decomposes and leaves by the action of an acid
- the above-mentioned leaving group remaining in the resin contained in the pattern after exposure is decomposed and removed by heat treatment after development or the like, whereby the thickness of the pattern can be made thinner than that immediately after exposure.
- the thinner the pattern obtained the easier it is to suppress light leakage. For this reason, according to the present invention, it is possible to form a pattern in which light leakage to other adjacent films is suppressed.
- the photosensitive composition of this invention is a case where it preserve
- the reason why such an effect can be obtained is presumed because, during storage, a resin whose solubility in an organic solvent is lowered due to the action of an acid in the composition and a photoacid generator are easily adapted. Presumed to be.
- the photosensitive composition of the present invention is preferably used as a composition for forming colored pixels, light shielding films, infrared transmission filter layer pixels, and the like.
- the colored pixels include pixels having a hue selected from red, blue, green, cyan, magenta, and yellow.
- the pixel of the infrared transmission filter layer has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and transmission in the wavelength range of 1100 to 1300 nm. Examples thereof include a pixel of a filter layer that satisfies the spectral characteristics having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more).
- the pixels of the infrared transmission filter layer are also preferably pixels of the filter layer satisfying any of the following spectral characteristics (1) to (4).
- the maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1300 nm is A filter layer pixel that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1300 nm is A filter layer pixel that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1300 nm is A filter layer pixel that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1300 nm is A filter layer pixel that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the photosensitive composition of the present invention When the photosensitive composition of the present invention is used as a composition for forming a pixel of an infrared transmission filter layer, the photosensitive composition of the present invention has a minimum absorbance Amin in a wavelength range of 400 to 640 nm and a wavelength of 1100 to 1300 nm. It is preferable that Amin / Bmax, which is a ratio with the maximum value Bmax of absorbance in the above range, satisfies the spectral characteristics of 5 or more. Amin / Bmax is more preferably 7.5 or more, further preferably 15 or more, and particularly preferably 30 or more.
- the absorbance A ⁇ at a certain wavelength ⁇ is defined by the following equation (1).
- a ⁇ ⁇ log (T ⁇ / 100) (1)
- a ⁇ is the absorbance at the wavelength ⁇
- T ⁇ is the transmittance (%) at the wavelength ⁇ .
- the absorbance value may be a value measured in a solution state or may be a value in a film formed using a photosensitive composition.
- the photosensitive composition is applied on a glass substrate by a method such as spin coating so that the film thickness after drying becomes a predetermined thickness, and a hot plate is used. It is preferable to measure using a film prepared by drying at 100 ° C. for 120 seconds.
- the photosensitive composition of the present invention When the photosensitive composition of the present invention is used as a composition for forming a pixel of an infrared transmission filter layer, the photosensitive composition of the present invention satisfies any of the following spectral characteristics (11) to (14). More preferably. (11): Amin1 / Bmax1, which is a ratio of the minimum absorbance Amin1 in the wavelength range of 400 to 640 nm and the maximum absorbance Bmax1 in the wavelength range of 800 to 1300 nm, is 5 or more, and is 7.5 or more Preferably, it is 15 or more, more preferably 30 or more.
- Amin2 / Bmax2 which is a ratio of the minimum absorbance Amin2 in the wavelength range of 400 to 750 nm and the maximum absorbance Bmax2 in the wavelength range of 900 to 1300 nm, is 5 or more, and is 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 750 nm and transmitting light having a wavelength of 850 nm or more.
- Amin3 / Bmax3 which is a ratio of the minimum absorbance Amin3 in the wavelength range of 400 to 850 nm and the maximum absorbance Bmax3 in the wavelength range of 1000 to 1300 nm, is 5 or more and 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 850 nm and transmitting light having a wavelength of 940 nm or more.
- Amin4 / Bmax4 which is a ratio of the minimum absorbance Amin4 in the wavelength range of 400 to 950 nm and the maximum absorbance Bmax4 in the wavelength range of 1100 to 1300 nm, is 5 or more and 7.5 or more Preferably, it is 15 or more, more preferably 30 or more. According to this aspect, it is possible to form a film capable of blocking light in the wavelength range of 400 to 950 nm and transmitting light having a wavelength of 1040 nm or more.
- the photosensitive composition of the present invention can be preferably used as a photosensitive composition for a solid-state imaging device.
- the photosensitive composition of this invention can be used preferably as a photosensitive composition for color filters. Specifically, it can be preferably used as a photosensitive composition for forming a pixel of a color filter, and can be more preferably used as a photosensitive composition for forming a pixel of a color filter used in a solid-state imaging device.
- the photosensitive composition of the present invention contains a color material.
- the color material include chromatic colorants, black colorants, infrared absorbing color materials, and the like.
- the color material may be a pigment or a dye.
- the average primary particle size of the pigment is preferably from 0.01 to 0.1 ⁇ m, more preferably from 0.01 to 0.05 ⁇ m.
- the average primary particle diameter of the pigment can be measured using a transmission electron microscope. As the transmission electron microscope, for example, a transmission microscope HT7700 manufactured by Hitachi High-Technologies Corporation can be used.
- the maximum length of a particle image obtained using a transmission electron microscope (Dmax: maximum length at two points on the contour of the particle image), and the maximum length vertical length (DV-max: two straight lines parallel to the maximum length) The shortest length connecting two straight lines perpendicularly) was measured, and the geometric mean value (Dmax ⁇ DV-max) 1/2 was taken as the particle diameter.
- the particle diameter of 100 particles was measured by this method, and the arithmetic average value was taken as the average particle diameter to obtain the average primary particle diameter of the pigment.
- the “average primary particle size” in the examples of the present specification is also the same as the arithmetic average value.
- the color material when a dye is used as the color material, it is easy to form a film with a clearer hue, for example, it is easy to form a film excellent in color separation with other pixels.
- the color material is preferably a component different from the pigment derivative. That is, in the present specification, it is preferable that the coloring material does not contain a pigment derivative.
- Chromatic colorant examples include a red colorant, a green colorant, a blue colorant, a yellow colorant, a purple colorant, and an orange colorant.
- the chromatic colorant may be a pigment or a dye.
- the pigment used as the chromatic colorant is preferably an organic pigment.
- the following are mentioned as an organic pigment.
- C. I. 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, 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, 22
- a metal containing at least one anion selected from an azo compound represented by the following formula (I) and an azo compound having a tautomer structure thereof, two or more metal ions, and a melamine compound Azo pigments can also be used.
- R 1 and R 2 are each independently —OH or —NR 5 R 6
- R 3 and R 4 are each independently ⁇ O or ⁇ NR 7
- R 5 to R 7 Each independently represents a hydrogen atom or an alkyl group.
- the alkyl group represented by R 5 to R 7 preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- the alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
- the alkyl group may have a substituent.
- the substituent is preferably a halogen atom, a hydroxy group, an alkoxy group, a cyano group or an amino group.
- R 1 and R 2 are preferably —OH.
- R 3 and R 4 are preferably ⁇ O.
- the melamine compound in the metal azo pigment is preferably a compound represented by the following formula (II).
- R 11 to R 13 each independently represents a hydrogen atom or an alkyl group.
- the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- the alkyl group may be linear, branched or cyclic, and is preferably linear or branched, more preferably linear.
- the alkyl group may have a substituent.
- the substituent is preferably a hydroxy group.
- at least one of R 11 ⁇ R 13 is a hydrogen atom, more preferably all of R 11 ⁇ R 13 is a hydrogen atom.
- the metal azo pigment includes at least one anion selected from the azo compound represented by the above formula (I) and an azo compound having a tautomer structure thereof, a metal ion containing at least Zn 2+ and Cu 2+ , It is preferable that it is a metal azo pigment of the aspect containing a melamine compound.
- the total amount of Zn 2+ and Cu 2+ is preferably 95 to 100 mol%, more preferably 98 to 100 mol%, based on 1 mol of all metal ions of the metal azo pigment.
- the content is more preferably 99.9 to 100 mol%, particularly preferably 100 mol%.
- the metal azo pigment may further contain a divalent or trivalent metal ion (hereinafter also referred to as metal ion Me1) other than Zn 2+ and Cu 2+ .
- the metal ions Me1 include Ni 2+ , Al 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , La 3+ , Ce 3+ , Pr 3+ , Nd 2+ , Nd 3+ , Sm 2+ , Sm 3+ , Eu 2+ , Eu 3+ , Gd 3+, Tb 3+, Dy 3+, Ho 3+, Yb 2+, Yb 3+, Er 3+, Tm 3+, Mg 2+, Ca 2+, Sr 2+, Mn 2+, Y 3+, Sc 3+, Ti 2+, Ti 3+, Nb 3+ , Mo 2+ , Mo 3+ , V 2+ , V 3+ , Zr 2+ , Zr 3+ , Cd 2+ , Cr 3+ , Pb 2+ , Ba 2+ , Al 3+ , Fe 2+ , Fe 3+ , Co 2+ , Co 3+ , la 3+, Ce 3+,
- the content of the metal ion Me1 is preferably 5 mol% or less, more preferably 2 mol% or less, and more preferably 0.1 mol% or less, based on 1 mol of all metal ions of the metal azo pigment. More preferably it is.
- paragraph numbers 0011 to 0062 and 0137 to 0276 in JP-A-2017-171912 paragraph numbers 0010 to 0062 and 0138 to 0295 in JP-A-2017-171913, and JP-A-2017-171914.
- the descriptions of paragraph numbers 0011 to 0062 and 0139 to 0190 of the publication and paragraph numbers 0010 to 0065 and 0142 to 0222 of JP-A-2017-171915 can be referred to, and the contents thereof are incorporated in the present specification.
- red pigment a compound having a structure in which an aromatic ring group in which a group in which an oxygen atom, a sulfur atom, or a nitrogen atom is bonded to an aromatic ring is bonded to a diketopyrrolopyrrole skeleton can also be used.
- a compound is preferably a compound represented by the formula (DPP1), and more preferably a compound represented by the formula (DPP2).
- R 11 and R 13 each independently represent a substituent
- R 12 and R 14 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group
- n11 and n13 each independently X 12 and X 14 each independently represent an oxygen atom, a sulfur atom or a nitrogen atom
- m12 represents 1, If 12 is a nitrogen atom, m12 represents 2, if X 14 is an oxygen atom or a sulfur atom, m14 represents 1, if X 14 is a nitrogen atom, m14 represents 2.
- Examples of the substituent represented by R 11 and R 13 include an alkyl group, aryl group, halogen atom, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, amide group, cyano group, nitro group, trifluoro group.
- a methyl group, a sulfoxide group, a sulfo group and the like are preferable examples.
- a halogenated zinc phthalocyanine pigment having an average number of halogen atoms in one molecule of 10 to 14, bromine atoms of 8 to 12 and chlorine atoms of 2 to 5 is used. You can also. Specific examples include the compounds described in International Publication No. WO2015 / 118720.
- an aluminum phthalocyanine compound having a phosphorus atom can be used as a blue pigment.
- Specific examples include compounds described in paragraphs 0022 to 0030 of JP2012-247491A and paragraph 0047 of JP2011-157478A.
- the dye is not particularly limited, and a known dye can be used.
- a known dye can be used.
- pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene Examples include phthalocyanine-based, benzopyran-based, indigo-based, and pyromethene-based dyes. Moreover, you may use the multimer of these dyes. Further, the dyes described in JP-A-2015-028144 and JP-A-2015-34966 can also be used.
- Black colorant examples of the black colorant include inorganic black colorants and organic black colorants.
- the inorganic black colorant is preferably a pigment (inorganic black pigment). It does not specifically limit as an inorganic black pigment, A well-known thing can be used. For example, carbon black, titanium black, graphite, etc. are mentioned, carbon black and titanium black are preferable, and titanium black is more preferable. Titanium black is black particles containing titanium atoms, and low-order titanium oxide and titanium oxynitride are preferable.
- the surface of titanium black can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, or zirconium oxide. Further, treatment with a water-repellent substance as disclosed in JP 2007-302836 A is also possible. Specific examples of the inorganic black pigment include Color Index (CI) Pigment Black 1, 7 and the like.
- Titanium black preferably has a small primary particle size and average primary particle size for each particle. Specifically, an average primary particle diameter in the range of 10 nm to 45 nm is preferable.
- titanium black is not particularly limited, BET (Brunauer, Emmett, Teller ) is preferably measured value is less than 5 m 2 / g or more 150 meters 2 / g by method, 20 m 2 / g or more 120 m 2 / More preferably, it is g or less.
- BET Brunauer, Emmett, Teller
- Examples of commercially available titanium black products include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, 13M-T (trade names: manufactured by Mitsubishi Materials Corporation), Tilac D ( (Trade name: manufactured by Ako Kasei Co., Ltd.).
- Titanium black can also be used as a dispersion.
- a dispersion containing titanium black particles and silica particles, in which the content ratio of Si atoms to Ti atoms in the dispersion is adjusted to a range of 0.20 to 0.50, and the like can be mentioned.
- the description in paragraphs 0020 to 0105 of JP2012-169556A can be referred to, and the contents thereof are incorporated in the present specification.
- Examples of the organic black colorant include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, and bisbenzofuranone compounds and perylene compounds are preferable.
- Examples of the bisbenzofuranone compounds include compounds described in JP-T 2010-534726, JP-2012-515233, JP-2012-515234, and the like, for example, “Irgaphor Black” manufactured by BASF It is available.
- Examples of perylene compounds include C.I. I. Pigment Black 31, 32 and the like.
- Examples of the azomethine compound include those described in JP-A Nos. 01-170601 and 02-034664, and can be obtained, for example, as “Chromofine Black A1103” manufactured by Dainichi Seika Co., Ltd.
- Infrared absorbing color material As the infrared absorbing color material, a compound having a maximum absorption wavelength in the wavelength range of 700 to 1300 nm, more preferably in the wavelength range of 700 to 1000 nm is preferable.
- the infrared absorbing color material may be a pigment or a dye.
- Infrared absorbing colorants are pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, diimonium compounds, dithiol compounds, triarylmethane compounds, pyromethene compounds, azomethine
- At least one selected from a compound, an anthraquinone compound and a dibenzofuranone compound is preferable, at least one selected from a pyrrolopyrrole compound, a cyanine compound, a squarylium compound, a phthalocyanine compound, a naphthalocyanine compound and a diimonium compound is more preferable, a pyrrolopyrrole compound, More preferably, at least one selected from a cyanine compound and a squarylium compound is used.
- Ropiroru compounds are particularly preferred.
- Examples of the pyrrolopyrrole compound include compounds described in paragraph Nos. 0016 to 0058 of JP-A-2009-263614, compounds described in paragraph Nos. 0037 to 0052 of JP-A-2011-068731, and those disclosed in International Publication WO2015 / 166873. Examples include the compounds described in paragraphs 0010 to 0033, the contents of which are incorporated herein.
- Examples of the squarylium compound include compounds described in paragraph Nos. 0044 to 0049 of JP2011-208101A, compounds described in paragraph Nos. 0060 to 0061 of JP6065169A, paragraph No. 0040 of International Publication WO2016 / 181987.
- Compounds described in WO2013 / 133099, compounds described in WO2014 / 088063, compounds described in JP2014-126642, and described in JP2016-146619A A compound described in JP-A-2015-176046, a compound described in JP-A-2017-025311, a compound described in International Publication WO2016 / 154882, a compound described in Japanese Patent No. 5884953, and a patent 60366 A compound according to 9 JP, compounds described in Japanese Patent No. 5810604, can be mentioned compounds described in JP-A-2017-068120, the contents of which are incorporated herein.
- Examples of the cyanine compound include compounds described in paragraph Nos. 0044 to 0045 of JP-A-2009-108267, compounds described in paragraph Nos. 0026 to 0030 of JP-A No. 2002-194040, and JP-A-2015-172004.
- the compounds described in JP-A-2015-172102, the compounds described in JP-A-2008-088426, the compounds described in JP-A-2017-031394, and the like are described in the present specification. Incorporated into.
- Examples of the diimonium compound include compounds described in JP-T-2008-528706, and the contents thereof are incorporated in the present specification.
- Examples of the phthalocyanine compound include a compound described in paragraph No. 0093 of JP2012-077153, an oxytitanium phthalocyanine described in JP2006-343631A, and paragraph numbers 0013 to 0029 of JP2013-195480A. And the contents of which are incorporated herein.
- the naphthalocyanine compound for example, the compound described in paragraph No. 0093 of JP2012-075153 can be mentioned, and the contents thereof are incorporated in the present specification.
- a tungsten compound or a metal boron compound can also be used as the infrared absorbing color material.
- the tungsten compound include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following formula (composition formula) (I) is preferable.
- M x W y O z (I)
- M represents a metal
- W represents tungsten
- O oxygen
- alkali metal alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al , Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like, preferably an alkali metal, and preferably Rb or Cs. More preferably, it is Cs.
- the metal represented by M may be one type or two or more types.
- tungsten oxide compound represented by the above formula (I) examples include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3 and the like. Cs 0.33 WO 3 or Rb 0.33 WO 3 is preferable, and Cs 0.33 WO 3 is more preferable.
- Tungsten compounds are available as commercial products.
- the tungsten oxide compound is, for example, a tungsten oxide compound
- the tungsten oxide compound can be obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere (see Japanese Patent No. 4096205).
- the tungsten oxide compound is available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.
- the metal boride is available as a commercial product, for example, as a dispersion of fine metal boride particles such as KHF-7 manufactured by Sum
- the content of the coloring material in the total solid content of the photosensitive composition is preferably 40% by mass or more, more preferably 50% by mass or more, and a film with further reduced crosstalk is easily obtained. For the reason, the content is more preferably 55% by mass or more, and particularly preferably 60% by mass or more.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and still more preferably 70% by mass or less from the viewpoint of film formability.
- the value of the content of the coloring material is preferably a value that does not include the content of the pigment derivative.
- the color material used in the photosensitive composition of the present invention preferably contains at least one selected from a chromatic colorant and a black colorant. Further, the content of the chromatic colorant and the black colorant in the total mass of the colorant is preferably 30% by mass or more, more preferably 50% by mass or more, and 70% by mass or more. Is more preferable. The upper limit can be 100% by mass, or 90% by mass or less.
- the pigment content in the total mass of the color material is preferably 50% by mass or more, more preferably 70% by mass or more, and 90% by mass. It is still more preferable that it is above.
- the content of the chromatic colorant in the total solid content of the photosensitive composition is preferably 40% by mass or more, and 50 More preferably, it is more preferably at least 55% by mass, even more preferably at least 55% by mass, and particularly preferably at least 60% by mass. Further, the content of the chromatic colorant in the total mass of the coloring material is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 65% by mass or more. The upper limit may be 100% by mass, and may be 95% by mass or less.
- the value of the content of the chromatic colorant is preferably a value not including the content of the pigment derivative.
- a black colorant preferably an inorganic black colorant, more preferably an inorganic black pigment
- the content of is preferably 40% by mass or more, more preferably 50% by mass or more, still more preferably 55% by mass or more, and particularly preferably 60% by mass or more.
- the content of the black colorant in the total mass of the coloring material is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.
- the upper limit may be 100% by mass, and may be 95% by mass or less.
- the color material used in the present invention satisfies at least one of the following requirements (1) to (3): preferable.
- Black is formed by a combination of two or more chromatic colorants including two or more chromatic colorants. It is preferable that black is formed by a combination of two or more colorants selected from a red colorant, a blue colorant, a yellow colorant, a purple colorant and a green colorant.
- Examples of the preferred combination of the above aspect (1) include the following.
- (1-1) An embodiment containing a red colorant and a blue colorant.
- (1-2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant.
- (1-3) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant.
- (1-4) An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant.
- (1-5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant.
- (1-6) An embodiment containing a red colorant, a blue colorant, and a green colorant.
- (1-7) An embodiment containing a yellow colorant and a purple colorant.
- a chromatic colorant By using the organic black colorant and the chromatic colorant in combination, excellent spectral characteristics can be easily obtained.
- the chromatic colorant used in combination with the organic black colorant include a red colorant, a blue colorant, and a purple colorant, and a red colorant and a blue colorant are preferable. These may be used alone or in combination of two or more.
- the mixing ratio of the chromatic colorant and the organic black colorant is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass with respect to 100 parts by mass of the organic black colorant.
- the content of the infrared absorbing color material in the total mass of the color material is preferably 5 to 40% by mass.
- the upper limit is preferably 30% by mass or less, and more preferably 25% by mass or less.
- the lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.
- the photosensitive composition of the present invention contains a resin.
- the resin is blended, for example, for the purpose of dispersing a pigment or the like in the composition or the purpose of a binder.
- a resin used mainly for dispersing pigments is also called a dispersant.
- such use of the resin is an example, and the resin can be used for purposes other than such use.
- the resin contains a resin whose solubility in an organic solvent is lowered by the action of an acid (hereinafter also referred to as resin (A)).
- resin (A) a resin whose solubility in an organic solvent is lowered by the action of an acid
- the resin (A) is preferably a resin having a group that is decomposed by the action of an acid to generate a polar group (hereinafter also referred to as “acid-decomposable group”). Moreover, it is preferable that resin (A) has a repeating unit which has an acid-decomposable group. Resin (A) can be used as a binder or a dispersing agent.
- known resins can be used as appropriate.
- resins disclosed in 0090 can be suitably used as the resin (A).
- the acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that decomposes and leaves by the action of an acid.
- Examples of polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfo groups, sulfonamido groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, (alkylsulfonyl) (alkylcarbonyl) imide groups, Such as bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) methylene group Examples include acidic groups (groups that dissociate in 2.38 mass% tetramethylammonium hydroxide aqueous solution), alcoholic hydroxyl groups, and the like.
- the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and means a hydroxyl group other than a hydroxyl group directly bonded on an aromatic ring (phenolic hydroxyl group).
- An aliphatic alcohol group substituted with a sex group (for example, a hexafluoroisopropanol group) is excluded.
- the alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
- Preferred polar groups include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfo group.
- Examples of the acid-decomposable group include groups in which the hydrogen atom of these groups is substituted with a group capable of decomposing and leaving by the action of an acid (leaving group).
- the leaving group is preferably a group represented by any one of formulas (Y1) to (Y4).
- the formula (Y1) is preferable because the leaving group is easily removed from the film at the lowest possible temperature by the heat treatment (baking) after exposure.
- Formula (Y1) —C (R 31 ) (R 32 ) (R 33 )
- Formula (Y2) —C ( ⁇ O) OC (R 31 ) (R 32 ) (R 33 )
- Formula (Y3) —C (R 36 ) (R 37 ) (OR 38 )
- R 31 to R 33 each independently represents an alkyl group.
- the alkyl group may be linear, branched or cyclic.
- the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- R 31 to R 33 are alkyl groups (straight or branched)
- at least two of R 31 to R 33 are preferably methyl groups.
- R 31 to R 33 each independently preferably represents a linear or branched alkyl group, and more preferably represents a linear alkyl group.
- two of R 31 to R 33 may be bonded to form a ring.
- Examples of the alkyl group represented by R 31 to R 33 include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl, cyclohexyl, norbornyl, tetracyclo A decanyl group, a tetracyclododecanyl group, and an adamantyl group are preferred.
- the ring formed by combining two of R 31 to R 33 includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group.
- a polycyclic cycloalkyl group such as an adamantyl group is preferred, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred.
- one of the methylene groups constituting the ring may be replaced with a group having a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group.
- R 31 is a methyl group or an ethyl group, and R 32 and R 33 are bonded to form the above-described cycloalkyl group. preferable.
- R 36 and R 37 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 36 and R 37 is an alkyl group or an aryl group, and R 38 is an alkyl group Represents a group or an aryl group, and R 36 or R 37 and R 38 may combine to form a ring.
- the alkyl group may be linear, branched or cyclic.
- the alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.
- One of R 36 and R 37 is preferably a hydrogen atom. Examples of the ring formed by combining R 36 or R 37 and R 38 include a tetrahydrofuranyl group and a tetrahydropyranyl group.
- Ar represents an aromatic ring group
- Rn represents an alkyl group or an aryl group.
- Rn and Ar may be bonded to each other to form a ring.
- the aromatic ring group represented by Ar is preferably an aryl group.
- the formula amount of the leaving group is preferably 170 or less, more preferably 150 or less, and even more preferably 110 or less.
- the lower limit is preferably 50 or more. If the leaving group has a formula weight of 170 or less, the leaving group is decomposed from the resin (A) by heat treatment after development even if the leaving group remains in the exposed resin (A). Easy to remove. For this reason, it is easy to form a thinner film.
- a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is preferable, and an acetal group or a tertiary alkyl ester group is more preferable.
- Resin (A) preferably has a repeating unit represented by the following formula (A1a) or (A1b) as a repeating unit having an acid-decomposable group.
- Xa 1 represents a hydrogen atom or an alkyl group.
- T represents a single bond or a divalent linking group.
- Y represents an acid-decomposable group.
- the number of carbon atoms of the alkyl group represented by Xa 1 is preferably 1 to 3.
- Xa 1 is preferably a hydrogen atom or a methyl group.
- Examples of the divalent linking group represented by T include an alkylene group, —COO—Rt— group, —O—Rt— group and the like.
- Rt represents an alkylene group having 1 to 5 carbon atoms.
- T is preferably a single bond or a —COO—Rt— group, and more preferably a single bond.
- Y is preferably any one of groups represented by formulas (Y1) to (Y4), and more preferably a group represented by formula (Y1).
- the acid-decomposable group represented by Y is preferably any one of groups represented by formulas (Y1) to (Y4).
- Resin (A) may have only one type of repeating unit having an acid-decomposable group or two or more types.
- the resin (A) preferably has a repeating unit represented by the following formula (A1a-1) or (A1b-1) as a repeating unit having an acid-decomposable group.
- Xa 1 represents a hydrogen atom or an alkyl group.
- T represents a single bond or a divalent linking group.
- Rx 1 to Rx 3 each independently represents an alkyl group. Any two of Rx 1 to Rx 3 may be bonded to form a ring structure.
- the number of carbon atoms of the alkyl group represented by Xa 1 is preferably 1 to 3.
- Xa 1 is preferably a hydrogen atom or a methyl group.
- Examples of the divalent linking group represented by T include an alkylene group, —COO—Rt— group, —O—Rt— group and the like.
- Rt represents an alkylene group having 1 to 5 carbon atoms.
- T is preferably a single bond or a —COO—Rt— group, and more preferably a single bond.
- the alkyl group for Rx 1 , Rx 2 and Rx 3 may be linear, branched or cyclic.
- the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 1 to 3 carbon atoms.
- a part of the carbon-carbon bond may be a double bond.
- the cyclic alkyl group includes a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Groups are preferred.
- the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 includes a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a norbornane ring, tetracyclo
- a polycyclic cycloalkyl ring such as a decane ring, a tetracyclododecane ring and an adamantane ring is preferred.
- a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable.
- the ring structure formed by combining two of Rx 1 , Rx 2 and Rx 3 the structures shown below are also preferable.
- the resin (A) preferably has a repeating unit described in paragraphs 0336 to 0369 of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group.
- Resin (A) is decomposed by the action of an acid described in paragraphs 0363 to 0364 of US Patent Application Publication No. 2016 / 0070167A1 as a repeating unit having an acid-decomposable group to produce an alcoholic hydroxyl group. You may have a repeating unit containing group.
- Resin (A) may contain one type of repeating unit having an acid-decomposable group, or two or more types in combination.
- the content of the repeating unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of repeating units having an acid-decomposable group, the total) is based on the total repeating units of the resin (A), 10 to 90 mol% is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is still more preferable.
- Resin (A) preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.
- Any lactone structure or sultone structure can be used as long as it has a lactone structure or sultone structure, but a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable.
- Preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), (LC1-16), (LC1-21) and (SL1-1).
- the lactone structure portion or the sultone structure portion may or may not have a substituent (Rb 2 ).
- Preferred substituents (Rb 2 ) include an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and Examples include acid-decomposable groups. More preferred are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group.
- n 2 represents an integer of 0 to 4. When n 2 is 2 or more, the plurality of substituents (Rb 2 ) may be the same or different. A plurality of substituents (Rb 2 ) may be bonded to form a ring.
- the repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following formula (LC).
- A represents an ester bond (group represented by —COO—) or an amide bond (group represented by —CONH—).
- n is the number of repetitions of the structure represented by —R 0 —Z—, and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, —R 0 —Z— does not exist and becomes a single bond.
- R 0 represents an alkylene group, a cycloalkylene group, or a combination thereof.
- R 0 independently represents an alkylene group, a cycloalkylene group, or a combination thereof when there are a plurality of R 0 .
- Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
- each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
- R 8 represents a monovalent organic group having a lactone structure or a sultone structure.
- R 7 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
- the alkylene group or cycloalkylene group of R 0 may have a substituent.
- Z is preferably an ether bond or an ester bond, and more preferably an ester bond.
- repeating unit having a lactone structure or a sultone structure include the repeating units described in paragraph numbers 0088 to 0091 of JP-A-2017-126044.
- Resin (A) may have a repeating unit having a carbonate structure.
- the carbonate structure is preferably a cyclic carbonate structure.
- the repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following formula (A-1).
- R A 1 represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
- n represents an integer of 0 or more.
- R A 2 represents a substituent.
- R A 2 each independently represents a substituent when n is 2 or more.
- A represents a single bond or a divalent linking group.
- Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with a group represented by —O—C ( ⁇ O) —O— in the formula.
- repeating unit having a carbonate structure examples include the repeating units described in paragraph numbers 0107 to 0108 of JP-A-2017-126044.
- the resin (A) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, described in paragraphs 0370 to 0414 of US Patent Application Publication No. 2016 / 0070167A1. It is also preferable to have a repeating unit.
- Resin (A) may contain one or more repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more kinds in combination.
- the content of a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in the resin (A) (selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure)
- the total (when there are a plurality of repeating units having at least one kind) is preferably 5 to 70 mol%, and preferably 10 to 65 mol%, based on all the repeating units of the resin (A). More preferred is 20 to 60 mol%.
- Resin (A) can also have a repeating unit having a polar group.
- the polar group include the groups described above, and a hydroxyl group, a cyano group, a carboxyl group, a fluorinated alcohol group, and the like are preferable.
- the repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Moreover, it is preferable that the repeating unit which has a polar group does not have an acid-decomposable group.
- the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornane group. Specific examples of the repeating unit having a polar group include the repeating units disclosed in paragraph numbers 0415 to 0433 of US Patent Application Publication No. 2016 / 0070167A1.
- Resin (A) may contain a repeating unit having a polar group alone or in combination of two or more.
- the content of the repeating unit having a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).
- the resin (A) can have a repeating unit having a crosslinkable group.
- the resin (A) contains a repeating unit having a crosslinkable group, a film having a high crosslink density can be formed, and a film excellent in various properties such as heat resistance, solvent resistance, and strength can be easily formed.
- the crosslinkable group include an epoxy group, a methylol group, an alkoxymethylol group, and an acyloxymethyl group.
- An epoxy group, an oxetanyl group, a methylol group, and an alkoxymethylol group are preferable, an epoxy group, an oxetanyl group are more preferable, and an epoxy group is preferable. Further preferred.
- Resin (A) may contain the repeating unit which has a polar group individually by 1 type, and may contain 2 or more types together.
- the content of the repeating unit having a polar group is preferably from 5 to 40 mol%, more preferably from 5 to 30 mol%, still more preferably from 10 to 25 mol%, based on all repeating units in the resin (A).
- Resin (A) can further have a repeating unit having no acid-decomposable group, polar group or crosslinkable group.
- the repeating unit having neither an acid-decomposable group, a polar group nor a crosslinkable group is preferably a repeating unit having an alicyclic hydrocarbon structure.
- Specific examples of the repeating unit having neither an acid-decomposable group, a polar group nor a crosslinkable group include paragraph numbers 0236 to 0237 of US Patent Application Publication No. 2016 / 0026083A1, and US Patent Application Publication No. 2016 / 0070167A1. Examples thereof include the repeating units disclosed in paragraph No. 0433 of the specification and paragraph Nos. 0135 to 0137 of JP-A No. 2017-126044.
- Resin (A) may contain one type of repeating unit having no acid-decomposable group, polar group or crosslinkable group, or may contain two or more types in combination.
- the content of the repeating unit having no acid-decomposable group, polar group or crosslinkable group is preferably 5 to 40 mol%, preferably 5 to 30 mol%, based on all repeating units in the resin (A). Is more preferably 5 to 25 mol%.
- all of the repeating units are composed of (meth) acrylate-based repeating units.
- all of the repeating units are methacrylate repeating units
- all of the repeating units are acrylate repeating units
- all of the repeating units include both methacrylate repeating units and acrylate repeating units.
- an acrylate type repeating unit is 50 mol% or less with respect to all the repeating units of resin (A).
- the weight average molecular weight of the resin (A) is preferably 3000 to 200000.
- the lower limit is preferably 6000 or more, more preferably 8000 or more, and still more preferably 10,000 or more.
- the upper limit is preferably 50000 or less, more preferably 25000 or less, and even more preferably 15000 or less.
- the dispersity (Mw / Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, still more preferably 1.0 to 2.0, and particularly preferably 1.1 to 2.0. preferable.
- the photosensitive composition of this invention can contain resin (henceforth resin (B)) other than resin (A) mentioned above as resin.
- a norbornene resin can be preferably used from the viewpoint of improving heat resistance. Examples of commercially available norbornene resins include the ARTON series (for example, ARTON F4520) manufactured by JSR Corporation.
- the resin as described in the Example of international publication WO2016 / 088645 can also be used for resin.
- a resin having an acid group can also be used as the resin (B).
- the acid group include a carboxyl group, a phosphate group, a sulfo group, and a phenolic hydroxyl group, and a carboxyl group is preferable.
- description in paragraph Nos. 0558 to 0571 of JP2012-208494A paragraph No. 0685 to 0700 in the corresponding US Patent Application Publication No. 2012/0235099
- JP2012-198408 The description of paragraph numbers 0076 to 0099 of the publication can be referred to, and the contents thereof are incorporated in the present specification.
- the resin which has an acid group can also use a commercial item.
- acrylic base FF-426 manufactured by Fujikura Kasei Co., Ltd.
- the acid value of the resin having an acid group is preferably 30 to 200 mgKOH / g.
- the lower limit is preferably 50 mgKOH / g or more, and more preferably 70 mgKOH / g or more.
- the upper limit is preferably 150 mgKOH / g or less, and more preferably 120 mgKOH / g or less.
- Resin (B) may have a polymerizable group.
- the polymerizable group include an allyl group, a methallyl group, and a (meth) acryloyl group.
- Commercially available resins having a polymerizable group include: Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscote R-264, KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA230AA), Plaxel CF200 series (all manufactured by Daicel Corporation), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), Acryl And RD-F8 (manufactured by Nippon Shokubai Co., Ltd.).
- the resin (B) is a monomer component containing a compound represented by the following formula (ED1) and / or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”).
- ED1 a compound represented by the following formula
- ED2 a compound represented by the following formula
- a polymer containing a repeating unit derived from is also preferred.
- R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
- R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
- the description in JP 2010-168539 A can be referred to.
- ether dimer for example, paragraph number 0317 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification. Only one type of ether dimer may be used, or two or more types may be used.
- the resin (B) may contain a repeating unit derived from a compound represented by the following formula (X).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkylene group having 2 to 10 carbon atoms
- R 3 has 1 to 20 carbon atoms which may contain a hydrogen atom or a benzene ring.
- n represents an integer of 1 to 15.
- the photosensitive composition of the present invention can also contain a resin as a dispersant.
- the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the acidic dispersant (acidic resin) represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acidic dispersant (acidic resin) is preferably a resin in which the amount of acid groups occupies 70 mol% or more when the total amount of acid groups and basic groups is 100 mol%. A resin consisting only of groups is more preferred.
- the acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant is preferably 40 to 105 mgKOH / g, more preferably 50 to 105 mgKOH / g, and still more preferably 60 to 105 mgKOH / g.
- the basic dispersant (basic resin) represents a resin in which the amount of basic groups is larger than the amount of acid groups.
- the basic dispersant (basic resin) is preferably a resin in which the amount of basic groups exceeds 50 mol% when the total amount of acid groups and 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 also preferably a graft copolymer. Since the graft copolymer has an affinity for the solvent by the graft chain, it is excellent in pigment dispersibility and dispersion stability after aging. Specific examples of the graft copolymer include resins having the following structure. The details of the graft copolymer can be referred to the descriptions in paragraphs 0025 to 0094 of JP2012-255128A, the contents of which are incorporated herein. Examples of the graft copolymer include resins described in JP-A-2012-255128, paragraphs 0072 to 0094, the contents of which are incorporated herein.
- the resin used as the dispersant is preferably an oligoimine copolymer containing a nitrogen atom in at least one of the main chain and the side chain.
- the dispersant is also available as a commercial product, and specific examples thereof include Disperbyk-111 (manufactured by BYK Chemie), Solsperse 76500 (manufactured by Nippon Lubrizol Co., Ltd.), and the like.
- pigment dispersants described in paragraph numbers 0041 to 0130 of JP-A-2014-130338 can also be used, the contents of which are incorporated herein.
- the resin content in the total solid content of the photosensitive composition is preferably 10 to 60% by mass.
- the upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.
- the lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more.
- the content of the resin (resin (A)) whose solubility in an organic solvent is reduced by the action of an acid in the total amount of resins contained in the photosensitive composition is preferably 40% by mass or more, and 50% by mass. More preferably, it is more preferably 60% by mass or more, still more preferably 70% by mass or more, particularly preferably 80% by mass or more, and preferably 90% by mass or more. Most preferred.
- the upper limit can be 100% by mass.
- the content of the resin (A) in the total solid content of the photosensitive composition is preferably 10 to 60% by mass.
- the upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.
- the lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more.
- the total content of the resin and the coloring material in the total solid content of the photosensitive composition is preferably 50 to 99% by mass.
- the upper limit is preferably 95% by mass or less, and more preferably 90% by mass or less.
- the lower limit is preferably 60% by mass or more, and more preferably 70% by mass or more.
- the photosensitive composition of the present invention contains a photoacid generator.
- the photoacid generator is a compound that generates an acid when irradiated with actinic rays or radiation.
- the photoacid generator used in the present invention is preferably a compound that generates an acid having a pKa of 4 or less when irradiated with actinic rays or radiation, and a compound that generates an acid having a pKa of 3 or less. More preferably, the compound generates an acid of 2 or less, and further preferably a compound that generates an acid of ⁇ 1 or less.
- pKa basically refers to pKa in water at 25 ° C.
- the acid having a pKa of 4 or less is preferably sulfonic acid or phosphonic acid, and more preferably sulfonic acid.
- Examples of the photoacid generator include onium salt compounds, trichloromethyl-s-triazines, sulfonium salts, iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds.
- onium salt compounds, imide sulfonate compounds, and oxime sulfonate compounds are preferable
- onium salt compounds and oxime sulfonate compounds are more preferable
- oxime sulfonate compounds are particularly preferable.
- JP-A-2016-206503, paragraphs 0048 to 0055 and JP-A-2017-126044, paragraphs 0210 to 0320 can be referred to, and the contents thereof are incorporated in the present specification.
- the compound represented by a following formula (ZI), (ZII), and (ZIII) is mentioned, for example.
- R 201 , R 202 and R 203 each independently represents an organic group.
- the organic group represented by R 201 , R 202 and R 203 preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms.
- Examples of the organic group represented by R 201 , R 202 and R 203 include an aryl group and an alkyl group.
- the aryl group of R 201 , R 202 and R 203 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like.
- Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
- the alkyl group for R 201 , R 202 and R 203 may be linear, branched or cyclic.
- the organic group of R 201 , R 202 and R 203 is an aryl group having 6 to 14 carbon atoms, a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cyclic group having 3 to 15 carbon atoms.
- An alkyl group is preferred.
- the aryl group and alkyl group described above may further have a substituent.
- substituents examples include a nitro group, a halogen atom such as a fluorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably an alkoxy group having 1 to 15 carbon atoms), an alkoxycarbonyl group (preferably a carbon number of 2 To 7 alkoxycarbonyl groups), acyl groups (preferably acyl groups having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably alkoxycarbonyloxy groups having 2 to 7 carbon atoms), thioalkyl groups, thioaryl groups and the like. However, it is not limited to these.
- two members out of R 201 to R 203 may combine to form a ring structure, and the formed ring structure includes an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group in the ring. It may contain a group.
- Examples of the group formed by combining two members out of R 201 to R 203 include an alkylene group (eg, butylene group, pentylene group).
- the description of paragraph numbers 0214 to 0267 in JP-A-2017-126044 can be referred to, and the contents thereof are incorporated herein.
- R 204 to R 207 each independently represents an aryl group or an alkyl group.
- the aryl group for R 204 to R 207 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
- the aryl group represented by R 204 to R 207 may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
- the alkyl group represented by R 204 to R 207 is preferably a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, and Pentyl group) and cyclic alkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).
- the aryl group and alkyl group of R 204 to R 207 may each independently have a substituent.
- substituents that the aryl group and alkyl group of R 204 to R 207 may have include an alkyl group, an aryl group, an alkoxy group, a halogen atom, a hydroxyl group, and a phenylthio group.
- Z ⁇ represents an anion.
- Z in and formula (ZII) - - Z in formula (ZI) is preferably a non-nucleophilic anion is (ability of causing a nucleophilic reaction is extremely low anion).
- Non-nucleophilic anions include, for example, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphor sulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyls). Carboxylate anion, etc.), sulfonylimide anion, bis (alkylsulfonyl) imide anion, tris (alkylsulfonyl) methide anion and the like.
- the aliphatic moiety in the aliphatic sulfonate anion and aliphatic carboxylate anion is preferably an alkyl group.
- the alkyl group may be linear, branched or cyclic.
- the alkyl group preferably has 1 to 30 carbon atoms.
- the aromatic group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms. Specific examples include a phenyl group, a tolyl group, and a naphthyl group.
- the alkyl group and aryl group mentioned above may have a substituent.
- substituents include nitro groups, halogen atoms such as fluorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), aryl groups (preferably having 6 to 6 carbon atoms).
- an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group (preferably 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), an alkylthio group (preferably 1 carbon atom)
- alkylsulfonyl group (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), aryloxysulfonyl group (preferably having 6 to 20 carbon atoms), alkylaryloxysulfonyl group (Preferably having 7 to 20 carbon atoms), alkyloxyalkyloxy groups (preferably having 5 to 20 carbon atoms), etc. It is below.
- examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).
- Examples of the sulfonylimide anion include saccharin anion.
- the alkyl group in the bis (alkylsulfonyl) imide anion and tris (alkylsulfonyl) methide anion is preferably an alkyl group having 1 to 5 carbon atoms.
- the alkyl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group substituted with a halogen atom, an alkoxy group, an alkylthio group, an alkyloxysulfonyl group, an aryloxysulfonyl group, a cycloalkylaryloxysulfonyl group, and the like, substituted with a fluorine atom or a fluorine atom
- the alkyl group formed is preferred.
- the alkyl groups in the bis (alkylsulfonyl) imide anion may be bonded to each other to form a ring structure.
- non-nucleophilic anions examples include fluorinated phosphorus (eg, PF 6 ⁇ ), fluorinated boron (eg, BF 4 ⁇ ), and fluorinated antimony (eg, SbF 6 ⁇ ).
- non-nucleophilic anion examples include an aliphatic sulfonate anion in which at least ⁇ -position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, and an alkyl group having a fluorine atom And a tris (alkylsulfonyl) methide anion in which the alkyl group is substituted with a fluorine atom.
- the non-nucleophilic anion is more preferably a perfluoroaliphatic sulfonic acid anion (preferably having 4 to 8 carbon atoms), a benzenesulfonic acid anion having a fluorine atom, more preferably a nonafluorobutanesulfonic acid anion, or perfluorooctanesulfonic acid.
- the description of paragraph numbers 0269 to 0310 in JP-A-2017-126044 can be referred to, and the contents thereof are incorporated herein.
- photoacid generator Any of the above cations and anions can be used in combination as a photoacid generator.
- Specific examples of the photoacid generator include the compounds described in paragraph numbers 0315 to 0320 of JP-A-2017-126044.
- an oxime sulfonate compound as a photoacid generator.
- Preferred examples of the oxime sulfonate compound include compounds having an oxime sulfonate structure represented by the following formula (OS-1).
- R 21 represents an alkyl group or an aryl group.
- the wavy line represents a bond with another group or atom constituting the oxime sulfonate compound.
- the alkyl group and aryl group represented by R 21 in the formula (OS-1) may have a substituent or may be unsubstituted.
- R 21 is an alkyl group
- R 21 is preferably a linear or branched alkyl group having 1 to 10 carbon atoms.
- the alkyl group of R 21 is a halogen atom, an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a cyclic alkyl group (such as a 7,7-dimethyl-2-oxonorbornyl group). It may be substituted with a bridged alicyclic group, preferably a bicycloalkyl group or the like.
- R 21 is preferably an aryl group having 6 to 11 carbon atoms, more preferably a phenyl group or a naphthyl group.
- the aryl group of R 21 may be substituted with an alkyl group, an alkoxy group, or a halogen atom.
- OS-1 for details of the compound containing an oxime sulfonate structure represented by the formula (OS-1), reference can be made to paragraph numbers 0066 to 0098 of International Publication No. WO2016 / 175220, the contents of which are incorporated herein.
- the photoacid generator used in the present invention may be in the form of a low molecular compound or may be incorporated in a part of the polymer. Further, the form of the low molecular compound and the form incorporated in a part of the polymer may coexist.
- the photoacid generator is preferably in the form of a low molecular compound.
- the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.
- the content of the photoacid generator in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass.
- the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, and still more preferably 2% by mass or more.
- the upper limit is preferably 15% by mass or less, more preferably 10% by mass or less, still more preferably 8% by mass or less, and particularly preferably 5% by mass or less.
- the content of the photoacid generator is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin (A) described above.
- the lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more.
- the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.
- content of a photo-acid generator is 0.00 with respect to a total of 100 mass parts of resin (A) mentioned above and an acid crosslinking agent. 1 to 50 parts by mass is preferred.
- the lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more.
- the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.
- a photo-acid generator may be used individually by 1 type, and may use 2 or more types together. When using 2 or more types together, it is preferable that those total amount is the said range.
- the photosensitive composition can contain an acid diffusion controller.
- the acid diffusion controller acts as a quencher that traps the acid generated from the photoacid generator or the like at the time of exposure and suppresses the reaction of the resin (A) in the unexposed area due to excess generated acid.
- Examples of the acid diffusion controller include a basic compound, a low-molecular compound having a nitrogen atom and a group capable of leaving by the action of an acid, a basic compound whose basicity decreases or disappears upon irradiation with actinic rays or radiation, or An onium salt that is a weak acid relative to the photoacid generator can be used.
- Preferred examples of the basic compound include compounds having structures represented by the following formulas (A) to (E).
- R 200 , R 201 and R 202 may be the same or different and each represents a hydrogen atom, an alkyl group or an aryl group, wherein R 201 and R 202 are bonded to each other. To form a ring.
- R 203 , R 204 , R 205 and R 206 may be the same or different and each represents an alkyl group having 1 to 20 carbon atoms.
- the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
- the alkyl groups in the general formulas (A) and (E) are more preferably unsubstituted.
- the basic compound examples include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine and the like.
- the basic compound examples include an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, Examples thereof include aniline derivatives having a hydroxyl group and / or an ether bond.
- an amine compound having a phenoxy group an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group can be preferably used.
- an amine compound having a phenoxy group an ammonium salt compound having a phenoxy group, an amine compound having a sulfonic acid ester group, and an ammonium salt compound having a sulfonic acid ester group can be preferably used.
- paragraph numbers 0307 to 0311 of International Publication No. WO2016 / 104565 the contents of which are incorporated herein.
- the content of the basic compound is preferably 0.001 to 10% by mass with respect to the total solid content of the photosensitive composition, 0.01 to 5 More preferably, it is mass%.
- the above-mentioned molar ratio is preferably 2.5 or more from the viewpoint of sensitivity and resolution, and is preferably 300 or less from the viewpoint of suppressing the reduction in resolution due to the thickening of the resist pattern over time until the heat treatment after exposure.
- the aforementioned molar ratio is more preferably from 5.0 to 200, still more preferably from 7.0 to 150.
- a low molecular weight compound having a nitrogen atom and a group capable of leaving by the action of an acid is an amine having a group on the nitrogen atom that is released by the action of an acid.
- a derivative is preferred.
- the group capable of leaving by the action of an acid an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, and a hemiaminal ether group are preferable, and a carbamate group and a hemiaminal ether group are particularly preferable.
- the molecular weight of the compound (D-1) is preferably 100 to 1,000, more preferably 100 to 700, and particularly preferably 100 to 500.
- Compound (D-1) may have a carbamate group having a protecting group on the nitrogen atom.
- the protecting group constituting the carbamate group can be represented by the following formula (d-1).
- each Rb independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, or an alkoxyalkyl group. Rb may be connected to each other to form a ring.
- the alkyl group, aryl group and aralkyl group represented by Rb may be substituted with a functional group such as a hydroxy group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group or an oxo group, an alkoxy group or a halogen atom. .
- Rb is preferably an alkyl group or an aryl group. More preferably, it is an alkyl group.
- Examples of the ring formed by connecting two Rb to each other include an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.
- a specific structure of the group represented by the formula (d-1) a structure disclosed in paragraph No. 0466 of US Patent Application Publication No. 2012 / 0135348A1 can be given, and the contents thereof are described in the present specification. Incorporated into.
- the compound (D-1) is preferably a compound having a structure represented by the following formula (6).
- Ra represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
- two Ras may be the same or different, and two Ras may be connected to each other to form a heterocyclic ring together with the nitrogen atom in the formula.
- the heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
- Rb has the same meaning as Rb in formula (d-1), and the preferred examples are also the same.
- l represents an integer of 0 to 2
- the alkyl group, aryl group, and aralkyl group as Ra are substituted with the same groups as those described above as the group that the alkyl group, aryl group, and aralkyl group as Rb may be substituted. May be.
- the compound represented by the formula (6) can be synthesized based on JP2007-298569A, JP2009-199021A, and the like.
- the basic compound whose basicity is reduced or disappeared by irradiation with actinic rays or radiation (hereinafter also referred to as “compound (PA)”) has a proton acceptor functional group and has actinic rays or radiation. Examples thereof include compounds that decompose by irradiation to decrease, disappear, or change from proton acceptor properties to acidic properties.
- the proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron.
- a functional group having a macrocyclic structure such as a cyclic polyether or a ⁇ -conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute.
- the nitrogen atom having an unshared electron pair that does not contribute to ⁇ conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.
- Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.
- the compound (PA) is decomposed by irradiation with actinic rays or radiation to generate a compound in which the proton acceptor property decreases or disappears, or the proton acceptor property is changed to acidic.
- the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group.
- the description of paragraph numbers 0312 to 0320 in International Publication No. WO2016 / 104565 can be referred to, and the contents thereof are incorporated herein.
- an onium salt that is a weak acid relative to the photoacid generator can be used as an acid diffusion control agent.
- an actinic ray when an acid generated from the photoacid generator upon irradiation with a bombardment collides with an onium salt having an unreacted weak acid anion, an onium salt having a strong acid anion is generated by releasing the weak acid by salt exchange.
- the content of the acid diffusion control agent is preferably 0.1 to 10% by mass in the total solid content of the photosensitive composition.
- the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
- the upper limit is preferably 8% by mass or less, and more preferably 5% by mass or less.
- the photosensitive composition of the present invention preferably contains an acid crosslinking agent. According to this aspect, a film having a high crosslinking density can be formed, and a film excellent in various properties such as heat resistance, solvent resistance, and strength can be easily formed.
- the acid crosslinking agent refers to a crosslinking agent that is crosslinked by the action of an acid.
- the acid crosslinking agent is not particularly limited as long as it can cause a crosslinking reaction by the action of an acid to cure the film.
- Examples include compounds having at least one group selected from an epoxy group, a methylol group, an alkoxymethylol group, and an acyloxymethyl group, and compounds having at least one epoxy group are preferred.
- Examples of the compound having an epoxy group include a compound having one or more epoxy groups in one molecule, and a compound having two or more epoxy groups is preferable. It is preferable to have 1 to 100 epoxy groups in one molecule.
- the upper limit of the epoxy group can be, for example, 10 or less, or 5 or less.
- the lower limit of the epoxy group is preferably 2 or more.
- the compound having an epoxy group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even a molecular weight of less than 1000), or a macromolecule (for example, a molecular weight of 1000 or more, in the case of a polymer, the weight average molecular weight is 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 preferably 10,000 or less, more preferably 5000 or less, and still more preferably 3000 or less.
- R EP1 to R EP3 each represent a hydrogen atom, a halogen atom, or an alkyl group, and the alkyl group may have a cyclic structure, and may have a substituent. Also good. R EP1 and R EP2 , R EP2 and R EP3 may be bonded to each other to form a ring structure.
- QEP represents a single bond or an nEP- valent organic group.
- R EP1 ⁇ R EP3 combines with Q EP may form a ring structure.
- nEP represents an integer of 2 or more, preferably 2 to 10, and more preferably 2 to 6. However, nEP is 2 when QEP is a single bond.
- R EP1 to R EP3 and Q EP can be referred to the descriptions in paragraph numbers 0087 to 0088 of Japanese Patent Application Laid-Open No. 2014-089408, the contents of which are incorporated herein.
- Specific examples of the compound represented by the formula (EP1) include a compound described in paragraph 0090 of JP2014-089408A and a compound described in paragraph number 0151 of JP2010-054632A. The contents are incorporated herein.
- ADEKA GLYCIROL series for example, ADEKA GLYCIROL ED-505 manufactured by ADEKA Co., Ltd.
- Epolide series for example, EPOLID GT401, etc. manufactured by Daicel Corporation. It is done.
- An epoxy resin can be preferably used as the compound having an epoxy group.
- the epoxy resin include an epoxy resin that is a glycidyl etherified product of a phenol compound, an epoxy resin that is a glycidyl etherified product of various novolak resins, an alicyclic epoxy resin, an aliphatic epoxy resin, a heterocyclic epoxy resin, and a glycidyl ester type.
- the epoxy equivalent of the epoxy resin is preferably 310 to 3300 g / eq, more preferably 310 to 1700 g / eq, and still more preferably 310 to 1000 g / eq.
- Examples of commercially available epoxy resins include 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, G-01758 (above, manufactured by NOF Corporation, epoxy group-containing polymer) and the like.
- Examples of the compound having an epoxy group include paragraph numbers 0034 to 0036 of JP2013-011869A, paragraphs 0147 to 0156 of JP2014043556A, and paragraphs 0085 to 0092 of JP2014089408A.
- the described compounds and the compounds described in JP-A-2017-179172 can also be used. These contents are incorporated herein.
- Examples of the compound having a methylol group include a compound in which a methylol group is bonded to a nitrogen atom or a carbon atom forming an aromatic ring.
- Examples of the compound having an alkoxymethyl group include compounds in which an alkoxymethyl group is bonded to a carbon atom that forms a nitrogen atom or an aromatic ring.
- examples of the compound having an acyloxymethyl group include compounds in which the acyloxymethyl group is bonded to a nitrogen atom or a carbon atom that forms an aromatic ring.
- methylol compound alkoxymethyl compound and acyloxymethyl compound, melamine compound, guanamine compound, glycoluril compound, urea compound, phenol compound substituted with at least one group selected from methylol group, alkoxymethyl group and acyloxymethyl group Naphthol compounds and hydroxyanthracene compounds.
- the melamine compound substituted with the above group is preferably a melamine compound having 2 to 6 groups as described above, and preferably a melamine compound having 5 to 6 groups as described above.
- the glycoluril compound substituted with the aforementioned group preferably has 2 to 4 groups described above, and more preferably 3 to 4 groups described above.
- the guanamine compound substituted with the aforementioned group preferably has 2 to 4 of the aforementioned groups, and more preferably 3 to 4 of the aforementioned groups.
- the urea compound substituted with the aforementioned group preferably has 2 to 4 groups described above, and more preferably 3 to 4 groups described above.
- the phenol compound substituted with the above-mentioned group it is preferable that at least a part of the 2nd and 4th positions of the phenol compound serving as a skeleton is substituted with the above group, and that all are substituted with the above group. Is more preferable.
- the naphthol compound substituted with the above-mentioned group it is preferable that at least a part of the ortho-position and para-position of the OH group is substituted with the above-mentioned group, and that all are substituted with the above-mentioned group. preferable.
- hydroxyanthracene compound substituted with the above-mentioned group it is preferable that at least a part of the ortho-position and para-position of the OH group is substituted with the above-mentioned group, and that all are substituted with the above-mentioned group. More preferred.
- the content of the acid crosslinking agent is preferably 0.1 to 30% by mass in the total solid content of the photosensitive composition.
- the lower limit is preferably 0.5% by mass or more, and more preferably 1% 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 acid crosslinking agent is preferably 0.1 to 50 parts by mass with respect to 100 parts by mass of the resin (A) described above.
- the lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 2 parts by mass or more.
- the upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and still more preferably 20 parts by mass or less.
- the total content of the resin (A) and the acid crosslinking agent is preferably 10 to 60% by mass in the total solid content of the photosensitive composition.
- the lower limit is preferably 15% by mass or more, and more preferably 20% by mass or more.
- the upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less. Only one type of acid crosslinking agent may be included, or two or more types may be included. When two or more types are included, the total amount thereof is preferably within the above range.
- the photosensitive composition of the present invention may contain a radical polymerizable monomer.
- the radical polymerizable monomer is not particularly limited as long as it is a compound that can be polymerized by the action of radicals.
- the radical polymerizable monomer is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having two or more groups having an ethylenically unsaturated bond, More preferably, the compound has 3 or more groups having an unsaturated bond.
- the upper limit of the number of groups having an ethylenically unsaturated bond is preferably 15 or less, and more preferably 6 or less.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) acryloyl group is preferable.
- the radical polymerizable monomer is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
- the molecular weight of the radical polymerizable monomer is preferably 200 to 3000.
- the upper limit of the molecular weight is preferably 2000 or less, and more preferably 1500 or less.
- the lower limit of the molecular weight is preferably 250 or more, and more preferably 300 or more.
- the content of the radical polymerizable monomer in the total solid content of the photosensitive composition is preferably 5% by mass or less, more preferably 4% by mass or less, and more preferably 3% by mass. % Or less is more preferable, 2% by mass or less is even more preferable, and 1% by mass or less is particularly preferable. Moreover, it is preferable that the photosensitive composition of this invention does not contain a radically polymerizable monomer substantially. According to this aspect, even if exposure light reaches a portion that is desired to be unexposed due to light leakage or the like, it is difficult to crosslink, and an effect that rectangularity is further improved can be expected.
- the case where the photosensitive composition of the present invention does not substantially contain a radical polymerizable monomer means that the content of the radical polymerizable monomer is 0.5% by mass or less in the total solid content of the photosensitive composition. It is preferable that it is 0.1 mass% or less, it is more preferable that it is 0.01 mass% or less, and it is still more preferable not to contain a radically polymerizable monomer.
- the photosensitive composition of the present invention may contain a radical photopolymerization initiator.
- photo radical polymerization initiators include trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, Onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds, coumarin compounds, etc., including oxime compounds, ⁇ -hydroxy ketone compounds, ⁇ -amino ketone compounds, and An acylphosphine compound is preferable, and an oxime compound and an ⁇ -aminoketone compound are more preferable.
- the content of the photo radical polymerization initiator in the total solid content of the photosensitive composition is preferably 4% by mass or less, more preferably 2% by mass or less. More preferably, it is more preferably 0.5% by mass or less, and still more preferably 0.05% by mass or less. Moreover, it is preferable that the photosensitive composition of this invention does not contain radical photopolymerization initiator substantially. According to this aspect, even if exposure light reaches a portion that is desired to be unexposed due to light leakage or the like, it is difficult to crosslink, and an effect that rectangularity is further improved can be expected.
- the photosensitive composition of the present invention can contain a pigment derivative.
- the pigment derivative include compounds having a structure in which a part of the chromophore is substituted with an acid group, a basic group or a phthalimidomethyl group.
- the chromophores constituting the pigment derivatives include quinoline skeleton, benzimidazolone skeleton, diketopyrrolopyrrole skeleton, azo skeleton, phthalocyanine skeleton, anthraquinone skeleton, quinacridone skeleton, dioxazine skeleton, and perinone.
- Examples include skeleton, perylene skeleton, thioindigo skeleton, isoindoline skeleton, isoindolinone skeleton, quinophthalone skeleton, selenium skeleton, metal complex skeleton, quinoline skeleton, benzimidazolone skeleton, diketo A pyrrolopyrrole skeleton, an azo skeleton, a quinophthalone skeleton, an isoindoline skeleton, and a phthalocyanine skeleton are preferable, and an azo skeleton and a benzimidazolone skeleton are more preferable.
- a sulfo group and a carboxyl group are preferable, and a sulfo group is more preferable.
- a basic group which a pigment derivative has an amino group is preferable and a tertiary amino group is more preferable.
- the content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass with respect to 100 parts by mass of the pigment. Only one pigment derivative may be used, or two or more pigment derivatives may be used in combination.
- the photosensitive composition of the present invention preferably contains a solvent.
- the solvent is preferably an organic solvent.
- the organic solvent include acetone, methyl ethyl ketone, cyclohexane, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, acetylacetone, cyclohexanone, Cyclopentanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxyethanol, diethylene glycol monomethyl ether, die Lenglycol monoethyl ether, diethylene glycol dimethyl
- aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as a solvent may be better reduced for environmental reasons (for example, 50 ppm by weight per part of organic solvent). million) or less, 10 mass ppm or less, or 1 mass ppm or less).
- methyl 3-ethoxypropionate ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -Consists of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, and propylene glycol methyl ether acetate.
- a solvent having a low metal content it is preferable to use a solvent having a low metal content, and the metal content of the solvent is preferably, for example, 10 mass ppb (parts per billion) or less. If necessary, a solvent having a mass ppt (parts per trillation) level may be used, and such a high-purity solvent is provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).
- Examples of the method for removing impurities such as metals from the solvent include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
- the filter pore diameter of the filter used for filtration is preferably 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 solvent may contain isomers (compounds having the same number of atoms but different structures). Moreover, only 1 type may be included and the isomer may be included multiple types.
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
- the content of the solvent in the photosensitive composition is preferably 10 to 95% by mass.
- the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, and 60% by mass. The above is even more preferable.
- the upper limit is preferably 90% by mass or less, and more preferably 85% by mass or less.
- the photosensitive composition of the present invention does not substantially contain an environmentally regulated substance from the viewpoint of environmental regulations.
- “substantially containing no environmentally regulated substance” means that the content of the environmentally regulated substance in the photosensitive composition is 50 mass ppm or less, and is 30 mass ppm or less. Preferably, it is more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less.
- environmentally regulated substances include benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, and the like.
- VOC Volatile Organic Registered
- VOC Volatile Organic Substances
- the method is strictly regulated. These compounds may be used as a solvent when producing each component used in the photosensitive composition of the present invention, and may be mixed into the photosensitive composition as a residual solvent. It is preferable to reduce these substances as much as possible from the viewpoint of human safety and consideration for the environment.
- As a method for reducing the environmentally regulated substance there is a method of heating and depressurizing the system so as to make it equal to or higher than the boiling point of the environmentally regulated substance to distill off the environmentally regulated substance from the system.
- distilling off a small amount of environmentally regulated substances it is also useful to azeotrope with a solvent having a boiling point equivalent to that of the corresponding solvent in order to increase efficiency.
- a polymerization inhibitor or the like is added and the solvent is distilled off under reduced pressure in order to prevent the radical polymerization reaction from proceeding during the vacuum distillation and causing cross-linking between molecules. May be.
- These distillation methods can be performed either at the raw material stage, the product obtained by reacting the raw material (for example, a resin solution after polymerization or a polyfunctional monomer solution), or a composition stage prepared by mixing these compounds. It is also possible in stages.
- the photosensitive composition of the present invention can contain a surfactant.
- a surfactant various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicon-based surfactant can be used.
- paragraph numbers 0238 to 0245 of International Publication No. WO2015 / 166679 can be referred to, the contents of which are incorporated herein.
- the surfactant is preferably a fluorosurfactant.
- a fluorosurfactant in the photosensitive composition, liquid properties (particularly fluidity) can be further improved, and liquid-saving properties can be further improved.
- a film with small thickness unevenness can be formed.
- the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and even more preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within the above range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the photosensitive composition.
- fluorosurfactant examples include surfactants described in paragraph Nos. 0060 to 0064 of JP-A-2014-041318 (paragraph Nos. 0060 to 0064 of the corresponding International Publication No. 2014/017669), JP-A-2011-11 Examples include surfactants described in paragraph Nos. 0117 to 0132 of No. 132503, the contents of which are incorporated herein. Examples of commercially available fluorosurfactants include Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, EXP, MFS.
- the fluorine-based surfactant has a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which the fluorine atom is volatilized by cleavage of the functional group containing the fluorine atom when heat is applied can be suitably used.
- a fluorosurfactant include Megafac DS series manufactured by DIC Corporation (Chemical Industry Daily, February 22, 2016) (Nikkei Sangyo Shimbun, February 23, 2016). -21.
- fluorosurfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound.
- a fluorosurfactant the description in JP-A-2016-216602 can be referred to, and the contents thereof are incorporated in the present specification.
- a block polymer can also be used as the fluorosurfactant.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meta).
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
- the following compounds are also exemplified as the fluorosurfactant used in the present invention. In the following formula,% indicating the ratio of repeating units is mol%.
- the weight average molecular weight of the above compound is preferably 3,000 to 50,000, for example, 14,000.
- a fluoropolymer having an ethylenically unsaturated group in the side chain can also be used. Specific examples thereof include the compounds described in paragraph numbers 0050 to 0090 and paragraph numbers 0289 to 0295 of JP2010-164965A. Examples of commercially available products include Megafac RS-101, RS-102, RS-718-K, and RS-72-K manufactured by DIC Corporation.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (BA F), Solsperse 20000 (Nippon Lubrizol Corporation), NCW-101, NCW-1001, NCW-1002 (Fuji Film Wako Pure Chemical Industries, Ltd.), Pionein D-
- cationic surfactants examples include organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.) and the like.
- anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Chemical Co., Ltd.), and the like.
- silicone-based surfactant examples include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torre Silicone SH21PA, Torree Silicone SH28PA, Torree Silicone SH29PA, Torree Silicone SH30PA, Torree Silicone SH8400 (above, Toray Dow Corning Co., Ltd.) )), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4442 (above, manufactured by Momentive Performance Materials), KP341, KF6001, KF6002 (above, manufactured by Shin-Etsu Silicone Co., Ltd.) , BYK307, BYK323, BYK330 (above, manufactured by BYK Chemie) and the like.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass in the total solid content of the photosensitive composition. Only one surfactant may be used, or two or more surfactants may be combined. When 2 or more types are included, the total amount thereof is preferably within the above range.
- the photosensitive composition of the present invention can contain a silane coupling agent.
- a silane coupling agent a silane compound having at least two functional groups having different reactivity in one molecule is preferable.
- the silane coupling agent is composed of at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, a ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group.
- a silane compound having for details of the silane coupling agent the description of paragraphs 0467 to 0476 of JP-A-2017-126044 can be referred to, and the contents thereof are incorporated in the present specification.
- the content of the silane coupling agent is preferably 0.1 to 10% by mass in the total solid content of the photosensitive composition.
- the lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more.
- the upper limit is preferably 8% by mass or less, and more preferably 5% by mass or less.
- the photosensitive composition of the present invention may contain only one type of silane coupling agent or two or more types. When 2 or more types are included, the total amount thereof is preferably within the above range.
- the photosensitive composition of the present invention can contain an ultraviolet absorber.
- an ultraviolet absorber a conjugated diene compound, an aminobutadiene compound, a methyldibenzoyl compound, a coumarin compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, a hydroxyphenyltriazine compound, or the like can be used.
- paragraph numbers 0052 to 0072 of JP2012-208374A and paragraph numbers 0317 to 0334 of JP2013068814A the contents of which are incorporated herein.
- UV-503 manufactured by Daito Chemical Co., Ltd.
- MYUA series Chemical Industry Daily, February 1, 2016
- the photosensitive composition of the present invention contains an ultraviolet absorber
- the content of the ultraviolet absorber is preferably 0.001 to 15% by mass in the total solid content of the photosensitive composition.
- the lower limit is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more.
- the upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.
- only 1 type may be used for an ultraviolet absorber and 2 or more types may be used for it. When using 2 or more types, it is preferable that a total amount becomes the said range.
- the photosensitive coloring composition of the present invention can contain a polymerization inhibitor.
- Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salt (ammonium salt, primary cerium salt, etc.) and the like.
- the content of the polymerization inhibitor is preferably 0.001 to 5% by mass in the total solid content of the photosensitive composition.
- the photosensitive composition of this invention may contain only 1 type of polymerization inhibitors, and may contain 2 or more types. When 2 or more types are included, the total amount thereof is preferably within the above range.
- the photosensitive composition of the present invention includes a sensitizer, a co-sensitizer, a crosslinking agent, a curing accelerator, a filler, a thermosetting accelerator, a plasticizer, a diluent, a fat sensitizer, conductive particles, and a filler.
- Additives such as an antifoaming agent, a flame retardant, a leveling agent, a peeling accelerator, an antioxidant, a surface tension adjusting agent, and a chain transfer agent may be added as necessary.
- JP2008-250074 The description of paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 of JP2013-195480A, and the like can be referred to, and the contents thereof are incorporated in this specification.
- the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph No. 0042 of JP-A-2011-090147), a thioether compound, or the like can be used.
- Examples of commercially available products include ADEKA Corporation's ADK STAB series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60, AO-60G, AO-80, AO- 330).
- the polyfunctional hindered amine antioxidant described in international publication WO2017 / 006600 and the antioxidant described in international publication WO2017 / 164024 can also be used as antioxidant.
- the photosensitive composition of the present invention may contain a latent antioxidant, if necessary.
- the latent antioxidant is a compound in which a site functioning as an antioxidant is protected with a protecting group, and is heated at 100 to 250 ° C. or heated at 80 to 200 ° C. in the presence of an acid / base catalyst.
- a compound that functions as an antioxidant due to elimination of the protecting group can be mentioned.
- Examples of the latent antioxidant include compounds described in International Publication WO2014 / 021023, International Publication WO2017 / 030005, and Japanese Unexamined Patent Publication No. 2017-008219.
- Examples of commercially available products include Adeka Arcles GPA-5001 (manufactured by ADEKA Corporation).
- the photosensitive composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface (such as flatness) and the film thickness.
- the value of the viscosity can be appropriately selected as necessary. For example, at 25 ° C., 0.3 to 50 mPa ⁇ s is preferable, and 0.5 to 20 mPa ⁇ s is more preferable. Viscosity is measured, for example, using a viscometer RE85L (rotor: 1 ° 34 'x R24, measurement range 0.6 to 1200 mPa ⁇ s) manufactured by Toki Sangyo Co., Ltd., with the temperature adjusted to 25 ° C. Can do.
- the container for the photosensitive composition of the present invention is not particularly limited, and a known container can be used.
- a container a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin and a seven types of resin are made into a seven-layer structure for the purpose of suppressing contamination of impurities in the raw materials and the photosensitive composition. It is also preferred to use bottles. Examples of such a container include a container described in JP-A-2015-123351.
- the photosensitive composition of the present invention can be prepared by mixing the aforementioned components. In preparing the photosensitive composition, all the components may be simultaneously dissolved or dispersed in a solvent to prepare the photosensitive composition. If necessary, two or more solutions in which each component is appropriately blended or A dispersion liquid may be prepared in advance, and these may be mixed at the time of use (at the time of application) to prepare a photosensitive composition.
- the photosensitive composition of the present invention contains a pigment
- the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
- Specific examples of means for carrying out these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, a high-pressure wet atomization, and an ultrasonic dispersion. It is done.
- the pulverization of the pigment in the sand mill it is preferable to use the beads having a small diameter, and to perform the treatment under the condition that the pulverization efficiency is increased by increasing the filling rate of the beads. Further, it is preferable to remove coarse particles by filtration, centrifugation, or the like after the pulverization treatment.
- the process and disperser for dispersing pigments “Dispersion Technology Encyclopedia, Issued by Information Technology Corporation, July 15, 2005”, “Dispersion technology centering on suspension (solid / liquid dispersion system) and industrial The process and the disperser described in Paragraph No. 0022 of Japanese Patent Application Laid-Open No. 2015-157893 can be used.
- the pigment may be refined in a salt milling process.
- materials, equipment, processing conditions, etc. used in the salt milling process for example, descriptions in JP-A Nos. 2015-194521 and 2012-046629 can be referred to.
- any filter can be used without particular limitation as long as it is a filter that has been conventionally used for filtration.
- fluororesin such as polytetrafluoroethylene (PTFE), polyamide resin such as nylon (eg nylon-6, nylon-6,6), polyolefin resin such as polyethylene and polypropylene (PP) (high density, ultra high molecular weight)
- PP polypropylene
- polypropylene including high density polypropylene
- nylon are preferable.
- the pore size of the filter is preferably from 0.01 to 7.0 ⁇ m, more preferably from 0.01 to 3.0 ⁇ m, still more preferably from 0.05 to 0.5 ⁇ m. If the hole diameter of a filter is the said range, a fine foreign material can be removed more reliably.
- the filter manufacturer's nominal value can be referred to for the filter pore size value.
- Various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Japan Integris Co., Ltd. (former Nihon Microlith Co., Ltd.), KITZ Microfilter Co., Ltd., etc. can be used.
- a fiber-like filter medium As the filter.
- the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber.
- examples of commercially available products include SBP type series (such as SBP008), TPR type series (such as TPR002 and TPR005), and SHPX type series (such as SHPX003) manufactured by Loki Techno.
- filters When using filters, different filters (for example, a first filter and a second filter) may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more. Moreover, you may combine the filter of a different hole diameter within the range mentioned above. Moreover, filtration with a 1st filter may be performed only with respect to a dispersion liquid, and after mixing other components, it may filter with a 2nd filter.
- membrane of this invention is a film
- the film of the present invention is preferably used as a colored pixel, a light shielding film, a pixel of an infrared transmission filter layer, or the like.
- Colored pixels include pixels having a hue selected from red, blue, green, cyan, magenta, and yellow.
- the pixel of the infrared transmission filter layer has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm, and transmission in the wavelength range of 1100 to 1300 nm.
- Examples thereof include a pixel of a filter layer that satisfies the spectral characteristics having a minimum value of 70% or more (preferably 75% or more, more preferably 80% or more).
- the pixels of the infrared transmission filter layer are also preferably pixels of the filter layer satisfying any of the following spectral characteristics (1) to (4).
- the maximum value of transmittance in the wavelength range of 400 to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 800 to 1300 nm is A filter layer pixel that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of transmittance in the wavelength range of 400 to 750 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 900 to 1300 nm is A filter layer pixel that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of transmittance in the wavelength range of 400 to 830 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1000 to 1300 nm is A filter layer pixel that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the maximum value of transmittance in the wavelength range of 400 to 950 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum value of transmittance in the wavelength range of 1100 to 1300 nm is A filter layer pixel that is 70% or more (preferably 75% or more, more preferably 80% or more).
- the light shielding film is formed and used on various members in the image display device or the sensor module (for example, the outer peripheral portion of the infrared cut filter, the outer peripheral portion of the solid-state image sensor, the outer peripheral portion of the wafer level lens, the back surface of the solid-state image sensor). be able to.
- the reflectance of the light shielding film is preferably 10% or less, more preferably 8% or less, further preferably 6% or less, and particularly preferably 4% or less.
- the reflectance of the light shielding film is a value obtained by making the light of 400 to 700 nm incident on the light shielding film at an incident angle of 5 ° and measuring the reflectance with a spectroscope (manufactured by Hitachi High-Technologies Corporation, UV4100).
- the thickness of the film of the present invention can be appropriately adjusted according to the use and purpose.
- the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
- the pattern forming method of the present invention includes a step of forming a photosensitive composition layer on a support using the above-described photosensitive composition of the present invention, and Irradiating the photosensitive composition layer with light and exposing it in a pattern; and Removing the photosensitive composition layer in the unexposed area using a developer containing an organic solvent, and developing the photosensitive composition layer. Further, if necessary, a step of baking after the photosensitive composition layer is formed on the support and before exposure (pre-baking step), and a step of baking the developed pattern (post-baking step) May be provided. Hereinafter, each step will be described.
- the photosensitive composition layer is formed on the support using the photosensitive composition.
- the support is not particularly limited and can be appropriately selected depending on the application. Examples thereof include a glass substrate, a solid-state image sensor substrate provided with a solid-state image sensor (light-receiving element), and a silicon substrate. Further, an undercoat layer may be provided on these substrates in order to improve adhesion with an upper layer, prevent diffusion of a substance, or planarize a surface.
- various methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be used.
- the photosensitive composition layer formed on the support may be dried (prebaked).
- pre-baking may not be performed.
- the prebaking temperature is preferably 120 ° C. or lower, more preferably 110 ° C. or lower, and further preferably 105 ° C. or lower.
- the lower limit may be 50 ° C. or higher, and may be 80 ° C. or higher.
- the pre-bake time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and further preferably 80 to 220 seconds. Pre-baking can be performed using a hot plate, an oven, or the like.
- the photosensitive composition layer is exposed to light in a pattern form (exposure process).
- pattern exposure can be performed by exposing the photosensitive composition layer formed on the support through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper.
- an exposure apparatus such as a stepper.
- the solubility with respect to the organic solvent of resin can be reduced by the effect
- the solubility with respect to the organic solvent of the photosensitive composition layer of an exposure part can be reduced.
- Examples of radiation (light) that can be used for exposure include g-line and i-line. Further, light having a wavelength of 300 nm or less (preferably light having a wavelength of 180 to 300 nm) can be used. Examples of the light having a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm) are preferable.
- exposure may be performed by continuously irradiating light, or exposure may be performed by irradiating in pulses (pulse exposure).
- pulse exposure is an exposure method in which exposure is performed by repeatedly irradiating and pausing light in a short cycle (for example, a millisecond level or less).
- the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and further preferably 30 nanoseconds or less.
- the lower limit of the pulse width is not particularly limited, but can be 1 femtosecond (fs) or more, and can be 10 femtoseconds or more.
- the frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and further preferably 4 kHz or more.
- the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and still more preferably 10 kHz or less.
- Maximum instantaneous intensity is preferably at 50000000W / m 2 or more, more preferably 100000000W / m 2 or more, more preferably 200000000W / m 2 or more.
- the upper limit of the maximum instantaneous intensity is preferably at 1000000000W / m 2 or less, more preferably 800000000W / m 2 or less, further preferably 500000000W / m 2 or less.
- the pulse width is the time during which light is irradiated in the pulse period.
- the frequency is the number of pulse periods per second.
- the maximum instantaneous illuminance is the average illuminance within the time during which light is irradiated in the pulse period.
- the pulse period is a period in which light irradiation and pause in pulse exposure are one cycle.
- Irradiation dose for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
- the oxygen concentration at the time of exposure can be selected as appropriate.
- a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially It may be exposed in an oxygen-free manner, or may be exposed in a high oxygen atmosphere (for example, 22%, 30%, or 50% by volume) in which the oxygen concentration exceeds 21% by volume.
- the exposure illuminance can be appropriately set, and is usually selected from the range of 1000 W / m 2 to 100,000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , or 35000 W / m 2 ). Can do.
- Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
- the photosensitive composition layer in the unexposed area is removed and developed using a developer containing an organic solvent (development process).
- development process a developer containing an organic solvent
- the photosensitive composition layer in the unexposed area is removed by the developer, and a pattern (negative pattern) is formed along the shape of the opening of the mask.
- organic solvents used in the developer include ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents, including ketone solvents, ester solvents, and ether solvents.
- ketone solvents and ester solvents are more preferable, and ester solvents are more preferable.
- ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, acetonyl acetone, ionone, diacetyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.
- ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate (isoamyl acetate), amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate.
- the solvents described in paragraphs 0715 to 0718 of US Patent Application Publication No. 2016 / 0070167A1 can be used.
- a plurality of the above solvents may be mixed, or a solvent other than the above or water may be mixed.
- the water content of the developer is preferably less than 50% by mass, more preferably less than 20% by mass, still more preferably less than 10% by mass, still more preferably less than 5% by mass, and particularly preferably substantially free of moisture. .
- the SP value (Solubility Parameter) of the organic solvent used in the developer is preferably 14 to 24 MPa 1/2 .
- the upper limit of the SP value of the organic solvent is 22 MPa 1/2 or less, more preferably 20 MPa 1/2 or less, still more preferably 18 MPa 1/2 or less.
- the lower limit of the SP value of the organic solvent is preferably at 15 MPa 1/2 or more, and more preferably 16 MPa 1/2 or more.
- the boiling point of the organic solvent used in the developer is preferably 100 to 140 ° C.
- the vapor pressure of the developer is preferably 5 kPa or less at 20 ° C., more preferably 3 kPa or less, and particularly preferably 2 kPa or less. If the vapor pressure of the developer is 5 kPa or less, excellent developability can be obtained.
- the organic solvent used in the developer is preferably butyl acetate, 2-heptanone, propylene glycol monomethyl ether acetate, isopentyl acetate (isoamyl acetate), ethyl lactate, cyclohexanone and isobutyl isobutyrate, more preferably butyl acetate.
- the content of the organic solvent in the developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. Particularly preferred.
- the content of butyl acetate in the developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferred.
- the developer can contain a surfactant, an antioxidant, a basic compound, a stabilizer, an antifoaming agent, and the like.
- a developing method for example, a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and left stationary for a certain time (paddle method), a substrate A method of spraying the developer on the surface (spray method) or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing method) is applied.
- the processing time (development time) is not particularly limited as long as the photosensitive composition layer in the unexposed area is sufficiently dissolved. For example, 10 to 300 seconds are preferable, and 20 to 120 seconds are more preferable.
- the temperature of the developer is preferably 0 to 50 ° C, more preferably 15 to 35 ° C.
- washing step using a rinsing liquid after the development step described above.
- the vapor pressure of the rinse liquid is preferably 0.05 to 5 kPa at 20 ° C., more preferably 0.1 to 5 kPa, and even more preferably 0.12 to 3 kPa.
- the vapor pressure of the rinsing liquid is within the above range, the temperature uniformity in the surface of the support is improved, and furthermore, swelling due to the penetration of the rinsing liquid can be suppressed in the pattern after the development step.
- the rinse solution is not particularly limited as long as it does not dissolve the pattern after the development step, and a solution containing a general organic solvent can be used.
- a solution containing a general organic solvent can be used.
- the organic solvent used in the rinsing liquid include hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.
- the water content of the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. If the water content of the rinse liquid is 10% by mass or less, good developability can be obtained.
- the rinse liquid can contain a surfactant, an antioxidant, a basic compound, a stabilizer, an antifoaming agent, and the like.
- the cleaning method using the rinsing liquid is not particularly limited.
- a method in which the rinsing liquid is continuously discharged onto a support rotating at a constant speed (rotary coating method), and a support in a tank filled with the rinsing liquid.
- a method of dipping the substrate for a certain time (dip method), a method of spraying a rinsing liquid on the surface of the support (spray method), or the like can be applied.
- Post-bake a heat treatment
- the heating temperature is preferably 100 to 240 ° C., for example, and more preferably 200 to 240 ° C.
- Post-baking can be carried out continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer), a high-frequency heater, etc., so that the film after development is in the above-mentioned condition. .
- the color filter of the present invention has the above-described film of the present invention.
- the thickness of the film can be appropriately adjusted according to the purpose.
- the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and further preferably 0.3 ⁇ m or more.
- the color filter of the present invention can be used for a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor), an image display device, or the like.
- the manufacturing method of the color filter of this invention contains the pattern formation method of this invention mentioned above.
- the method for producing a color filter of the present invention is preferably performed by repeating the pattern forming method of the present invention described above twice or more.
- the color filter manufacturing method of the present invention includes forming the first pixel by using the pattern forming method of the present invention described above, and then forming the first pixel by using the pattern forming method of the present invention described above. It is preferable to form the second pixel in the missing portion. According to this aspect, it is possible to form a pixel having good rectangularity and less light leakage. When three or more types of pixels are formed, it is preferable that the above-described pattern forming method of the present invention is repeated for each type of pixel to form a target pixel in the missing portion of each pixel.
- the solid-state imaging device of the present invention has the above-described film of the present invention.
- the configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration that includes the film of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
- the substrate has a transfer electrode made of a plurality of photodiodes and polysilicon constituting a light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.)). And a device protective film made of silicon nitride or the like formed on the photodiode and the transfer electrode so as to cover only the entire surface of the light shielding film and the photodiode light receiving portion. And having a color filter on the device protective film.
- CCD charge coupled device
- CMOS complementary metal oxide semiconductor
- the device has a condensing means (for example, a microlens, etc., the same shall apply hereinafter) under the color filter (on the side close to the substrate) on the device protective film, or a constitution having the condensing means on the color filter.
- the color filter may have a structure in which a film forming each colored pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
- the partition walls preferably have a low refractive index for each colored pixel.
- Examples of the image pickup apparatus having such a structure include apparatuses described in JP 2012-227478 A and JP 2014-179577 A.
- the image pickup apparatus including the solid-state image pickup device of the present invention can be used for an in-vehicle camera and a monitoring camera in addition to a digital camera and an electronic apparatus (such as a mobile phone) having an image pickup function.
- the film of the present invention can be used for image display devices such as liquid crystal display devices and organic electroluminescence display devices.
- image display devices such as liquid crystal display devices and organic electroluminescence display devices.
- the liquid crystal display device is described in, for example, “Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Co., Ltd., published in 1994)”.
- the liquid crystal display device to which the present invention can be applied is not particularly limited, and can be applied to, for example, various types of liquid crystal display devices described in the “next generation liquid crystal display technology”.
- ⁇ Preparation of pigment dispersion> The raw materials shown in the table below were mixed and dispersed for 3 hours using a zirconia bead having a diameter of 0.3 mm in a bead mill (high pressure disperser NANO-3000-10 with a decompression mechanism (manufactured by Nippon BEE Co., Ltd.)). A pigment dispersion was prepared. The numerical value showing the compounding quantity as described below is a mass part.
- (resin) b-1 Resin synthesized by the following method (resin whose solubility in organic solvents decreases due to the action of acid) 32.62 g of propylene glycol monomethyl ether acetate (PGMEA) was placed in a three-necked flask equipped with a nitrogen introduction tube and a cooling tube, and the temperature was raised to 86 ° C. To this were added 16.65 g of benzyl methacrylate (BzMA), 19.19 g of tetrahydrofuran-2-yl-acrylate (THFAA), and 5.76 g of t-butyl methacrylate (t-BuMA).
- PGMEA propylene glycol monomethyl ether acetate
- the photosensitive composition was prepared by mixing the raw materials described in the following table.
- the numerical value showing the compounding quantity described in the following table is part by mass.
- butyl acetate, 2-heptanone, propylene glycol monomethyl ether acetate (PGMEA), isoamyl acetate, ethyl lactate, cyclohexanone, isobutyl isobutyrate, or an alkaline developer (water) is applied to the photosensitive composition layer after exposure.
- shower development was performed at 23 ° C. for 60 seconds using tetramethylammonium oxide (TMAH 0.3 mass% aqueous solution). Thereafter, rinsing was performed using pure water in a spin shower. Subsequently, the pattern was obtained by performing heat processing (post-baking) for 1 hour using 200 degreeC oven.
- the width of the pattern formed on the silicon substrate and the length of the diagonal line of the pattern were observed from directly above the silicon substrate using a length measuring SEM (scanning electron microscope).
- the rectangularity was evaluated according to the following criteria. As the value of (pattern diagonal length / 1.41) ⁇ 100 is closer to 100, the rectangularity is better. 6: (Diagonal length of pattern / 1.41) ⁇ 100 is more than 99 and 101 or less. 5: The value of (Diagonal length of pattern / 1.41) ⁇ 100 is more than 98 and 99 or less, or more than 101 and 102 or less. 4: The value of (Diagonal length of pattern / 1.41) ⁇ 100 is more than 97 and 98 or less, or more than 102 and 103 or less.
- (Diagonal length of pattern / 1.41) ⁇ 100 is more than 96 and 97 or less, or more than 103 and 104 or less.
- 2 The value of (Diagonal length of pattern / 1.41) ⁇ 100 is more than 95 and 96 or less, or more than 104 and 105 or less.
- 1 (Diagonal length of pattern / 1.41) ⁇ 100 is 95 or less, or exceeds 105.
- the exposed photosensitive composition layer was subjected to shower development at 23 ° C. for 60 seconds using an alkali developer (tetramethylammonium hydroxide (TMAH) 0.3 mass% aqueous solution) as a developer. Thereafter, rinsing was performed using pure water in a spin shower.
- TMAH tetramethylammonium hydroxide
- a transparent pixel pattern (hereinafter, also referred to as “pattern 1”) was obtained by performing heat treatment (post-baking) for 1 hour using an oven at 200 ° C.
- the photosensitive composition described in the following table is applied by spin coating, and heat treatment (prebaking) is performed for 120 seconds using a hot plate at 100 ° C.
- a photosensitive composition layer having a thickness of 0.9 ⁇ m was formed.
- an i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
- exposure was performed (exposure amount 500 mJ / cm 2 ) through a mask having a 10 ⁇ m square pattern.
- butyl acetate, 2-heptanone, propylene glycol monomethyl ether acetate (PGMEA), isoamyl acetate, ethyl lactate, cyclohexanone, isobutyl isobutyrate, or an alkaline developer (water) is applied to the photosensitive composition layer after exposure.
- shower development was performed at 23 ° C.
- TMAH tetramethylammonium oxide
- rinsing was performed using pure water in a spin shower.
- heat treatment post-baking
- a pattern made of the photosensitive composition described in the following table hereinafter, also referred to as pattern 2 is formed in the missing portion of the pattern of the transparent pixel. Formed).
- the light amount at the wavelength ⁇ max with the maximum transmittance is A
- the light amount at the wavelength ⁇ max detected through the pattern 1 is B
- the pattern 2 based on the following formula: The light leakage of was evaluated.
- T 100 ⁇ B / A 6: The value of T is less than 2. 5: The value of T is 2 or more and less than 4. 4: The value of T is 4 or more and less than 6. 3: The value of T is 6 or more and less than 10. 2: The value of T is 10 or more and less than 12. 1: The value of T is 12 or more.
- a photosensitive composition for forming a green pixel is applied to an 8-inch (20.32 cm) glass substrate by spin coating, and heat-treated (pre-baked) for 120 seconds using a hot plate at 100 ° C. to obtain a thickness of 0
- a photosensitive composition layer having a thickness of 9 ⁇ m was formed.
- an i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
- exposure was performed (exposure amount: 500 mJ / cm 2 ) through a mask having a 3 ⁇ m square pattern.
- the exposed photosensitive composition layer was subjected to shower development at 23 ° C. for 60 seconds using butyl acetate as a developer.
- rinsing was performed using pure water in a spin shower.
- a green pixel pattern was formed by performing heat treatment (post-baking) for 1 hour using an oven at 200 ° C.
- a photosensitive composition for red pixel formation is applied onto a glass substrate on which a green pixel pattern is formed by spin coating, and heat treatment (pre-baking) is performed for 120 seconds using a 100 ° C. hot plate.
- a photosensitive composition layer having a thickness of 0.9 ⁇ m was formed.
- using an i-line stepper exposure apparatus FPA-3000i5 + manufactured by Canon Inc.
- the exposed photosensitive composition layer was subjected to shower development at 23 ° C. for 60 seconds using butyl acetate as a developer. Thereafter, rinsing was performed using pure water in a spin shower. Next, a heat treatment (post-bake) for 1 hour was performed using an oven at 200 ° C., thereby forming a red pixel pattern in a gap portion of the green pixel pattern.
- a heat treatment post-bake
- the evaluation was “6”.
- the photosensitive composition of Example 1-6 was used as the photosensitive composition for forming the green pixel
- the photosensitive composition of Example 2-6 was used as the photosensitive composition for forming the red pixel. The composition was used.
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Abstract
Description
<1> 有機溶剤を含む現像液で現像してネガ型パターンを形成するために用いられる感光性組成物であって、
色材と、酸の作用により有機溶剤に対する溶解性が低下する樹脂と、光酸発生剤と、を含む感光性組成物。
<2> 感光性組成物の全固形分中における色材の含有量が55質量%以上である、<1>に記載の感光性組成物。
<3> 感光性組成物に含まれる樹脂の合計量中における酸の作用により有機溶剤に対する溶解性が低下する樹脂の含有量が40質量%以上である、<1>または<2>に記載の感光性組成物。
<4> 感光性組成物の全固形分中における酸の作用により有機溶剤に対する溶解性が低下する樹脂の含有量が10~60質量%である、<1>~<3>のいずれか1つに記載の感光性組成物。
<5> 酸の作用により有機溶剤に対する溶解性が低下する樹脂は、酸の作用により分解して極性基を生じる基を含む、<1>~<4>のいずれか1つに記載の感光性組成物。
<6> 酸の作用により有機溶剤に対する溶解性が低下する樹脂は、酸の作用により分解して脱離する基で極性基が保護された構造を有する、<1>~<5>のいずれか1つに記載の感光性組成物。
<7> 酸の作用により分解して脱離する基は、式(Y1)~(Y4)のいずれかで表される基である、<6>に記載の感光性組成物;
式(Y1):-C(R31)(R32)(R33)
式(Y2):-C(=O)OC(R31)(R32)(R33)
式(Y3):-C(R36)(R37)(OR38)
式(Y4):-C(Rn)(H)(Ar)
式(Y1)、(Y2)中、R31~R33は、各々独立にアルキル基を表し、R31~R33のうちの2つが結合して環を形成していてもよい;
式(Y3)中、R36およびR37は、各々独立に、水素原子、アルキル基またはアリール基を表し、R36およびR37の少なくとも一方がアルキル基またはアリール基であり、R38は、アルキル基またはアリール基を表し、R36またはR37と、R38とが結合して環を形成してもよい;
式(Y4)中、Arは、芳香環基を表し、Rnは、アルキル基またはアリール基を表す。RnとArとは互いに結合して環を形成してもよい。
<8> 酸の作用により分解して脱離する基の式量が170以下である、<6>または<7>に記載の感光性組成物。
<9> 更に、酸架橋剤を含む、<1>~<8>のいずれか1つに記載の感光性組成物。
<10> 感光性組成物の全固形分中における光ラジカル重合開始剤の含有量が4質量%以下である、<1>~<9>のいずれか1つに記載の感光性組成物。
<11> 感光性組成物の全固形分中におけるラジカル重合性モノマーの含有量が5質量%以下である、<1>~<10>のいずれか1つに記載の感光性組成物。
<12> <1>~<11>のいずれか1つに記載の感光性組成物から得られる膜。
<13> <1>~<11>のいずれか1つに記載の感光性組成物を用いて支持体上に感光性組成物層を形成する工程と、
感光性組成物層に対して、光を照射してパターン状に露光する工程と、
未露光部の感光性組成物層を、有機溶剤を含む現像液を用いて除去して現像する工程と、を有するパターンの形成方法。
<14> <13>に記載のパターンの形成方法を用いて第1の画素を形成した後、
<13>に記載のパターンの形成方法を用いて第1の画素の抜け部に第2の画素を形成する、カラーフィルタの製造方法。
<15> <12>に記載の膜を有するカラーフィルタ。
<16> <12>に記載の膜を有する固体撮像素子。
<17> <12>に記載の膜を有する画像表示装置。
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、樹脂の重量平均分子量(Mw)、数平均分子量(Mn)、及び分散度(分子量分布ともいう)(Mw/Mn)は、GPC(Gel Permeation Chromatography)装置(東ソー製HLC-8120GPC)によるGPC測定(溶媒:テトラヒドロフラン、流量(サンプル注入量):10μL、カラム:東ソー社製TSK gel Multipore HXL-M、カラム温度:40℃、流速:1.0mL/分、検出器:示差屈折率検出器(Refractive Index Detector))によるポリスチレン換算値として定義される。
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「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。
本発明の感光性組成物は、有機溶剤を含む現像液で現像してネガ型パターンを形成するために用いられる感光性組成物であって、
色材と、酸の作用により有機溶剤に対する溶解性が低下する樹脂と、光酸発生剤と、を含むことを特徴とする。
(1):波長400~640nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長800~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層の画素。
(2):波長400~750nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長900~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層の画素。
(3):波長400~830nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1000~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層の画素。
(4):波長400~950nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1100~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層の画素。
Aλ=-log(Tλ/100) ・・・(1)
Aλは、波長λにおける吸光度であり、Tλは、波長λにおける透過率(%)である。
本発明において、吸光度の値は、溶液の状態で測定した値であってもよく、感光性組成物を用いて製膜した膜での値であってもよい。膜の状態で吸光度を測定する場合は、ガラス基板上にスピンコート等の方法により、乾燥後の膜の厚さが所定の厚さとなるように感光性組成物を塗布し、ホットプレートを用いて100℃、120秒間乾燥して調製した膜を用いて測定することが好ましい。
(11):波長400~640nmの範囲における吸光度の最小値Amin1と、波長800~1300nmの範囲における吸光度の最大値Bmax1との比であるAmin1/Bmax1が5以上であり、7.5以上であることが好ましく、15以上であることがより好ましく、30以上であることが更に好ましい。この態様によれば、波長400~640nmの範囲の光を遮光して、波長720nm以上の光を透過可能な膜を形成することができる。
(12):波長400~750nmの範囲における吸光度の最小値Amin2と、波長900~1300nmの範囲における吸光度の最大値Bmax2との比であるAmin2/Bmax2が5以上であり、7.5以上であることが好ましく、15以上であることがより好ましく、30以上であることが更に好ましい。この態様によれば、波長400~750nmの範囲の光を遮光して、波長850nm以上の光を透過可能な膜を形成することができる。
(13):波長400~850nmの範囲における吸光度の最小値Amin3と、波長1000~1300nmの範囲における吸光度の最大値Bmax3との比であるAmin3/Bmax3が5以上であり、7.5以上であることが好ましく、15以上であることがより好ましく、30以上であることが更に好ましい。この態様によれば、波長400~850nmの範囲の光を遮光して、波長940nm以上の光を透過可能な膜を形成することができる。
(14):波長400~950nmの範囲における吸光度の最小値Amin4と、波長1100~1300nmの範囲における吸光度の最大値Bmax4との比であるAmin4/Bmax4が5以上であり、7.5以上であることが好ましく、15以上であることがより好ましく、30以上であることが更に好ましい。この態様によれば、波長400~950nmの範囲の光を遮光して、波長1040nm以上の光を透過可能な膜を形成することができる。
本発明の感光性組成物は、色材を含む。色材としては、有彩色着色剤、黒色着色剤、赤外線吸収色材などが挙げられる。色材は顔料であってもよく、染料であってもよい。顔料の平均一次粒子径は、0.01~0.1μmが好ましく、0.01~0.05μmがより好ましい。なお、顔料の平均一次粒子径は、透過型電子顕微鏡を用いて測定できる。透過型電子顕微鏡としては、例えば、日立ハイテクノロジーズ社製の透過型顕微鏡HT7700を用いることができる。透過型電子顕微鏡を用いて得た粒子像の最大長(Dmax:粒子画像の輪郭上の2点における最大長さ)、および最大長垂直長(DV-max:最大長に平行な2本の直線で画像を挟んだ時、2直線間を垂直に結ぶ最短の長さ)を測長し、その相乗平均値(Dmax×DV-max)1/2を粒子径とした。この方法で100個の粒子の粒子径を測定し、その算術平均値を平均粒子径として、顔料の平均一次粒子径とした。本明細書の実施例における「平均一次粒子径」も上記の算術平均値と同じである。色材として顔料を用いた場合は、得られる膜について、耐熱性、耐光性といったいわゆる環境耐性をより向上させることができる。また、色材として染料を用いた場合は、より鮮明な色相の膜を形成しやすく、例えば、他の画素と色分離に優れた膜を形成しやすい。
なお、本明細書において、色材は顔料誘導体とは異なる成分であることが好ましい。すなわち、本明細書において色材には顔料誘導体は含まれないことが好ましい。
有彩色着色剤としては、赤色着色剤、緑色着色剤、青色着色剤、黄色着色剤、紫色着色剤、オレンジ色着色剤などが挙げられる。有彩色着色剤は、顔料であってもよく、染料であってもよい。
カラーインデックス(C.I.)Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214等(以上、黄色顔料)、
C.I.Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等(以上、オレンジ色顔料)、
C.I.Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279等(以上、赤色顔料)、
C.I.Pigment Green 7,10,36,37,58,59,62,63等(以上、緑色顔料)、
C.I.Pigment Violet 1,19,23,27,32,37,42等(以上、紫色顔料)、
C.I.Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80等(以上、青色顔料)。
これら有機顔料は、単独で若しくは種々組合せて用いることができる。
黒色着色剤としては、無機黒色着色剤、有機黒色着色剤が挙げられる。
赤外線吸収色材としては、波長700~1300nmの範囲、より好ましくは波長700~1000nmの範囲に極大吸収波長を有する化合物が好ましい。赤外線吸収色材は、顔料であってもよく、染料であってもよい。
Mは金属、Wはタングステン、Oは酸素を表す。
0.001≦x/y≦1.1
2.2≦z/y≦3.0
(2):有機黒色着色剤を含む。
(3):上記(1)または(2)において、更に赤外線吸収色材を含む。
(1-1)赤色着色剤と青色着色剤とを含有する態様。
(1-2)赤色着色剤と青色着色剤と黄色着色剤とを含有する態様。
(1-3)赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤とを含有する態様。
(1-4)赤色着色剤と青色着色剤と黄色着色剤と紫色着色剤と緑色着色剤とを含有する態様。
(1-5)赤色着色剤と青色着色剤と黄色着色剤と緑色着色剤とを含有する態様。
(1-6)赤色着色剤と青色着色剤と緑色着色剤とを含有する態様。
(1-7)黄色着色剤と紫色着色剤とを含有する態様。
本発明の感光性組成物は樹脂を含有する。樹脂は、例えば顔料などを組成物中で分散させる用途やバインダーの用途で配合される。なお、主に顔料などを分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。
樹脂(A)としては、酸の作用により分解して極性基を生じる基(以下、「酸分解性基」とも言う)を有する樹脂であることが好ましい。また、樹脂(A)は、酸分解性基を有する繰り返し単位を有することが好ましい。樹脂(A)は、バインダーや分散剤として用いることができる。
式(Y2):-C(=O)OC(R31)(R32)(R33)
式(Y3):-C(R36)(R37)(OR38)
式(Y4):-C(Rn)(H)(Ar)
R31~R33の2つが結合して形成される環としては、シクロペンチル基、及び、シクロヘキシル基などの単環のシクロアルキル基、並びに、ノルボルニル基、テトラシクロデカニル基、テトラシクロドデカニル基、及び、アダマンチル基などの多環のシクロアルキル基が好ましく、炭素数5~6の単環のシクロアルキル基がより好ましい。上記のシクロアルキル基は、例えば、環を構成するメチレン基の1つが、酸素原子等のヘテロ原子、又は、カルボニル基等のヘテロ原子を有する基で置き換わっていてもよい。
式(Y1)又は(Y2)で表される基は、例えば、R31がメチル基又はエチル基であり、R32とR33とが結合して上述のシクロアルキル基を形成している態様が好ましい。
R36またはR37と、R38とが結合して形成される環としては、テトラヒドロフラニル基、テトラヒドロピラニル基等が挙げられる。
Tが表す2価の連結基としては、アルキレン基、-COO-Rt-基、-O-Rt-基等が挙げられる。Rtは、炭素数1~5のアルキレン基を表す。Tは、単結合又は-COO-Rt-基が好ましく、単結合がより好ましい。Yは、式(Y1)~(Y4)で表される基のいずれかであることが好ましく、式(Y1)で表される基であることがより好ましい。
Zは、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表す。Zは、複数個ある場合には各々独立に、単結合、エーテル結合、エステル結合、アミド結合、ウレタン結合又はウレア結合を表す。
R8は、ラクトン構造又はスルトン構造を有する1価の有機基を表す。
R7は、水素原子、ハロゲン原子又は1価の有機基(好ましくはメチル基)を表す。
樹脂(A)は、極性基を有する繰り返し単位を、1種単独で含んでもよく、2種以上を併用して含んでもよい。極性基を有する繰り返し単位の含有量は、樹脂(A)中の全繰り返し単位に対して、5~40モル%が好ましく、5~30モル%がより好ましく、10~25モル%が更に好ましい。
本発明の感光性組成物は、樹脂として上述した樹脂(A)以外の樹脂(以下、樹脂(B)ともいう)を含有することができる。
本発明の感光性組成物は光酸発生剤を含有する。光酸発生剤は、活性光線又は放射線が照射されることにより酸を発生する化合物である。本発明で使用される光酸発生剤としては、活性光線又は放射線が照射されることによりpKaが4以下の酸を発生する化合物であることが好ましく、pKaが3以下の酸を発生する化合物であることがより好ましく、2以下の酸を発生する化合物であることが更に好ましく、-1以下の酸を発生する化合物であることが特に好ましい。なお本発明において、pKaは、基本的に25℃の水中におけるpKaを指す。水中で測定できないものは、測定に適する溶剤に変更し測定したものを指す。具体的には、化学便覧等に記載のpKaが参考にできる。pKaが4以下の酸としては、スルホン酸またはホスホン酸であることが好ましく、スルホン酸であることがより好ましい。
また、光酸発生剤の含有量は、上述した樹脂(A)の100質量部に対して0.1~50質量部が好ましい。下限は、0.5質量部以上が好ましく、1質量部以上がより好ましく、2質量部以上が更に好ましい。上限は、40質量部以下が好ましく、30質量部以下がより好ましく、20質量部以下が更に好ましい。
また、本発明の感光性組成物が後述する酸架橋剤を含有する場合、光酸発生剤の含有量は、上述した樹脂(A)と酸架橋剤との合計100質量部に対して0.1~50質量部が好ましい。下限は、0.5質量部以上が好ましく、1質量部以上がより好ましく、2質量部以上が更に好ましい。上限は、40質量部以下が好ましく、30質量部以下がより好ましく、20質量部以下が更に好ましい。
光酸発生剤は、1種単独で使用してもよいし、2種以上を併用してもよい。2種以上を併用する場合は、それらの合計量が上記範囲であることが好ましい。
感光性組成物は、酸拡散制御剤を含有することができる。酸拡散制御剤は、露光時に光酸発生剤等から発生する酸をトラップし、余分な発生酸による、未露光部における上述した樹脂(A)の反応を抑制するクエンチャーとして作用するものである。酸拡散制御剤としては、塩基性化合物、窒素原子を有し酸の作用により脱離する基を有する低分子化合物、活性光線又は放射線の照射により塩基性が低下又は消失する塩基性化合物、又は、光酸発生剤に対して相対的に弱酸となるオニウム塩を使用することができる。
これら一般式(A)及び(E)中のアルキル基は、無置換であることがより好ましい。
本発明の感光性組成物は、酸架橋剤を含有することが好ましい。この態様によれば、架橋密度の高い膜を形成でき、耐熱性、耐溶剤性、強度などの各種特性に優れた膜を形成し易い。なお、本明細書において酸架橋剤とは、酸の作用によって架橋する架橋剤のことである。
また、酸架橋剤の含有量は、上述した樹脂(A)の100質量部に対して0.1~50質量部が好ましい。下限は、0.5質量部以上が好ましく、1質量部以上がより好ましく、2質量部以上が更に好ましい。上限は、40質量部以下が好ましく、30質量部以下がより好ましく、20質量部以下が更に好ましい。
また、上述した樹脂(A)と酸架橋剤の合計の含有量は、感光性組成物の全固形分中10~60質量%であることが好ましい。下限は15質量%以上が好ましく、20質量%以上がより好ましい。上限は50質量%以下が好ましく、40質量%以下更に好ましい。
酸架橋剤を1種類のみ含んでいても良いし、2種類以上含んでいても良い。2種類以上含む場合は、それらの合計量が上記範囲となることが好ましい。
本発明の感光性組成物はラジカル重合性モノマーを含有してもよい。ラジカル重合性モノマーとしては、ラジカルの作用により重合可能な化合物であればよく、特に限定はない。ラジカル重合性モノマーとしては、エチレン性不飽和結合を有する基を1個以上有する化合物であることが好ましく、エチレン性不飽和結合を有する基を2個以上有する化合物であることがより好ましく、エチレン性不飽和結合を有する基を3個以上有する化合物であることが更に好ましい。エチレン性不飽和結合を有する基の個数の上限は、たとえば、15個以下が好ましく、6個以下がより好ましい。エチレン性不飽和結合を有する基としては、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、(メタ)アクリロイル基が好ましい。ラジカル重合性モノマーは、3~15官能の(メタ)アクリレート化合物であることが好ましく、3~6官能の(メタ)アクリレート化合物であることがより好ましい。
本発明の感光性組成物は光ラジカル重合開始剤を含有してもよい。光ラジカル重合開始剤としては、例えば、トリハロメチルトリアジン化合物、ベンジルジメチルケタール化合物、α-ヒドロキシケトン化合物、α-アミノケトン化合物、アシルホスフィン化合物、ホスフィンオキサイド化合物、メタロセン化合物、オキシム化合物、トリアリールイミダゾールダイマー、オニウム化合物、ベンゾチアゾール化合物、ベンゾフェノン化合物、アセトフェノン化合物、シクロペンタジエン-ベンゼン-鉄錯体、ハロメチルオキサジアゾール化合物、クマリン化合物などが挙げられ、オキシム化合物、α-ヒドロキシケトン化合物、α-アミノケトン化合物、および、アシルホスフィン化合物が好ましく、オキシム化合物、α-アミノケトン化合物がより好ましい。光ラジカル重合開始剤の詳細については、特開2017-126044号公報の段落番号0013~0031を参酌でき、この内容は本明細書に組み込まれる。
本発明の感光性組成物は、顔料誘導体を含有することができる。顔料誘導体としては、発色団の一部分を、酸基、塩基性基またはフタルイミドメチル基で置換した構造を有する化合物が挙げられる。顔料誘導体を構成する発色団としては、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、フタロシアニン系骨格、アンスラキノン系骨格、キナクリドン系骨格、ジオキサジン系骨格、ペリノン系骨格、ペリレン系骨格、チオインジゴ系骨格、イソインドリン系骨格、イソインドリノン系骨格、キノフタロン系骨格、スレン系骨格、金属錯体系骨格等が挙げられ、キノリン系骨格、ベンゾイミダゾロン系骨格、ジケトピロロピロール系骨格、アゾ系骨格、キノフタロン系骨格、イソインドリン系骨格およびフタロシアニン系骨格が好ましく、アゾ系骨格およびベンゾイミダゾロン系骨格がより好ましい。顔料誘導体が有する酸基としては、スルホ基、カルボキシル基が好ましく、スルホ基がより好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、三級アミノ基がより好ましい。顔料誘導体の具体例としては、例えば、特開2011-252065号公報の段落番号0162~0183の記載を参酌でき、この内容は本明細書に組み込まれる。顔料誘導体の含有量は、顔料100質量部に対し、1~30質量部が好ましく、3~20質量部がさらに好ましい。顔料誘導体は、1種のみを用いてもよいし、2種以上を併用してもよい。
本発明の感光性組成物は、溶剤を含有することが好ましい。溶剤は有機溶剤が好ましい。有機溶剤としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、3-メトキシプロパノール、メトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、3-メトキシプロピルアセテート、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、乳酸エチル、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などが挙げられるが、これらに限定されない。ただし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、10質量ppm以下、あるいは1質量ppm以下とすることができる)。
本発明の感光性組成物は、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。界面活性剤については、国際公開WO2015/166779号公報の段落番号0238~0245を参酌でき、この内容は本明細書に組み込まれる。
本発明の感光性組成物は、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、一分子中に少なくとも2種の反応性の異なる官能基を有するシラン化合物が好ましい。シランカップリング剤は、ビニル基、エポキシ基、スチレン基、メタクリル基、アミノ基、イソシアヌレート基、ウレイド基、メルカプト基、スルフィド基、および、イソシアネート基から選ばれる少なくとも1種の基と、アルコキシ基とを有するシラン化合物が好ましい。シランカップリング剤の詳細については、特開2017-126044号公報の段落番号0467~0476の記載を参酌でき、これらの内容は本明細書に組み込まれる。本発明の感光性組成物がシランカップリング剤を含有する場合、シランカップリング剤の含有量は、感光性組成物の全固形分中0.1~10質量%が好ましい。下限は、0.5質量%以上が好ましく、1質量%以上がより好ましい。上限は8質量%以下が好ましく、5質量%以下がより好ましい。本発明の感光性組成物は、シランカップリング剤を、1種のみを含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
本発明の感光性組成物は、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、アミノブタジエン化合物、メチルジベンゾイル化合物、クマリン化合物、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などを用いることができる。これらの詳細については、特開2012-208374号公報の段落番号0052~0072、特開2013-068814号公報の段落番号0317~0334の記載を参酌でき、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、例えば、UV-503(大東化学(株)製)などが挙げられる。また、ベンゾトリアゾール化合物としてはミヨシ油脂製のMYUAシリーズ(化学工業日報、2016年2月1日)を用いてもよい。本発明の感光性組成物が紫外線吸収剤を含有する場合、紫外線吸収剤の含有量は、感光性組成物の全固形分中0.001~15質量%が好ましい。下限は、0.01質量%以上が好ましく、0.1質量%以上がより好ましい。上限は、10質量%以下が好ましく、5質量%以下がより好ましく、3質量%以下が更に好ましい。また、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。
本発明の感光性着色組成物は、重合禁止剤を含有することができる。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン塩(アンモニウム塩、第一セリウム塩等)等が挙げられる。本発明の感光性組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、感光性組成物の全固形分中0.001~5質量%が好ましい。本発明の感光性組成物は、重合禁止剤を1種のみを含んでいてもよいし、2種以上含んでいてもよい。2種以上含む場合は、それらの合計量が上記範囲となることが好ましい。
本発明の感光性組成物には、増感剤、共増感剤、架橋剤、硬化促進剤、フィラー、熱硬化促進剤、可塑剤、希釈剤、感脂化剤、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、酸化防止剤、表面張力調整剤、連鎖移動剤等の添加剤を必要に応じて加えてもよい。これらの成分は、例えば、特開2012-003225号公報の段落番号0183~0228(対応する米国特許出願公開第2013/0034812号明細書の段落番号0237~0309)、特開2008-250074号公報の段落番号0101~0102、段落番号0103~0104、段落番号0107~0109、特開2013-195480号公報の段落番号0159~0184等の記載を参酌でき、これらの内容は本明細書に組み込まれる。また、酸化防止剤としては、例えばフェノール化合物、リン系化合物(例えば特開2011-090147号公報の段落番号0042に記載の化合物)、チオエーテル化合物などを用いることができる。市販品としては、例えば(株)ADEKA製のアデカスタブシリーズ(AO-20、AO-30、AO-40、AO-50、AO-50F、AO-60、AO-60G、AO-80、AO-330など)が挙げられる。また、酸化防止剤として、国際公開WO2017/006600号公報に記載された多官能ヒンダードアミン酸化防止剤、国際公開WO2017/164024号公報に記載された酸化防止剤を用いることもできる。
本発明の感光性組成物は、前述の成分を混合して調製できる。感光性組成物の調製に際しては、全成分を同時に溶剤に溶解または分散して感光性組成物を調製してもよいし、必要に応じては、各成分を適宜配合した2つ以上の溶液または分散液をあらかじめ調製し、使用時(塗布時)にこれらを混合して感光性組成物として調製してもよい。
本発明の膜は、上述した本発明の感光性組成物から得られる膜である。本発明の膜は、着色画素、遮光膜、赤外線透過フィルタ層の画素などとして好ましく用いられる。
(1):波長400~640nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長800~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層の画素。
(2):波長400~750nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長900~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層の画素。
(3):波長400~830nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1000~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層の画素。
(4):波長400~950nmの範囲における透過率の最大値が20%以下(好ましくは15%以下、より好ましくは10%以下)であり、波長1100~1300nmの範囲における透過率の最小値が70%以上(好ましくは75%以上、より好ましくは80%以上)であるフィルタ層の画素。
本発明のパターンの形成方法は、上述した本発明の感光性組成物を用いて支持体上に感光性組成物層を形成する工程と、
感光性組成物層に対して、光を照射してパターン状に露光する工程と、
未露光部の感光性組成物層を、有機溶剤を含む現像液を用いて除去して現像する工程と、を有する。さらに、必要に応じて、感光性組成物層を支持体上に形成した後であって露光する前にベークする工程(プリベーク工程)、および、現像されたパターンをベークする工程(ポストベーク工程)を設けてもよい。以下、各工程について説明する。
次に、本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した本発明の膜を有する。本発明のカラーフィルタにおいて、膜の膜厚は、目的に応じて適宜調整できる。膜厚は、20μm以下が好ましく、10μm以下がより好ましく、5μm以下がさらに好ましい。膜厚の下限は、0.1μm以上が好ましく、0.2μm以上がより好ましく、0.3μm以上が更に好ましい。本発明のカラーフィルタは、CCD(電荷結合素子)やCMOS(相補型金属酸化膜半導体)などの固体撮像素子や画像表示装置などに用いることができる。
次に、本発明のカラーフィルタの製造方法について説明する。本発明のカラーフィルタの製造方法は、上述した本発明のパターン形成方法を含む。本発明のカラーフィルタの製造方法は、上述した本発明のパターン形成方法を2回以上繰り返して行うことが好ましい。
本発明の固体撮像素子は、上述した本発明の膜を有する。本発明の固体撮像素子の構成としては、本発明の膜を備え、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。
本発明の膜は、液晶表示装置や有機エレクトロルミネッセンス表示装置などの、画像表示装置に用いることができる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス(佐々木昭夫著、(株)工業調査会、1990年発行)」、「ディスプレイデバイス(伊吹順章著、産業図書(株)平成元年発行)」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術(内田龍男編集、(株)工業調査会、1994年発行)」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
下記表に記載の原料を0.3mm径のジルコニアビーズを使用し、ビーズミル(減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製))で、3時間、混合および分散して、顔料分散液を調製した。下記に記載の配合量を表す数値は質量部である。
PG58: C.I.Pigment Green58
PG7: C.I.Pigment Green7
PY185: C.I.Pigment Yellow185
PY139: C.I.Pigment Yellow139
PR254: C.I.Pigment Red254
b-1:以下の方法で合成した樹脂(酸の作用により有機溶剤に対する溶解性が低下する樹脂)
窒素導入管および冷却管を取り付けた三口フラスコにプロピレングリコールモノメチルエーテルアセテート(PGMEA)の32.62gを入れ、86℃に昇温した。ここに、ベンジルメタクリレート(BzMA)の16.65gと、テトラヒドロフラン-2-イル-アクリレート(THFAA)の19.19gと、t-ブチルメタクリレート(t-BuMA)の5.76gとを加えた。この混合溶液に、ジメチル-2,2’-アゾビス(2-メチルプロピオネート)(V-601、富士フイルム和光純薬(株)製))の0.8082g(モノマーに対して1.30mol%)をPGMEAの32.62gに溶解した溶液を2時間かけて滴下した。その後、反応液を2時間攪拌し、反応を終了させた。反応液をヘプタン中に再沈することで生じた白色粉体をろ過により回収することで、樹脂b-1を得た。樹脂b-1の重量平均分子量(Mw)は30,000であった。Mwが1,000以下の成分の量は3質量%であった。
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
下記表に記載の原料を混合して感光性組成物を調製した。下記表に記載の配合量を表す数値は質量部である。
e-1:EHPE3150((株)ダイセル製)
各感光性組成物を、ガラス容器に入れて密封し、5℃で10ヶ月間保管した後、室温に戻し、以下の評価1、評価2を行って性能評価を行った。
下記表に記載の感光性組成物をそれぞれ、8インチ(20.32cm)のシリコン基板にスピンコート法で塗布し、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、厚さ0.9μmの感光性組成物層を形成した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して1μm四方のパターンを有するマスクを介して露光(露光量500mJ/cm2)した。次いで、露光後の感光性組成物層に対し、現像液として酢酸ブチル、2-ヘプタノン、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)、酢酸イソアミル、乳酸エチル、シクロヘキサノン、イソ酪酸イソブチル、またはアルカリ現像液(水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液)を用いて、23℃で60秒間シャワー現像を行った。その後、純水を用いてスピンシャワーにてリンスを行った。次いで、200℃のオーブンを用いて、1時間の熱処理(ポストベーク)を行うことにより、パターンを得た。
シリコン基板の真上から、シリコン基板上に形成されたパターンの幅およびパターンの対角線の長さを、測長SEM(走査型電子顕微鏡)を用いて観察した。以下の基準で矩形性を評価した。(パターンの対角線の長さ/1.41)×100の値が100に近いほど矩形性がよい。
6:(パターンの対角線の長さ/1.41)×100の値が99を超え101以下である。
5:(パターンの対角線の長さ/1.41)×100の値が98を超え99以下であるか、あるいは、101を超え102以下である。
4:(パターンの対角線の長さ/1.41)×100の値が97を超え98以下であるか、あるいは、102を超え103以下である。
3:(パターンの対角線の長さ/1.41)×100の値が96を超え97以下であるか、あるいは、103を超え104以下である。
2:(パターンの対角線の長さ/1.41)×100の値が95を超え96以下であるか、あるいは、104を超え105以下である。
1:(パターンの対角線の長さ/1.41)×100の値が95以下であるか、あるいは、105を超える。
透明画素形成用の感光性組成物をガラス基板上にスピンコート法で塗布し、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、厚さ0.9μmの感光性組成物層を形成した。なお、透明画素形成用の感光性組成物として、特開2014-63125の段落番号0353に記載の高屈折率材料(二酸化チタン含有硬化性組成物B01)を用いた。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して10μm四方のパターンを有するマスクを介して露光(露光量500mJ/cm2)した。次いで、露光後の感光性組成物層に対し、現像液としてアルカリ現像液(水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液)を用いて、23℃で60秒間シャワー現像を行った。その後、純水を用いてスピンシャワーにてリンスを行った。次いで、200℃のオーブンを用いて、1時間の熱処理(ポストベーク)を行うことにより、透明画素のパターン(以下、パターン1ともいう)を得た。
次に、パターン1が形成されたガラス基板上に、下記表に記載の感光性組成物をスピンコート法で塗布し、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、厚さ0.9μmの感光性組成物層を形成した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して10μm四方のパターンを有するマスクを介して露光(露光量500mJ/cm2)した。次いで、露光後の感光性組成物層に対し、現像液として酢酸ブチル、2-ヘプタノン、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)、酢酸イソアミル、乳酸エチル、シクロヘキサノン、イソ酪酸イソブチル、またはアルカリ現像液(水酸化テトラメチルアンモニウム(TMAH)0.3質量%水溶液)を用いて、23℃で60秒間シャワー現像を行った。その後、純水を用いてスピンシャワーにてリンスを行った。次いで、200℃のオーブンを用いて、1時間の熱処理(ポストベーク)を行うことにより、透明画素のパターンの抜け部に、下記表に記載の感光性組成物からなるパターン(以下、パターン2ともいう)を形成した。
T=100×B/A
6:Tの値が2未満である。
5:Tの値が2以上4未満である。
4:Tの値が4以上6未満である。
3:Tの値が6以上10未満である。
2:Tの値が10以上12未満である。
1:Tの値が12以上である。
緑色画素形成用の感光性組成物を、8インチ(20.32cm)のガラス基板にスピンコート法で塗布し、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、厚さ0.9μmの感光性組成物層を形成した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して3μm四方のパターンを有するマスクを介して露光(露光量500mJ/cm2)した。次いで、露光後の感光性組成物層に対し、現像液として酢酸ブチルを用いて、23℃で60秒間シャワー現像を行った。その後、純水を用いてスピンシャワーにてリンスを行った。次いで、200℃のオーブンを用いて、1時間の熱処理(ポストベーク)を行うことにより、緑色画素のパターンを形成した。
次に、緑色画素のパターンが形成されたガラス基板上に、赤色画素形成用の感光性組成物をスピンコート法で塗布し、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、厚さ0.9μmの感光性組成物層を形成した。次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して3μm四方のパターンを有するマスクを介して露光(露光量500mJ/cm2)した。次いで、露光後の感光性組成物層に対し、現像液として酢酸ブチルを用いて、23℃で60秒間シャワー現像を行った。その後、純水を用いてスピンシャワーにてリンスを行った。次いで、200℃のオーブンを用いて、1時間の熱処理(ポストベーク)を行うことにより、緑色画素のパターンの抜け部に、赤色画素のパターンを形成した。
緑色画素および赤色画素のそれぞれの矩形性について、評価1に準拠して評価したところ、緑色画素および赤色画素の矩形性は、いずれも「6」の評価であった。
また、緑色画素および赤色画素の分光を顕微分光装置を使用して隣の画素への光漏れ(クロストーク)を測定し、評価2に準拠して評価したところ、「6」の評価であった。
なお、試験例6では、緑色画素形成用の感光性組成物として、実施例1-6の感光性組成物を用い、赤色画素形成用の感光性組成物として、実施例2-6の感光性組成物を用いた。
Claims (17)
- 有機溶剤を含む現像液で現像してネガ型パターンを形成するために用いられる感光性組成物であって、
色材と、酸の作用により有機溶剤に対する溶解性が低下する樹脂と、光酸発生剤と、を含む感光性組成物。 - 前記感光性組成物の全固形分中における前記色材の含有量が55質量%以上である、請求項1に記載の感光性組成物。
- 前記感光性組成物に含まれる樹脂の合計量中における前記酸の作用により有機溶剤に対する溶解性が低下する樹脂の含有量が40質量%以上である、請求項1または2に記載の感光性組成物。
- 前記感光性組成物の全固形分中における前記酸の作用により有機溶剤に対する溶解性が低下する樹脂の含有量が10~60質量%である、請求項1~3のいずれか1項に記載の感光性組成物。
- 前記酸の作用により有機溶剤に対する溶解性が低下する樹脂は、酸の作用により分解して極性基を生じる基を含む、請求項1~4のいずれか1項に記載の感光性組成物。
- 前記酸の作用により有機溶剤に対する溶解性が低下する樹脂は、酸の作用により分解して脱離する基で極性基が保護された構造を有する、請求項1~5のいずれか1項に記載の感光性組成物。
- 前記酸の作用により分解して脱離する基は、式(Y1)~(Y4)のいずれかで表される基である、請求項6に記載の感光性組成物;
式(Y1):-C(R31)(R32)(R33)
式(Y2):-C(=O)OC(R31)(R32)(R33)
式(Y3):-C(R36)(R37)(OR38)
式(Y4):-C(Rn)(H)(Ar)
式(Y1)、(Y2)中、R31~R33は、各々独立にアルキル基を表し、R31~R33のうちの2つが結合して環を形成していてもよい;
式(Y3)中、R36およびR37は、各々独立に、水素原子、アルキル基またはアリール基を表し、R36およびR37の少なくとも一方がアルキル基またはアリール基であり、R38は、アルキル基またはアリール基を表し、R36またはR37と、R38とが結合して環を形成してもよい;
式(Y4)中、Arは、芳香環基を表し、Rnは、アルキル基またはアリール基を表す;RnとArとは互いに結合して環を形成してもよい。 - 前記酸の作用により分解して脱離する基の式量が170以下である、請求項6または7に記載の感光性組成物。
- 更に、酸架橋剤を含む、請求項1~8のいずれか1項に記載の感光性組成物。
- 前記感光性組成物の全固形分中における光ラジカル重合開始剤の含有量が4質量%以下である、請求項1~9のいずれか1項に記載の感光性組成物。
- 前記感光性組成物の全固形分中におけるラジカル重合性モノマーの含有量が5質量%以下である、請求項1~10のいずれか1項に記載の感光性組成物。
- 請求項1~11のいずれか1項に記載の感光性組成物から得られる膜。
- 請求項1~11のいずれか1項に記載の感光性組成物を用いて支持体上に感光性組成物層を形成する工程と、
前記感光性組成物層に対して、光を照射してパターン状に露光する工程と、
未露光部の感光性組成物層を、有機溶剤を含む現像液を用いて除去して現像する工程と、を有するパターンの形成方法。 - 請求項13に記載のパターンの形成方法を用いて第1の画素を形成した後、
請求項13に記載のパターンの形成方法を用いて第1の画素の抜け部に第2の画素を形成する、カラーフィルタの製造方法。 - 請求項12に記載の膜を有するカラーフィルタ。
- 請求項12に記載の膜を有する固体撮像素子。
- 請求項12に記載の膜を有する画像表示装置。
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