WO2017164161A1 - 感光性組成物、カラーフィルタ、パターン形成方法、固体撮像素子および画像表示装置 - Google Patents
感光性組成物、カラーフィルタ、パターン形成方法、固体撮像素子および画像表示装置 Download PDFInfo
- Publication number
- WO2017164161A1 WO2017164161A1 PCT/JP2017/011186 JP2017011186W WO2017164161A1 WO 2017164161 A1 WO2017164161 A1 WO 2017164161A1 JP 2017011186 W JP2017011186 W JP 2017011186W WO 2017164161 A1 WO2017164161 A1 WO 2017164161A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- mass
- photosensitive composition
- polymerizable monomer
- photopolymerization initiator
- Prior art date
Links
- 0 C*CC(*)(C1)COCC1(*(C)C)C(OC)=O Chemical compound C*CC(*)(C1)COCC1(*(C)C)C(OC)=O 0.000 description 3
Classifications
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
- C09B47/08—Preparation from other phthalocyanine compounds, e.g. cobaltphthalocyanineamine complex
- C09B47/10—Obtaining compounds having halogen atoms directly bound to the phthalocyanine skeleton
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- 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
- 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
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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
-
- 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
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
-
- 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
Definitions
- the present invention relates to a photosensitive composition, a color filter, a pattern forming method, a solid-state imaging device, and an image display device.
- CCD charge coupled device
- the color filter is formed using a photosensitive composition containing a colorant, a polymerizable monomer, and a photopolymerization initiator.
- Patent Document 1 describes an invention relating to a photosensitive composition containing a pigment, a transparent resin, a photopolymerizable compound, and a photopolymerization initiator containing an oxime compound having a nitro group.
- Patent Document 2 halogenated zinc phthalocyanine has been studied.
- the zinc halide phthalocyanine has a particularly low i-line transmittance compared to other phthalocyanines (for example, halogenated copper phthalocyanine and non-halogenated phthalocyanine). .
- other phthalocyanines for example, halogenated copper phthalocyanine and non-halogenated phthalocyanine.
- the adhesiveness with the base material etc. of a cured film tends to be insufficient.
- the concentration of zinc halide phthalocyanine in the photosensitive composition is increased or the thickness of the cured film is increased, the adhesiveness of the cured film to the substrate or the like tends to be insufficient.
- a method of increasing the content of the photopolymerization initiator can be considered in order to improve the adhesion of the cured film to the base material.
- the pattern is thicker than the desired line width during pattern formation. The pattern forming property tends to be lowered.
- an object of the present invention is to provide a photosensitive composition, a color filter, a pattern forming method, a solid-state imaging device, and an image display device capable of forming a cured film having excellent adhesion and pattern forming properties. .
- the present inventor has found that the above object can be achieved by using a photosensitive composition described later, and has completed the present invention. That is, the present invention is as follows.
- Photopolymerization initiator I A polymerizable monomer M having two or more groups having an ethylenically unsaturated double bond; Containing zinc halide phthalocyanine,
- the polymerizable monomer M contains a polymerizable monomer M 1 having three groups having an ethylenically unsaturated double bond
- the photopolymerization initiator I includes a photopolymerization initiator I 1 having a molar extinction coefficient at a wavelength of 365 nm of 12,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more,
- the photosensitive composition whose ratio of the mass of the photoinitiator I and the mass of the polymerizable monomer M is 0.15 or less by the mass of the photoinitiator I / the mass of the polymerizable
- the polymerizable monomer M is a polymerizable monomer M 1 containing 50 to 100% by weight, the photosensitive composition according to ⁇ 1>.
- the polymerizable monomer M 1 has an alkyleneoxy group, ⁇ 1> or photosensitive composition according to ⁇ 2>.
- the photopolymerization initiator I 1 comprises at least one selected from oxime compounds having an oxime compound and a naphthalene ring having a nitro group, a photosensitive according to any one of ⁇ 1> to ⁇ 3> Composition.
- the photopolymerization initiator I 1 contains a compound represented by the following formula (I-1), ⁇ 1> ⁇ photosensitive composition according to any one of ⁇ 4>;
- Ar 1 and Ar 2 each independently represent an aromatic ring
- Ar 3 represents an aryl group
- R 2 and R 3 each independently represents an alkyl group or an aryl group
- At least one of Ar 1 to Ar 3 , R 2 and R 3 has a fluorine atom, a group containing a fluorine atom or a nitro group as a substituent.
- the polymerizable monomer M is a polymerizable monomer M 2 having a group having an ethylenically unsaturated double bond four or more containing 50% by weight or less, in any one of ⁇ 1> to ⁇ 5>
- the photosensitive composition as described.
- ⁇ 7> A color filter using the photosensitive composition according to any one of ⁇ 1> to ⁇ 6>.
- ⁇ 8> A step of forming a photosensitive composition layer on a support using the photosensitive composition according to any one of ⁇ 1> to ⁇ 6>, and forming the photosensitive composition layer into a pattern
- a pattern forming method including a step of exposing and a step of developing and removing an unexposed portion to form a pattern.
- ⁇ 9> The pattern forming method according to ⁇ 8>, wherein the exposure is performed with i-line.
- 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, unless otherwise specified.
- the light used for exposure generally includes active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
- active rays or radiation such as an emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
- a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
- the total solid content means the total mass of components obtained by removing the solvent from all components of the composition.
- “(meth) acrylate” represents both and / or acrylate and methacrylate
- (meth) acryl” represents both and / or acrylic and “(meth) acrylic”.
- Allyl represents both and / or allyl and methallyl
- (meth) acryloyl represents both and / or acryloyl and methacryloyl.
- the term “process” not only indicates an independent process, but even if it cannot be clearly distinguished from other processes, the term “process” is used as long as the intended action of the process is achieved. included.
- a weight average molecular weight (Mw) and a number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).
- the pigment means an insoluble compound that is difficult to dissolve in a specific solvent.
- the pigment used in the present invention preferably has a solubility at 25 ° C. of 0.1 g / 100 g Solvent or less for both propylene glycol monomethyl ether acetate and water.
- the photosensitive composition of the present invention comprises A photoinitiator I; A polymerizable monomer M having two or more groups having an ethylenically unsaturated double bond; Containing zinc halide phthalocyanine, The polymerizable monomer M contains a polymerizable monomer M 1 having three groups having an ethylenically unsaturated double bond,
- the photopolymerization initiator I includes a photopolymerization initiator I 1 having a molar extinction coefficient at a wavelength of 365 nm of 12,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more,
- the ratio of the mass of the photopolymerization initiator I to the mass of the polymerizable monomer M is 0.15 or less in terms of the mass of the photopolymerization initiator I / the mass of the polymerizable monomer M.
- the photosensitive composition which can form the cured film excellent in adhesiveness and pattern formation property is obtained.
- the reason why such an effect can be obtained is estimated as follows. That is, a photosensitive composition containing a halogenated zinc phthalocyanine is obtained by using a photopolymerization initiator I 1 having a molar extinction coefficient at a wavelength of 365 nm of 12,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more as the photopolymerization initiator I. It is presumed that the sensitivity to i-line in an object could be improved.
- the polymerizable monomer M has a polymerizable group having three groups having an ethylenically unsaturated double bond.
- the optical density of the film at a wavelength of 365 nm is 2.0 or more. Is preferably 2.1 or more, more preferably 2.2 or more.
- the upper limit is not particularly limited, but can be 5.0 or less.
- the higher the optical density at a wavelength of 365 nm the more difficult it is to form a film having good adhesion to a support.
- a film having a high optical density at a wavelength of 365 nm is applied to a support. Can be formed with good adhesion. For this reason, the higher the optical density, the more remarkable the effect of the present invention.
- the optical density is a value expressed by the logarithm of the degree of absorption, and is a value defined by the following equation.
- OD ( ⁇ ) Log 10 [T ( ⁇ ) / I ( ⁇ )] ⁇ represents a wavelength
- T ( ⁇ ) represents a transmitted light amount at the wavelength ⁇
- I ( ⁇ ) represents an incident light amount at the wavelength ⁇ .
- a colorant that absorbs light at a wavelength of 365 nm is included. This can be achieved by appropriately adjusting the content of the colorant in the total solid content.
- the optical density of the film is a value measured by using a spectrometer UV4100 (manufactured by Hitachi High-Technologies Corporation) with the incidence of light having a wavelength of 365 nm.
- a spectrometer UV4100 manufactured by Hitachi High-Technologies Corporation
- the photosensitive composition of the present invention contains a halogenated zinc phthalocyanine.
- Zinc halide phthalocyanine is a compound in which the central metal zinc is located in a region surrounded by four nitrogens of the isoindole ring.
- the halogenated zinc phthalocyanine may be a dye (halogenated zinc phthalocyanine dye), but as a halogenated zinc phthalocyanine dye which is preferably a pigment (halogenated zinc phthalocyanine pigment), JP-A No. 2014-043555 and The description in Japanese Patent Application Laid-Open No. 2014-043556 can be referred to, and the contents thereof are incorporated in the present specification.
- the halogenated zinc phthalocyanine pigment is preferably a compound represented by the following formula (A1).
- arbitrary 8 to 16 of X 1 to X 16 represent a halogen atom, and the rest represent a hydrogen atom or a substituent.
- halogen atom examples include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom, and a bromine atom and a chlorine atom are particularly preferable.
- substituent the description in paragraph numbers 0025 to 0027 of JP2013-209623A can be referred to, and the contents thereof are incorporated in the present specification.
- halogenated zinc phthalocyanine pigment examples include, for example, the embodiments shown in the following ⁇ 1> and ⁇ 2> as preferable examples.
- ⁇ 1> A zinc halide phthalocyanine pigment having an average number of halogen atoms in one molecule of phthalocyanine of 8 to 12.
- X 1 to X 16 preferably contain one or more chlorine atoms, bromine atoms, and hydrogen atoms.
- X 1 to X 16 are preferably 0 to 4 chlorine atoms, 8 to 12 bromine atoms, and 0 to 4 hydrogen atoms.
- Halogenated zinc phthalocyanine having an average number of halogen atoms in one molecule of phthalocyanine of 10 to 14, an average number of bromine atoms of 8 to 12, and an average number of chlorine atoms of 2 to 5 Pigments.
- Specific examples thereof include compounds described in WO2015 / 118720.
- the zinc halide phthalocyanine pigment is, for example, C.I., which is a compound classified as a pigment in the color index (CI; issued by The Society of Dyer's and Colorists). I. Pigment green 58, 59, etc. can also be used.
- the content of the halogenated zinc phthalocyanine is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 30% by mass or more based on the total solid content in the photosensitive composition.
- the upper limit is preferably 80% by mass or less, more preferably 75% by mass or less, and further preferably 70% by mass or less.
- the content of the halogenated zinc phthalocyanine pigment is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more based on the total solid content in the photosensitive composition.
- 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.
- One kind of the halogenated zinc phthalocyanine pigment may be used. Further, two or more kinds of compounds having different combinations of X 1 to X 16 in the formula (A1) may be included. When 2 or more types are included, the total amount is preferably within the above range.
- the photosensitive composition of the present invention may further contain a colorant (other colorant) other than zinc halide phthalocyanine.
- the other colorant may be either a dye or a pigment, or a combination of both.
- the pigment include conventionally known various inorganic pigments or organic pigments. Further, considering that it is preferable to have a high transmittance, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having an average particle size as small as possible. 0.01 to 0.1 ⁇ m is preferable, and 0.01 to 0.05 ⁇ m is more preferable.
- inorganic pigments include metal compounds such as black pigments, metal oxides, and metal complex salts.
- black pigments such as carbon black and titanium black, iron, cobalt, aluminum, cadmium, lead, copper
- metal oxides such as titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.
- Examples of the organic pigment include the following.
- Examples of the dye include JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, Japanese Patent No. 2592207, and US Pat. No. 4,808,501. Disclosed in US Pat. No. 505950, US Pat. No. 5,667,920, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115, JP-A-6-194828, and the like. Can be used.
- pyrazole azo compounds When classified as chemical structure, pyrazole azo compounds, pyromethene compounds, anilinoazo compounds, triphenylmethane compounds, anthraquinone compounds, benzylidene compounds, oxonol compounds, pyrazolotriazole azo compounds, pyridone azo compounds, cyanine compounds, phenothiazine compounds, pyrrolopyrazole azomethine compounds, etc. Can be used.
- a dye multimer may be used.
- the dye multimer is preferably a dye used by being dissolved in a solvent, but may form particles.
- the dye multimer is dispersed in a solvent or the like.
- the particulate dye multimer can be obtained, for example, by emulsion polymerization. Specific examples thereof include compounds and production methods described in JP-A-2015-214682.
- compounds described in JP 2011-213925 A, JP 2013-041097 A, JP 2015-028144 A, JP 2015-030742 A, and the like can also be used. .
- quinophthalone compounds described in paragraph numbers 0011 to 0034 of JP2013-54339A can also be used.
- the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue pigment. Specific examples include compounds described in paragraph numbers 0022 to 0030 of JP2012-247491A and paragraph number 0047 of JP2011-157478A.
- the other colorant is preferably a yellow colorant.
- the yellow colorant include azo compounds, quinophthalone compounds, pyrazolone compounds, benzimidazolone compounds, quinoxaline compounds, azomethine compounds, quinophthalone compounds, isoindolinone compounds, isoindoline compounds, and anthraquinone compounds. According to this aspect, it is easy to obtain good spectroscopy. In particular, it is easy to manufacture a color filter having a spectrum suitable as a color filter for forming a green pixel.
- the other colorant is preferably an isoindoline compound. According to this aspect, it is easy to obtain good spectroscopy.
- the content of the other colorant is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the zinc halide phthalocyanine.
- the upper limit is more preferably 90 parts by mass or less, and still more preferably 80 parts by mass or less.
- the lower limit is more preferably 15 parts by mass or more, and still more preferably 20 parts by mass or more. If it is the said range, the spectral characteristic preferable on color reproducibility will be acquired.
- the photosensitive composition of the present invention contains a polymerizable monomer M having two or more groups having an ethylenically unsaturated double bond.
- the group having an ethylenically unsaturated double bond include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group.
- the polymerizable monomer M having two or more groups having an ethylenically unsaturated double bond include bifunctional or higher functional (meth) acrylates.
- the polymerizable monomer M is preferably a radical polymerizable monomer.
- the molecular weight of the polymerizable monomer M is preferably 100 to 3,000.
- the upper limit is more preferably 2,000 or less, further preferably 1,500 or less, and even more preferably 1,200 or less.
- the lower limit is more preferably 150 or more, and further preferably 250 or more.
- the polymerizable monomer M is preferably a compound other than a polymer. Examples of the compound other than the polymer include compounds having no molecular weight distribution.
- the content of the polymerizable monomer M is preferably 0.1 to 50% by mass with respect to the total solid content of the photosensitive composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 45% by mass or less, and further preferably 40% by mass or less.
- the polymerizable monomer M 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 a total amount becomes the said range.
- the polymerizable monomer M one containing a polymerizable monomer M 1 having three groups having an ethylenically unsaturated double bond (hereinafter also referred to as a trifunctional polymerizable monomer) is used.
- the trifunctional polymerizable monomer is preferably a trifunctional (meth) acrylate.
- the molecular weight of the trifunctional polymerizable monomer is preferably 250 to 1,300.
- the upper limit is more preferably 850 or less.
- the lower limit is more preferably 290 or more.
- the trifunctional polymerizable monomer may have an acid group such as a carboxy group, a sulfo group, and a phosphoric acid group, or may not have an acid group. From the reason that the permeability of the developer is increased, it is preferable that the developer does not have an acid group.
- the trifunctional polymerizable monomer may have a hydroxy group or may not have a hydroxy group. It is preferable that the developer does not have a hydroxy group because the developer has high permeability.
- the trifunctional polymerizable monomer preferably has an alkyleneoxy group.
- a trifunctional polymerizable monomer having an alkyleneoxy group By using a trifunctional polymerizable monomer having an alkyleneoxy group, an appropriate flexibility can be imparted to a cured film formed from the photosensitive composition, and pattern chipping or peeling at the time of development can be suppressed. The residual film ratio after development can be further increased.
- Examples of the trifunctional polymerizable monomer having an alkyleneoxy group include a compound represented by the following formula (M-1).
- M-1 represents a group having an ethylenically unsaturated double bond
- R 1 represents an alkylene group
- m represents an integer of 1 to 30
- L 1 represents a trivalent linking group.
- Examples of the group having an ethylenically unsaturated double bond represented by A 1 include a vinyl group, a (meth) allyl group, a (meth) acryloyl group, and a (meth) acryloyloxy group, and a (meth) acryloyloxy group is preferable. .
- the number of carbon atoms of the alkylene group represented by R 1 is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, particularly preferably 2 or 3, and most preferably 2.
- the alkylene group represented by R 1 is preferably linear or branched, and more preferably linear. Specific examples of the alkylene represented by R 1 include an ethylene group and a linear or branched propylene group.
- M represents an integer of 1 to 30, preferably an integer of 1 to 20, more preferably an integer of 1 to 10, more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.
- Examples of the trivalent linking group represented by L 1 include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a group composed of a combination thereof, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a complex.
- the aliphatic hydrocarbon group represented by L 1 preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and still more preferably 1 to 15 carbon atoms.
- the aliphatic hydrocarbon group may be linear, branched or cyclic, and is preferably branched.
- the number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and still more preferably 6 to 10.
- the heterocyclic group may be a non-aromatic heterocyclic group or an aromatic heterocyclic group.
- the heterocyclic group is preferably a 5-membered ring or a 6-membered ring. Examples of the hetero atom constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.
- the number of heteroatoms constituting the heterocyclic group is preferably 1 to 3.
- the heterocyclic group may be a single ring or a condensed ring.
- the trifunctional polymerizable monomer having an alkyleneoxy group is preferably a compound represented by the following formula (M-2).
- Formula (M-2) In the formula, L 1 represents a trivalent linking group, and R 1 represents a hydrogen atom or a methyl group. L 1 in formula (M-2) has the same meaning as L 1 in formula (M-1), and the preferred range is also the same.
- trifunctional polymerizable monomer examples include trimethylolpropane tri (meth) acrylate, trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (Meth) acrylate, pentaerythritol tri (meth) acrylate, etc. are mentioned. Moreover, the compound of the following structure is also mentioned.
- the trifunctional polymerizable monomer M 1 is preferably contained in the polymerizable monomer M in an amount of 50% by mass or more.
- the lower limit is more preferably 55% by mass or more, further preferably 65% by mass or more, and further preferably 80% by mass or more.
- the upper limit may be 100% by mass.
- Trifunctional polymerizable monomers M 1 may be only one kind, may contain two or more kinds. When containing trifunctional polymerizable monomers M 1 2 or more, it is preferred that the total is within the above range.
- the polymerizable monomer M preferably has the following aspect ⁇ 1> or ⁇ 2>.
- polymerizable monomer M is substantially trifunctional polymerizable monomers M 1 only mode that is configured in.
- the polymerizable monomer M has a trifunctional polymerizable monomer M 1 and a polymerizable monomer M 2 having 4 or more groups having an ethylenically unsaturated double bond (hereinafter also referred to as a tetrafunctional or higher functional polymerizable monomer). ).
- the adhesion can be further improved.
- the polymerizable monomer M is A is constituted only by substantially trifunctional polymerizable monomers M 1, trifunctional polymerizable monomers M 1 preferably contains more than 99 mass% in the polymerizable monomer M 99.5% by mass or more is more preferable, and it is more preferable that it is composed of only a trifunctional polymerizable monomer.
- the permeability of the developer to the cured film formed from the photosensitive composition can be increased. Furthermore, it is possible to impart an appropriate hardness to the cured film and make it difficult for the pattern to be peeled off even when pressure is applied to the film during rinsing, and the remaining film ratio of the pattern after development can be increased.
- the tetrafunctional or higher functional polymerizable monomer M 2 is preferably contained in the polymerizable monomer M at a ratio of 50% by mass or less.
- the upper limit is more preferably 35% by mass or less, and still more preferably 20% by mass or less.
- the lower limit is preferably 0.1% by mass or more, more preferably 1% by mass or more, and further preferably 3% by mass or more.
- a polymerizable monomer having two groups having an ethylenically unsaturated double bond (hereinafter also referred to as a bifunctional polymerizable monomer) is not substantially contained.
- “Containing substantially no bifunctional polymerizable monomer” means that the content of the bifunctional polymerizable monomer in the polymerizable monomer M is preferably 1% by mass or less, and more preferably 0.5% by mass or less. It is preferable that no bifunctional polymerizable monomer is contained.
- the average functional group number of the polymerizable monomer M is preferably 2.0 to 8.0, more preferably 2.5 to 7, and further preferably 3.0 to 6.0. preferable.
- the polymerizable monomer M 2 having 4 or more functional groups is preferably a polymerizable monomer having 4 to 15 groups having an ethylenically unsaturated double bond, and 4 to 10 groups having an ethylenically unsaturated double bond.
- a polymerizable monomer having more than one is more preferable, and a polymerizable monomer having 4 to 6 groups having an ethylenically unsaturated double bond is more preferable.
- Tetrafunctional or higher polymerizable monomer M 2 is preferably a tetra- or higher-functional (meth) acrylate.
- Examples of the tetrafunctional or higher polymerizable monomer M 2 include paragraph numbers 0095 to 0108 in JP-A-2009-288705, paragraph number 0227 in JP-A-2013-29760, and paragraph number 0254 in JP-A-2008-292970.
- the compounds described in 0257 can be referred to, the contents of which are incorporated herein.
- Tetrafunctional or higher polymerizable monomer M 2 is, (KAYARAD D-320 is commercially; manufactured by Nippon Kayaku Co.) dipentaerythritol tetraacrylate, KAYARAD D as dipentaerythritol penta (meth) acrylate (commercially available -310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd., A-DPH-12E; manufactured by Shin-Nakamura Chemical Co., Ltd.) ), And a structure in which these (meth) acryloyl groups are bonded via an ethylene glycol or propylene glycol residue (for example, SR454, SR499, commercially available from Sartomer).
- SR454, SR499 commercially available from Sartomer
- oligomer types can also be used.
- KAYARAD RP-1040 and DPCA-20 manufactured by Nippon Kayaku Co., Ltd.
- Aronix M-402, Aronix TO-1382, Aronix TO-2349 can also be used.
- the tetrafunctional or higher functional polymerizable monomer M 2 may have an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group.
- Examples include Aronix M-402, Aronix TO-1382, Aronix TO-2349, and the like.
- the acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mgKOH / g, and more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable monomer is 0.1 mgKOH / g or more, the development and dissolution properties of the cured film formed from the photosensitive composition are better, and if it is 40 mgKOH / g or less, in production and handling, More advantageous. Furthermore, curability is more excellent.
- the tetrafunctional or higher polymerizable monomer M 2 compounds having a caprolactone structure is also preferable.
- Compounds having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as the KAYARAD DPCA series, and examples include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.
- Tetrafunctional or higher polymerizable monomer M 2 can also be used a polymerizable monomer having an alkyleneoxy group.
- the polymerizable monomer having an alkyleneoxy group is preferably a polymerizable monomer having at least one selected from an ethyleneoxy group and a propyleneoxy group, more preferably a polymerizable monomer having an ethyleneoxy group, and 4 to 20 ethyleneoxy groups. More preferred are tetra- to hexa-functional (meth) acrylate compounds.
- Examples of commercially available polymerizable monomers having an alkyleneoxy group include SR-494, a tetrafunctional acrylate having four ethyleneoxy groups manufactured by Sartomer, and six pentyleneoxy groups manufactured by Nippon Kayaku Co., Ltd. And DPCA-60, which is a hexafunctional acrylate.
- Tetrafunctional or higher polymerizable monomers include urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765. And urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. . Further, addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 are used. Is also preferable.
- urethane oligomer UAS-10 UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.) UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) and the like.
- the photosensitive composition of the present invention contains a photopolymerization initiator I.
- the photopolymerization initiator is not particularly limited as long as it is a compound having the ability to initiate polymerization of the polymerizable monomer M by the action of light, and can be appropriately selected from known photopolymerization initiators.
- a compound having photosensitivity to light in the ultraviolet region to the visible region is preferable.
- action with a photoexcited sensitizer may be sufficient.
- the photopolymerization initiator I is preferably a compound having photosensitivity to i-line.
- the photopolymerization initiator I includes a photopolymerization initiator I 1 having a molar extinction coefficient at a wavelength of 365 nm of 12,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
- the upper limit of the molar absorption coefficient at a wavelength of 365nm of the photopolymerization initiator I 1 is preferably 40,000L ⁇ mol -1 ⁇ cm -1 or less, more preferably 35,000L ⁇ mol -1 ⁇ cm -1 or less, 30, More preferably, it is 000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or less.
- the molar extinction coefficient of the photopolymerization initiator at a wavelength of 365 nm is obtained by dissolving the photopolymerization initiator in a solvent to prepare a 5 mol% solution (measurement solution) of the photopolymerization initiator. It was calculated by measuring the absorbance. Specifically, the prepared measurement solution was put in a glass cell having a width of 1 cm, and the absorbance was measured using an Agilent Technologies UV-Vis-NIR spectrum meter (Cary 5000). The molar extinction coefficient (L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 ) was calculated. In the above formula, ⁇ represents the molar extinction coefficient (L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 ), A represents the absorbance, c represents the concentration (mol / L), and 1 represents the optical path length (cm).
- examples of the solvent used for preparing the measurement solution include acetonitrile and chloroform.
- the photopolymerization initiator is a compound that dissolves in acetonitrile
- a measurement solution is prepared using acetonitrile.
- the photopolymerization initiator is a compound that does not dissolve in acetonitrile but dissolves in chloroform
- a measurement solution is prepared using chloroform.
- the photopolymerization initiator is a compound that does not dissolve in acetonitrile and chloroform but dissolves in dimethyl sulfoxide
- a measurement solution is prepared using dimethyl sulfoxide.
- the photopolymerization initiator I 1 may be any compound as long as the molar absorption coefficient at a wavelength of 365 nm is 12,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more.
- an oxime compound is mentioned.
- the photopolymerization initiator I 1 is preferably at least one selected from an oxime compound having a nitro group and an oxime compound having a naphthalene ring. These compounds have a high molar extinction coefficient at a wavelength of 365 nm. By including such a compound, the sensitivity to the i-line of the photosensitive composition is increased, and a pattern with good adhesion is easily formed.
- the naphthalene ring is preferably condensed with another ring to form a condensed ring.
- the condensed ring containing a naphthalene ring include the following structures, and (CB-1) is preferred.
- R represents a hydrogen atom or a substituent.
- the photopolymerization initiator I 1 is preferably a compound represented by the following formula (I-1).
- Ar 1 and Ar 2 each independently represent an aromatic ring
- Ar 3 represents an aryl group
- R 2 and R 3 each independently represents an alkyl group or an aryl group
- At least one of Ar 1 to Ar 3 , R 2 and R 3 has a fluorine atom, a group having a fluorine atom or a nitro group as a substituent.
- the aromatic ring represented by Ar 1 and Ar 2 is preferably an aromatic hydrocarbon ring.
- the aromatic ring represented by Ar 1 and Ar 2 may be a single ring or a condensed ring.
- the number of carbon atoms constituting the aromatic ring is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aromatic ring is particularly preferably a benzene ring and a naphthalene ring. Of these, at least one of Ar 1 and Ar 2 is preferably a benzene ring, and Ar 1 is more preferably a benzene ring.
- Ar 2 is preferably a benzene ring or a naphthalene ring.
- the aromatic ring represented by Ar 1 and Ar 2 may have a substituent or may be unsubstituted.
- substituents include an alkyl group, an aryl group, a heterocyclic group, a nitro group, a cyano group, a halogen atom, —OR X1 , —SR X1 , —COR X1 , —COOR X1 , —OCOR X1 , —NR X1 R X2 , —NHCOR X1 , —CONR X1 R X2 , —NHCONR X1 R X2 , —NHCOOR X1 , —SO 2 R X1 , —SO 2 OR X1 , —NHSO 2 R X1 , —OR X3 —OR X1 and the like can be mentioned.
- R X1 and R X2 each independently represent a hydrogen atom, an alkyl group, an ary
- halogen atom examples include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
- the alkyl group as a substituent and the alkyl group represented by R X1 and R X2 preferably have 1 to 20 carbon atoms.
- the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
- part or all of the hydrogen atoms may be substituted with a halogen atom (preferably a fluorine atom).
- part or all of the hydrogen atoms may be substituted with the above substituents.
- the number of carbon atoms of the aryl group as a substituent and the aryl group represented by R X1 and R X2 is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aryl group may be a single ring or a condensed ring. In the aryl group, part or all of the hydrogen atoms may be substituted with the above substituents.
- the heterocyclic group as a substituent and the heterocyclic group represented by R X1 and R X2 are preferably 5-membered rings or 6-membered rings.
- the heterocyclic group may be a single ring or a condensed ring.
- the number of carbon atoms constituting the heterocyclic group is preferably from 3 to 30, more preferably from 3 to 18, and even more preferably from 3 to 12.
- the number of heteroatoms constituting the heterocyclic group is preferably 1 to 3.
- the hetero atom constituting the heterocyclic group is preferably a nitrogen atom, an oxygen atom or a sulfur atom. In the heterocyclic group, part or all of the hydrogen atoms may be substituted with the above substituents.
- the alkylene group represented by R X3 preferably has 1 to 20 carbon atoms.
- the alkylene group may be linear, branched or cyclic, but is preferably linear or branched.
- the number of carbon atoms of the aryl group represented by Ar 3 is preferably 6 to 20, more preferably 6 to 15, and particularly preferably 6 to 10.
- the aryl group represented by Ar 3 is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group.
- the aryl group represented by Ar 3 may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituents.
- R 2 and R 3 each independently represents an alkyl group or an aryl group.
- the alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, further preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
- the alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
- the alkyl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituents.
- the aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and still more preferably 6 to 10 carbon atoms.
- the aryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituents.
- At least one of Ar 1 to Ar 3 , R 2 and R 3 has a fluorine atom, a group containing a fluorine atom or a nitro group as a substituent, and at least one of Ar 1 to Ar 3 One preferably has a fluorine atom, a group containing a fluorine atom or a nitro group as a substituent, and at least one of Ar 1 to Ar 3 more preferably has a group containing a fluorine atom or a nitro group as a substituent. . Further, a nitro group, it is preferable that Ar 2 has.
- Ar 3 preferably has a fluorine atom and a group containing a fluorine atom.
- the group containing a fluorine atom is preferably an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing alkyl group) or a group containing an alkyl group having a fluorine atom (hereinafter also referred to as a fluorine-containing group).
- fluorine-containing group examples include —OR X11 , —SR X11 , —COR X11 , —COOR X11 , —OCOR X11 , —NR X11 R X12 , —NHCOR X11 , —CONR X11 R X12 , —NHCONR X11 R X12 , —NHCOOR At least one group selected from X11 , —SO 2 R X11 , —SO 2 OR X11, and —NHSO 2 R X11 is preferable.
- R X11 represents a fluorine-containing alkyl group
- R X12 represents a hydrogen atom, an alkyl group, a fluorine-containing alkyl group, an aryl group, or a heterocyclic group.
- the fluorine-containing group is more preferably —OR X11 .
- the group containing a fluorine atom preferably has a terminal structure represented by the following formula (F1) or formula (F2). * In the formula represents a connecting hand. * -CHF 2 (F1) * -CF 3 (F2)
- the fluorine-containing alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, still more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms.
- the fluorine-containing alkyl group may be linear, branched or cyclic, but is preferably linear or branched.
- the fluorine-containing alkyl group preferably has a fluorine atom substitution rate of 40 to 100%, more preferably 50 to 100%, and still more preferably 60 to 100%.
- the substitution rate of the fluorine atom in a fluorine-containing alkyl group is the value which represented the ratio by which the hydrogen atom of the alkyl group was substituted by the fluorine atom in percentage.
- the alkyl group, aryl group and heterocyclic group represented by R X12 have the same meanings as those described above for the alkyl group, aryl group and heterocyclic group represented by R X1 and R X2 .
- oxime compound having a fluorine atom examples include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-T-2014-500852, and JP 2013-164471 A. (C-3) described in the above. This content is incorporated herein. Moreover, the following compound is also mentioned.
- oxime compound having a nitro group examples include compounds described in paragraph Nos. 0029 to 0037 of JP 2010-256891, and paragraph Nos. 0007 to 0033 of JP 2010-15025 A.
- the following compound is also mentioned.
- the photopolymerization initiator I further contains a photopolymerization initiator having a molar extinction coefficient at a wavelength of 365 nm of less than 12000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 (hereinafter also referred to as other photopolymerization initiator). You can also.
- photopolymerization initiators include, for example, halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, oxime Examples include oxime compounds such as derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
- trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, oniums
- a compound selected from the group consisting of a compound, a benzothiazole compound, a benzophenone compound, a hydroxyacetophenone compound, an aminoacetophenone compound, a cyclopentadiene-benzene-iron complex and a salt thereof, a halomethyloxadiazole compound, and a 3-aryl-substituted coumarin compound preferable.
- hydroxyacetophenone compounds As other photopolymerization initiators, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. Examples thereof include aminoacetophenone compounds described in JP-A-10-291969 and acylphosphine compounds described in Japanese Patent No. 4225898.
- hydroxyacetophenone compound IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, and IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone compound As the aminoacetophenone compound, IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone compound the compounds described in JP2009-191179A can also be used.
- acylphosphine compound IRGACURE-819 or DAROCUR-TPO (trade name: both manufactured by BASF) can be used.
- an oxime compound as another photopolymerization initiator.
- the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, compounds described in JP-A No. 2006-342166, and JP-A No. 2016.
- the compounds described in JP-A No. 21012 can be used.
- oxime compound examples include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3- ON, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutan-2-one, and 2-ethoxy And carbonyloxyimino-1-phenylpropan-1-one.
- Oxime compounds are described in J. Org. C. S. Perkin II (1979) pp. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. 202-232, JP-A 2000-66385, JP-A 2000-80068, JP-T 2004-534797, JP-A 2006-342166, and the like can also be used.
- IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 are also preferably used.
- TRONLY TR-PBG-304, TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD)
- Adeka Arcles 30 Adekaoptomer N-1919 (photopolymerization initiator 2 disclosed in JP2012-14052A) (manufactured by ADEKA Co., Ltd.) can also be used.
- oxime compounds other than those described above compounds described in JP-T 2009-519904, in which an oxime is linked to the nitrogen atom of carbazole, and compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety
- a ketoxime compound described in International Publication WO2009 / 131189 a compound described in US Pat. No. 7,556,910 containing a triazine skeleton and an oxime skeleton in the same molecule, an absorption maximum at 405 nm, and a g-line light source
- compounds described in JP-A-2009-221114 having good sensitivity may be used.
- the oxime compound is preferably a compound represented by the following formula (OX-1).
- the oxime compound may be an oxime compound in which the oxime N—O bond is in the (E) form, the oxime N—O bond may be in the (Z) form, or the (E) form. And a mixture of (Z) isomers.
- R and B each independently represent a monovalent substituent
- A represents a divalent organic group
- Ar represents an aryl group.
- the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
- the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
- these groups may have one or more substituents.
- the substituent mentioned above may be further substituted by another substituent.
- the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
- the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
- an oxime compound having a fluorene ring can also be used.
- Specific examples of the oxime compound having a fluorene ring include compounds described in JP-A-2014-137466. This content is incorporated herein.
- an oxime compound having a benzofuran skeleton can also be used.
- Specific examples include OE-01 to OE-75 described in International Publication WO2015 / 036910.
- the other photopolymerization initiator is preferably a compound having a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, and more preferably a compound having a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm. Further, compounds having high absorbance at 365 nm and 405 nm are particularly preferable.
- the content of the photopolymerization initiator I is preferably 0.1 to 50% by mass, more preferably 0.5 to 30% by mass, and still more preferably 1%, based on the total solid content of the photosensitive composition. ⁇ 20% by weight. Within this range, better sensitivity and pattern formability can be obtained.
- the photosensitive composition of the present invention may contain only one type of photopolymerization initiator I, or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.
- the content of the photopolymerization initiator I 1 having a molar extinction coefficient of 12,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more at a wavelength of 365 nm is 25% relative to the mass of the photopolymerization initiator I.
- the content is preferably at least mass%, more preferably at least 30 mass%, and even more preferably at least 50 mass%.
- the photopolymerization initiator I 1 included in the photopolymerization initiator I may be only one type or two or more types. When containing a photopolymerization initiator I 1 2 or more, it is preferable that the total amount thereof falls within the above range.
- the photopolymerization initiator I is also preferably contain only substantially photopolymerization initiator I 1. According to this aspect, it is easier to achieve both adhesion and pattern formation.
- the photopolymerization initiator I is a is composed of only substantially photopolymerization initiator I 1, relative to the weight of the photopolymerization initiator I, a photopolymerization initiator I 1 99 wt% content it is preferred to, more preferably contains more than 99.5 wt%, more preferably it contains only photoinitiator I 1.
- the photopolymerization initiator I comprises a photopolymerization initiator I 1, it is also preferred to include a photopolymerization initiator I 1 other than the photopolymerization initiator (other photopolymerization initiator). According to this aspect, an effect of increasing the remaining film ratio after development of the cured film formed from the photosensitive composition can be expected.
- Photopolymerization initiator I is a photopolymerization initiator I 1, if it contains other photoinitiators, the content of the other photopolymerization initiator, relative to 100 parts by mass of the photopolymerization initiator I 1 25 to 300 parts by mass, preferably 50 to 200 parts by mass, and more preferably 50 to 100 parts by mass.
- the proportion of the photopolymerization initiator I 1 and the other photopolymerization initiator in the above range it is possible to increase the yield of residual film thickness after development of the cured film formed from the photosensitive composition.
- the ratio of the mass of the photopolymerization initiator I to the mass of the polymerizable monomer M is 0.15 or less. 0.12 or less is preferable, and 0.10 or less is more preferable.
- the lower limit is preferably 0.02 or more, and more preferably 0.04 or more.
- the mass of the photopolymerization initiator I, ethylenically unsaturated double the ratio between the mass of the polymerizable monomer M 1 having three group having a bond is preferably 0.01 to 0.70, more preferably 0.05 to 0.50, and still more preferably 0.07 to 0.30.
- Ratio of mass of photopolymerization initiator I 1 having a molar extinction coefficient of 12,000 L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 or more at a wavelength of 365 nm to mass of polymerizable monomer M (mass of photopolymerization initiator I 1 / polymerizability)
- the mass of the monomer M (hereinafter also referred to as I 1 / M) is preferably from 0.01 to 0.70, more preferably from 0.01 to 0.40, and even more preferably from 0.02 to 0.30.
- the ratio to the mass is preferably 0.01 to 0.40, preferably 0.01 to 0.30 is more preferable, and 0.02 to 0.20 is even more preferable.
- the photosensitive composition of this invention can contain the compound (henceforth an epoxy compound) which has an epoxy group.
- the epoxy compound include compounds having one or more epoxy groups in one molecule, and compounds having two or more are preferable.
- the epoxy compound preferably has 1 to 100 epoxy groups in one molecule.
- the lower limit is more preferably 2 or more.
- the upper limit may be 10 or less, and may be 5 or less.
- the epoxy compound is preferably a compound having at least one selected from an aromatic ring and an aliphatic ring, and more preferably a compound having an aliphatic ring.
- the epoxy group is preferably bonded to the aromatic ring or the aliphatic ring via a single bond or a linking group.
- the linking group include an alkylene group, an arylene group, —O—, —NR ′ — (R ′ represents a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent. And a hydrogen atom is preferred), —SO 2 —, —CO—, —O—, —S— and a group formed by combining these.
- the epoxy compound is a compound having an aliphatic ring
- a compound in which the epoxy group is directly bonded (single bond) to the aliphatic ring is preferable.
- a compound having an aromatic ring a compound in which an epoxy group is bonded to the aromatic ring via a linking group is preferable.
- the linking group is preferably an alkylene group or a group comprising a combination of an alkylene group and —O—.
- the epoxy compound a compound having a structure in which two or more aromatic rings are connected by a hydrocarbon group can also be used as the epoxy compound.
- the hydrocarbon group is preferably an alkylene group having 1 to 6 carbon atoms. It is preferable that the epoxy group is connected via the connecting group.
- the epoxy compound may be a low molecular compound (for example, a molecular weight of less than 1,000) or a high molecular compound (for example, a molecular weight of 1,000 or more, and in the case of a polymer, the weight average molecular weight is 1,000 or more). Good.
- the weight average molecular weight of the epoxy compound is preferably 200 to 100,000, more preferably 500 to 50,000.
- the upper limit of the weight average molecular weight is more preferably 10,000 or less, further preferably 5,000 or less, and still more preferably 3000 or less.
- Examples of the bisphenol F type epoxy resin include jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, made by DIC Corporation), LCE-21, RE-602S. (Nippon Kayaku Co., Ltd.) and the like.
- phenol novolac type epoxy resins jER152, jER154, jER157S70, jER157S65 (Mitsubishi Chemical Co., Ltd.), EPICLON N-740, EPICLON N-770, EPICLON N-775 (above, DIC Corporation), etc. Is mentioned.
- Cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695 (above, manufactured by DIC Corporation) ), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like.
- Aliphatic epoxy resins include ADEKA RESIN EP-4080S, EP-4085S, EP-4088S (manufactured by ADEKA), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEAD PB 3600, PB 4700 (above, manufactured by Daicel Corporation), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX-850L (above, manufactured by Nagase ChemteX Corporation), etc. Can be mentioned.
- ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Mitsubishi Chemical Corporation), and the like.
- the compound represented by a following formula (EP1) can also be used for an epoxy compound.
- R EP1 to R EP3 each independently represent a hydrogen atom, a halogen atom or an alkyl group, and the alkyl group may have a cyclic structure, and has a substituent. It may be. R EP1 and R EP2 , R EP2 and R EP3 may be bonded to each other to form a ring.
- QEP represents a single bond or an nEP- valent organic group.
- R EP1 ⁇ R EP3 combines with Q EP may form a ring.
- nEP represents an integer of 1 or more, preferably 2 to 10, and more preferably 2 to 6. However, n EP is 2 when Q EP 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 glycidyl trityl ether. Further, there are compounds described in paragraph No. 0090 of JP2014-089408A, the contents of which are incorporated herein.
- the content of the epoxy compound is preferably 0.1 to 40% by mass with respect to the total solid content of the photosensitive composition.
- the lower limit is more preferably 0.5% by mass or more, and further preferably 1% by mass or more.
- the upper limit is more preferably 30% by mass or less, and further preferably 20% by mass or less.
- An epoxy compound 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 a sum total becomes the said range.
- the photosensitive composition of the present invention contains substantially no epoxy compound. “Containing substantially no epoxy compound” is preferably 0.05% by mass or less, more preferably 0.01% by mass or less, and still more preferably not contained, based on the total solid content of the photosensitive composition.
- the photosensitive composition of the present invention preferably contains a resin.
- the resin is blended, for example, for the purpose of dispersing a pigment or the like in the composition and the purpose of a binder.
- the resin mainly used for dispersing the pigment is also referred to as a dispersant.
- such use of the resin is merely an example, and the resin can be used for other purposes.
- the resin content is preferably 1 to 80% by mass with respect to the total solid content of the photosensitive composition.
- the lower limit is more preferably 5% by mass or more, and further preferably 10% by mass or more.
- the upper limit is more preferably 70% by mass or less, and still more preferably 60% by mass or less.
- the photosensitive composition of the present invention preferably contains a dispersant as a resin.
- a dispersant when a pigment is used, it is preferable to include a dispersant.
- the dispersant include an acidic dispersant (acidic resin) and a basic dispersant (basic resin).
- the dispersant preferably includes at least an acidic dispersant, and more preferably only an acidic dispersant.
- the dispersant contains at least an acidic dispersant, the dispersibility of the pigment is improved, and the uneven brightness of the cured film formed from the photosensitive resin is less likely to occur. Furthermore, since excellent developability is obtained in the cured film, pattern formation can be suitably performed by photolithography.
- content of an acidic dispersing agent in the total mass of a dispersing agent is 99 mass% or more, for example, that a dispersing agent is only an acidic dispersing agent, and it may also be 99.9 mass% or more. it can.
- the acidic dispersant 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 carboxy group.
- the acid value of the acidic dispersant (acidic resin) is preferably 5 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 dispersant examples include a polymer dispersant [for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth). Acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.
- a polymer dispersant for example, polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth).
- Acrylic copolymer, naphthalenesulfonic acid formalin condensate] polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine and the like.
- Polymer dispersants can be classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
- the polymer dispersant acts to adsorb on the surface of the pigment and prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
- a dispersant described in paragraphs 0028 to 0124 of JP2011-070156A and a dispersant described in JP2007-277514A are also preferably used, and the contents thereof are incorporated herein.
- L 10 represents an (n + k) -valent linking group
- L 11 and L 12 each independently represent a single bond or a divalent linking group
- a 10 represents a dye structure, a complex Ring structure, acidic group, group having basic nitrogen atom, urea group, urethane group, group having coordinating oxygen atom, hydrocarbon group having 4 or more carbon atoms, alkoxysilyl group, epoxy group, isocyanate group, and hydroxy
- a monovalent organic group containing at least one site selected from the group is represented, and n A 10 and L 11 may be the same or different independently.
- the k L 12 and P 10 may be the same or different.
- k represents 1 to 8
- n represents 2 to 9
- P 10 represents a monovalent polymer chain having a repeating unit.
- L 10 to L 12 , P 10 and A 10 can be referred to the descriptions in paragraph numbers 0041 to 0098 of JP-A-2007-277514, the contents of which are incorporated herein.
- Specific examples of the resin represented by the formula (D) include resins described in paragraph numbers 0327 to 0347 of JP-A-2007-277514, the contents of which are incorporated herein.
- a graft copolymer containing a repeating unit represented by any of the following formulas (1) to (4) can also be used.
- W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH
- X 1 , X 2 , X 3 , X 4 , and X 5 each independently represents a hydrogen atom or a monovalent group
- Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group
- Z 1 , Z 2 , Z 3 and Z 4 each independently represent a monovalent group
- R 3 represents an alkylene group
- R 4 represents a hydrogen atom or a monovalent group
- n, m, p, and q each represent Independently represents an integer of 1 to 500
- j and k each independently represent an integer of 2 to 8, and when p is 2 to 500 in the formula (3), a plurality of R 3 are the same as each other Or in formula (4), when q is 2 to 500, a plurality of them are present.
- 5 and R 4 may be different from one another the same.
- W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
- X 1 , X 2 , X 3 , X 4 , and X 5 are preferably each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and each independently a hydrogen atom or a methyl group. Are more preferable, and a methyl group is particularly preferable.
- Y 1 , Y 2 , Y 3 , and Y 4 each independently represent a divalent linking group, and the linking group is not particularly limited in structure.
- the structure of the monovalent group represented by Z 1 , Z 2 , Z 3 , and Z 4 is not particularly limited.
- an alkyl group, a hydroxy group, an alkoxy group, an aryloxy group, a heteroaryloxy group examples thereof include an alkyl thioether group, an aryl thioether group, a heteroaryl thioether group, and an amino group.
- the monovalent group represented by Z 1 , Z 2 , Z 3 , and Z 4 is preferably a group having a steric repulsion effect from the viewpoint of improving dispersibility, and is independently an alkyl group having 5 to 24 carbon atoms.
- an alkoxy group is more preferable, and each independently a branched alkyl group having 5 to 24 carbon atoms, a cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group having 5 to 24 carbon atoms is more preferable.
- the alkyl group contained in the alkoxy group may be linear, branched or cyclic.
- n, m, p, and q are each independently an integer of 1 to 500.
- j and k each independently represent an integer of 2 to 8.
- J and k in the formulas (1) and (2) are preferably integers of 4 to 6 and most preferably 5 from the viewpoints of dispersion stability and developability.
- R 3 represents an alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, and more preferably an alkylene group having 2 or 3 carbon atoms.
- p is 2 to 500, a plurality of R 3 may be the same or different from each other.
- R 4 represents a hydrogen atom or a monovalent organic group.
- the monovalent organic group is not particularly limited in terms of structure.
- R 4 preferably includes a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and more preferably a hydrogen atom or an alkyl group.
- R 4 is an alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl group having 5 to 20 carbon atoms is preferable, and a straight chain having 1 to 20 carbon atoms is preferred.
- a chain alkyl group is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is particularly preferable.
- a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
- the details of the graft copolymer can be referred to the description in paragraphs 0025 to 0094 of JP2012-255128A, the contents of which are incorporated herein.
- Specific examples of the graft copolymer include, for example, resins described in JP-A-2012-255128, paragraphs 0072 to 0094, the contents of which are incorporated herein.
- an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and the side chain can be used.
- the oligoimine-based dispersant has a repeating unit having a partial structure X having a functional group of pKa14 or less and a side chain containing a side chain Y having 40 to 10,000 atoms, and has a main chain and a side chain.
- a resin having at least one basic nitrogen atom is preferred.
- the basic nitrogen atom is not particularly limited as long as it is a basic nitrogen atom.
- oligoimine-based dispersant the description in paragraphs 0102 to 0174 of JP 2012-255128 A can be referred to, and the above contents are incorporated in this specification.
- resins described in paragraph numbers 0168 to 0174 of JP 2012-255128 A can be used.
- the dispersant is also available as a commercial product. Specific examples of such a dispersant include “DA-7301” manufactured by Enomoto Kasei Co., Ltd., “Disperbyk-101 (polyamidoamine phosphate)” manufactured by BYK Chemie, 107 (carvone).
- Acid ester 110 (copolymer containing acid group), 111 (phosphate dispersing agent), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ""BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid)” manufactured by BYKChemie, "EFKA4047, 4050-4165 (polyurethane)", EFKA4330-4340 (block copolymer), 4400-4402 (modified) manufactured by EFKA Polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight poly) "Lubonic acid salt", 6220 (fatty acid polyester), 6745 (phthalocyanine derivative), 6750 (azo pigment derivative) "," Ajisper PB821, PB822, PB880, PB881 "manufactured by Ajinomoto Fine Techno Co., Ltd.,” Kyoeisha Chemical Co., Ltd.
- Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 manufactured by San Nopco Co., Ltd.
- Adeka Pluronic L31, F38, L42, L44, L61, L64, F68, L72 manufactured by ADEKA Corporation , P95, F77, P84, F87, P94, L101, P103, F108, L121, P-123 ”,“ Ionet S-20 ”manufactured by Sanyo Chemical Co., Ltd., and the like.
- resin described as said dispersing agent can also be used for uses other than a dispersing agent. For example, it can be used as a binder.
- the photosensitive composition of the present invention preferably contains an alkali-soluble resin as a resin.
- the alkali-soluble resin can also be used as a dispersant or a binder.
- the molecular weight of the alkali-soluble resin is not particularly defined, but the weight average molecular weight (Mw) is preferably 5,000 to 100,000.
- the number average molecular weight (Mn) is preferably 1,000 to 20,000.
- the alkali-soluble resin can be appropriately selected from resins having a group that promotes alkali solubility. Examples of the group that promotes alkali solubility (hereinafter also referred to as an acid group) include a carboxy group, a phosphate group, a sulfo group, and a phenolic hydroxy group, and a carboxy group is preferred.
- the alkali-soluble resin may have only one type of acid group or two or more types.
- the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin from the viewpoint of heat resistance. From the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
- the alkali-soluble resin is preferably a polymer having a carboxy group in the side chain.
- alkali-soluble phenol resins such as methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, and novolac resin And the like.
- a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
- Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
- alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate Etc
- Examples of the vinyl compound include styrene, ⁇ -methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer, and the like.
- Examples of other monomers include N-substituted maleimide monomers described in JP-A-10-300922, such as N-phenylmaleimide and N-cyclohexylmaleimide. Only one kind of these other monomers copolymerizable with (meth) acrylic acid may be used, or two or more kinds may be used.
- alkali-soluble resin examples include benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, and benzyl (meth) acrylate.
- a multi-component copolymer composed of / (meth) acrylic acid / other monomers can be preferably used.
- FF-426 manufactured by Fujikura Kasei
- an alkali-soluble resin having a polymerizable group can also be used.
- the polymerizable group include a (meth) allyl group and a (meth) acryloyl group.
- an alkali-soluble resin having a polymerizable group an alkali-soluble resin having a polymerizable group in the side chain is useful.
- alkali-soluble resin having a polymerizable group examples include Dianal NR series (produced by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (produced by COOH-containing polyurethane acrylic oligomer Co., Ltd., 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 Corporation), Examples include ACRYCURE RD-F8 (manufactured by Nippon Shokubai Co., Ltd.) and DP-1305 (manufactured by Fuji Fine Chemicals Co., Ltd.).
- the alkali-soluble resin includes at least one compound selected from the compound represented by the following formula (ED1) and the compound represented by the formula (1) in JP 2010-168539 A (hereinafter referred to as “ether dimer”). It is also preferable to include a polymer obtained by polymerizing a monomer component including “.
- R 1 and R 2 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
- 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.
- Examples of the polymer obtained by polymerizing a monomer component containing an ether dimer include the following structures.
- the alkali-soluble resin may contain a repeating unit derived from the 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 represents a hydrogen atom or a benzene ring that may contain a benzene ring.
- 20 alkyl groups are represented.
- n represents an integer of 1 to 15.
- the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
- the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain a benzene ring.
- Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
- the alkali-soluble resin can be referred to the description in paragraph Nos. 0558 to 0571 in JP 2012-208494 A (corresponding to paragraph numbers 0685 to 0700 in US 2012/0235099). Incorporated in the description. Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 of JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraphs 0088 to 0098 of JP 2012-208474 A The binder resin described in the description and the binder resin used in the examples, the binder resin described in paragraphs 0022 to 0032 of JP2012-137531A and the binder resin used in the examples, JP2013-024934A Binder resin described in paragraph Nos.
- the acid value of the alkali-soluble resin is preferably 30 to 500 mgKOH / g.
- the lower limit is more preferably 50 mgKOH / g or more, and further preferably 70 mgKOH / g or more.
- the upper limit is more preferably 400 mgKOH / g or less, further preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and still more preferably 120 mgKOH / g or less.
- the content of the alkali-soluble resin is preferably 1 to 80% by mass with respect to the total solid content of the photosensitive composition.
- the lower limit is more preferably 2% by mass or more, and further preferably 3% by mass or more.
- the upper limit is more preferably 70% by mass or less, and still more preferably 60% by mass or less.
- the photosensitive composition of this invention may contain only 1 type of alkali-soluble resin, and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
- the photosensitive composition of the present invention preferably contains a solvent.
- the solvent is preferably an organic solvent.
- the organic solvent is not particularly limited as long as the solubility of each component and the applicability of the photosensitive composition are satisfied.
- Examples of the organic solvent include the following.
- Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkoxyacetate ( For example, methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl esters of 3-alkoxypropionic acid (eg, Methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc
- 2-alkoxypropionic acid alkyl esters eg, methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc.
- 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).
- Solvents may be used alone or in combination of two or more. When two or more solvents are used in combination, particularly preferred are methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, Two types selected from heptanone, cyclohexanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol methyl ether, propylene glycol monomethyl ether acetate (1-methoxy-2-propyl acetate) and 2-methoxy-1-propyl acetate It is a mixed solution comprised by the above.
- the solvent preferably contains 2-methoxy-1-propyl acetate.
- the content of 2-methoxy-1-propyl acetate is preferably 0.001 to 5% by mass with respect to the mass of the photosensitive composition.
- the upper limit is more preferably 3% by mass or less, and further preferably 2% by mass or less.
- the content of 2-methoxy-1-propyl acetate is preferably 0.01 to 0.5% by mass with respect to the mass of the solvent.
- the lower limit is more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more.
- the upper limit is more preferably 0.4% by mass or less, and further preferably 0.2% by mass or less.
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide. Further, it is preferable to use an organic solvent having a low metal content.
- the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less. If necessary, the organic solvent having a metal content of mass ppt (parts per trill) level may be used, and such a high-purity solvent is provided by Toyo Gosei Co., Ltd. (Chemical Industry Daily) , November 13, 2015).
- the content of the solvent is preferably such that the total solid content of the photosensitive composition is 5 to 80% by mass.
- the lower limit is more preferably 10% by mass or more.
- the upper limit is more preferably 60% by mass or less, further preferably 50% by mass or less, and further preferably 40% by mass or less.
- a curing accelerator may be added to the photosensitive composition of the present invention.
- the curing accelerator include aromatic amine compounds and thiol compounds.
- the aromatic amine compound may be a monofunctional aromatic amine compound having one amino group or a polyfunctional aromatic amine compound having two or more amino groups.
- the aromatic amine compound is preferably a compound represented by the following formula (Am-1) or the following formula (Am-2), and more preferably a compound represented by the following formula (Am-2).
- R a1 to R a6 each independently represents a hydrogen atom or a substituent, and at least one of R a1 to R a6 represents —NR 100 R 101 or —NR 100 R 101 Represents a group having R 100 and R 101 each independently represents a hydrogen atom or a substituent. Of R a1 to R a6 , two adjacent groups may combine to form a ring.
- R b1 to R b10 each independently represents a hydrogen atom or a substituent, and at least one of R b1 to R b10 represents —NR 100 R 101 or —NR 100 R 101 Represents a group having Of R b1 to R b10 , two adjacent groups may combine to form a ring.
- a 1 represents a single bond or a divalent linking group.
- R 100 and R 101 each independently represents a hydrogen atom or a substituent.
- Examples of the substituent represented by R 100 and R 101 include an alkyl group, an aryl group, and a heterocyclic group, and an alkyl group is preferable.
- 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.
- the alkyl group is preferably linear or branched, and more preferably linear.
- Examples of the substituent represented by R a1 to R a6 and R b1 to R b10 include an alkyl group and a nitro group.
- the divalent linking group represented by A 1 includes an alkylene group, —O—, —CO—, —OCO—, —COO—, —SO 2 —, —SO—, —S—, and combinations thereof.
- the alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
- the alkylene group is preferably linear or branched.
- the alkylene group may be unsubstituted or may have a substituent. Examples of the substituent include a halogen atom.
- aromatic amine compound examples include aniline, N, N-dimethylaniline, N-ethyl-N-methylaniline, N, N-diethylaniline, 4-nitroaniline, N, N-dimethyl-4-nitroaniline.
- 4,4'-diaminobiphenyl 3,5-bistrifluoromethyl-1,2-diaminobenzene, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,3-bis (4-aminophenyl) Succinonitrile, 4,4'-diaminobenzophenone, 4,4'-diaminophenylbenzoate, 4,4'-diaminodiphenylsulfone, 1,4-diamino-2-chlorobenzene, 1,4-diamino-2-bromobenzene 1,4-diamino-2-iodobenzene, 1,4-diamino-2-nitrobenzene, 1,4-diamy -2-trifluoromethylbenzene, 2,5-diaminobenzonitrile, 2,5-diaminoacetophenone, 2,5-diaminobenzoic acid, 2,2'-dichlor
- thiol compound examples include polyfunctional thiol compounds having two or more mercapto groups in the molecule.
- the polyfunctional thiol compound may be added for the purpose of improving stability, odor, resolution, developability, adhesion and the like.
- the polyfunctional thiol compound is preferably a secondary alkanethiol, and particularly preferably a compound having a structure represented by the following formula (T1).
- T1 In the formula (T1), n represents an integer of 2 to 4, and L represents a divalent to tetravalent linking group.
- the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, particularly preferably n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
- Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by the formula (T2) is particularly preferable.
- the thiol compounds can be used singly or in combination.
- a methylol compound for example, a compound exemplified as a crosslinking agent in paragraph No. 0246 of JP-A-2015-34963
- an amine for example, a compound exemplified as a crosslinking agent in paragraph No. 0246 of JP-A-2015-34963
- an amine for example, a phosphonium salt, an amidine salt
- an amide compound for example, JP-A-2013-41165, curing agent described in paragraph No. 0186
- base generator for example, ionic compound described in JP-A-2014-55114
- cyanate compound for example, JP-A-2012-150180
- an alkoxysilane compound for example, an alkoxysilane compound having an epoxy group described in JP2011-255304A
- an onium salt compound for example, JP2015-34963A
- an acid generator Illustrated as an acid generator in paragraph 0216 Compounds, compounds described in JP-A-2009-180949) or the like can be used.
- the content of the curing accelerator is preferably 0.3 to 8.9% by mass with respect to the total solid content of the photosensitive composition, 0.8 More preferred is ⁇ 6.4 mass%.
- the content of the aromatic amine compound is preferably 2 to 6 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the epoxy compound. According to this aspect, good curability is easily obtained.
- the photosensitive composition of the present invention preferably contains a pigment derivative.
- the pigment derivative include compounds having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl group.
- the pigment derivative is preferably a pigment derivative having an acidic group or a basic group from the viewpoint of dispersibility and dispersion stability.
- organic pigment for constituting the pigment derivative examples include diketopyrrolopyrrole pigments, azo pigments, phthalocyanine pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thioindigo pigments , Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.
- a sulfo group, a carboxy group, and its quaternary ammonium base are preferable, a carboxy group and a sulfo group are more preferable, and a sulfo group is especially preferable.
- the basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
- the description of paragraph numbers 0162 to 0183 in JP 2011-252065 A can be referred to, and the contents thereof are incorporated herein.
- the content of the pigment derivative is preferably 1 to 30% by mass and more preferably 3 to 20% by mass with respect to the total 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 this invention may contain various surfactant from a viewpoint of improving applicability
- various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
- the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and the uniformity of coating thickness and liquid-saving properties are further improved.
- Can be improved That is, in the case of forming a film using a coating liquid to which a photosensitive composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid is reduced, and the coating surface is wetted. The coating property is improved and the coating property to the coated surface is improved. For this reason, it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
- the fluorine content in the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
- fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, RS-72-K (above DIC Corporation), Florard FC430, FC431, FC171 (above, Sumitomo 3M Limited), Surflon S-382, SC -101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (above, the product made by OMNOVA) etc.
- fluorine-based surfactant compounds described in paragraph numbers 0015 to 0158 of JP-A No. 2015-117327 and compounds described in paragraph numbers of 0117 to 0132 of JP-A No. 2011-132503 can also be used.
- a block polymer can also be used as the fluorosurfactant, and specific examples include compounds described in JP-A-2011-89090.
- an acrylic compound having a molecular structure having a functional group containing a fluorine atom as a fluorine-based surfactant, in which the functional group containing the fluorine atom is cleaved and the fluorine atom volatilizes when heated is 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, and these may be used.
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used, and the following compounds are also exemplified as the fluorine-based surfactant used in the present invention.
- 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 be used as the fluorosurfactant.
- Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraph Nos. 0289 to 0295 of JP2010-164965A, for example, Megafac RS-101, RS-102, RS-718K manufactured by DIC Corporation. Etc.
- Nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane and their ethoxylates and propoxylates (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF ), Tetronic 304, 701, 704, 901, 904, 150R1 (B SF), Solsperse 20000 (Nippon Lubrizol Co., Ltd.), NCW-101, NCW-1001, NCW-1002 (Wako Pure Chemical Industries, Ltd.), Pionein D-
- cationic surfactant 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 surfactants include Torre Silicone DC3PA, Torre Silicone SH7PA, Torre Silicone DC11PA, Torresilicone 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 Big Chemie Japan Co., Ltd.) and the like.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the photosensitive composition.
- the photosensitive composition of the present invention preferably contains a silane coupling agent.
- the silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
- the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can generate a siloxane bond by a hydrolysis reaction or a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, and an acyloxy group.
- the silane coupling agent is preferably a silane compound having an amino group and an alkoxy group as functional groups.
- silane coupling agents include N- ⁇ -aminoethyl- ⁇ -aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name: KBM-602), N- ⁇ -aminoethyl- ⁇ -amino.
- Propyltrimethoxysilane (trade name KBM-603, manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (trade name KBE-602, manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ - Aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-903), ⁇ -aminopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBE-903), 3-methacryloxypropyltri Methoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name KBM-503) is available.
- the silane coupling agent the description of paragraph numbers 0155 to 0158 in JP2013-254047A can be referred to, the contents of which are incorporated here
- the content of the silane coupling agent is preferably 0.001 to 20% by mass relative to the total solid content of the photosensitive composition. It is more preferably from 01 to 10% by mass, particularly preferably from 0.1 to 5% by mass.
- the photosensitive composition of this invention may contain only 1 type of silane coupling agents, and may contain 2 or more types. When 2 or more types are included, the total amount is preferably within the above range.
- the photosensitive composition of the present invention preferably contains 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 0.01 to 5% by mass with respect to the total solid content of the photosensitive composition.
- the photosensitive composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When 2 or more types are included, the total amount is preferably within the above range.
- the photosensitive composition of the present invention may contain an ultraviolet absorber.
- an ultraviolet absorber a conjugated diene compound is preferable. Examples of commercially available ultraviolet absorbers include UV-503 (manufactured by Daito Chemical Co., Ltd.).
- an ultraviolet absorber an aminodiene compound, a salicylate compound, a benzophenone compound, a benzotriazole compound, an acrylonitrile compound, or a triazine compound can be used. Specific examples thereof include compounds described in JP2013-68814A.
- MYUA series Cosmetic Industry Daily, February 1, 2016 manufactured by Miyoshi Oil and Fat may be used.
- the content of the ultraviolet absorber is preferably 0.1 to 10% by mass with respect to the total solid content of the photosensitive composition. More preferably, the content is 1 to 5% by mass, and particularly preferably 0.1 to 3% by mass. Moreover, in this invention, only 1 type may be sufficient as an ultraviolet absorber, and 2 or more types may be sufficient as it. In the case of two or more types, the total amount is preferably within the above range.
- the photosensitive composition of the present invention may contain various additives such as fillers, adhesion promoters, antioxidants, anti-aggregation agents and the like as necessary.
- additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
- antioxidant for example, phenol compounds, phosphorus compounds (for example, compounds described in paragraph No. 0042 of JP2011-90147A), thioether compounds, and 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, and AO).
- the photosensitive composition of the present invention may contain a sensitizer and a light stabilizer described in paragraph No. 0078 of JP-A No. 2004-295116 and a thermal polymerization inhibitor described in paragraph No. 0081 of the publication. it can.
- the photosensitive composition may contain a metal element, but from the viewpoint of suppressing the occurrence of defects, the content of the Group 2 elements (calcium, magnesium, etc.) in the photosensitive composition is 50 mass. It is preferably not more than ppm, and is preferably controlled to 0.01 to 10 ppm by mass. Further, the total amount of the inorganic metal salt in the photosensitive composition is preferably 100 ppm by mass or less, and more preferably controlled to 0.5 to 50 ppm by mass.
- the photosensitive composition of the present invention can be prepared by mixing the aforementioned components.
- each component may be blended at once, or may be blended sequentially after each component is dissolved or dispersed in a solvent.
- the photosensitive composition may be prepared by dissolving or dispersing all the components in a solvent at the same time. If necessary, each component may be appropriately used as two or more solutions or dispersions at the time of use (application). May be prepared by mixing them.
- any filter can be used without particular limitation as long as it 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 and ultra high molecular weight polypropylene
- nylon are preferable.
- the filter has a pore size of about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m. By setting it as this range, it becomes possible to remove a fine foreign material reliably. It is also preferable to use a fiber-shaped filter medium.
- the fiber-shaped filter medium include polypropylene fiber, nylon fiber, and glass fiber.
- SBP type series such as SBP008) and TPR type series (such as TPR002 and TPR005) manufactured by Loki Techno Co., Ltd.
- a filter cartridge of the SHPX type series (such as SHPX003) can be used.
- filters When using filters, different filters may be combined. At that time, the filtration with the first filter may be performed only once or may be performed twice or more. Moreover, you may combine the 1st filter of a different hole diameter within the range mentioned above.
- the pore diameter here can refer to the nominal value of the filter manufacturer. Examples of commercially available filters include various types provided by Nippon Pole Co., Ltd. (DFA4201NXEY, etc.), Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (former Nihon Microlith Co., Ltd.), or KITZ Micro Filter Co., Ltd. You can choose from filters.
- As the second filter a filter formed of the same material as the first filter described above can be used. For example, the filtration with the first filter may be performed only with the dispersion, and after the other components are mixed, the filtration with the second filter may be performed.
- the photosensitive composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface (flatness, etc.) and adjusting 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.
- a viscometer RE85L rotor: 1 ° 34 ′ ⁇ R24, measuring range 0.6 to 1200 mPa ⁇ s
- Toki Sangyo Co., Ltd. is used, and the temperature is adjusted to 25 ° C. It can be measured in the applied state.
- the water content in the photosensitive composition of the present invention is usually 3% by mass or less, preferably in the range of 0.01 to 1.5% by mass, and in the range of 0.1 to 1.0% by mass. It is more preferable.
- the water content can be measured by the Karl Fischer method.
- the color filter of the present invention is formed using the above-described photosensitive composition of the present invention.
- the thickness of the color filter of the present invention can be appropriately adjusted according to the purpose.
- the 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 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 solid-state imaging devices such as CCD (charge coupled device) and CMOS (complementary metal oxide semiconductor), image display devices, and the like.
- the voltage holding ratio of the liquid crystal display element provided with the color filter is preferably 70% or more, and more preferably 90% or more.
- Known means for obtaining a high voltage holding ratio can be appropriately incorporated. Typical examples include the use of a high-purity material (for example, reduction of ionic impurities) and the amount of acidic functional groups in the composition. Control.
- the voltage holding ratio can be measured, for example, by the method described in Paragraph No. 0243 of JP2011-008004A, Paragraph Nos. 0123 to 0129 of JP2012-224847A, and the like.
- the pattern forming method of the present invention includes a step of forming a photosensitive composition layer on a support using the photosensitive composition of the present invention, a step of exposing the photosensitive composition layer in a pattern, and an unexposed state. Forming a pattern by developing and removing the portion. As needed, you may have the process (prebaking process) of baking a photosensitive composition layer, and the process (post-baking process) of baking the developed pattern. It is desired that the volume resistance value of each pattern (pixel) is high. Specifically, the volume resistance value of the pixel is preferably 10 9 ⁇ ⁇ cm or more, and more preferably 10 11 ⁇ ⁇ cm or more. The upper limit is not defined, for example, preferably not more than 10 14 ⁇ ⁇ cm. The volume resistance value of the pixel can be measured using, for example, an ultrahigh resistance meter 5410 (manufactured by Advantest).
- Step of Forming Photosensitive Composition Layer In the step of forming the photosensitive composition layer, the photosensitive composition layer is formed on the support using the photosensitive composition.
- a solid-state imaging device substrate in which a solid-state imaging device (light receiving device) such as a CCD or CMOS is provided on a substrate (for example, a silicon substrate) can be used.
- the photosensitive composition layer may be formed on the solid-state image sensor formation surface side (front surface) of the solid-state image sensor substrate, or may be formed on the solid-state image sensor non-formation surface side (back surface). If necessary, an undercoat layer may be provided on the support in order to improve adhesion to the upper layer, prevent diffusion of substances, or planarize the substrate 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 150 ° C. or lower, more preferably 120 ° C. or lower, and further preferably 110 ° 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 with a hot plate, an oven, or the like.
- Exposure process the photosensitive composition layer is exposed in a pattern (exposure process).
- pattern exposure can be performed by exposing the photosensitive composition layer through a mask having a predetermined mask pattern using an exposure apparatus such as a stepper. Thereby, an exposed part can be hardened.
- Radiation (light) that can be used for exposure is preferably ultraviolet rays such as g-line and i-line, and i-line is more preferable.
- Irradiation dose (exposure dose) for example, preferably 0.03 ⁇ 2.5J / cm 2, more preferably 0.05 ⁇ 1.0J / cm 2.
- the oxygen concentration at the time of exposure can be appropriately selected.
- a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (for example, preferably 15% by volume or less, more preferably 5% by volume).
- exposure may be carried out more preferably substantially oxygen-free, and in a high oxygen atmosphere with an oxygen concentration exceeding 21% by volume (for example, preferably 22% by volume or more, more preferably 30% by volume or more, further preferably May be exposed at 50% by volume or more).
- the exposure illuminance can be appropriately set and is usually 1,000 W / m 2 to 100,000 W / m 2 (for example, preferably 5,000 W / m 2 or more, more preferably 15,000 W / m 2).
- Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10,000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20,000W / m 2.
- the unexposed portion is developed and removed to form a pattern.
- the development removal of the unexposed portion can be performed using a developer.
- the developer is preferably an alkaline developer that does not damage the underlying solid-state imaging device or circuit.
- the temperature of the developer is preferably 20 to 30 ° C., for example.
- the development time is preferably 20 to 180 seconds.
- the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
- alkaline agent used in the developer examples include ammonia water, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, Organic alkalinity such as tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5,4,0] -7-undecene Compounds.
- an alkaline aqueous solution obtained by diluting these alkaline agents with pure water is preferably used.
- concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
- an inorganic alkaline compound sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate, etc. are mentioned, for example.
- a surfactant may be used for the developer.
- surfactant examples include the surfactant described in the above-described curable composition, and a nonionic surfactant is preferable.
- the developing solution which consists of such alkaline aqueous solution generally it is preferable to wash
- Post-baking is a heat treatment after development for complete film curing.
- the post-baking temperature is preferably 100 to 240 ° C., for example. From the viewpoint of film curing, 200 to 230 ° C. is more preferable.
- the Young's modulus of the film after post-baking is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
- the post-bake temperature is preferably 150 ° C. or lower, more preferably 120 ° C. or lower.
- 100 ° C. or lower is more preferable, and 90 ° C. or lower is particularly preferable.
- the lower limit can be, for example, 50 ° C. or higher.
- Post-baking is a continuous or batch process using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so that the film after development (cured film) satisfies the above conditions. It can be carried out. Further, when a pattern is formed by a low temperature process, post baking is not necessary.
- the cured film preferably has high flatness. Specifically, the surface roughness Ra is preferably 100 nm or less, more preferably 40 nm or less, and further preferably 15 nm or less.
- the contact angle of water on the cured film can be appropriately set to a preferable value, but is typically in the range of 50 to 110 °.
- the contact angle can be measured using, for example, a contact angle meter CV-DT • A type (manufactured by Kyowa Interface Science Co., Ltd.).
- the solid-state imaging device of the present invention has the above-described color filter 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 color filter of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations.
- CCD charge coupled device
- CMOS complementary metal oxide semiconductor
- Device protection consisting of silicon nitride, etc., which has a light-shielding film that opens only on the photodiode and the transfer electrode on the photodiode and the transfer electrode, and is formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the photodiode light-receiving part It has a film, and has a color filter on the device protective film.
- a configuration having a light condensing means for example, a micro lens, etc., the same applies hereinafter
- the color filter may have a structure in which a cured film that forms 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 not only for a digital camera and an electronic device (such as a mobile phone) having an image pickup function, but also for an in-vehicle camera or a surveillance camera.
- the color filter of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device.
- an image display device such as a liquid crystal display device or an organic electroluminescence display device.
- 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”.
- the photopolymerization initiator was dissolved in acetonitrile to prepare a 5 mol% acetonitrile solution of the photopolymerization initiator.
- the acetonitrile solution prepared to the above-mentioned concentration was put in a glass cell having a width of 1 cm, and the absorbance was measured using an Agilent Technologies UV-Vis-NIR spectrum meter (Cary 5000).
- the coefficient (L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 ) was calculated.
- ⁇ represents the molar extinction coefficient (L ⁇ mol ⁇ 1 ⁇ cm ⁇ 1 )
- A represents the absorbance
- c represents the concentration (mol / L)
- 1 represents the optical path length (cm).
- the optical density of the film was measured by using a spectrometer UV4100 (manufactured by Hitachi High-Technologies Corporation) with light having a wavelength of 365 nm incident.
- Pigment dispersion 5 Composition of Pigment Dispersion Liquid 5
- Pigment dispersions 1 to 5 Pigment dispersions 1 to 5 described above
- Resin A Resin A described above
- Resin B A methacrylic acid, methyl methacrylate, n-butyl methacrylate, and 2-hydroxyethyl methacrylate copolymer was synthesized by the method described in Paragraph No. 0071 of JP2010-256891A. The weight average molecular weight of the obtained resin B was 40,000.
- Polymerizable monomer A Aronix M-350 (Toagosei Co., Ltd., compound with the following structure)
- Polymerizable monomer B KAYARAD DPCA (manufactured by Nippon Kayaku Co., Ltd., a mixture having a molar ratio of the left compound to the right compound of 7: 3)
- Polymerizable monomer C NK ester A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd., dipentaerythritol hexaacrylate)
- Polymerizable monomer D NK ester A-TMM-3 (manufactured by Shin-Nakamura Chemical Co., Ltd.)
- Polymerizable monomer E KAYARAD TMPTA (manufactured by Nippon Kayaku Co., Ltd., trimethylolpropane triacrylate)
- Photopolymerization initiator 1 the following compound (molar extinction coefficient at a wavelength of 365
- ⁇ Pattern formation> Apply CT-4000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) to an 8 inch (1 inch is 2.54 cm) silicon wafer using a spin coater to a thickness of 0.1 ⁇ m after post-baking. Then, an undercoat layer was formed by heating at 220 ° C. for 300 seconds using a hot plate to obtain a silicon wafer with an undercoat layer (support). The photosensitive composition is applied onto a silicon wafer (support) with an undercoat layer using a spin coater so that the thickness after drying is 2 ⁇ m, and is heated at 100 ° C. for 120 seconds using a hot plate ( Pre-baking).
- the support on which the pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is supplied in a shower form from the jet nozzle from above the rotation center while rotating the substrate at a rotation speed of 200 rpm by a rotating device. For 30 seconds, and then spin-dried.
- the obtained pattern was heat-treated at 220 ° C. for 300 seconds (post-bake) to produce a Bayer pattern having a pixel portion width of 3.0 ⁇ m square.
- the pattern exposure conditions are as follows.
- the line width after the patterning was measured by observing with an electron microscope for line width measurement S9260A (manufactured by Hitachi High-Technologies Corporation). The average value of the five pixel measurement dimensions was used as the line width setting value.
- Eopt exposure energy for resolving the above pattern (3.0 ⁇ m square Bayer pattern) was determined, and pattern formation was evaluated according to the following criteria.
- ⁇ Residual film ratio after development> Apply CT-4000L (manufactured by FUJIFILM Electronics Materials Co., Ltd.) to an 8 inch (1 inch is 2.54 cm) silicon wafer using a spin coater to a thickness of 0.1 ⁇ m after post-baking. Then, by heating (post-baking) at 220 ° C. for 300 seconds using a hot plate, an undercoat layer was formed to obtain a silicon wafer with an undercoat layer (support). The photosensitive composition is applied onto a silicon wafer (support) with an undercoat layer using a spin coater so that the thickness after drying is 2 ⁇ m, and is heated at 100 ° C. for 120 seconds using a hot plate ( Pre-baking).
- the support on which the pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and pure water is supplied in a shower form from the jet nozzle from above the rotation center while rotating the substrate at a rotation speed of 200 rpm by a rotating device. For 30 seconds, and then spin-dried.
- the remaining film ratio of Eopt in a 3.0 ⁇ m square Bayer pattern is a ratio between the thickness of the film after development and the thickness of the film before development.
- the examples were excellent in adhesion and pattern formability.
- the comparative example was inferior to the example in at least one of adhesion and pattern forming property.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Nonlinear Science (AREA)
- Chemical & Material Sciences (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Structural Engineering (AREA)
- Architecture (AREA)
- Materials For Photolithography (AREA)
- Liquid Crystal (AREA)
- Solid State Image Pick-Up Elements (AREA)
- Devices For Indicating Variable Information By Combining Individual Elements (AREA)
- Optical Filters (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
<1> 光重合開始剤Iと、
エチレン性不飽和二重結合を有する基を2個以上有する重合性モノマーMと、
ハロゲン化亜鉛フタロシアニンとを含み、
重合性モノマーMは、エチレン性不飽和二重結合を有する基を3個有する重合性モノマーM1を含有し、
光重合開始剤Iは、波長365nmにおけるモル吸光係数が12,000L・mol-1・cm-1以上の光重合開始剤I1を含み、
光重合開始剤Iの質量と重合性モノマーMの質量との比が、光重合開始剤Iの質量/重合性モノマーMの質量で、0.15以下である、感光性組成物。
<2> 重合性モノマーMは、重合性モノマーM1を50~100質量%含有する、<1>に記載の感光性組成物。
<3> 重合性モノマーM1は、アルキレンオキシ基を有する、<1>または<2>に記載の感光性組成物。
<4> 光重合開始剤I1は、ニトロ基を有するオキシム化合物およびナフタレン環を有するオキシム化合物から選ばれる少なくとも1種を含む、<1>~<3>のいずれか1つに記載の感光性組成物。
<5> 光重合開始剤I1は、下記式(I-1)で表される化合物を含有する、<1>~<4>のいずれか1つに記載の感光性組成物;
Ar3は、アリール基を表し、
R2およびR3は、それぞれ独立に、アルキル基またはアリール基を表し、
Ar1~Ar3、R2およびR3の少なくとも一つは、フッ素原子、フッ素原子を含む基またはニトロ基を置換基として有する。
<6> 重合性モノマーMは、エチレン性不飽和二重結合を有する基を4個以上有する重合性モノマーM2を50質量%以下含有する、<1>~<5>のいずれか1つに記載の感光性組成物。
<7> <1>~<6>のいずれか1つに記載の感光性組成物を用いた、カラーフィルタ。
<8> <1>~<6>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、感光性組成物層をパターン状に露光する工程と、未露光部を現像除去してパターンを形成する工程とを含む、パターン形成方法。
<9> 露光をi線で行う、<8>に記載のパターン形成方法。
<10> <7>に記載のカラーフィルタを有する、固体撮像素子。
<11> <7>に記載のカラーフィルタを有する、画像表示装置。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さない基(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含む。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の合計質量をいう。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アリル」は、アリルおよびメタリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において「工程」との語は、独立した工程を表すだけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィ(GPC)により測定したポリスチレン換算値として定義される。
本明細書において、顔料は、特定の溶剤に対し溶解しにくい不溶性の化合物を意味する。典型的には、組成物中に粒子として分散された状態で存在する化合物を意味する。本発明に用いられる顔料は、例えば、プロピレングリコールモノメチルエーテルアセテートおよび水のいずれに対しても、25℃における溶解度が0.1g/100gSolvent以下が好ましい。
本発明の感光性組成物は、
光重合開始剤Iと、
エチレン性不飽和二重結合を有する基を2個以上有する重合性モノマーMと、
ハロゲン化亜鉛フタロシアニンを含み、
重合性モノマーMは、エチレン性不飽和二重結合を有する基を3個有する重合性モノマーM1を含有し、
光重合開始剤Iは、波長365nmにおけるモル吸光係数が12,000L・mol-1・cm-1以上の光重合開始剤I1を含み、
光重合開始剤Iの質量と重合性モノマーMの質量との比が、光重合開始剤Iの質量/重合性モノマーMの質量で、0.15以下である。
すなわち、光重合開始剤Iとして、波長365nmにおけるモル吸光係数が12,000L・mol-1・cm-1以上の光重合開始剤I1を用いたことで、ハロゲン化亜鉛フタロシアニンを含む感光性組成物における、i線に対する感度を向上することができたと推測される。このため、ハロゲン化亜鉛フタロシアニンを含む感光性組成物を用いて支持体上に膜を形成した際において、膜の下部(支持体との界面)まで硬化させることができ、支持体との密着性を高めることができる。
また、i線に対する感度を高めすぎると、パターン形成性が低下する傾向にあるが、本発明によれば、重合性モノマーMとして、エチレン性不飽和二重結合を有する基を3個有する重合性モノマーM1を含有するものを用い、かつ、光重合開始剤Iの質量と重合性モノマーMの質量との比(光重合開始剤Iの質量/重合性モノマーMの質量)を0.15以下としたことで、感光性組成物の感度が高くなりすぎることを抑制できる。このため、優れたパターン形成性を維持しつつ、支持体などとの密着性を高めることが可能になったと推測される。
なお、光学濃度は吸収度合を対数で表示した値であって、下記式で定義される値である。
OD(λ)=Log10[T(λ)/I(λ)]
λは、波長を表し、T(λ)は、波長λにおける透過光量を表し、I(λ)は波長λにおける入射光量を表す。
乾燥後の厚さが2.0μmの膜を形成した際における、波長365nmにおける膜の光学濃度を、2.0以上とするには、例えば、波長365nmの光を吸収する着色剤を含有させたり、全固形分中の着色剤の含有量を適宜調整することなどにより達成できる。例えば、ハロゲン化亜鉛フタロシアニン含有量を高める方法が一例として挙げられる。
なお、本発明において、膜の光学濃度は、波長365nmの光を入射し、その透過率を分光器UV4100((株)日立ハイテクノロジーズ製)により測定した値である。
以下、本発明の感光性組成物の各成分について説明する。
本発明の感光性組成物は、ハロゲン化亜鉛フタロシアニンを含む。ハロゲン化亜鉛フタロシアニンは、中心金属の亜鉛が、イソインドール環の4個の窒素で囲まれた領域内に位置する化合物である。
ハロゲン化亜鉛フタロシアニンは、染料(ハロゲン化亜鉛フタロシアニン染料)であってもよいが、顔料(ハロゲン化亜鉛フタロシアニン顔料)であることが好ましいハロゲン化亜鉛フタロシアニン染料としては、特開2014-043555号公報および特開2014-043556号公報の記載を参酌でき、この内容は本明細書に組み込まれる。
ハロゲン化亜鉛フタロシアニン顔料は、下記式(A1)で表される化合物が好ましい。
<1> フタロシアニン1分子中のハロゲン原子の平均個数が8~12個であるハロゲン化亜鉛フタロシアニン顔料。この態様において、X1~X16は、塩素原子、臭素原子、水素原子を合わせて1個以上含むことが好ましい。また、X1~X16は、塩素原子が0~4個、臭素原子が8~12個、水素原子が0~4個であることが好ましい。具体例としては、特開2007-284592号公報の段落番号0013~0039、0084~0085の記載を参酌することができ、これらの内容は本明細書に組み込まれる。
<2> フタロシアニン1分子中のハロゲン原子の平均個数が10~14個であり、臭素原子の平均個数が8~12個であり、塩素原子の平均個数が2~5個であるハロゲン化亜鉛フタロシアニン顔料。具体例としては、WO2015/118720号公報に記載の化合物が挙げられる。
ハロゲン化亜鉛フタロシアニン顔料の含有量は、感光性組成物中の全固形分に対して、10質量%以上であることが好ましく、20質量%以上がより好ましく、30質量%以上が更に好ましい。上限は、80質量%以下が好ましく、75質量%以下がより好ましく、70質量%以下が更に好ましい。ハロゲン化亜鉛フタロシアニン顔料は、1種であってもよい。また、上記式(A1)のX1~X16が異なる組み合わせの化合物を2種以上含むものであってもよい。2種以上含む場合は、合計量が上記範囲となることが好ましい。
本発明の感光性組成物は、ハロゲン化亜鉛フタロシアニン以外の着色剤(他の着色剤)をさらに含んでいてもよい。他の着色剤は、染料および顔料のいずれでもよく、両者を併用してもよい。顔料としては、従来公知の種々の無機顔料または有機顔料を挙げることができる。また、無機顔料であれ有機顔料であれ、高透過率であることが好ましいことを考慮すると、平均粒子径がなるべく小さい顔料の使用が好ましく、ハンドリング性をも考慮すると、顔料の平均粒子径は、0.01~0.1μmが好ましく、0.01~0.05μmがより好ましい。
C.I.ピグメントイエロー1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214等、
C.I.ピグメントオレンジ 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等、
C.I.ピグメントレッド 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,270,272,279
C.I.ピグメントグリーン 7,10,36,37
C.I.ピグメントバイオレット 1,19,23,27,32,37,42
C.I.ピグメントブルー 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80。
これら有機顔料は、単独で、もしくは種々組合せて用いることができる。
また、青色顔料として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開2012-247591号公報の段落番号0022~0030、特開2011-157478号公報の段落番号0047に記載の化合物などが挙げられる。
本発明の感光性組成物は、エチレン性不飽和二重結合を有する基を2個以上有する重合性モノマーMを含む。エチレン性不飽和二重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、(メタ)アクリロイルオキシ基などが挙げられる。エチレン性不飽和二重結合を有する基を2個以上有する重合性モノマーMとしては、2官能以上の(メタ)アクリレートなどが挙げられる。重合性モノマーMは、ラジカル重合性モノマーであることが好ましい。
本発明において、重合性モノマーMは、ポリマー以外の化合物であることが好ましい。ポリマー以外の化合物としては、分子量分布を有さない化合物などが挙げられる。
3官能重合性モノマーの分子量は、250~1,300が好ましい。上限は、850以下がより好ましい。下限は、290以上がより好ましい。
アルキレンオキシ基を有する3官能重合性モノマーとしては、下記式(M-1)で表される化合物が挙げられる。
式(M-1)
L1が表す脂肪族炭化水素基の炭素数は、1~30が好ましく、1~20がより好ましく、1~15がさらに好ましい。脂肪族炭化水素基は、直鎖、分岐、環状のいずれでもよく、分岐が好ましい。
芳香族炭化水素基の炭素数は、6~30が好ましく、6~20がより好ましく、6~10がさらに好ましい。
複素環基は、非芳香族の複素環基であってもよく、芳香族複素環基であってもよい。複素環基は、5員環または6員環が好ましい。複素環基を構成するヘテロ原子の種類としては、窒素原子、酸素原子、硫黄原子などが挙げられる。複素環基を構成するヘテロ原子の数は1~3が好ましい。複素環基は、単環であってもよく、縮合環であってもよい。
式(M-2)
3官能重合性モノマーM1は、1種のみであってもよく、2種以上含んでいてもよい。3官能重合性モノマーM1を2種以上含む場合は、合計が上記範囲であることが好ましい。
<1>重合性モノマーMが、実質的に3官能重合性モノマーM1のみで構成されている態様。
<2>重合性モノマーMが、3官能重合性モノマーM1と、エチレン性不飽和二重結合を有する基を4個以上有する重合性モノマーM2(以下、4官能以上の重合性モノマーともいう)とで構成されている態様。
また、<2>の態様において、重合性モノマーMの平均官能基数は、2.0~8.0個が好ましく、2.5~7個がより好ましく、3.0~6.0個がさらに好ましい。
カプロラクトン構造を有する化合物は、例えば、日本化薬(株)からKAYARAD DPCAシリーズとして市販されており、DPCA-20、DPCA-30、DPCA-60、DPCA-120等が挙げられる。
市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ(株)製)、UA-7200(新中村化学工業(株)製)、DPHA-40H(日本化薬(株)製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、AI-600(共栄社化学(株)製)などが挙げられる。
本発明の感光性組成物は、光重合開始剤Iを含有する。
光重合開始剤としては、光の作用により重合性モノマーMの重合を開始する能力を有する化合物であれば、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視領域の光線に対して感光性を有する化合物が好ましい。また、光励起された増感剤と何らかの作用を生じ、活性ラジカルを生成する化合物であってもよい。光重合開始剤Iは、i線に対して感光性を有する化合物が好ましい。
なお、本発明において、光重合開始剤の波長365nmにおけるモル吸光係数は、光重合開始剤を溶剤に溶解させて、光重合開始剤の5mol%溶液(測定溶液)を調製し、前述の測定溶液の吸光度を測定することで算出した。具体的には、調製された測定溶液を幅1cmのガラスセルに入れ、Agilent Technologies社製UV-Vis-NIRスペクトルメーター(Cary5000)を用いて吸光度を測定し、下記式に当てはめて、波長365nmにおけるモル吸光係数(L・mol-1・cm-1)を算出した。
Ar3は、アリール基を表し、
R2およびR3は、それぞれ独立に、アルキル基またはアリール基を表し、
Ar1~Ar3、R2およびR3の少なくとも一つは、フッ素原子、フッ素原子を有する基またはニトロ基を置換基として有する。
Ar1およびAr2が表す芳香族環は、置換基を有していてもよく、無置換であってもよい。置換基としては、アルキル基、アリール基、複素環基、ニトロ基、シアノ基、ハロゲン原子、-ORX1、-SRX1、-CORX1、-COORX1、-OCORX1、-NRX1RX2、-NHCORX1、-CONRX1RX2、-NHCONRX1RX2、-NHCOORX1、-SO2RX1、-SO2ORX1、-NHSO2RX1、-ORX3-ORX1などが挙げられる。RX1およびRX2は、それぞれ独立に、水素原子、アルキル基、アリール基または複素環基を表す。RX3は、アルキレン基を表す。
置換基としてのアルキル基、ならびに、RX1およびRX2が表すアルキル基の炭素数は、1~20が好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。アルキル基は、水素原子の一部または全部がハロゲン原子(好ましくは、フッ素原子)で置換されていてもよい。また、アルキル基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。
置換基としてのアリール基、ならびに、RX1およびRX2が表すアリール基の炭素数は、6~20が好ましく、6~15がより好ましく、6~10がさらに好ましい。アリール基は、単環であってもよく、縮合環であってもよい。また、アリール基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。
置換基としての複素環基、ならびに、RX1およびRX2が表す複素環基は、5員環または6員環が好ましい。複素環基は、単環であってもよく、縮合環であってもよい。複素環基を構成する炭素原子の数は3~30が好ましく、3~18がより好ましく、3~12がさらに好ましい。複素環基を構成するヘテロ原子の数は1~3が好ましい。複素環基を構成するヘテロ原子は、窒素原子、酸素原子または硫黄原子が好ましい。また、複素環基は、水素原子の一部または全部が、上記置換基で置換されていてもよい。
RX3が表すアルキレン基の炭素数は、1~20が好ましい。アルキレン基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。
アルキル基の炭素数は、1~20が好ましく、1~15がより好ましく、1~10がさらに好ましく、1~4が特に好ましい。アルキル基は、直鎖、分岐、環状のいずれでもよいが、直鎖または分岐が好ましい。アルキル基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述した置換基が挙げられる。
アリール基の炭素数は、6~20が好ましく、6~15がより好ましく、6~10がさらに好ましい。アリール基は、置換基を有していてもよく、無置換であってもよい。置換基としては、上述した置換基が挙げられる。
含フッ素基としては、-ORX11、-SRX11、-CORX11、-COORX11、-OCORX11、-NRX11RX12、-NHCORX11、-CONRX11RX12、-NHCONRX11RX12、-NHCOORX11、-SO2RX11、-SO2ORX11および-NHSO2RX11から選ばれる少なくとも1種の基が好ましい。RX11は、含フッ素アルキル基を表し、RX12は、水素原子、アルキル基、含フッ素アルキル基、アリール基または複素環基を表す。含フッ素基は、-ORX11がより好ましい。
フッ素原子を含む基は、下記式(F1)または式(F2)で表される末端構造を有することが好ましい。式中の*は、連結手を表す。
*-CHF2 (F1)
*-CF3 (F2)
含フッ素アルキル基は、フッ素原子の置換率が、40~100%であることが好ましく、50~100%であることがより好ましく、60~100%であることがさらに好ましい。なお、含フッ素アルキル基におけるフッ素原子の置換率とは、アルキル基の水素原子が、フッ素原子に置換された割合を百分率で表した値である。
市販品ではIRGACURE-OXE01、IRGACURE-OXE02、IRGACURE-OXE03、IRGACURE-OXE04(以上、BASF社製)も好適に用いられる。また、TRONLY TR-PBG-304、TRONLY TR-PBG-309、TRONLY TR-PBG-305(常州強力電子新材料有限公司(CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO.,LTD)製)、アデカアークルズNCI-930、アデカオプトマーN-1919(特開2012-14052号公報の光重合開始剤2)(以上、(株)ADEKA製)も用いることができる。
式(OX-1)中、Rで表される1価の置換基としては、1価の非金属原子団であることが好ましい。
1価の非金属原子団としては、アルキル基、アリール基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、複素環基、アルキルチオカルボニル基、アリールチオカルボニル基等が挙げられる。また、これらの基は、1以上の置換基を有していてもよい。また、前述した置換基は、さらに他の置換基で置換されていてもよい。
置換基としてはハロゲン原子、アリールオキシ基、アルコキシカルボニル基、アリールオキシカルボニル基、アシルオキシ基、アシル基、アルキル基、アリール基等が挙げられる。
式(OX-1)中、Bで表される一価の置換基としては、アリール基、複素環基、アリールカルボニル基、または、複素環カルボニル基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
式(OX-1)中、Aで表される2価の有機基としては、炭素数1~12のアルキレン基、アルキニレン基が好ましい。これらの基は1以上の置換基を有していてもよい。置換基としては、前述した置換基が例示できる。
波長365nmにおけるモル吸光係数が12,000L・mol-1・cm-1以上の光重合開始剤I1の質量と重合性モノマーMの質量との比(光重合開始剤I1の質量/重合性モノマーMの質量、以下I1/Mともいう)は、0.01~0.70であることが好ましく、0.01~0.40がより好ましく、0.02~0.30がさらに好ましい。
波長365nmにおけるモル吸光係数が12,000L・mol-1・cm-1以上の光重合開始剤I1の質量と、エチレン性不飽和二重結合を有する基を3個有する重合性モノマーM1の質量との比(光重合開始剤I1の質量/重合性モノマーM1の質量、以下I1/M1ともいう)は、0.01~0.40であることが好ましく、0.01~0.30がより好ましく、0.02~0.20がさらに好ましい。
本発明の感光性組成物は、エポキシ基を有する化合物(以下、エポキシ化合物ともいう)を含むことができる。エポキシ化合物は、1分子内にエポキシ基を1つ以上有する化合物が挙げられ、2つ以上有する化合物が好ましい。エポキシ化合物は、エポキシ基を1分子内に1~100個有することが好ましい。下限は、2個以上がより好ましい。上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。
REP1~REP3、QEPの詳細については、特開2014-089408号公報の段落番号0087~0088の記載を参酌でき、この内容は本明細書に組み込まれる。式(EP1)で表される化合物の具体例としては、グリシジルトリチルエーテルが挙げられる。また、特開2014-089408号公報の段落番号0090に記載の化合物などが挙げられ、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、エポキシ化合物を実質的に含有しないことも好ましい。エポキシ化合物を実質的に含有しないとは、感光性組成物の全固形分に対し、0.05質量%以下が好ましく、0.01質量%以下がより好ましく、含有しないことが一層好ましい。
本発明の感光性組成物は、樹脂を含むことが好ましい。樹脂は、例えば、顔料などを組成物中で分散させる用途、バインダーの用途で配合される。なお、主に顔料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を目的で使用することもできる。
本発明の感光性組成物は、樹脂として分散剤を含むことが好ましい。特に、顔料を用いた場合、分散剤を含むことが好ましい。分散剤としては、酸性分散剤(酸性樹脂)、塩基性分散剤(塩基性樹脂)が挙げられる。
分散剤は、少なくとも酸性分散剤を含むことが好ましく、酸性分散剤のみであることがより好ましい。分散剤が、少なくとも酸性分散剤を含むことにより、顔料の分散性が向上し、感光性樹脂から形成される硬化膜の輝度ムラが生じにくくなる。さらには、硬化膜において優れた現像性が得られるので、フォトリソグラフィにて、好適にパターン形成を行うことができる。なお、分散剤が酸性分散剤のみであるとは、例えば、分散剤の全質量中における酸性分散剤の含有量が99質量%以上であることが好ましく、99.9質量%以上とすることもできる。
また、塩基性分散剤(塩基性樹脂)とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤(塩基性樹脂)は、酸基の量と塩基性基の量の合計量を100モル%としたときに、塩基性基の量が50モル%を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基が好ましい。
なお、上記の分散剤として説明した樹脂は、分散剤以外の用途で使用することもできる。例えば、バインダーとして用いることもできる。
本発明の感光性組成物は、樹脂としてアルカリ可溶性樹脂を含有することが好ましい。なお、アルカリ可溶性樹脂は、分散剤やバインダーとして用いることもできる。
アルカリ可溶性樹脂は、アルカリ可溶性を促進する基を有する樹脂の中から適宜選択することができる。アルカリ可溶性を促進する基(以下、酸基ともいう)としては、例えば、カルボキシ基、リン酸基、スルホ基、フェノール性ヒドロキシ基などが挙げられ、カルボキシ基が好ましい。アルカリ可溶性樹脂は、酸基を1種のみ有していてもよく、2種以上有していてもよい。
重合性基を有するアルカリ可溶性樹脂の市販品としては、ダイヤナールNRシリーズ(三菱レイヨン(株)製)、Photomer6173(COOH含有 polyurethane acrylic oligomer.Diamond Shamrock Co.,Ltd.製)、ビスコートR-264、KSレジスト106(いずれも大阪有機化学工業(株)製)、サイクロマーPシリーズ(例えば、ACA230AA)、プラクセルCF200シリーズ(いずれも(株)ダイセル製)、Ebecryl3800(ダイセルユーシービー(株)製)、アクリキュアーRD-F8((株)日本触媒製)、DP-1305(富士ファインケミカルズ(株)製)などが挙げられる。
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。有機溶剤は、各成分の溶解性や感光性組成物の塗布性を満足すれば特に制限はない。
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)。
また、2-メトキシ-1-プロピルアセテートの含有量は、溶剤の質量に対して、0.01~0.5質量%が好ましい。下限は、0.05質量%以上がより好ましく、0.1質量%以上がさらに好ましい。上限は、0.4質量%以下がより好ましく、0.2質量%以下がさらに好ましい。
本発明の感光性組成物は、硬化促進剤を添加してもよい。硬化促進剤としては、芳香族アミン化合物やチオール化合物などが挙げられる。
本発明の感光性組成物がエポキシ化合物を含む場合、芳香族アミン化合物を含むことが好ましい。この態様によれば、良好な硬化性が得られやすい。芳香族アミン化合物は、アミノ基を1個有する単官能の芳香族アミン化合物であってもよく、アミノ基を2個以上有する多官能芳香族アミン化合物であってもよい。芳香族アミン化合物は、下記式(Am-1)または下記式(Am-2)で表される化合物が好ましく、下記式(Am-2)で表される化合物がより好ましい。
式(Am-2)において、Rb1~Rb10は、それぞれ独立して、水素原子または置換基を表し、Rb1~Rb10の少なくとも一つは、-NR100R101または-NR100R101を有する基を表す。Rb1~Rb10のうち、隣接する二つの基は、結合して環を形成してもよい。A1は、単結合または2価の連結基を表す。R100およびR101は、それぞれ独立して、水素原子または置換基を表す。
Ra1~Ra6、および、Rb1~Rb10が表す置換基は、例えば、アルキル基、ニトロ基などが挙げられる。
A1が表す2価の連結基としては、アルキレン基、-O-、-CO-、-OCO-、-COO-、-SO2-、-SO-、-S-、およびこれらの組み合わせからなる基が挙げられる。アルキレン基の炭素数は、1~10が好ましく、1~5がより好ましい。アルキレン基は、直鎖、分岐が好ましい。アルキレン基は無置換であってもよく、置換基を有していてもよい。置換基としては、例えば、ハロゲン原子などが挙げられる。
チオール化合物としては、分子内に2個以上のメルカプト基を有する多官能チオール化合物などが挙げられる。多官能チオール化合物は、安定性、臭気、解像性、現像性、密着性等の改良を目的として添加してもよい。多官能チオール化合物は、2級のアルカンチオール類であることが好ましく、特に下記式(T1)で表される構造を有する化合物であることが好ましい。
式(T1)
また、芳香族アミン化合物の含有量は、エポキシ化合物100質量部に対して、2~6質量部が好ましく、1~10質量部がより好ましい。この態様によれば、良好な硬化性が得られやすい。
本発明の感光性組成物は、顔料誘導体を含有することが好ましい。顔料誘導体としては、有機顔料の一部分を、酸性基、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。顔料誘導体は、分散性および分散安定性の観点から、酸性基または塩基性基を有する顔料誘導体が好ましい。
本発明の感光性組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有させてもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。
フッ素系界面活性剤として、フッ素原子を有する(メタ)アクリレート化合物に由来する繰り返し単位と、アルキレンオキシ基(好ましくはエチレンオキシ基、プロピレンオキシ基)を2以上(好ましくは5以上)有する(メタ)アクリレート化合物に由来する繰り返し単位とを含む、含フッ素高分子化合物も好ましく用いることができ、下記化合物も本発明で用いられるフッ素系界面活性剤として例示される。
フッ素系界面活性剤は、エチレン性不飽和基を側鎖に有する含フッ素重合体をフッ素系界面活性剤として用いることもできる。具体例としては、特開2010-164965号公報の段落番号0050~0090および段落番号0289~0295に記載された化合物、例えばDIC(株)製のメガファックRS-101、RS-102、RS-718K等が挙げられる。
界面活性剤の含有量は、感光性組成物の全固形分に対して、0.001~2.0質量%であることが好ましく、0.005~1.0質量%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含有することも好ましい。なお、本発明において、シランカップリング剤は、加水分解性基とそれ以外の官能基とを有するシラン化合物を意味する。また、加水分解性基とは、珪素原子に直結し、加水分解反応または縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基などが挙げられる。
本発明の感光性組成物は、重合禁止剤を含有することも好ましい。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に対して、0.01~5質量%であることが好ましい。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してもよい。紫外線吸収剤としては、共役ジエン系化合物が好ましい。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、紫外線吸収剤として、アミノジエン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、トリアジン化合物を用いることができる。具体例としては、特開2013-68814号公報に記載の化合物が挙げられる。ベンゾトリアゾール化合物として、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に対して、0.1~10質量%であることが好ましく、0.1~5質量%がより好ましく、0.1~3質量%が特に好ましい。また、本発明においては、紫外線吸収剤は、1種のみでもよく、2種以上でもよい。2種以上の場合は、合計量が上記範囲となることが好ましい。
本発明の感光性組成物には、必要に応じて、各種添加物、例えば、充填剤、密着促進剤、酸化防止剤、凝集防止剤等を配合することができる。これらの添加物としては、特開2004-295116号公報の段落番号0155~0156に記載のものを挙げることができ、これらの内容は本明細書に組み込まれる。酸化防止剤としては、例えば、フェノール化合物、リン系化合物(例えば特開2011-90147号公報の段落番号0042に記載の化合物)、チオエーテル化合物などを用いることができる。市販品としては、例えば、(株)ADEKA製のアデカスタブシリーズ(AO-20、AO-30、AO-40、AO-50、AO-50F、AO-60、AO-60G、AO-80、AO-330など)が挙げられる。酸化防止剤は2種以上を混合して使用してもよい。本発明の感光性組成物においては、特開2004-295116号公報の段落番号0078に記載の増感剤や光安定剤、同公報の段落番号0081に記載の熱重合防止剤を含有することができる。
本発明の感光性組成物は、前述の成分を混合して調製することができる。感光性組成物の調製に際しては、各成分を一括配合してもよいし、各成分を溶剤に、溶解または分散した後に逐次配合してもよい。また、配合する際の投入順序や作業条件は特に制約を受けない。例えば、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、各成分を適宜2つ以上の溶液または分散液としておいて、使用時(塗布時)にこれらを混合して調製してもよい。
フィルタの孔径は、0.01~7.0μm程度が適しており、好ましくは0.01~3.0μm程度、より好ましくは0.05~0.5μm程度である。この範囲とすることにより、微細な異物を確実に除去することが可能となる。また、ファイバ状のろ材を用いることも好ましい。ファイバ状のろ材としては、例えば、ポリプロピレンファイバ、ナイロンファイバ、グラスファイバ等が挙げられ、具体的には、(株)ロキテクノ製のSBPタイプシリーズ(SBP008など)、TPRタイプシリーズ(TPR002、TPR005など)、SHPXタイプシリーズ(SHPX003など)のフィルタカートリッジを用いることができる。
また、上述した範囲内で異なる孔径の第1のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール(株)(DFA4201NXEYなど)、アドバンテック東洋(株)、日本インテグリス(株)(旧日本マイクロリス(株))または(株)キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
第2のフィルタは、上述した第1のフィルタと同様の材料等で形成されたものを使用することができる。
例えば、第1のフィルタでのろ過は、分散液のみで行い、他の成分を混合した後で、第2のフィルタでのろ過を行ってもよい。
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、上述した本発明の感光性組成物を用いてなるものである。本発明のカラーフィルタの厚さは、目的に応じて適宜調整できる。厚さは、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。厚さの下限は、0.1μm以上が好ましく、0.2μm以上がより好ましく、0.3μm以上がさらに好ましい。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。
本発明のパターン形成方法は、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、感光性組成物層をパターン状に露光する工程と、未露光部を現像除去してパターンを形成する工程とを含む。必要に応じて、感光性組成物層をベークする工程(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)を有してもよい。
各パターン(画素)の体積抵抗値は高いことが望まれる。具体的には、画素の体積抵抗値は109Ω・cm以上であることが好ましく、1011Ω・cm以上であることがより好ましい。上限は規定されないが、例えば1014Ω・cm以下であることが好ましい。画素の体積抵抗値は、例えば超高抵抗計5410((株)アドバンテスト製)を用いて測定することができる。
感光性組成物層を形成する工程では、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。
感光性組成物層は、固体撮像素子用基板の固体撮像素子形成面側(おもて面)に形成してもよいし、固体撮像素子非形成面側(裏面)に形成してもよい。
支持体上には、必要により、上部の層との密着改良、物質の拡散防止、または基板表面の平坦化のために、下塗り層を設けてもよい。
プリベークを行う場合、プリベーク温度は、150℃以下が好ましく、120℃以下がより好ましく、110℃以下がさらに好ましい。下限は、例えば、50℃以上とすることができ、80℃以上とすることもできる。プリベーク温度を150℃以下で行うことにより、例えば、イメージセンサの光電変換膜を有機素材で構成した場合において、これらの特性をより効果的に維持することができる。
プリベーク時間は、10~300秒が好ましく、40~250秒がより好ましく、80~220秒がさらに好ましい。プリベークは、ホットプレート、オーブン等で行うことができる。
次に、感光性組成物層を、パターン状に露光する(露光工程)。例えば、感光性組成物層に対し、ステッパー等の露光装置を用いて、所定のマスクパターンを有するマスクを介して露光することで、パターン露光することができる。これにより、露光部分を硬化することができる。
露光に際して用いることができる放射線(光)としては、g線、i線等の紫外線が好ましく、i線がより好ましい。照射量(露光量)は、例えば、0.03~2.5J/cm2が好ましく、0.05~1.0J/cm2がより好ましい。
露光時における酸素濃度については適宜選択することができ、大気下で行う他に、例えば酸素濃度が19体積%以下の低酸素雰囲気下(例えば、好ましくは15体積%以下、より好ましくは5体積%以下、さらに好ましくは実質的に無酸素)で露光してもよく、酸素濃度が21体積%を超える高酸素雰囲気下(例えば、好ましくは22体積%以上、より好ましくは30体積%以上、さらに好ましくは50体積%以上)で露光してもよい。また、露光照度は適宜設定することが可能であり、通常1,000W/m2~100,000W/m2(例えば、好ましくは5,000W/m2以上、より好ましくは15,000W/m2以上、さらに好ましくは35,000W/m2以上)の範囲から選択することができる。酸素濃度と露光照度は適宜条件を組み合わせてよく、例えば、酸素濃度10体積%で照度10,000W/m2、酸素濃度35体積%で照度20,000W/m2などとすることができる。
次に、未露光部を現像除去してパターンを形成する。未露光部の現像除去は、現像液を用いて行うことができる。これにより、露光工程における未露光部の感光性組成物層が現像液に溶出し、光硬化した部分だけが残る。
現像液としては、下地の固体撮像素子や回路などにダメージを起さない、アルカリ現像液が望ましい。
現像液の温度は、例えば、20~30℃が好ましい。現像時間は、20~180秒が好ましい。また、残渣除去性を向上するため、現像液を60秒ごとに振り切り、さらに新たに現像液を供給する工程を数回繰り返してもよい。
また、現像液のアルカリ剤には無機アルカリ性化合物を用いてもよい。無機アルカリ性化合物としては、例えば、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム、炭酸水素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウムなどが挙げられる。
また、現像液には、界面活性剤を用いてもよい。界面活性剤の例としては、上述した硬化性組成物で説明した界面活性剤が挙げられ、ノニオン系界面活性剤が好ましい。
なお、このようなアルカリ性水溶液からなる現像液を使用した場合には、一般に現像後純水で洗浄(リンス)することが好ましい。
ポストベークは、現像後の膜(硬化膜)を、上記条件になるようにホットプレートやコンベクションオーブン(熱風循環式乾燥機)、高周波加熱機等の加熱手段を用いて、連続式あるいはバッチ式で行うことができる。また、低温プロセスによりパターンを形成する場合は、ポストベークは行わなくてもよい。
硬化膜は高い平坦性を有することが好ましい。具体的には、表面粗さRaが100nm以下であることが好ましく、40nm以下であることがより好ましく、15nm以下であることがさらに好ましい。下限は規定されないが、例えば0.1nm以上であることが好ましい。表面粗さの測定は、例えばVeeco社製のAFM(原子間力顕微鏡)Dimension3100を用いて測定することができる。
また、硬化膜上の水の接触角は適宜好ましい値に設定することができるが、典型的には、50~110°の範囲である。接触角は、例えば接触角計CV-DT・A型(協和界面科学(株)製)を用いて測定できる。
本発明の固体撮像素子は、上述した本発明のカラーフィルタを有する。本発明の固体撮像素子の構成としては、本発明のカラーフィルタを備え、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。
本発明の固体撮像素子を備えた撮像装置は、デジタルカメラや、撮像機能を有する電子機器(携帯電話等)の他、車載カメラや監視カメラ用としても用いることができる。
本発明のカラーフィルタは、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。
樹脂の重量平均分子量は、以下の方法で測定した。
カラムの種類:TOSOH TSKgel Super HZM-Hと、TOSOH TSKgel Super HZ4000と、TOSOH TSKgel Super HZ2000とを連結したカラム
展開溶媒:テトラヒドロフラン
カラム温度:40℃
流量(サンプル注入量):1.0μL(サンプル濃度:0.1質量%)
装置名:東ソー製HLC-8220GPC
検出器:RI(屈折率)検出器
検量線ベース樹脂:ポリスチレン
光重合開始剤をアセトニトリルに溶解させて、光重合開始剤の5mol%アセトニトリル溶液を調製した。前述の濃度に調製したアセトニトリル溶液を幅1cmのガラスセルに入れ、Agilent Technologies社製UV-Vis-NIRスペクトルメーター(Cary5000)を用いて吸光度を測定し、下記式に当てはめて、波長365nmにおけるモル吸光係数(L・mol-1・cm-1)を算出した。
膜の光学濃度は、波長365nmの光を入射し、その透過率を分光器UV4100(日立ハイテクノロジーズ社製)により測定した。
下記組成の混合液を、0.3mm径のジルコニアビーズを使用して、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、2時間、混合して、顔料分散液1~6を調製した。
・C.I.ピグメントグリーン58 ・・・12.1部
・C.I.ピグメントイエロー185 ・・・3.0部
・樹脂(Disperbyk-101、BYKChemie社製) ・・・7.2部
・プロピレングリコールメチルエーテルアセテート ・・・77.77部
・C.I.ピグメントグリーン58 ・・・15.1部
・樹脂(Disperbyk-101、BYKChemie社製) ・・・7.2部
・プロピレングリコールメチルエーテルアセテート ・・・77.77部
・C.I.ピグメントイエロー139 ・・・12.9部
・樹脂(Disperbyk-101、BYKChemie社製) ・・・5.2部
・プロピレングリコールメチルエーテルアセテート ・・・81.9部
・C.I.ピグメントグリーン36 ・・・8.9部
・C.I.ピグメントイエロー151 ・・・2.7部
・分散剤(ソルスパース20000:日本ルーブリゾール(株)製) ・・・2.8部
・樹脂A(下記構造、重量平均分子量=11,000、繰り返し単位における比はモル比である。特開2012-173356号公報の段落番号0304~0307に記載の方法で合成した。) ・・・5.5部
顔料分散液1において、C.I.ピグメントグリーン58を、ハロゲン化亜鉛フタロシアニン顔料(臭素原子:塩素原子:水素原子=10:3:3)に変更した以外は、顔料分散液1と同様にして、顔料分散液5を調製した。
下記の表1に示す原料を、表1に示す割合(質量部)で混合および攪拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、感光性組成物を調製した。なお、下記表におけるI/Mは、光重合開始剤の質量と重合性モノマーの質量との比(光重合開始剤の質量/重合性モノマーの質量)である。また、各感光性組成物を用いて、厚さ2μmの膜を製造した際の、膜の365nmにおける光学濃度を併せて記載する。
・顔料分散液1~5:上述した顔料分散液1~5
・樹脂A:上述した樹脂A
・樹脂B:特開2010-256891号公報の段落番号0071に記載の方法で、メタクリル酸、メチルメタクリレート、n-ブチルメタクリレート、2-ヒドロキシエチルメタクリレート共重合体を合成した。得られた樹脂Bの重量平均分子量=40,000であった。
・重合性モノマーA:アロニックスM-350(東亞合成(株)製、下記構造の化合物)
・重合性モノマーD:NKエステル A-TMM-3(新中村化学工業(株)製)
・光重合開始剤1:下記化合物(波長365nmにおけるモル吸光係数=12,600L・mol-1・cm-1)
・光重合開始剤4:IRGACURE-OXE01(BASF社製、波長365nmにおけるモル吸光係数=3,300L・mol-1・cm-1)
・重合禁止剤:p-メトキシフェノール
・有機溶剤1:プロピレングリコールメチルエーテルアセテート
・有機溶剤2:シクロヘキサノン
・エポキシ化合物:EHPE3105((株)ダイセル製)
・紫外線吸収剤:UV-503(大東化学(株)製)
・界面活性剤:下記混合物(重量平均分子量=14,000)。下記の式中、繰り返し単位の割合を示す%は質量%である。
8インチ(1インチは2.54cmである)シリコンウエハに、CT-4000L(富士フイルムエレクトロニクスマテリアルズ(株)製)をポストベーク後に厚さが0.1μmになるようにスピンコーターを用いて塗布し、ホットプレートを用いて220℃で300秒間加熱して下塗り層を形成し、下塗り層付シリコンウエハ(支持体)を得た。
感光性組成物を、下塗り層付シリコンウエハ(支持体)上に、乾燥後の厚さが2μmになるようにスピンコーターを用いて塗布し、ホットプレートを用いて100℃で120秒間加熱処理(プリベーク)を行った。次いで、i線(波長365nm)のステッパー露光装置FPA-5510iZ(Canon(株)製)を使用し、3.0μm四方のベイヤーパターンを有するマスクを通して、下記の条件でパターン露光を行った。その後、パターン露光された膜が形成されている支持体を、スピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2060(富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行ない、パターンを形成した。
パターンが形成された支持体を、真空チャック方式で水平回転テーブルに固定し、回転装置によって基板を回転数200rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給して30秒間リンス処理を行ない、その後スピン乾燥した。
得られたパターンを220℃で300秒間加熱処理(ポストベーク)して、画素部の幅が3.0μm四方のベイヤーパターンを作製した。
パターン露光条件は以下のとおりである。
照明条件:NA3/σ=0.57/0.40
露光照度(W/m2):10,000
露光量:25mJ/cm2から1,700mJ/cm2ステップで露光量を変化させ、オプティマム露光エネルギー(Eopt)を検査した。なお、オプティマム露光エネルギーとは、マスク設計値をウエハ上で再現できる露光エネルギーの条件のことである。
酸素濃度(体積%):21体積%(大気条件)
上記パターン(3.0μm四方のベイヤーパターン)を解像する、オプティマム露光エネルギー(Eopt)を決定し、以下の基準でパターン形成性を評価した。
A:Eoptが、300mJ/cm2以上1,000mJ/cm2以下
B:Eoptが、50mJ/cm2以上300mJ/cm2未満、または、1,000mJ/cm2を超え1,700mJ/cm2以下
C:Eoptが、50mJ/cm2未満、または、1,700mJ/cm2を超える
3.0μm四方のベイヤーパターンが全く剥がれない露光量(密着露光量)を決定し、以下の基準で密着性を評価した。
A:Eopt>密着露光量
B:Eopt=密着露光量
C:Eopt<密着露光量
8インチ(1インチは2.54cmである)シリコンウエハに、CT-4000L(富士フイルムエレクトロニクスマテリアルズ(株)製)をポストベーク後に厚さが0.1μmになるようにスピンコーターを用いて塗布し、ホットプレートを用いて220℃で300秒間加熱(ポストベーク)して下塗り層を形成し、下塗り層付シリコンウエハ(支持体)を得た。
感光性組成物を、下塗り層付シリコンウエハ(支持体)上に、乾燥後の厚さが2μmになるようにスピンコーターを用いて塗布し、ホットプレートを用いて100℃で120秒間加熱処理(プリベーク)を行った。次いで、i線(波長365nm)のステッパー露光装置FPA-5510iZ(Canon(株)製)を使用し、2cm四方のアイランドパターンを有するマスクを通して、下記の条件でパターン露光を行った。その後、パターン露光された膜が形成されている支持体を、スピン・シャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2060(富士フイルムエレクトロニクスマテリアルズ(株)製)を用いて23℃で60秒間パドル現像を行ない、パターンを形成した。
パターンが形成された支持体を、真空チャック方式で水平回転テーブルに固定し、回転装置によって基板を回転数200rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給して30秒間リンス処理を行ない、その後スピン乾燥した。パターン露光条件は以下のとおりである。
照明条件:NA3/σ=0.57/0.40
露光照度(W/m2):10,000
露光量:25mJ/cm2から1,700mJ/cm2ステップで露光量を変化させ、得られたパターンを非接触型光学式膜厚計(F-50、ミカサ(株)製)で各露光量での厚さを測定した。3.0μm四方のベイヤーパターンでのEoptの残膜率にて下記評価を行った。
なお、残膜率は、現像後の膜の厚さと現像前の膜の厚さとの比率である。
A:残膜率が95%以上
B:残膜率が90%以上95%未満
C:残膜率が90%未満
Claims (11)
- 光重合開始剤Iと、
エチレン性不飽和二重結合を有する基を2個以上有する重合性モノマーMと、
ハロゲン化亜鉛フタロシアニンとを含み、
前記重合性モノマーMは、エチレン性不飽和二重結合を有する基を3個有する重合性モノマーM1を含有し、
前記光重合開始剤Iは、波長365nmにおけるモル吸光係数が12,000L・mol-1・cm-1以上の光重合開始剤I1を含み、
前記光重合開始剤Iの質量と前記重合性モノマーMの質量との比が、光重合開始剤Iの質量/重合性モノマーMの質量で、0.15以下である、感光性組成物。 - 前記重合性モノマーMは、前記重合性モノマーM1を50~100質量%含有する、請求項1に記載の感光性組成物。
- 前記重合性モノマーM1は、アルキレンオキシ基を有する、請求項1または2に記載の感光性組成物。
- 前記光重合開始剤I1は、ニトロ基を有するオキシム化合物およびナフタレン環を有するオキシム化合物から選ばれる少なくとも1種を含む、請求項1~3のいずれか1項に記載の感光性組成物。
- 前記重合性モノマーMは、エチレン性不飽和二重結合を有する基を4個以上有する重合性モノマーM2を50質量%以下含有する、請求項1~5のいずれか1項に記載の感光性組成物。
- 請求項1~6のいずれか1項に記載の感光性組成物を用いた、カラーフィルタ。
- 請求項1~6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をパターン状に露光する工程と、
未露光部を現像除去してパターンを形成する工程とを含む、パターン形成方法。 - 前記露光をi線で行う、請求項8に記載のパターン形成方法。
- 請求項7に記載のカラーフィルタを有する、固体撮像素子。
- 請求項7に記載のカラーフィルタを有する、画像表示装置。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020187027317A KR102138068B1 (ko) | 2016-03-25 | 2017-03-21 | 감광성 조성물, 컬러 필터, 패턴 형성 방법, 고체 촬상 소자 및 화상 표시 장치 |
JP2018507326A JP6731475B2 (ja) | 2016-03-25 | 2017-03-21 | 感光性組成物、カラーフィルタ、パターン形成方法、固体撮像素子および画像表示装置 |
US16/137,856 US11009739B2 (en) | 2016-03-25 | 2018-09-21 | Photosensitive composition, color filter, pattern forming method, solid-state imaging device, and image display device |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016-061485 | 2016-03-25 | ||
JP2016061485 | 2016-03-25 |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/137,856 Continuation US11009739B2 (en) | 2016-03-25 | 2018-09-21 | Photosensitive composition, color filter, pattern forming method, solid-state imaging device, and image display device |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017164161A1 true WO2017164161A1 (ja) | 2017-09-28 |
Family
ID=59899493
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2017/011186 WO2017164161A1 (ja) | 2016-03-25 | 2017-03-21 | 感光性組成物、カラーフィルタ、パターン形成方法、固体撮像素子および画像表示装置 |
Country Status (5)
Country | Link |
---|---|
US (1) | US11009739B2 (ja) |
JP (1) | JP6731475B2 (ja) |
KR (1) | KR102138068B1 (ja) |
TW (1) | TWI736595B (ja) |
WO (1) | WO2017164161A1 (ja) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109870877A (zh) * | 2017-11-03 | 2019-06-11 | 东友精细化工有限公司 | 着色感光性树脂组合物、彩色滤光片和图像显示装置 |
CN110018615A (zh) * | 2018-01-10 | 2019-07-16 | 东友精细化工有限公司 | 绿色感光性树脂组合物、彩色滤光片和图像显示装置 |
JP2019128540A (ja) * | 2018-01-26 | 2019-08-01 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性着色組成物及びカラーフィルタ |
CN110133964A (zh) * | 2018-02-09 | 2019-08-16 | 东友精细化工有限公司 | 绿色感光性树脂组合物、彩色滤光片和图像显示装置 |
JP2019184763A (ja) * | 2018-04-06 | 2019-10-24 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
WO2020017576A1 (ja) * | 2018-07-20 | 2020-01-23 | 三菱ケミカル株式会社 | 感光性着色樹脂組成物、硬化物、画像表示装置及び照明 |
WO2020066438A1 (ja) * | 2018-09-26 | 2020-04-02 | 富士フイルム株式会社 | 着色感光性樹脂組成物、膜、カラーフィルタ、カラーフィルタの製造方法、構造体、固体撮像素子及び画像表示装置 |
CN111133381A (zh) * | 2017-09-29 | 2020-05-08 | 富士胶片株式会社 | 着色感光性组成物及滤光器的制造方法 |
JP2020086317A (ja) * | 2018-11-29 | 2020-06-04 | 東京応化工業株式会社 | 感光性樹脂組成物、パターン化された硬化膜の製造方法、及びパターン化された硬化膜 |
JP2020148990A (ja) * | 2019-03-15 | 2020-09-17 | 三菱ケミカル株式会社 | 感光性着色樹脂組成物、硬化物、及び画像表示装置 |
JP2020177038A (ja) * | 2019-04-15 | 2020-10-29 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
JPWO2020004601A1 (ja) * | 2018-06-29 | 2021-08-02 | 株式会社Adeka | オキシムエステル化合物およびこれを含有する光重合開始剤 |
WO2023243414A1 (ja) * | 2022-06-13 | 2023-12-21 | 富士フイルム株式会社 | 樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TWI657311B (zh) * | 2017-12-29 | 2019-04-21 | 住華科技股份有限公司 | 感光性樹脂組成物、及應用其之彩色光阻結構和顯示器 |
CN118311830A (zh) * | 2018-02-16 | 2024-07-09 | 富士胶片株式会社 | 感光性组合物 |
KR102598243B1 (ko) * | 2021-02-25 | 2023-11-03 | 동우 화인켐 주식회사 | 화상표시장치용 격벽, 이를 제조하는 방법 및 상기 격벽을 포함하는 화상표시장치 |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011099974A (ja) * | 2009-11-05 | 2011-05-19 | Fujifilm Corp | 着色感光性組成物、カラーフィルタ、及び液晶表示装置 |
JP2011118275A (ja) * | 2009-12-07 | 2011-06-16 | Toppan Printing Co Ltd | 緑色感光性樹脂組成物及び液晶表示装置 |
JP2012173327A (ja) * | 2011-02-17 | 2012-09-10 | Fujifilm Corp | 着色感放射線性組成物、パターンの形成方法、カラーフィルタの製造方法、カラーフィルタ、および固体撮像素子 |
JP2013152278A (ja) * | 2012-01-24 | 2013-08-08 | Toppan Printing Co Ltd | 感光性組成物、固体撮像装置用カラーフィルタおよびその製造方法 |
JP2014052470A (ja) * | 2012-09-06 | 2014-03-20 | Toyo Ink Sc Holdings Co Ltd | 感光性着色組成物、着色膜及びカラーフィルタ |
JP2014137466A (ja) * | 2013-01-16 | 2014-07-28 | Jsr Corp | 感放射線性着色組成物、着色硬化膜及び表示素子 |
JP2014202802A (ja) * | 2013-04-02 | 2014-10-27 | 東洋インキScホールディングス株式会社 | 感光性着色組成物、着色膜及びカラーフィルタ |
JP2015125402A (ja) * | 2013-12-27 | 2015-07-06 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性着色組成物、カラーフィルタ、及びカラーフィルタの製造方法 |
JP2016191047A (ja) * | 2015-03-30 | 2016-11-10 | 住友化学株式会社 | 着色硬化性樹脂組成物 |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR100708327B1 (ko) * | 2002-07-24 | 2007-04-17 | 다이니폰 인사츠 가부시키가이샤 | 컬러 필터용 녹색 안료, 녹색 안료 분산체, 감광성 착색조성물, 컬러 필터 및 액정 패널 |
WO2008078678A1 (ja) * | 2006-12-27 | 2008-07-03 | Adeka Corporation | オキシムエステル化合物及び該化合物を含有する光重合開始剤 |
KR100920603B1 (ko) * | 2006-12-28 | 2009-10-08 | 제일모직주식회사 | 감광성 수지 조성물 및 그로부터 제조되는 컬러필터 |
JP2008266382A (ja) * | 2007-04-17 | 2008-11-06 | Fujifilm Corp | フタロシアニン顔料ナノ粒子分散物の製造方法、及びその分散物を含有するカラーフィルタ用インクジェットインクの製造方法、並びにその分散物を含有する着色感光性樹脂組成物、感光性転写材料、及びカラーフィルタ、それらを用いた液晶表示装置及びccdデバイス |
JP5535692B2 (ja) * | 2009-03-17 | 2014-07-02 | 富士フイルム株式会社 | 着色硬化性組成物、カラーフィルタ、及びカラーフィルタの製造方法 |
JP2010256891A (ja) | 2009-04-01 | 2010-11-11 | Toyo Ink Mfg Co Ltd | 感光性着色組成物およびカラーフィルタ |
JP5623818B2 (ja) * | 2009-09-18 | 2014-11-12 | 富士フイルム株式会社 | 着色硬化性組成物、カラーフィルタ、及びカラーフィルタの製造方法 |
JP5606868B2 (ja) * | 2010-10-22 | 2014-10-15 | 富士フイルム株式会社 | 光重合性組成物、カラーフィルタ、その製造方法、及び、固体撮像素子 |
JP2012172003A (ja) * | 2011-02-18 | 2012-09-10 | Fujifilm Corp | 着色組成物の製造方法、着色組成物、カラーフィルタ、液晶表示装置、及び有機el表示装置 |
JP2013117645A (ja) * | 2011-12-02 | 2013-06-13 | Toppan Printing Co Ltd | 固体撮像素子に用いられるカラーフィルタ用感光性着色組成物及びカラーフィルタ |
JP5688116B2 (ja) * | 2013-05-13 | 2015-03-25 | 太陽ホールディングス株式会社 | 光硬化性熱硬化性樹脂組成物、そのドライフィルム及び硬化物並びにそれらを用いたプリント配線板 |
JP6178164B2 (ja) * | 2013-08-23 | 2017-08-09 | 富士フイルム株式会社 | 感光性着色組成物、カラーフィルタ、カラーフィルタの製造方法、有機el液晶表示装置 |
CN105829925B (zh) * | 2014-02-07 | 2019-04-30 | Dic株式会社 | 滤色器用绿色颜料组合物以及滤色器 |
TWI790145B (zh) * | 2015-03-30 | 2023-01-11 | 日商富士軟片股份有限公司 | 著色感光性組成物、硬化膜、圖案形成方法、帶遮光膜的紅外線截止濾光片、固體攝像元件、圖像顯示裝置及紅外感測器 |
-
2017
- 2017-03-20 TW TW106109078A patent/TWI736595B/zh active
- 2017-03-21 JP JP2018507326A patent/JP6731475B2/ja active Active
- 2017-03-21 KR KR1020187027317A patent/KR102138068B1/ko active IP Right Grant
- 2017-03-21 WO PCT/JP2017/011186 patent/WO2017164161A1/ja active Application Filing
-
2018
- 2018-09-21 US US16/137,856 patent/US11009739B2/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011099974A (ja) * | 2009-11-05 | 2011-05-19 | Fujifilm Corp | 着色感光性組成物、カラーフィルタ、及び液晶表示装置 |
JP2011118275A (ja) * | 2009-12-07 | 2011-06-16 | Toppan Printing Co Ltd | 緑色感光性樹脂組成物及び液晶表示装置 |
JP2012173327A (ja) * | 2011-02-17 | 2012-09-10 | Fujifilm Corp | 着色感放射線性組成物、パターンの形成方法、カラーフィルタの製造方法、カラーフィルタ、および固体撮像素子 |
JP2013152278A (ja) * | 2012-01-24 | 2013-08-08 | Toppan Printing Co Ltd | 感光性組成物、固体撮像装置用カラーフィルタおよびその製造方法 |
JP2014052470A (ja) * | 2012-09-06 | 2014-03-20 | Toyo Ink Sc Holdings Co Ltd | 感光性着色組成物、着色膜及びカラーフィルタ |
JP2014137466A (ja) * | 2013-01-16 | 2014-07-28 | Jsr Corp | 感放射線性着色組成物、着色硬化膜及び表示素子 |
JP2014202802A (ja) * | 2013-04-02 | 2014-10-27 | 東洋インキScホールディングス株式会社 | 感光性着色組成物、着色膜及びカラーフィルタ |
JP2015125402A (ja) * | 2013-12-27 | 2015-07-06 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性着色組成物、カラーフィルタ、及びカラーフィルタの製造方法 |
JP2016191047A (ja) * | 2015-03-30 | 2016-11-10 | 住友化学株式会社 | 着色硬化性樹脂組成物 |
Cited By (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP7390189B2 (ja) | 2017-09-29 | 2023-12-01 | 富士フイルム株式会社 | 着色感光性組成物および光学フィルタの製造方法 |
JPWO2019065476A1 (ja) * | 2017-09-29 | 2020-11-05 | 富士フイルム株式会社 | 着色感光性組成物および光学フィルタの製造方法 |
CN111133381B (zh) * | 2017-09-29 | 2024-02-13 | 富士胶片株式会社 | 着色感光性组成物及滤光器的制造方法 |
CN111133381A (zh) * | 2017-09-29 | 2020-05-08 | 富士胶片株式会社 | 着色感光性组成物及滤光器的制造方法 |
US20200225576A1 (en) * | 2017-09-29 | 2020-07-16 | Fujifilm Corporation | Photosensitive coloring composition and method of manufacturing optical filter |
CN109870877A (zh) * | 2017-11-03 | 2019-06-11 | 东友精细化工有限公司 | 着色感光性树脂组合物、彩色滤光片和图像显示装置 |
CN110018615A (zh) * | 2018-01-10 | 2019-07-16 | 东友精细化工有限公司 | 绿色感光性树脂组合物、彩色滤光片和图像显示装置 |
JP2019128540A (ja) * | 2018-01-26 | 2019-08-01 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性着色組成物及びカラーフィルタ |
JP7119387B2 (ja) | 2018-01-26 | 2022-08-17 | 東洋インキScホールディングス株式会社 | カラーフィルタ用感光性着色組成物及びカラーフィルタ |
CN110133964A (zh) * | 2018-02-09 | 2019-08-16 | 东友精细化工有限公司 | 绿色感光性树脂组合物、彩色滤光片和图像显示装置 |
JP2019184763A (ja) * | 2018-04-06 | 2019-10-24 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
JP7010119B2 (ja) | 2018-04-06 | 2022-01-26 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
JP7394759B2 (ja) | 2018-06-29 | 2023-12-08 | 株式会社Adeka | オキシムエステル化合物およびこれを含有する光重合開始剤 |
US12013637B2 (en) | 2018-06-29 | 2024-06-18 | Adeka Corporation | Oxime ester compound and photopolymerization initiator containing same |
JPWO2020004601A1 (ja) * | 2018-06-29 | 2021-08-02 | 株式会社Adeka | オキシムエステル化合物およびこれを含有する光重合開始剤 |
EP3819291A4 (en) * | 2018-06-29 | 2022-04-27 | Adeka Corporation | OXIMESTER COMPOUND AND PHOTOPOLYMERIZATION INITIATOR CONTAINING IT |
JPWO2020017576A1 (ja) * | 2018-07-20 | 2021-08-12 | 三菱ケミカル株式会社 | 感光性着色樹脂組成物、硬化物、画像表示装置及び照明 |
JP7435445B2 (ja) | 2018-07-20 | 2024-02-21 | 三菱ケミカル株式会社 | 感光性着色樹脂組成物、硬化物、画像表示装置及び照明 |
WO2020017576A1 (ja) * | 2018-07-20 | 2020-01-23 | 三菱ケミカル株式会社 | 感光性着色樹脂組成物、硬化物、画像表示装置及び照明 |
JPWO2020066438A1 (ja) * | 2018-09-26 | 2021-08-30 | 富士フイルム株式会社 | 着色感光性樹脂組成物、膜、カラーフィルタ、カラーフィルタの製造方法、構造体、固体撮像素子及び画像表示装置 |
WO2020066438A1 (ja) * | 2018-09-26 | 2020-04-02 | 富士フイルム株式会社 | 着色感光性樹脂組成物、膜、カラーフィルタ、カラーフィルタの製造方法、構造体、固体撮像素子及び画像表示装置 |
JP7313136B2 (ja) | 2018-11-29 | 2023-07-24 | 東京応化工業株式会社 | 感光性樹脂組成物、パターン化された硬化膜の製造方法、及びパターン化された硬化膜 |
JP2020086317A (ja) * | 2018-11-29 | 2020-06-04 | 東京応化工業株式会社 | 感光性樹脂組成物、パターン化された硬化膜の製造方法、及びパターン化された硬化膜 |
JP7247676B2 (ja) | 2019-03-15 | 2023-03-29 | 三菱ケミカル株式会社 | 感光性着色樹脂組成物、硬化物、及び画像表示装置 |
JP2020148990A (ja) * | 2019-03-15 | 2020-09-17 | 三菱ケミカル株式会社 | 感光性着色樹脂組成物、硬化物、及び画像表示装置 |
JP2020177038A (ja) * | 2019-04-15 | 2020-10-29 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
JP7255331B2 (ja) | 2019-04-15 | 2023-04-11 | 東洋インキScホールディングス株式会社 | カラーフィルタ用着色組成物、フィルタセグメント、およびカラーフィルタ |
WO2023243414A1 (ja) * | 2022-06-13 | 2023-12-21 | 富士フイルム株式会社 | 樹脂組成物、膜、光学フィルタ、固体撮像素子および画像表示装置 |
Also Published As
Publication number | Publication date |
---|---|
US20190018282A1 (en) | 2019-01-17 |
TW201734642A (zh) | 2017-10-01 |
US11009739B2 (en) | 2021-05-18 |
TWI736595B (zh) | 2021-08-21 |
KR102138068B1 (ko) | 2020-07-27 |
JPWO2017164161A1 (ja) | 2019-02-14 |
JP6731475B2 (ja) | 2020-07-29 |
KR20180112055A (ko) | 2018-10-11 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6731475B2 (ja) | 感光性組成物、カラーフィルタ、パターン形成方法、固体撮像素子および画像表示装置 | |
US11073760B2 (en) | Coloring composition, color filter, pattern forming method, solid-stage imaging element, and image display device | |
JP6801071B2 (ja) | 着色硬化性組成物、カラーフィルタ、固体撮像素子、画像表示装置および、硬化膜の製造方法 | |
TWI773679B (zh) | 著色組成物、彩色濾光片、圖案形成方法、固體攝像元件以及圖像顯示裝置 | |
JP6591540B2 (ja) | 硬化性組成物、硬化性組成物の製造方法、膜、赤外線カットフィルタ、赤外線透過フィルタ、パターン形成方法および装置 | |
WO2017099019A1 (ja) | 感放射線性樹脂組成物、硬化膜、パターン形成方法、固体撮像素子および画像表示装置 | |
JP7126537B2 (ja) | 着色組成物、着色組成物の製造方法、カラーフィルタ、パターン形成方法、固体撮像素子、および、画像表示装置 | |
TWI740063B (zh) | 著色組成物、硬化膜、圖案形成方法、濾色器、固體攝像元件及圖像顯示裝置 | |
JP7057412B2 (ja) | 着色組成物、顔料分散液、顔料分散液の製造方法、硬化膜、カラーフィルタ、固体撮像素子および画像表示装置 | |
JP6604928B2 (ja) | 着色組成物、膜および膜の製造方法 | |
US11169439B2 (en) | Coloring composition and method for producing film | |
JP6587697B2 (ja) | 着色組成物、カラーフィルタ、パターン形成方法、固体撮像素子および画像表示装置 | |
WO2019172005A1 (ja) | 感光性着色組成物、硬化膜、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 | |
TWI759512B (zh) | 著色組成物、硬化膜、圖案形成方法、彩色濾光片、固體攝像元件及圖像顯示裝置 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
WWE | Wipo information: entry into national phase |
Ref document number: 2018507326 Country of ref document: JP |
|
ENP | Entry into the national phase |
Ref document number: 20187027317 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17770203 Country of ref document: EP Kind code of ref document: A1 |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 17770203 Country of ref document: EP Kind code of ref document: A1 |