WO2017150093A1 - 組成物、組成物の製造方法、硬化膜、カラーフィルタ、遮光膜、固体撮像素子および画像表示装置 - Google Patents
組成物、組成物の製造方法、硬化膜、カラーフィルタ、遮光膜、固体撮像素子および画像表示装置 Download PDFInfo
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- WO2017150093A1 WO2017150093A1 PCT/JP2017/004363 JP2017004363W WO2017150093A1 WO 2017150093 A1 WO2017150093 A1 WO 2017150093A1 JP 2017004363 W JP2017004363 W JP 2017004363W WO 2017150093 A1 WO2017150093 A1 WO 2017150093A1
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- titanium nitride
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- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/28—Nitrogen-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/076—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with titanium or zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
Definitions
- the present invention relates to a composition, a method for producing the composition, a cured film, a color filter, a light shielding film, a solid-state imaging device, and an image display device.
- compositions containing titanium nitride are known.
- a composition containing titanium nitride is used for various purposes, for example, for producing a light-shielding film provided in a liquid crystal display device, a solid-state imaging device, or the like.
- a color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast.
- a black matrix is provided for the purpose of preventing noise generation and improving image quality.
- portable terminals of electronic devices such as mobile phones and PDAs (Personal Digital Assistants) are equipped with small and thin imaging units.
- Such an imaging unit generally includes a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, a lens for forming a subject image on the solid-state imaging device, It has.
- a solid-state imaging device such as a CCD (Charge Coupled Device) image sensor and a CMOS (Complementary Metal-Oxide Semiconductor) image sensor, a lens for forming a subject image on the solid-state imaging device, It has.
- Patent Document 1 includes “at least a light shielding material, a resin and a solvent, and at least titanium nitride particles as a light shielding material.
- a black resin composition for a resin black matrix, wherein a diffraction angle 2 ⁇ of a peak derived from the (200) plane of the titanium nitride particles when CuK ⁇ rays are used as an X-ray source is 42.5 ° or more and 42.8 °.
- the following black resin composition for resin black matrix is disclosed (Claim 1).
- the composition containing titanium nitride particles (titanium nitride-containing particles) as described above may be used to form a cured film processed into a pattern on a substrate on which an electrode pattern is formed. is there. Therefore, the present inventors applied a composition containing titanium nitride-containing particles on a substrate on which an electrode pattern was formed to produce a cured film formed in a pattern. Depending on the type of electrode, it has become clear that the electrode pattern deteriorates (corrosion) or a desired pattern cannot be obtained (decrease in patternability).
- the present inventors have found that a cured film excellent in patterning properties and electrode anticorrosion properties can be produced when the content of Fe atoms in the titanium nitride-containing particles is within a predetermined range.
- the headline, the present invention has been reached. That is, the present inventor has found that the above problem can be solved by the following configuration.
- the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the titanium nitride-containing particle is 42.6 ° or more and 43.5 ° or less when CuK ⁇ ray is used as the X-ray source.
- the titanium nitride-containing particles further contain Si atoms, The composition according to the above [1] or [2], wherein the content of the Si atoms in the titanium nitride-containing particles is more than 0.002% and less than 0.3% by mass.
- Particle number measuring method A sample solution is prepared by diluting the composition 500 times with propylene glycol monomethyl ether acetate. Measure with a particle image analyzer.
- composition according to any one of [1] to [4] above further comprising two or more organic solvents.
- composition according to any one of [1] to [5] further comprising a binder resin.
- composition according to any one of [1] to [6] above further comprising a polymerizable compound.
- composition according to any one of [1] to [7] further comprising a polymerization initiator.
- composition according to any one of [1] to [9] above, wherein the content of the titanium nitride-containing particles is 20 to 70% by mass with respect to the total solid content of the composition. [11] In addition, it contains water The composition according to any one of [1] to [10], wherein the water content is 0.1 to 1% by mass relative to the total mass of the composition. [12] In addition, it contains a dispersant, In any one of the above [1] to [11], the dispersant has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. The composition as described.
- the present invention it is possible to provide a composition capable of producing a cured film excellent in patterning properties and electrode corrosion resistance. Moreover, according to this invention, the manufacturing method of a composition, a cured film, a color filter, a light shielding film, a solid-state image sensor, and an image display apparatus can also be provided.
- 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 description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent.
- the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- Actinic light or “radiation” in the present specification means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), X-rays, and electron beams. .
- light means actinic rays or radiation.
- exposure in this specification is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, X-rays, EUV light, etc., but also electron beams, ion beams, etc. The exposure with the particle beam is also included in the exposure.
- (meth) acrylate represents acrylate and methacrylate
- (meth) acryl represents acrylic and methacryl
- (meth) acryloyl represents acryloyl and methacryloyl
- (meth) ) Acrylamide refers to acrylamide and methacrylamide.
- “monomer” and “monomer” are synonymous.
- the monomer in the present invention is distinguished from an oligomer and a polymer and refers to a compound having a weight average molecular weight of 2,000 or less.
- the polymerizable compound means a compound having a polymerizable group, and may be a monomer or a polymer.
- the polymerizable group refers to a group that participates in a polymerization reaction.
- composition of the present invention contains titanium nitride-containing particles containing Fe atoms, and the content of the Fe atoms in the titanium nitride-containing particles is more than 0.001% and less than 0.4% by mass. . According to the composition of this invention, the cured film excellent in patterning property and the corrosion resistance of an electrode can be produced. As a result of intensive studies, the present inventors have found that the content of Fe atoms in the titanium nitride-containing particles is related to patterning properties and anticorrosion properties of the electrodes.
- the Fe atoms contained in the titanium nitride-containing particles are excellent in adhesion to the electrode and the substrate, and the titanium nitrides in the titanium nitride-containing particles were attached to the electrode and the substrate via the Fe atoms. Conceivable. For this reason, it is considered that Fe atoms remain on the electrode and the substrate after the patterning of the cured film such as development processing, and the titanium nitride is easily removed. Therefore, it is estimated that the patterning property of the cured film is improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or more.
- the anticorrosion property of the electrode has been improved by setting the content of Fe atoms in the titanium nitride-containing particles to a predetermined amount or less.
- the composition of the present invention contains titanium nitride-containing particles containing Fe atoms.
- the titanium nitride-containing particles are preferably used as a black pigment.
- a gas phase reaction method is usually used, and specific examples include an electric furnace method and a thermal plasma method.
- the thermal plasma method is preferable because it is less contaminated with impurities, easily has a uniform particle diameter, and has high productivity.
- Examples of the method for generating thermal plasma include direct current arc discharge, multiphase arc discharge, radio frequency (RF) plasma, and hybrid plasma, and high frequency plasma in which impurities from the electrode are less mixed is preferable.
- titanium powder is evaporated by high-frequency thermal plasma, nitrogen is introduced into the apparatus as a carrier gas, and titanium powder is nitrided in the cooling process. And a method of synthesizing titanium nitride-containing particles.
- the thermal plasma method is not limited to the above.
- the method for producing titanium nitride-containing particles contained in the composition of the present invention is not particularly limited, but the production method described in paragraphs ⁇ 0037> to ⁇ 0089> of International Publication No. 2010/147098 can be referred to. it can.
- the Ag powder of International Publication No. 2010/147098 instead of the Ag powder of International Publication No. 2010/147098, using a component containing Fe and / or a component containing Si, which will be described later, and a mixture of this and a titanium powder material (titanium particles) as a raw material, Titanium nitride-containing particles contained in the composition of the present invention can be produced.
- the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles is preferably of high purity.
- the titanium powder material is not particularly limited, but a titanium element having a purity of 99.99% or more is preferable, and a material having 99.999% or more is more preferably used.
- the titanium powder material (titanium particles) used for the production of titanium nitride-containing particles may contain atoms other than titanium atoms.
- examples of other atoms that can be contained in the titanium powder material include Fe atoms and Si atoms.
- the content of Fe atoms is preferably more than 0.001% by mass with respect to the total mass of the titanium powder material. Thereby, the patterning property of a cured film is more excellent.
- the titanium powder material contains Fe atoms the content of Fe atoms is preferably less than 0.4% by mass with respect to the total amount of the titanium powder material.
- the corrosion resistance of the electrode by a cured film is more excellent (it can suppress more that a cured film corrodes an electrode). That is, when the Fe atom contained in the titanium powder material used for the production of the titanium nitride-containing particles is within the above range (over 0.001 mass, less than 0.4 mass%), the effect of the present invention is more remarkable. Can get to.
- the titanium powder material contains Si atoms
- the content of Si atoms is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium powder material. The content is more preferably from 0.15% by mass, and even more preferably from 0.02 to 0.1% by mass.
- the patterning property of the cured film is further improved. Further, when the content of Si atoms is less than 0.3% by mass, the polarity of the outermost layer of the obtained titanium nitride-containing particles is stabilized, and the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed It is considered that the adsorbing property of the dispersant on the surface is improved, and the undispersed material of the titanium nitride-containing particles is reduced, thereby suppressing the generation of particles.
- the effect of the present invention can be obtained more remarkably.
- grain is less than 1 mass% with respect to the total mass of a titanium powder material, and less than 0.1 mass% Is more preferable, and it is further more preferable not to contain substantially.
- the effect of this invention can be acquired more notably because the water
- the titanium nitride-containing particles are obtained by using a thermal plasma method, whereby a peak diffraction angle 2 ⁇ (details will be described later) derived from the (200) plane when CuK ⁇ rays are used as an X-ray source, It becomes easy to adjust to a range of 42.6 ° to 43.5 °.
- the method for causing the titanium nitride-containing particles to contain Fe atoms is not particularly limited.
- Fe atoms used as a raw material for the above-described titanium nitride-containing particles.
- the method of introducing is mentioned. More specifically, when titanium is produced by the crawl method or the like, a reaction vessel that is made of a material containing Fe atoms such as stainless steel (SUS), or a press machine for crushing titanium and By using a material containing Fe atoms as the material of the pulverizer, Fe atoms can be attached to the surface of the titanium particles.
- SUS stainless steel
- the titanium nitride-containing particles can contain Fe atoms.
- Fe atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, and sulfides. And oxysulfide may be included in any form.
- the Fe atoms contained in the titanium nitride-containing particles may exist as impurities at the position between the crystal lattices, or may exist as impurities in the amorphous state at the crystal grain boundaries.
- the content of Fe atoms in the titanium nitride-containing particles is more than 0.001% by mass and less than 0.4% by mass with respect to the total mass of the titanium nitride-containing particles. Of these, 0.01 to 0.2% by mass is preferable, and 0.02 to 0.1% by mass is more preferable.
- the content of Fe atoms is more than 0.001% by mass, the patterning property of the cured film is excellent.
- the content of Fe atoms is less than 0.4% by mass, the corrosion resistance of the electrode by the cured film is excellent (the cured film can be inhibited from corroding the electrode).
- the content of Fe atoms in the titanium nitride-containing particles is within the above range, the effects of the present invention (the patterning property of the cured film and the anticorrosive property of the electrode) are remarkably exhibited.
- the content of Fe atoms in the titanium nitride-containing particles is measured by ICP (High Frequency Inductively Coupled Plasma) emission spectroscopy.
- the titanium nitride-containing particles preferably further contain Si atoms (silicon atoms). Thereby, the patterning property of a cured film improves more.
- the reason why the patterning property is improved by containing Si atoms is considered to be the same as the above-described Fe atoms.
- the content of Si atoms in the titanium nitride-containing particles is preferably more than 0.002% by mass and less than 0.3% by mass with respect to the total mass of the titanium nitride-containing particles, and 0.01 to 0.15 More preferably, it is more preferably 0.02 to 0.1% by mass. When the content of Si atoms is more than 0.002% by mass, the patterning property of the cured film is further improved.
- the polarity of the outermost layer of the titanium nitride-containing particles is stabilized by being less than 0.3% by mass, and the adsorptivity of the dispersant to the titanium nitride-containing particles when the titanium nitride-containing particles are dispersed. It is considered that there is an effect of suppressing particle generation by improving and reducing the undispersed particles of titanium nitride-containing particles.
- the content of Si atoms in the titanium nitride-containing particles is measured by the same method as that for Fe atoms.
- the method for incorporating Si atoms into the titanium nitride-containing particles is not particularly limited.
- Si atoms are introduced at the stage of obtaining titanium particles (titanium powder) used as a raw material for the above-described titanium nitride-containing particles.
- the method etc. are mentioned. More specifically, when titanium is produced by a crawl method or the like, a reaction vessel made of a material containing Si atoms is used, or Si atom is used as a material for a press machine and a grinder for crushing titanium. Si atoms can be attached to the surface of the titanium particles.
- Si atoms can be contained in the titanium nitride-containing particles.
- Si atoms contained in titanium nitride-containing particles are ions, metal compounds (including complex compounds), intermetallic compounds, alloys, oxides, composite oxides, nitrides, oxynitrides, sulfides, and acids. It may be contained in any form such as sulfide.
- Si atoms contained in the titanium nitride-containing particles may be present as impurities at the position between the crystal lattices, or may be present as impurities in the amorphous state at the crystal grain boundaries.
- the content of titanium atoms (Ti atoms) in the titanium nitride-containing particles is preferably 10 to 85% by mass and preferably 15 to 75% by mass with respect to the total mass of the titanium nitride-containing particles. More preferred is 20 to 70% by mass.
- the content of Ti atoms in the titanium nitride-containing particles can be analyzed by ICP emission spectroscopy.
- the content of nitrogen atoms (N atoms) in the titanium nitride-containing particles is preferably 3 to 60% by mass and preferably 5 to 50% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is 10 to 40% by mass.
- the nitrogen atom content can be analyzed by an inert gas melting-thermal conductivity method.
- Titanium nitride-containing particles contain titanium nitride (TiN) as a main component, and usually become noticeable when oxygen is mixed during the synthesis and when the particle diameter is small. A part of oxygen atoms may be contained.
- the content of oxygen atoms in the titanium nitride-containing particles is preferably 1 to 40% by mass, more preferably 1 to 35% by mass with respect to the total mass of the titanium nitride-containing particles. More preferably, it is ⁇ 30% by mass.
- the oxygen atom content can be analyzed by an inert gas melting-infrared absorption method.
- the specific surface area of the titanium nitride-containing particles is preferably 5 m 2 / g or more and 100 m 2 / g or less, and more preferably 10 m 2 / g or more and 60 m 2 / g or less.
- the specific surface area can be determined by the BET method.
- the titanium nitride-containing particles may be composite fine particles composed of titanium nitride particles and metal fine particles.
- Composite fine particles refer to particles in which titanium nitride particles and metal fine particles are complexed or in a highly dispersed state.
- “composite” means that the particles are composed of both titanium nitride and metal components
- “highly dispersed” means that the titanium nitride particles and metal particles are It means that the particles exist individually and the small amount of particles are not aggregated and are uniformly and uniformly dispersed.
- the metal fine particles are not particularly limited.
- at least one selected from copper, silver, gold, platinum, palladium, nickel, tin, cobalt, rhodium and iridium, and alloys thereof is preferable, and copper, silver, gold, platinum and tin, and these It is more preferable that it is at least one selected from these alloys. From the viewpoint of better moisture resistance, silver is preferred.
- the content of the metal fine particles in the titanium nitride-containing particles is preferably 5% by mass or more and 50% by mass or less, and preferably 10% by mass or more and 30% by mass or less with respect to the total mass of the titanium nitride-containing particles. Is more preferable.
- the titanium nitride-containing particles preferably have a diffraction angle 2 ⁇ of a peak derived from the (200) plane when CuK ⁇ rays are used as an X-ray source and more than 42.6 ° and 43.5 ° or less.
- a cured film (for example, a black matrix) obtained using a composition containing titanium nitride-containing particles having such characteristics is high while keeping the concentration of titanium nitride-containing particles in the composition low. It is possible to achieve the OD value. As a result, the cured film can ensure high adhesion.
- TiN has a peak derived from the (200) plane as a strongest peak
- TiO has a (200 )
- the diffraction angle 2 ⁇ of the peak derived from the (200) plane of the titanium nitride-containing particle is preferably more than 42.6 ° and less than 43.5 ° from the viewpoint of stability of the particle over time. From the viewpoint of excellent process margin, it is more preferably 42.7 ° or more and less than 43.5 °, and from the viewpoint of excellent reproducibility of particle performance, it is more preferably 42.7 ° or more and less than 43.4 °.
- the crystallite size constituting the titanium nitride-containing particles can be determined from the half width of the X-ray diffraction peak, and is calculated using Scherrer's formula.
- the crystallite size is preferably 20 nm or more, more preferably 20 to 50 nm.
- the transmitted light of the cured film exhibits a blue to blue purple color having a peak wavelength of 475 nm or less, and has high light-shielding properties.
- a black matrix having both ultraviolet sensitivity can be obtained.
- the crystallite size is 20 nm or more, the proportion of the active particle surface with respect to the particle volume is reduced, providing a good balance, and the titanium nitride-containing particles have more excellent heat resistance and / or durability. It becomes.
- the content of titanium nitride-containing particles is preferably 20 to 70% by mass, more preferably 30 to 70% by mass, and 40 to 70% by mass with respect to the total solid content of the composition. More preferred is 45 to 70% by mass.
- the light shielding property is improved when the content of the titanium nitride-containing particles is 20% by mass or more.
- the content of the titanium nitride-containing particles is 70% by mass or less, the temporal stability of the composition is improved.
- solid content intends the component which comprises the cured film formed with a composition, and a solvent is not contained. For example, since the polymerizable compound described later is a component constituting the cured film, even a liquid (liquid) is included in the solid content.
- the particle diameter D90 of the titanium nitride-containing particles in the composition is preferably 5 to 100 nm, more preferably 10 to 75 nm, and even more preferably 10 to 60 nm.
- the particle size of the titanium nitride-containing particles in the composition is measured using a device according to a particle size distribution measuring device Nanotrac UPA-150EX manufactured by Microtrack.
- the number of titanium nitride-containing particles having a size of 10 ⁇ m or more determined by the following particle number measurement method is preferably 100 or less, more preferably 0 to 100, More preferably, it is 0-20. This improves the filterability of the composition.
- Particle number measurement method A sample solution is prepared by diluting the composition of the present invention 500 times with propylene glycol monomethyl ether acetate, and the number of titanium nitride-containing particles having a size of 10 ⁇ m or more contained in 10 ml of the sample solution is determined by a flow equation. Measure with a particle image analyzer.
- the size of the titanium nitride-containing particles can be measured using a flow particle image analyzer (Flow Particle Image Analyzer).
- Flow Particle Image Analyzer Flow Particle Image Analyzer
- Specific examples of the flow type particle image analyzer include a flow type particle image analyzer FPIA-3000 manufactured by Sysmex Corporation.
- the FPIA-3000 is an apparatus that measures particle images using an imaging flow cytometry method and performs particle analysis.
- the size of the titanium nitride-containing particles is determined by using a flow-type particle image analyzer with a flat and flat transparent flow cell (thickness: about 200 ⁇ m) in the flow path (flow path extending along the flow direction). By passing through a sample solution diluted with the composition.
- the flow type particle image analyzer is mounted so that the strobe and the CCD camera are located on the opposite sides of the flow cell in order to form an optical path that passes in the direction intersecting the thickness direction of the flow cell. .
- the strobe emits strobe light at 1/60 second intervals while the sample solution flows through the flow path.
- each particle flowing through the flow cell is photographed as a two-dimensional image having a certain range parallel to the flow cell. From the area of the two-dimensional image of each particle, the diameter of a circle having the same area is calculated as the “size” of the present invention.
- the sample used for measurement is preferably prepared by diluting the composition with a solvent such as an organic solvent or water.
- the sample is a dispersion containing titanium nitride-containing particles in a dispersed state.
- the composition containing titanium nitride-containing particles is preferably diluted with a solvent such as an organic solvent or water so that the solid content is 10 to 40% by mass. More preferably, the titanium nitride-containing particles are redispersed after the components are dissolved in the solvent. More preferably, the sample is further diluted 10 to 2000 times with a dispersion obtained by redispersing titanium nitride-containing particles.
- the state of the dispersion in which the titanium nitride-containing particles are dispersed is preferably a state in which the average particle diameter (D90) of the titanium nitride-containing particles measured by the dynamic light scattering method is 1 ⁇ m or less.
- the measuring device using the dynamic light scattering method is not particularly limited, and examples thereof include a product name “Nanotrack UPA-150EX” manufactured by Microtrack Corporation.
- the composition of the present invention preferably contains a dispersant.
- a dispersing agent contributes to the improvement of dispersibility of pigments, such as a titanium nitride content particle mentioned above.
- a dispersing agent and the binder resin mentioned later are different components.
- the dispersant for example, a known pigment dispersant can be appropriately selected and used. Of these, polymer compounds are preferable.
- dispersant examples include polymer dispersants [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 type Copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkyl amine, and pigment derivatives.
- the polymer compounds can be further classified into linear polymers, terminal-modified polymers, graft polymers, and block polymers based on their structures.
- the polymer compound is adsorbed on the surface of the dispersion such as a black pigment which is a preferred embodiment of the titanium nitride-containing particles and a pigment used in combination, and acts to prevent reaggregation of the dispersion. Therefore, a terminal-modified polymer, a graft polymer, and a block polymer having an anchor site to the pigment surface are preferable. On the other hand, by modifying the surface of the titanium nitride-containing particles, the adsorptivity of the polymer compound can be promoted.
- the polymer compound preferably has a structural unit having a graft chain.
- structural unit is synonymous with “repeating unit”.
- Such a polymer compound having a structural unit having a graft chain is excellent in dispersibility of colored pigments such as black pigments and dispersion stability after aging because the graft chain has an affinity with a solvent. It is. Further, due to the presence of the graft chain, the polymer compound having a structural unit having a graft chain has an affinity with a polymerizable compound or other resin that can be used in combination. As a result, it becomes difficult to produce a residue by alkali development.
- the graft chain When the graft chain becomes longer, the steric repulsion effect becomes higher and the dispersibility of the pigment and the like is improved. On the other hand, if the graft chain is too long, the adsorptive power to a colored pigment such as a black pigment is lowered, and the dispersibility of the pigment or the like tends to be lowered.
- the graft chain preferably has 40 to 10,000 atoms excluding hydrogen atoms, more preferably 50 to 2000 atoms excluding hydrogen atoms, and the number of atoms excluding hydrogen atoms. More preferred is 60-500.
- the graft chain means from the base of the main chain of the copolymer (the atom bonded to the main chain in a group branched from the main chain) to the end of the group branched from the main chain.
- the graft chain preferably has a polymer structure.
- a polymer structure include a poly (meth) acrylate structure (for example, a poly (meth) acrylic structure), a polyester structure, a polyurethane structure, a polyurea structure, and a polyamide structure. And a polyether structure.
- the graft chain is made of at least one selected from the group consisting of a polyester structure, a polyether structure and a poly (meth) acrylate structure. It is preferably a graft chain having, and more preferably a graft chain having at least one of a polyester structure and a polyether structure.
- the macromonomer having such a graft chain is not particularly limited, but a macromonomer having a reactive double bond group can be preferably used.
- AA-6 trade name, Toagosei Co., Ltd.
- AA-10 Product name, manufactured by Toagosei Co., Ltd.
- AB-6 trade name, manufactured by Toagosei Co., Ltd.
- AS-6 trade name, manufactured by Toagosei Co., Ltd.
- AN-6 trade name, manufactured by Toagosei Co., Ltd.
- AW-6 trade name, manufactured by Toagosei Co., Ltd.
- AA-714 trade name, manufactured by Toagosei Co., Ltd.
- AY-707 trade name, manufactured by Toagosei Co., Ltd.
- AY-714 trade name, manufactured by Toagosei Co., Ltd.
- AK-5 trade name, manufactured by Toagosei Co., Ltd.
- AA-6 (trade name, manufactured by Toagosei Co., Ltd.), AA-10 (trade name, manufactured by Toagosei Co., Ltd.), AB-6 (trade name, manufactured by Toagosei Co., Ltd.) AS-6 (trade name, manufactured by Toagosei Co., Ltd.), AN-6 (trade name, manufactured by Toagosei Co., Ltd.), and Bremer PME-4000 (trade name, manufactured by NOF Corporation). It is done.
- the dispersant of the present invention preferably has at least one structure selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and cyclic or chain polyester. More preferably, the dispersant of the present invention is at least one selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, and chain polyester. More preferably, the dispersant of the present invention is at least one selected from the group consisting of polymethyl acrylate, polymethyl methacrylate, polycaprolactone, and polyvalerolactone.
- the dispersant may have the above structure alone in one dispersant, or may have a plurality of these structures in one dispersant.
- the polycaprolactone structure means a structure having a ring-opened structure of ⁇ -caprolactone as a repeating unit.
- the polyvalerolactone structure means a structure having a ring-opened structure of ⁇ -valerolactone as a repeating unit.
- Specific examples of the dispersant having a polycaprolactone structure include those in which j and k are 5 in the following formula (1) and the following formula (2).
- Specific examples of the dispersant having a polyvalerolactone structure include those in which j and k in the following formula (1) and the following formula (2) are 4.
- dispersant having a polymethyl acrylate structure examples include those in which X 5 in the following formula (4) is a hydrogen atom and R 4 is a methyl group. Further, specific examples of the dispersant having a polymethyl methacrylate structure include those in which X 5 in the following formula (4) is a methyl group and R 4 is a methyl group.
- the polymer compound preferably includes a structural unit represented by any one of the following formulas (1) to (4) as a structural unit having a graft chain, and includes the following formula (1A), the following formula (2A), It is more preferable to include a structural unit represented by any of the following formula (3A), the following formula (3B), and the following (4).
- W 1 , W 2 , W 3 , and W 4 each independently represent an oxygen atom or NH.
- W 1 , W 2 , W 3 , and W 4 are preferably oxygen atoms.
- X 1 , X 2 , X 3 , X 4 , and X 5 each independently represent a hydrogen atom or a monovalent organic group.
- X 1 , X 2 , X 3 , X 4 , and X 5 are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms (the number of carbon atoms) from the viewpoint of synthesis restrictions.
- 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.
- Specific examples of the divalent linking group represented by Y 1 , Y 2 , Y 3 , and Y 4 include the following (Y-1) to (Y-21) linking groups.
- a and B mean binding sites with the left end group and the right end group in formulas (1) to (4), respectively. Of the structures shown below, (Y-2) or (Y-13) is more preferable from the viewpoint of ease of synthesis.
- Z 1 , Z 2 , Z 3 , and Z 4 each independently represent a monovalent organic group.
- the structure of the organic group is not particularly limited. Specifically, an alkyl group, a hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, a heteroarylthioether group, an amino group, etc. Is mentioned.
- the organic group represented by Z 1 , Z 2 , Z 3 , and Z 4 those having a steric repulsion effect are particularly preferable from the viewpoint of improving dispersibility, and each independently has 5 to 24 carbon atoms.
- 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 particularly 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 viewpoint of dispersion stability and developability of the composition.
- R 3 represents a branched or straight chain alkylene group, preferably an alkylene group having 1 to 10 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms. When 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, and 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.
- the alkyl group is preferably 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, A linear alkyl group having 1 to 20 carbon atoms is more preferable, and a linear alkyl group having 1 to 6 carbon atoms is more preferable.
- a plurality of X 5 and R 4 present in the graft copolymer may be the same or different from each other.
- the polymer compound may have a structural unit having a graft chain, which has two or more different structures. That is, the polymer compound molecule may contain structural units represented by formulas (1) to (4) having different structures, and n, m in formulas (1) to (4). , P, and q each represents an integer of 2 or more, in Formula (1) and Formula (2), j and k may contain structures different from each other in the side chain. In the formula (4), a plurality of R 3 , R 4 and X 5 present in the molecule may be the same or different from each other.
- the structural unit represented by the formula (1) is more preferably a structural unit represented by the following formula (1A) from the viewpoint of dispersion stability and developability of the composition.
- the structural unit represented by the formula (2) is more preferably a structural unit represented by the following formula (2A) from the viewpoint of dispersion stability and developability of the composition.
- X 1, Y 1, Z 1 and n are the same as X 1, Y 1, Z 1 and n in Formula (1), and preferred ranges are also the same.
- X 2, Y 2, Z 2 and m are as defined X 2, Y 2, Z 2 and m in the formula (2), and preferred ranges are also the same.
- the structural unit represented by formula (3) is more preferably a structural unit represented by the following formula (3A) or formula (3B) from the viewpoint of dispersion stability and developability of the composition. .
- X 3, Y 3, Z 3 and p are as defined X 3, Y 3, Z 3 and p in formula (3), and preferred ranges are also the same.
- the polymer compound has a structural unit represented by the formula (1A) as a structural unit having a graft chain.
- the structural unit having a graft chain (for example, the structural unit represented by the above formulas (1) to (4)) is 2 to 90% of the total mass of the polymer compound in terms of mass. It is preferably included in a range, and more preferably in a range of 5 to 30%. When the structural unit having a graft chain is contained within this range, the dispersibility of the black pigment is high, and the developability when forming a cured film is good.
- the polymer compound preferably has a hydrophobic structural unit different from the structural unit having a graft chain (that is, not corresponding to the structural unit having a graft chain).
- the hydrophobic structural unit is a structural unit having no acid group (for example, carboxylic acid group, sulfonic acid group, phosphoric acid group, phenolic hydroxyl group, etc.).
- the hydrophobic structural unit is preferably a structural unit derived from (corresponding to) a compound (monomer) having a ClogP value of 1.2 or more, more preferably derived from a compound having a ClogP value of 1.2 to 8. A structural unit. Thereby, the effect of this invention can be expressed more reliably.
- ClogP values are available from Daylight Chemical Information System, Inc. It is a value calculated by the program “CLOGP” available from This program provides the value of “computation logP” calculated by Hansch, Leo's fragment approach (see below). The fragment approach is based on the chemical structure of a compound, which divides the chemical structure into substructures (fragments) and estimates the logP value of the compound by summing the logP contributions assigned to that fragment. Details thereof are described in the following documents. In the present invention, the ClogP value calculated by the program CLOGP v4.82 is used. A. J. et al. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.I. Hansch, P.A. G. Sammunens, J. et al. B.
- log P means the common logarithm of the partition coefficient P (Partition Coefficient), and quantitatively determines how an organic compound is distributed in the equilibrium of a two-phase system of oil (generally 1-octanol) and water. It is a physical property value expressed as a numerical value, and is represented by the following formula.
- logP log (Coil / Cwater)
- Coil represents the molar concentration of the compound in the oil phase
- Cwater represents the molar concentration of the compound in the aqueous phase.
- the polymer compound preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (i) to (iii) as hydrophobic structural units.
- R 1 , R 2 , and R 3 are each independently a hydrogen atom, a halogen atom (for example, fluorine, chlorine, bromine, etc.), or a carbon number of 1 to 6
- An alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.) is represented.
- R 1 , R 2 , and R 3 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group.
- R 2 and R 3 are particularly preferably a hydrogen atom.
- X represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
- L is a single bond or a divalent linking group.
- a divalent aliphatic group for example, alkylene group, substituted alkylene group, alkenylene group, substituted alkenylene group, alkynylene group, substituted alkynylene group
- divalent aromatic group for example, arylene group
- Substituted arylene group divalent heterocyclic group, oxygen atom (—O—), sulfur atom (—S—), imino group (—NH—), substituted imino group (—NR 31 —, where R 31 Includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl group (—CO—), and combinations thereof.
- the divalent aliphatic group may have a cyclic structure or a branched structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group may be an unsaturated aliphatic group or a saturated aliphatic group, but is preferably a saturated aliphatic group.
- the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group and a heterocyclic group.
- the carbon number of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
- the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
- the heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group or heterocyclic group.
- L is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
- the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
- the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
- Z is an aliphatic group (eg, alkyl group, substituted alkyl group, unsaturated alkyl group, substituted unsaturated alkyl group), aromatic group (eg, aryl group, substituted aryl group, arylene group, substituted arylene group). , A heterocyclic group, or a combination thereof. These groups include an oxygen atom (—O—), a sulfur atom (—S—), an imino group (—NH—), a substituted imino group (—NR 31 —, wherein R 31 is an aliphatic group, an aromatic group Group or heterocyclic group) or a carbonyl group (—CO—) may be contained.
- the aliphatic group may have a cyclic structure or a branched structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group further includes a ring assembly hydrocarbon group and a bridged cyclic hydrocarbon group. Examples of the ring assembly hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and 4-cyclohexyl. A phenyl group and the like are included.
- bridged cyclic hydrocarbon ring for example, bicyclic such as pinane, bornane, norpinane, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.) Hydrocarbon ring, homobredan, adamantane, tricyclo [5.2.1.0 2,6 ] decane, tricyclic hydrocarbon ring such as tricyclo [4.3.1.1 2,5 ] undecane ring, tetracyclo [4 .4.0.1 2,5 .
- the bridged cyclic hydrocarbon ring includes a condensed cyclic hydrocarbon ring such as perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, perhydroindene.
- a condensed ring in which a plurality of 5- to 8-membered cycloalkane rings such as a phenalene ring are condensed is also included.
- the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group. Further, the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, an aromatic group, and a heterocyclic group. However, the aliphatic group does not have an acid group as a substituent.
- the carbon number of the aromatic group is preferably 6 to 20, more preferably 6 to 15, and further preferably 6 to 10.
- the aromatic group may have a substituent.
- the substituent include a halogen atom, an aliphatic group, an aromatic group, and a heterocyclic group.
- the aromatic group does not have an acid group as a substituent.
- the heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
- the heterocycle may be condensed with another heterocycle, aliphatic ring or aromatic ring.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
- the heterocyclic group does not have an acid group as a substituent.
- R 4 , R 5 , and R 6 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (eg, Methyl group, ethyl group, propyl group, etc.), Z, or LZ.
- L and Z are as defined above.
- R 4 , R 5 and R 6 are preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 1 , R 2 , and R 3 are a hydrogen atom or a methyl group, and L is a single bond, an alkylene group, or an oxyalkylene structure.
- a compound in which X is an oxygen atom or an imino group and Z is an aliphatic group, a heterocyclic group or an aromatic group is preferable.
- R 1 is a hydrogen atom or a methyl group
- L is an alkylene group
- Z is an aliphatic group, a heterocyclic group or an aromatic group. Is preferred.
- R 4 , R 5 , and R 6 are a hydrogen atom or a methyl group, and Z is an aliphatic group, a heterocyclic group, or an aromatic group. Certain compounds are preferred.
- Examples of typical compounds represented by formulas (i) to (iii) include radically polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, and the like.
- Examples of typical compounds represented by formulas (i) to (iii) compounds described in paragraphs 0089 to 0093 of JP2013-249417A can be referred to, and the contents thereof are described in the present specification. Incorporated into.
- the hydrophobic structural unit is preferably contained in a range of 10 to 90%, more preferably in a range of 20 to 80% with respect to the total mass of the polymer compound in terms of mass. When the content is in the above range, sufficient pattern formation can be obtained.
- the polymer compound can introduce a functional group capable of forming an interaction with a colored pigment such as a black pigment.
- the polymer compound preferably further has a structural unit having a functional group capable of forming an interaction with a colored pigment such as a black pigment.
- the functional group capable of forming an interaction with the colored pigment such as the black pigment include an acid group, a basic group, a coordination group, and a reactive functional group.
- the polymer compound has an acid group, a basic group, a coordinating group, or a reactive functional group
- the structural unit having an acid group, the structural unit having a basic group, or a coordinating group respectively. It is preferable to have a structural unit having or a reactive structural unit.
- the polymer compound since the polymer compound further has an alkali-soluble group such as a carboxylic acid group as the acid group, the polymer compound can be provided with developability for pattern formation by alkali development. That is, by introducing an alkali-soluble group into the polymer compound, the polymer compound as a dispersant that contributes to the dispersion of a colored pigment such as a black pigment has alkali solubility in the composition of the present invention.
- a composition containing such a polymer compound has excellent light-shielding properties in the exposed area, and the alkali developability in the unexposed area is improved.
- a high molecular compound has a structural unit which has an acid group
- the acid group in the structural unit having an acid group easily interacts with a color pigment such as a black pigment, and the polymer compound stably disperses the color pigment such as a black pigment, This is presumably because the viscosity of the polymer compound to be dispersed is low and the polymer compound itself is easily dispersed stably.
- the structural unit having an alkali-soluble group as an acid group may be the same structural unit as the above-described structural unit having a graft chain or a different structural unit. Is a structural unit different from the hydrophobic structural unit described above (that is, does not correspond to the hydrophobic structural unit described above).
- Examples of the acid group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably a carboxylic acid Group, sulfonic acid group, and at least one of phosphoric acid groups, and particularly preferable is that the adsorbing power to a colored pigment such as a black pigment is good and the dispersibility of the colored pigment is high, Carboxylic acid group. That is, the polymer compound preferably further has a structural unit having at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.
- the polymer compound may have one or more structural units having an acid group.
- the polymer compound may or may not contain a structural unit having an acid group.
- the content of the structural unit having an acid group is based on the total mass of the polymer compound in terms of mass. Preferably, it is 5 to 80%, and more preferably 10 to 60% from the viewpoint of suppressing damage of image strength due to alkali development.
- Examples of the basic group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment include a primary amino group, a secondary amino group, a tertiary amino group, and a heterocyclic ring containing an N atom, In addition, there are amide groups and the like, and a preferable one is a tertiary amino group from the viewpoint of good adsorbing power to a colored pigment such as a black pigment and high dispersibility of the colored pigment.
- the polymer compound can have one or more of these basic groups.
- the polymer compound may or may not contain a structural unit having a basic group, but when it is contained, the content of the structural unit having a basic group is calculated by mass conversion to the total mass of the polymer compound. On the other hand, it is preferably 0.01% or more and 50% or less, and more preferably 0.01% or more and 30% or less from the viewpoint of suppression of developability inhibition.
- a coordinating group that is a functional group capable of forming an interaction with a colored pigment such as a black pigment, and a functional group having reactivity
- a acetylacetoxy group for example, an acetylacetoxy group, a trialkoxysilyl group, an isocyanate group, an acid anhydride, And acid chloride etc. are mentioned.
- a preferable one is an acetylacetoxy group in terms of good adsorbing power to a colored pigment such as a black pigment and high dispersibility of the colored pigment.
- the polymer compound may have one or more of these groups.
- the polymer compound may or may not contain a structural unit having a coordinating group or a structural unit having a reactive functional group, but when it is contained, the content of these structural units is: In terms of mass, it is preferably 10% or more and 80% or less, and more preferably 20% or more and 60% or less from the viewpoint of inhibition of developability inhibition with respect to the total mass of the polymer compound.
- the polymer compound in the present invention has a functional group capable of interacting with a colored pigment such as a black pigment in addition to the graft chain, it forms an interaction with various colored pigments such as the black pigment as described above.
- the functional group is not particularly limited as long as the functional group can be introduced, and how these functional groups are introduced, but the polymer compound is represented by the following general formulas (iv) to (vi) It is preferable to have one or more structural units selected from structural units derived from monomers.
- R 11 , R 12 , and R 13 each independently represent a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
- R 11 , R 12 , and R 13 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group.
- R 12 and R 13 are each particularly preferably a hydrogen atom.
- X 1 in the general formula (iv) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
- Y in the general formula (v) represents a methine group or a nitrogen atom.
- L 1 represents a single bond or a divalent linking group.
- the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups, and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 31 ′ —
- R 31 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
- the divalent aliphatic group may have a cyclic structure or a branched structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
- the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
- the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
- the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
- One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 32 , where R 32 is a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
- L 1 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L 1 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
- the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
- the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
- Z 1 represents a functional group capable of forming an interaction with a color pigment such as a black pigment in addition to the graft chain, and includes a carboxylic acid group and a tertiary amino group. It is preferable that it is a carboxylic acid group.
- R 14 , R 15 , and R 16 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), or an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), - represents a Z 1 or L 1 -Z 1,.
- L 1 and Z 1 has the same meaning as L 1 and Z 1 in the above, are the preferable examples.
- R 14 , R 15 and R 16 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom.
- R 11 , R 12 , and R 13 are each independently a hydrogen atom or a methyl group, and L 1 is an alkylene group or an oxyalkylene structure.
- a compound in which X 1 is an oxygen atom or an imino group and Z 1 is a carboxylic acid group is preferable.
- R 11 is a hydrogen atom or a methyl group
- L 1 is an alkylene group
- Z 1 is a carboxylic acid group
- Y is methine. Compounds that are groups are preferred.
- R 14 , R 15 , and R 16 are each independently a hydrogen atom or a methyl group, and L 1 is a single bond or an alkylene group, A compound in which Z is a carboxylic acid group is preferred.
- monomers represented by general formula (iv) to general formula (vi).
- monomers include methacrylic acid, crotonic acid, isocrotonic acid, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule (for example, 2-hydroxyethyl methacrylate) and succinic anhydride.
- a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a phthalic anhydride a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and a tetrahydroxyphthalic anhydride , A reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and trimellitic anhydride, a reaction product of a compound having an addition polymerizable double bond and a hydroxyl group in the molecule and pyromellitic anhydride, Acrylic acid, acrylic acid dimer, acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid, 4-vinylbenzoic acid, vinylphenol, and - such as hydroxyphenyl methacrylamide.
- the content of the structural unit having a functional group capable of forming an interaction with a colored pigment such as a black pigment is from the viewpoint of interaction with the colored pigment such as a black pigment, dispersion stability, and permeability to a developer.
- 0.05 mass% to 90 mass% is preferable with respect to the total mass of the polymer compound, 1.0 mass% to 80 mass% is more preferable, and 10 mass% to 70 mass% is still more preferable.
- the polymer compound is a structural unit having a graft chain, a hydrophobic structural unit, and a colored pigment such as a black pigment, as long as the effects of the present invention are not impaired.
- Other structural units having various functions different from structural units having a functional group capable of forming an interaction for example, structural units having a functional group having an affinity for a dispersion medium used in a dispersion
- Examples of such other structural units include structural units derived from radically polymerizable compounds selected from acrylonitriles and methacrylonitriles.
- the polymer compound may use one or more of these other structural units, and the content thereof is preferably 0% or more and 80% or less in terms of mass with respect to the total mass of the polymer compound. Especially preferably, it is 10% or more and 60% or less. When the content is in the above range, sufficient pattern formability is maintained.
- the acid value of the polymer compound is preferably in the range of 0 mgKOH / g to 160 mgKOH / g, more preferably in the range of 10 mgKOH / g to 140 mgKOH / g, and still more preferably in the range of 20 mgKOH / g to 120 mgKOH / g.
- the range is as follows. When the acid value of the polymer compound is 160 mgKOH / g or less, pattern peeling during development when forming a cured film is more effectively suppressed. Moreover, if the acid value of a high molecular compound is 10 mgKOH / g or more, alkali developability will become more favorable.
- the acid value of the polymer compound is 20 mgKOH / g or more, precipitation of colored pigments such as black pigments can be further suppressed, the number of coarse particles can be reduced, and the temporal stability of the composition is further improved. it can.
- the acid value of the polymer compound can be calculated, for example, from the average content of acid groups in the polymer compound.
- the resin which has a desired acid value can be obtained by changing content of the structural unit containing the acid group which is a structural component of a high molecular compound.
- the weight average molecular weight of the polymer compound in the present invention is 4,000 as a polystyrene conversion value by a GPC (gel permeation chromatography) method from the viewpoint of pattern peeling inhibition during development and developability when forming a cured film. It is preferably 300 or more and 300 or less, more preferably 5,000 or more and 200,000 or less, further preferably 6,000 or more and 100,000 or less, and 10,000 or more and 50,000 or less. It is particularly preferred.
- the GPC method uses HLC-8020GPC (manufactured by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6 mm ID ⁇ 15 cm) as columns and THF (tetrahydrofuran) as an eluent. ).
- the polymer compound can be synthesized based on a known method, and examples of the solvent used when synthesizing the polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, and ethylene glycol monomethyl.
- Ether ethylene glycol monoethyl ether, 2-methoxyethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene,
- Examples include ethyl acetate, methyl lactate, and ethyl lactate. These solvents may be used alone or in combination of two or more.
- Acrybase FFS-6752, Acrybase FFS-187, Acrycure-RD-F8, and Cyclomer P can also be used.
- Commercially available amphoteric resins include, for example, DISPERBYK-130, DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180, DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERB manufactured by BYK Chemie.
- polymer compound As specific examples of the polymer compound, the polymer compounds described in paragraphs 0127 to 0129 of JP2013-249417A can be referred to, and the contents thereof are incorporated in the present specification.
- graft copolymers described in JP-A 2010-106268, paragraphs 0037 to 0115 corresponding to paragraphs 0075 to 0133 in US2011 / 0124824.
- it has a side chain structure in which acidic groups in paragraphs 0028 to 0084 (corresponding to columns 0075 to 0133 of US 2011/0279759) of JP 2011-153283 A are bonded via a linking group.
- Polymeric compounds containing constituents can be used, the contents of which can be incorporated and incorporated herein.
- the content of the dispersant is preferably from 0.1 to 50% by mass, more preferably from 0.5 to 30% by mass, based on the total solid content of the composition.
- a dispersing agent may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the content ratio of the dispersant to the titanium nitride-containing particles ((dispersant content (mass%) in the composition) / (content of titanium nitride-containing particles in the composition) (% By mass))
- D / P is preferably 0.05 to 0.30, more preferably 0.10 to 0.30, and more preferably 0.12 to More preferably, it is 0.30.
- the content ratio of the dispersant to the Fe atom content [(dispersant content (mass%) in the composition) / (Fe atom content (mass%) in the composition] ))] Is preferably at least 0.8, more preferably at least 1.0, and even more preferably at least 1.5.
- the upper limit is preferably 270 or less, more preferably 150 or less, and even more preferably 50 or less.
- the content (mass%) of Fe atoms in the composition is the titanium content contained in the composition in the content (mass%) of Fe atoms in the titanium nitride-containing particles obtained as described above. It can be calculated by multiplying the content (% by mass) of the nitride-containing particles.
- a desired effect is notably acquired because the content rate of the dispersing agent with respect to content of Fe atom exists in the said range.
- the content ratio is in the range of 1.5 to 50, the desired effect can be obtained more remarkably.
- the reason for this is considered to be that Fe atoms in the composition and the dispersing agent interact with each other and affect patterning properties (curability and developability).
- the content ratio of the polymerizable compound to the content of the Fe atom is preferably 0.7 or more, more preferably 0.85 or more, and further preferably 1.0 or more.
- the upper limit is preferably 50 or less, more preferably 11 or less, and even more preferably 7.0 or less.
- calculation of content (mass%) of Fe atom in a composition can be performed as mentioned above. A desired effect is notably acquired because the content rate of the polymeric compound with respect to content of Fe atom exists in the said range.
- the content ratio is in the range of 1.0 to 7.0, the desired effect can be obtained more remarkably.
- the reason for this is considered to be that the Fe atom in the composition interacts with the polymerizable compound and affects the patternability (curability and developability).
- the composition of the present invention preferably contains a binder resin.
- a binder resin a linear organic polymer is preferably used.
- a linear organic polymer a well-known thing can be used arbitrarily.
- a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development.
- an alkali-soluble resin a resin having a group that promotes alkali-solubility
- the binder resin is a linear organic polymer that promotes at least one alkali solubility in a molecule (preferably a molecule having a (meth) acrylic copolymer or a styrene copolymer as the main chain). It can be suitably selected from alkali-soluble resins having a group to be used.
- polyhydroxystyrene resins, polysiloxane resins, (meth) acrylic resins, (meth) acrylamide resins, (meth) acrylic / (meth) acrylamide copolymer resins, epoxy resins and Polyimide resins are preferred, and (meth) acrylic resins, (meth) acrylamide resins, (meth) acryl / (meth) acrylamide copolymer resins and polyimide resins are preferred from the viewpoint of control of developability.
- Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. Especially, what is soluble in an organic solvent and can be developed with a weak alkaline aqueous solution is preferable, and an alkali-soluble resin having a structural unit derived from (meth) acrylic acid is more preferable.
- These acid groups may be used alone or in combination of two or more.
- binder resin examples include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, Those described in Kaikai 54-92723, JP-A-59-53836, and JP-A-59-71048, ie, resins or acid anhydrides obtained by homopolymerizing or copolymerizing monomers having a carboxyl group Resins in which an acid anhydride unit is hydrolyzed, half-esterified or half-amidated by homopolymerizing a monomer having a monomer, and epoxy acrylate obtained by modifying an epoxy resin with an unsaturated monocarboxylic acid and an acid anhydride Can be mentioned.
- radical polymers having a carboxylic acid group in the side chain such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-
- Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, and 4-carboxyl styrene.
- Examples of monomers having an acid anhydride include And maleic anhydride.
- an acidic cellulose derivative having a carboxylic acid group in the side chain is also exemplified.
- those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.
- 2001-318463 has film strength and developability. It is excellent in balance and is suitable.
- polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer.
- alcohol-soluble nylon and polyether which is a reaction product of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin are also useful.
- a polyimide resin described in International Publication No. 2008/123097 is also useful.
- a known radical polymerization method can be applied for the production of the binder resin.
- Those skilled in the art can easily set polymerization conditions such as temperature, pressure, the type and amount of the radical initiator, and the type of the solvent when producing the alkali-soluble resin by the radical polymerization method.
- a polymer having a structural unit having a graft chain and a structural unit having an acid group (alkali-soluble group) as the binder resin.
- the definition of the structural unit which has a graft chain is synonymous with the structural unit which has the graft chain which the dispersing agent mentioned above has, and its suitable range is also the same.
- the acid group include a carboxylic acid group, a sulfonic acid group, a phosphoric acid group, or a phenolic hydroxyl group, and preferably at least one of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group. More preferred is a carboxylic acid group.
- the structural unit having an acid group preferably has one or more structural units selected from structural units derived from monomers represented by the following general formulas (vii) to (ix).
- R 21 , R 22 , and R 23 are each independently a hydrogen atom, a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, etc.), or a carbon number Represents an alkyl group of 1 to 6 (for example, methyl group, ethyl group, propyl group, etc.).
- R 21 , R 22 and R 23 are preferably each independently a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably Each independently represents a hydrogen atom or a methyl group.
- R 21 and R 23 are each particularly preferably a hydrogen atom.
- X 2 in the general formula (vii) represents an oxygen atom (—O—) or an imino group (—NH—), and is preferably an oxygen atom.
- Y in the general formula (viii) represents a methine group or a nitrogen atom.
- L 2 represents a single bond or a divalent linking group.
- the divalent linking group include a divalent aliphatic group (for example, an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group, and a substituted alkynylene group), a divalent aromatic group (for example, , Arylene groups, and substituted arylene groups), divalent heterocyclic groups, oxygen atoms (—O—), sulfur atoms (—S—), imino groups (—NH—), substituted imino bonds (—NR 41 ′ —
- R 41 ′ includes an aliphatic group, an aromatic group or a heterocyclic group), a carbonyl bond (—CO—), and combinations thereof.
- the divalent aliphatic group may have a cyclic structure or a branched structure.
- the aliphatic group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms.
- the aliphatic group is preferably a saturated aliphatic group rather than an unsaturated aliphatic group.
- the aliphatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aromatic group, and a heterocyclic group.
- the number of carbon atoms of the divalent aromatic group is preferably 6 to 20, more preferably 6 to 15, and most preferably 6 to 10.
- the aromatic group may have a substituent. Examples of the substituent include a halogen atom, a hydroxyl group, an aliphatic group, an aromatic group, and a heterocyclic group.
- the divalent heterocyclic group preferably has a 5-membered or 6-membered ring as the heterocycle.
- One or more heterocycles, aliphatic rings or aromatic rings may be condensed with the heterocycle.
- the heterocyclic group may have a substituent. Examples of substituents include halogen atoms, hydroxy groups, oxo groups ( ⁇ O), thioxo groups ( ⁇ S), imino groups ( ⁇ NH), substituted imino groups ( ⁇ N—R 42 , where R 42 represents a fatty acid Aromatic group, aromatic group or heterocyclic group), aliphatic group, aromatic group and heterocyclic group.
- L 2 is preferably a single bond, an alkylene group or a divalent linking group containing an oxyalkylene structure.
- the oxyalkylene structure is more preferably an oxyethylene structure or an oxypropylene structure.
- L 2 may contain a polyoxyalkylene structure containing two or more oxyalkylene structures.
- the polyoxyalkylene structure is preferably a polyoxyethylene structure or a polyoxypropylene structure.
- the polyoxyethylene structure is represented by — (OCH 2 CH 2 ) n—, where n is preferably an integer of 2 or more, and more preferably an integer of 2 to 10.
- Z 2 is an acid group, preferably a carboxylic acid group.
- R 24 , R 25 , and R 26 are each independently a hydrogen atom, a halogen atom (eg, fluorine, chlorine, bromine, etc.), an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group, propyl group, etc.), - represents a Z 2 or L 2 -Z 2,.
- L 2 and Z 2 has the same meaning as L 2 and Z 2 in the above, and preferred examples are also the same.
- R 24 , R 25 , and R 26 are each independently preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and more preferably a hydrogen atom.
- R 21 , R 22 , and R 23 are each independently a hydrogen atom or a methyl group, and L 2 is an alkylene group or an oxyalkylene structure.
- a compound in which X 2 is an oxygen atom or an imino group and Z 2 is a carboxylic acid group is preferable.
- R 21 is a hydrogen atom or a methyl group
- L 2 is an alkylene group
- Z 2 is a carboxylic acid group
- Y is methine.
- Compounds that are groups are preferred.
- a compound in which R 24 , R 25 , and R 26 are each independently a hydrogen atom or a methyl group and Z 2 is a carboxylic acid group is preferable.
- the binder resin can be synthesized by the same method as the dispersant having a structural unit having a graft chain described above, and the preferred acid value and weight average molecular weight are the same.
- the binder resin may have one or more structural units having an acid group.
- the content of the structural unit having an acid group is preferably 5 to 95%, in terms of mass, with respect to the total mass of the binder resin, and more preferably from the viewpoint of suppressing damage to the image strength due to alkali development. 10 to 90%.
- the content of the binder resin in the composition of the present invention is preferably 0.1 to 30% by mass and more preferably 0.3 to 25% by mass with respect to the total solid content of the composition.
- Binder resin may be used individually by 1 type, and may be used together 2 or more types. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the composition of the present invention preferably contains a polymerizable compound.
- the polymerizable compound is preferably a compound having one or more groups having an ethylenically unsaturated bond, more preferably a compound having 2 or more, further preferably 3 or more, and particularly preferably 5 or more.
- the upper limit is 15 or less, for example.
- Examples of the group having an ethylenically unsaturated bond include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the polymerizable compound may be in any of chemical forms such as a monomer, a prepolymer, an oligomer, a mixture thereof, and a multimer thereof. Monomers are preferred.
- the molecular weight of the polymerizable compound is preferably 100 to 3000, and more preferably 250 to 1500.
- the polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, more preferably a 3 to 6 functional (meth) acrylate compound.
- monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof.
- esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds are esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
- a dehydration condensation reaction product of an acid ester or amide with a monofunctional or polyfunctional carboxylic acid is also preferably used.
- reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups
- a reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable.
- the compounds described in paragraphs [0095] to [0108] of JP-A-2009-288705 can also be suitably used in the present invention.
- the polymerizable compound is also preferably a compound having at least one group having an ethylenically unsaturated bond and having a boiling point of 100 ° C. or higher under normal pressure.
- the compounds described in paragraph 0227 of JP2013-29760A and paragraphs 0254 to 0257 of JP2008-292970A can be referred to, the contents of which are incorporated herein.
- the polymerizable compounds are dipentaerythritol triacrylate (KAYARAD D-330 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (KAYARAD D-320 as a commercial product; manufactured by Nippon Kayaku Co., Ltd.).
- Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa (meth) acrylate (as a commercial product, manufactured as KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.) A-DPH-12E (manufactured by Shin-Nakamura Chemical Co., Ltd.), and structures in which these (meth) acryloyl groups are mediated by ethylene glycol or propylene glycol residues (eg, commercially available from Sartomer, SR454, SR499) ) Is preferred.
- oligomer types can also be used.
- NK ester A-TMMT penentaerythritol tetraacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd.
- Preferred embodiments of the polymerizable compound are shown below.
- the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
- an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid is preferable, and a non-aromatic carboxylic acid anhydride is reacted with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
- a polymerizable compound having a group is more preferable, and in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol. Examples of commercially available products include Aronix TO-2349, M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
- the preferred acid value of the polymerizable compound having an acid group is 0.1 to 40 mgKOH / g, more preferably 5 to 30 mgKOH / g. If the acid value of the polymerizable compound is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and if it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability is excellent.
- the polymerizable compound is also preferably a compound having a caprolactone structure.
- the compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule. Mention may be made of ⁇ -caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying polyhydric alcohols such as glycerin, diglycerol, trimethylolmelamine, (meth) acrylic acid and ⁇ -caprolactone. Of these, compounds having a caprolactone structure represented by the following general formula (Z-1) are preferred.
- R 1 represents a hydrogen atom or a methyl group
- m represents a number of 1 or 2
- “*” represents a bond
- R 1 represents a hydrogen atom or a methyl group, and “*” represents a bond.
- polymerizable compound a compound represented by the following general formula (Z-4) or (Z-5) can also be used.
- each E independently represents — ((CH 2 ) y CH 2 O). — Or — ((CH 2 ) y CH (CH 3 ) O) —, each y independently represents an integer of 0 to 10, and each X independently represents a (meth) acryloyl group, a hydrogen atom Or a carboxyl group.
- the total number of (meth) acryloyl groups is 3 or 4
- each m independently represents an integer of 0 to 10
- the total of each m is an integer of 0 to 40 .
- the total number of (meth) acryloyl groups is 5 or 6
- each n independently represents an integer of 0 to 10
- the total of each n is an integer of 0 to 60 .
- m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and further preferably an integer of 4 to 8.
- n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
- the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and even more preferably an integer of 6 to 12.
- — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — in general formula (Z-4) or general formula (Z-5) is oxygen A form in which the end on the atom side is bonded to X is preferred.
- the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
- a form in which all six Xs are acryloyl groups in the general formula (Z-5), a compound in which all six Xs are acryloyl groups, Among these, an embodiment in which at least one is a mixture with a compound having a hydrogen atom is preferable. With such a configuration, the developability can be further improved.
- the total content of the compound represented by the general formula (Z-4) or the general formula (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
- the compound represented by the general formula (Z-4) or (Z-5) is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol, which is a conventionally known process. It can be synthesized from a step of bonding a ring-opening skeleton by reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
- pentaerythritol derivatives and / or dipentaerythritol derivatives are more preferable.
- Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
- exemplary compounds (a), (f) b), (e) and (f) are preferred.
- Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, Nippon Kayaku Examples thereof include DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
- Examples of the polymerizable compound include urethane acrylates described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, 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. Also, 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. Thus, it is possible to obtain a composition excellent in the photosensitive speed.
- the polymerizable compound used in the present invention has an SP (solubility parameter) value of preferably 9.50 or more, more preferably 10.40 or more, and even more preferably 10.60 or more.
- SP value is determined by the Hoy method unless otherwise specified (HL Hoy Journal of Paining, 1970, Vol. 42, 76-118). The SP value is shown with the unit omitted, but the unit is cal 1/2 cm ⁇ 3/2 .
- the composition also preferably has a polymerizable compound having a cardo skeleton from the viewpoint of improving development residue.
- a polymerizable compound having a cardo skeleton a polymerizable compound having a 9,9-bisarylfluorene skeleton is preferable, and a compound represented by the following formula (Q3) is more preferable.
- Ar 11 to Ar 14 each independently represents an aryl group containing a benzene ring surrounded by a broken line.
- X 1 to X 4 each independently represents a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
- a and b each independently represents an integer of 1 to 5, and c and d each independently represents an integer of 0 to 4.
- R 1 to R 4 each independently represents a substituent, e, f, g and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g and h are Ar 11 to Ar 14 respectively.
- X 1 to X 4 and R 1 to R 4 are each It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
- the aryl group containing a benzene ring surrounded by a broken line represented by Ar 11 to Ar 14 is preferably an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms (For example, a phenyl group or a naphthyl group) is more preferable, and a phenyl group (only a benzene ring surrounded by a broken line) is further preferable.
- X 1 to X 4 each independently represents a substituent having a polymerizable group, and the carbon atom in the substituent may be substituted with a hetero atom.
- the substituent having a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an aliphatic group having a polymerizable group.
- the aliphatic group having a polymerizable group represented by X 1 to X 4 is not particularly limited, but is preferably an alkylene group having 1 to 12 carbon atoms other than the polymerizable group, and having 2 to 10 carbon atoms. An alkylene group is more preferable, and an alkylene group having 2 to 5 carbon atoms is more preferable.
- aliphatic group having a polymerizable group represented by X 1 to X 4 when the aliphatic group is substituted with a heteroatom, it is substituted with —NR— (R is a substituent), an oxygen atom, or a sulfur atom.
- R is a substituent
- the non-adjacent —CH 2 — in the aliphatic group is more preferably substituted with an oxygen atom or a sulfur atom, and the non-adjacent —CH 2 — in the aliphatic group is More preferably, it is substituted with an oxygen atom.
- the aliphatic group having a polymerizable group represented by X 1 to X 4 is preferably substituted at one or two sites by a hetero atom, more preferably substituted at one site by a hetero atom, Ar 11 to Ar More preferably, one position adjacent to the aryl group containing a benzene ring surrounded by a broken line represented by 14 is substituted with a heteroatom.
- a polymerizable group capable of radical polymerization or cationic polymerization hereinafter, also referred to as a radical polymerizable group and a cationic polymerizable group, respectively
- radical polymerizable group a generally known radical polymerizable group can be used, and a polymerizable group having an ethylenically unsaturated bond capable of radical polymerization can be mentioned as a preferred one.
- examples thereof include a vinyl group and a (meth) acryloyloxy group.
- a (meth) acryloyloxy group is preferable, and an acryloyloxy group is more preferable.
- cationic polymerizable group a generally known cationic polymerizable group can be used.
- an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro orthoester group, A vinyloxy group etc. can be mentioned.
- alicyclic ether groups and vinyloxy groups are preferable, and epoxy groups, oxetanyl groups, and vinyloxy groups are particularly preferable.
- the polymerizable group contained in the substituent contained in Ar 1 to Ar 4 is preferably a radical polymerizable group.
- Two or more of Ar 1 ⁇ Ar 4 includes a substituent having a polymerizable group, preferably contains a substituent 2-4 of Ar 1 ⁇ Ar 4 has a polymerizable group, Ar 1 ⁇ Ar More preferably, 2 or 3 out of 4 contain a substituent having a polymerizable group, and more preferably 2 out of Ar 1 to Ar 4 contain a substituent having a polymerizable group.
- X 1 to X 4 are each independently benzene surrounded by a broken line Even if it is substituted with a ring, it may be substituted with a ring other than the benzene ring surrounded by a broken line.
- a and b each independently represent an integer of 1 to 5, preferably 1 or 2, and more preferably a and b are all 1.
- c and d each independently represents an integer of 0 to 5, preferably 0 or 1, and more preferably c and d are both 0.
- R 1 to R 4 each independently represents a substituent.
- the substituent represented by R 1 to R 4 is not particularly limited, and examples thereof include halogen atoms, halogenated alkyl groups, alkyl groups, alkenyl groups, acyl groups, hydroxyl groups, hydroxyalkyl groups, alkoxy groups, aryl groups, hetero groups An aryl group, an alicyclic group, etc. can be mentioned.
- the substituent represented by R 1 to R 4 is preferably an alkyl group, an alkoxy group or an aryl group, more preferably an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or a phenyl group.
- R 1 to R 4 are each It may be independently substituted with a benzene ring surrounded by a broken line, or may be substituted with a ring other than the benzene ring surrounded by a broken line.
- e, f, g, and h each independently represent an integer of 0 or more, and the upper limit values of e, f, g, and h can each be a substituent that Ar 11 to Ar 14 can have.
- the value obtained by subtracting a, b, c, or d from the number of. e, f, g and h are each independently preferably 0 to 8, more preferably 0 to 2, and still more preferably 0.
- Ar 11 to Ar 14 are each independently a polycyclic aromatic hydrocarbon group containing a benzene ring surrounded by a broken line as one of the condensed rings, e, f, g and h are preferably 0 or 1 , 0 is more preferable.
- Examples of the compound represented by the formula (Q3) include 9,9-bis [4- (2-acryloyloxyethoxy) phenyl] fluorene.
- Examples of the polymerizable compound having a 9,9-bisarylfluorene skeleton compounds described in JP 2010-254732 A can also be suitably used.
- Examples of the polymerizable compound having such a cardo skeleton include, but are not limited to, on-coat EX series (manufactured by Nagase Sangyo Co., Ltd.) and Ogsol (manufactured by Osaka Gas Chemical Co., Ltd.).
- the content of the polymerizable compound is preferably 0.1 to 40% by mass with respect to the total solid content of the 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.
- One type of polymerizable compound may be used alone, or two or more types may be used in combination. When using 2 or more types together, it is preferable that a total amount becomes the said range.
- the composition of the present invention preferably contains a polymerization initiator.
- a polymerization initiator There is no restriction
- the composition of the present invention contains a photopolymerization initiator and the above-described polymerizable compound in addition to the titanium nitride-containing particles, the composition is cured by irradiation with actinic rays or radiation. Sometimes called.
- the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
- the photopolymerization initiator preferably contains at least one compound having a molar extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
- Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives. Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
- Examples of the halogenated hydrocarbon compound having a triazine skeleton include those described in Wakabayashi et al., Bull. Chem. Soc.
- trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
- compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
- trihalomethyltriazine compound More preferred are trihalomethyltriazine compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, ⁇ -aminoketone
- composition of the present invention when used for the production of a light-shielding film of a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape, so that development is possible with no residue in the unexposed area. It is important that From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator.
- an oxime compound as the photopolymerization initiator.
- stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low.
- an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device. Further, the use of an oxime compound can improve the color transfer.
- the photopolymerization initiator for example, paragraphs 0265 to 0268 of JP2013-29760A can be referred to, and the contents thereof are incorporated in the present specification.
- hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 and an acylphosphine initiator described in Japanese Patent No. 4225898 can also be used.
- hydroxyacetophenone-based initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379EG (trade names: all manufactured by BASF) can be used.
- aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long wave light source such as 365 nm or 405 nm can also be used.
- acylphosphine initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names: both manufactured by BASF) can be used.
- the photopolymerization initiator include oxime compounds.
- an oxime initiator is preferable because it has high sensitivity and high polymerization efficiency, can be cured regardless of the color material concentration, and can be easily designed with a high color material concentration.
- Specific examples of the oxime compound include compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166.
- Examples of the oxime compound that can be suitably used in the present invention include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3- (4-toluenesulfonyloxy) iminobutane Examples include -2-one and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
- J.H. C. S. Perkin II (1979) pp. 1653-1660) J.M.
- TR-PBG-304 manufactured by Changzhou Powerful Electronic New Materials Co., Ltd.
- Adeka Arcles NCI-831 and Adeka Arcles NCI-930 manufactured by ADEKA
- N-1919 carboxylated polystyrene
- An agent manufactured by ADEKA
- oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039 in which a nitro group is introduced at the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, the triazine skeleton and the oxime skeleton are the same molecule A compound described in US Pat. No. 7,556,910 contained therein, a compound described in Japanese Patent Application Laid-Open No.
- the oxime compound is preferably a compound represented by the following formula (OX-1).
- the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (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 or 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, a cycloalkylene group, 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 fluorine atom can also be used as a photopolymerization initiator.
- Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
- a compound represented by the following general formula (1) or (2) can also be used as a photopolymerization initiator.
- R 1 and R 2 are each independently an alkyl group having 1 to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or When R 1 and R 2 are phenyl groups, the phenyl groups may be bonded to each other to form a fluorene group, and R 3 and R 4 are each independently Represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms, and X is a single bond or carbonyl group Indicates a group.
- R 1, R 2, R 3 and R 4 have the same meanings as R 1, R 2, R 3 and R 4 in the formula (1)
- R 5 is -R 6, -OR 6 , —SR 6 , —COR 6 , —CONR 6 R 6 , —NR 6 COR 6 , —OCOR 6 , —COOR 6 , —SCOR 6 , —OCSR 6 , —COSR 6 , —CSOR 6 , —CN
- halogen R 6 represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 4 to 20 carbon atoms
- X represents a direct bond or a carbonyl group, and a represents an integer of 0 to 4.
- R 1 and R 2 are preferably each independently a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a cyclohexyl group, or a phenyl group.
- R 3 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a xylyl group.
- R 4 is preferably an alkyl group having 1 to 6 carbon atoms or a phenyl group.
- R 5 is preferably a methyl group, an ethyl group, a phenyl group, a tolyl group or a naphthyl group.
- X is preferably a direct bond.
- Specific examples of the compounds represented by formula (1) and formula (2) include, for example, compounds described in paragraph numbers 0076 to 0079 of JP-A No. 2014-137466. This content is incorporated herein.
- oxime compounds that are preferably used in the present invention are shown below, but the present invention is not limited thereto.
- the oxime compound preferably has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, more preferably has a maximum absorption wavelength in the wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 405 nm.
- the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably 1,000 to 300,000, more preferably 2,000 to 300,000, more preferably 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
- For the molar extinction coefficient of the compound a known method can be used.
- an ethyl acetate solvent is used at a concentration of 0.01 g / L. It is preferable to measure. You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
- the content of the polymerization initiator is preferably 0.1 to 30% by mass relative to the total solid content in the composition, and is preferably 1 to 25% by mass. %, More preferably 1 to 10% by mass.
- the composition of the present invention may contain only one kind of polymerization initiator, or may contain two or more kinds. When two or more types are included, the total amount is preferably within the above range.
- the composition of the present invention preferably contains an organic solvent.
- organic solvents include, for example, acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether.
- Acetylacetone, cyclohexanone, cyclopentanone, diacetone alcohol ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol Nomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, ⁇ -butyrolactone, acetic acid Examples include, but are not limited to, ethyl, butyl acetate, methyl lactate, and ethyl lactate.
- the composition of the present invention may contain one kind of organic solvent or two or more kinds of organic solvents, but the titanium nitride-containing particles of the composition of the present invention may be prepared during the preparation of the composition of the present invention. It is preferable to contain two or more kinds of organic solvents from the viewpoint that the particle size fluctuation can be suppressed.
- the above-mentioned methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, -It is preferably composed of two or more selected from the group consisting of heptanone, cyclohexanone, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether, and propylene glycol monomethyl ether acetate.
- the content of the organic solvent is preferably 10 to 90% by mass and more preferably 60 to 90% by mass with respect to the total mass of the composition. preferable.
- the total amount is preferably within the above range.
- the composition of the present invention may contain water. Water may be intentionally added, or may be inevitably contained in the composition by adding each component contained in the composition of the present invention.
- the water content is preferably 0.01 to 1% by mass, more preferably 0.05 to 0.8% by mass, and more preferably 0.1 to 0.00% by mass with respect to 100% by mass of the composition. More preferably, it is 7 mass%.
- the water content is within the above range, the generation of pinholes when a cured film is produced can be suppressed, or the moisture resistance of the cured film can be improved.
- a colorant other than the titanium nitride-containing particles described above (hereinafter also simply referred to as “colorant”) can be used.
- the colorant is used, for example, for adjusting the chromaticity of the composition, and part of the titanium nitride can be replaced with the colorant as long as the OD value does not decrease.
- examples of such a colorant include pigments (organic pigments of black organic pigments and chromatic organic pigments, and inorganic pigments) and dyes.
- a pigment as the colorant. Thereby, it is easy to manufacture a film having a small standard deviation of transmittance in the wavelength range of 400 to 700 nm.
- a black pigment a black organic pigment and a black inorganic pigment
- Examples of the pigment include various conventionally known pigments.
- Examples of chromatic organic pigments include the following. However, the present invention is not limited to these.
- a zinc halide phthalocyanine pigment having an average number of halogen atoms in the molecule of 10 to 14, bromine atoms on average 8 to 12, and chlorine atoms on average 2 to 5 should be used. Is also possible. Specific examples include the compounds described in International Publication No. 2015/118720. These organic pigments can be used alone or in various combinations in order to increase color purity.
- black pigments can be used as the black pigment.
- examples thereof include carbon black and the following black metal-containing inorganic pigments.
- a metal oxide or metal containing one or more metal elements selected from the group consisting of Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn, Ti, and Ag Nitrogen can be mentioned. These may be used alone or as a mixture of two or more. Moreover, you may prepare so that it may have desired light-shielding property by using in combination with the inorganic pigment of another hue further to a black pigment.
- inorganic pigments examples include, for example, zinc white, lead white, lithopone, titanium oxide, chromium oxide, iron oxide, precipitated barium sulfate and barite powder, red lead, iron oxide red, yellow lead , Zinc yellow (1 type of zinc yellow, 2 types of zinc yellow), ultramarine blue, prussian blue (potassium ferrocyanide) zircon gray, praseodymium yellow, chrome titanium yellow, chrome green, peacock, victoria green, bitumen blue (Prussian blue) ), Vanadium zirconium blue, chrome tin pink, pottery red, salmon pink and the like.
- these black pigments and other inorganic pigments having other hues are used not only independently but also in combination with a plurality of types of pigments for the purpose of expressing light-shielding properties in a wide wavelength range from ultraviolet to infrared. Is possible.
- the black pigment is preferably carbon black or tiran black, and titanium black is particularly preferred from the viewpoint of light-shielding properties in a wide wavelength range from ultraviolet to infrared.
- Titanium black is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride.
- titanium oxynitride includes titanium oxynitride such as International Publication No. 2008/123097, JP-A 2009-58946, JP-A 2010-14848, JP-A 2010-97210, and JP-A 2011-2274670. Further, a mixture of titanium oxynitride and titanium carbide as disclosed in JP 2010-95716 can be used.
- titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water-repellent substance as disclosed in JP-A-2007-302836.
- Titanium black is a composite oxide such as Cu, Fe, Mn, V, Ni, etc., and one or more black pigments such as cobalt oxide, iron oxide, and carbon black for the purpose of adjusting dispersibility and colorability. You may contain in combination.
- Titanium black can be produced by heating a mixture of titanium dioxide and titanium metal in a reducing atmosphere for reduction (Japanese Patent Laid-Open No. 49-5432), or ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride.
- a method of reducing titanium in a reducing atmosphere containing hydrogen Japanese Patent Laid-Open No. 57-205322
- a method of reducing titanium dioxide or titanium hydroxide at high temperature in the presence of ammonia Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No.
- JP-A-61-201610 JP-A-61-201610
- a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at high temperature in the presence of ammonia JP-A-61-201610
- the present invention is not limited to these.
- the specific surface area of titanium black is not particularly limited, but the value measured by the BET (Brunauer, Emmett, Teller) method is preferably 5 m2 / g or more and 150 m2 / g or less, and is 20 m2 / g or more and 120 m2 / g or less. It is more preferable.
- Examples of commercially available titanium black include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, 13M-T (trade name: manufactured by Mitsubishi Materials Corporation), Tilack D (trade name: manufactured by Ako Kasei Co., Ltd.) and the like.
- the average primary particle diameter of the black pigment is preferably 5 nm or more, and preferably 10 nm or more. From the same viewpoint, the upper limit is preferably 10 ⁇ m or less, more preferably 1 ⁇ m or less, and even more preferably 100 nm or less.
- the average primary particle diameter of the black pigment is a value measured by the following method. A mixed liquid containing a black pigment is diluted 80 times with propylene glycol monomethyl ether acetate, and the obtained diluted liquid is measured using a dynamic light scattering method. This measurement is an average particle diameter obtained by using Microtrack (trade name) UPA-EX150 manufactured by Nikkiso Co., Ltd.
- titanium black is contained as a dispersion in the composition, and the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more in terms of mass. Is preferable, 0.05 to 0.5 is more preferable, and 0.07 to 0.4 is still more preferable.
- the to-be-dispersed bodies include both those in which titanium black is in the state of primary particles and those in the state of aggregates (secondary particles). In order to change the Si / Ti of the object to be dispersed (for example, 0.05 or more), the following means can be used.
- a dispersion is obtained by dispersing titanium oxide and silica particles using a disperser, and the dispersion is subjected to reduction treatment at a high temperature (for example, 850 to 1000 ° C.), whereby titanium black particles are mainly formed.
- a dispersed material containing Si and Ti as components can be obtained.
- the reduction treatment can also be performed in an atmosphere of a reducing gas such as ammonia.
- titanium oxide include TTO-51N (trade name: manufactured by Ishihara Sangyo). Titanium oxide prepared by the plasma method can be suitably used because its particle size is smaller than commercially available titanium oxide fine particles (see the Journal of the Japan Institute of Metals Vol. 63 No. 1 (1999) 74-81) .
- silica particles examples include AEROSIL (registered trademark) 90, 130, 150, 200, 255, 300, 380 (trade name: manufactured by Evonik).
- a dispersing agent may be used for the dispersion of titanium oxide and silica particles. Examples of the dispersant include those described in the section of the dispersant described later.
- the dispersion may be performed in a solvent. Examples of the solvent include water and organic solvents. What is demonstrated in the column of the organic solvent mentioned later is mentioned. Titanium black in which Si / Ti is adjusted to 0.05 or more, for example, can be obtained by, for example, the methods described in paragraph numbers [0005] and paragraph numbers [0016] to [0021] of JP-A-2008-266045. Can be produced.
- the composition containing this dispersion by adjusting the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion containing titanium black and Si atoms to a suitable range (for example, 0.05 or more).
- a suitable range for example, 0.05 or more.
- a residue contains the component derived from compositions, such as a titanium black particle and a resin component. The reason why the residue is reduced is not yet clear, but the above-mentioned dispersed material tends to have a small particle size (for example, the particle size is 30 nm or less).
- the adsorptivity of the entire film with the underlying layer is reduced, and this is presumed to contribute to the improvement of the development removal property of the uncured composition (particularly titanium black) in the formation of the light-shielding film.
- titanium black is excellent in light-shielding property for light in a wide wavelength range from ultraviolet light to infrared light. Therefore, the above-described dispersion containing titanium black and Si atoms (preferably Si / Ti is converted into mass)
- the light-shielding film formed by using a material having a thickness of 0.05 or more exhibits excellent light-shielding properties.
- the content ratio (Si / Ti) of Si atoms to Ti atoms in the dispersion is, for example, the method (1-1) or the method (1-2) described in paragraph 0033 of JP2013-249417A ). Whether or not the content ratio (Si / Ti) of Si atoms and Ti atoms in the dispersion is 0.05 or more for the dispersion to be contained in the light-shielding film obtained by curing the composition Is determined using the method (2) described in paragraph 0035 of JP2013-249417A.
- the above-described titanium black can be used.
- complex oxides such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, aniline
- a Si-containing material such as silica
- silica examples include precipitated silica, fumed silica, colloidal silica, and synthetic silica. These may be appropriately selected and used.
- fine particle type silica examples include silica described in paragraph 0039 of JP2013-249417A, and the contents thereof are incorporated in the present specification.
- a tungsten compound and a metal boride can also be used.
- Tungsten compounds and metal borides have high absorption for infrared rays (light having a wavelength of about 800 to 1200 nm) (that is, they have high light shielding properties (shielding properties) for infrared rays) and absorption for visible light. It is a low infrared shielding material.
- the photosensitive composition of this invention can form a pattern with high light-shielding property in an infrared region, and high translucency in a visible light region by containing a tungsten compound and / or a metal boride.
- the tungsten compound and the metal boride have a small absorption even for light having a wavelength shorter than the visible range used for exposure of a high-pressure mercury lamp, KrF, ArF, or the like used for image formation.
- tungsten compound examples include a tungsten oxide compound, a tungsten boride compound, a tungsten sulfide compound, and the like, and a tungsten oxide compound represented by the following general formula (composition formula) (I) is preferable.
- composition formula) (I) M x W y O z (I) M represents a metal, W represents tungsten, and O represents oxygen. 0.001 ⁇ x / y ⁇ 1.1 2.2 ⁇ z / y ⁇ 3.0
- alkali metal for example, alkali metal, alkaline earth metal, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Sn, Pb, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and the like can be mentioned, and an alkali metal is preferable. 1 type or 2 types or more may be sufficient as the metal of M.
- M is preferably an alkali metal, more preferably Rb or Cs, and even more preferably Cs.
- infrared rays can be sufficiently shielded, and when it is 1.1 or less, generation of an impurity phase in the tungsten compound can be more reliably avoided. it can.
- z / y is 2.2 or more, chemical stability as a material can be further improved, and when it is 3.0 or less, infrared rays can be sufficiently shielded.
- tungsten oxide compound represented by the general formula (I) examples include Cs 0.33 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3 and the like. Cs 0.33 WO 3 or Rb 0.33 WO 3 is preferable, and Cs 0.33 WO 3 is more preferable.
- the tungsten compound is preferably fine particles.
- the average particle diameter of the tungsten fine particles is preferably 800 nm or less, more preferably 400 nm or less, and further preferably 200 nm or less. When the average particle diameter is in such a range, the tungsten fine particles are less likely to block visible light by light scattering, and thus the translucency in the visible light region can be further ensured. From the viewpoint of avoiding light scattering, the average particle size is preferably as small as possible, but for reasons such as ease of handling during production, the average particle size of the tungsten fine particles is usually 1 nm or more.
- two or more tungsten compounds can be used.
- Tungsten compounds are commercially available, but when the tungsten compound is, for example, a tungsten oxide compound, the tungsten oxide compound is obtained by a method of heat-treating the tungsten compound in an inert gas atmosphere or a reducing gas atmosphere. (See Japanese Patent No. 4096205). Further, the tungsten oxide compound is also available as a dispersion of tungsten fine particles such as YMF-02 manufactured by Sumitomo Metal Mining Co., Ltd.
- lanthanum boride LaB 6
- PrB 6 praseodymium boride
- NdB 6 cerium boride
- CeB 6 cerium boride
- YB 6 yttrium boride
- boride Titanium TiB 2
- zirconium boride ZrB 2
- hafnium boride HfB 2
- vanadium boride VB 2
- tantalum boride TaB 2
- CrB 2 chromium boride
- boride One type or two or more types of molybdenum (MoB 2 , Mo 2 B 5 , MoB), tungsten boride (W 2 B 5 ) and the like can be mentioned, and lanthanum boride (LaB 6 ) is preferable.
- the metal boride is preferably fine particles.
- the average particle diameter of the metal boride fine particles is preferably 800 nm or less, more preferably 300 nm or less, and further preferably 100 nm or less.
- the average particle size is preferably as small as possible.
- the average particle size of the metal boride fine particles is usually 1 nm or more.
- two or more metal borides can be used.
- the metal boride is available as a commercial product, for example, as a dispersion of metal boride fine particles such as KHF-07AH manufactured by Sumitomo Metal Mining Co., Ltd.
- Examples of the dye include, for example, JP-A No. 64-90403, JP-A No. 64-91102, JP-A No. 1-94301, JP-A No. 6-11614, No. 2592207, and US Pat. No. 4,808,501.
- dye currently disclosed by 194828 gazette etc. 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 as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A.
- the composition of the present invention may contain extender pigments as necessary in addition to the colorant.
- extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, titanium white, and hydrotalcite. These extender pigments can be used alone or in admixture of two or more.
- the amount of extender used is usually 0 to 100 parts by weight, preferably 5 to 50 parts by weight, and more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the colorant.
- the colorant and extender can be used with their surface modified with a polymer in some cases.
- Coloring agents may be used alone or in combination of two or more.
- a coloring agent you may contain colored organic pigments, such as red, blue, yellow, green, and purple.
- a light-shielding pigment specifically, titanium nitride-containing particles
- a colored organic pigment it is preferable to use the colored organic pigment in an amount of 1 to 40% by mass based on the light-shielding pigment.
- a red pigment and a light-shielding pigment in combination.
- Pigment Red 254 is preferable as the red pigment, although not particularly limited.
- the content of the colorant is preferably 20 to 80% by mass, more preferably 30 to 70% by mass, based on the total solid content of the composition, 35 More preferred is ⁇ 60% by mass.
- the composition of the present invention may contain a pigment derivative.
- the pigment derivative include a compound having a structure in which a part of an organic pigment is substituted with an acidic group, a basic group, or a phthalimidomethyl group.
- 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 sulfonic acid group As an acidic group which a pigment derivative has, a sulfonic acid group, a carboxylic acid group, and its quaternary ammonium base are preferable, a carboxylic acid group and a sulfonic acid group are more preferable, and a sulfonic acid group is especially preferable.
- the basic group possessed by the pigment derivative is preferably an amino group, particularly preferably a tertiary amino group.
- Specific examples of the pigment derivative include the following compounds.
- the descriptions in paragraphs 0162 to 0183 of JP2011-252065 A can be referred to, and the contents thereof are incorporated in this specification.
- 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 colorant.
- the composition of the present invention may contain only one type of pigment derivative or two or more types of pigment derivatives. When two or more types are included, the total amount is preferably within the above range.
- silane coupling agent is a compound having a hydrolyzable group and other functional groups in the molecule.
- a hydrolyzable group such as an alkoxy group is bonded to a silicon atom.
- the hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond by a hydrolysis reaction and / or a condensation reaction.
- Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy group.
- the hydrolyzable group has a carbon atom, the number of carbon atoms is preferably 6 or less, and more preferably 4 or less.
- the silane coupling agent preferably does not contain a fluorine atom and a silicon atom (excluding a silicon atom to which a hydrolyzable group is bonded). Includes silicon atoms (excluding silicon atoms to which hydrolyzable groups are bonded), alkylene groups substituted with silicon atoms, straight chain alkyl groups having 8 or more carbon atoms, and branched alkyl groups having 3 or more carbon atoms Desirably not.
- the silane coupling agent preferably has a group represented by the following formula (Z). * Represents a bonding position.
- R Z1 represents a hydrolyzable group, and the definition thereof is as described above.
- the silane coupling agent preferably has one or more curable functional groups selected from the group consisting of a (meth) acryloyloxy group, an epoxy group, and an oxetanyl group.
- the curable functional group may be directly bonded to the silicon atom, or may be bonded to the silicon atom via a linking group.
- a radically polymerizable group is also mentioned as a suitable aspect of the curable functional group contained in the said silane coupling agent.
- the molecular weight of the silane coupling agent is not particularly limited, and is often 100 to 1000 from the viewpoint of handleability, and is preferably 270 or more and more preferably 270 to 1000 from the viewpoint that the effect of the present invention is more excellent.
- silane coupling agent X represented by the formula (W).
- R z1 represents a hydrolyzable group, and the definition is as described above.
- R z2 represents a curable functional group, the definition is as described above, and the preferred range is also as described above.
- Lz represents a single bond or a divalent linking group.
- examples of the divalent linking group include an alkylene group which may be substituted with a halogen atom, an arylene group which may be substituted with a halogen atom, —NR 12 —, —CONR 12 -, - CO -, - CO 2 -, SO 2 NR 12 -, - O -, - S -, - SO 2 -, or combinations thereof.
- a group consisting of a combination with one kind of group is preferable, an alkylene group which may be substituted by a halogen atom having 2 to 10 carbon atoms, —CO 2 —, —O—, —CO—, —CONR 12 —, or A group consisting of a combination of these groups is more preferred.
- R 12 represents a hydrogen atom or a methyl group.
- N- ⁇ -aminoethyl- ⁇ -aminopropyl-methyldimethoxysilane (trade name KBM-602 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-trimethoxy Silane (trade name KBM-603 manufactured by Shin-Etsu Chemical Co., Ltd.), N- ⁇ -aminoethyl- ⁇ -aminopropyl-triethoxysilane (trade name KBE-602 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-trimethoxysilane (Trade name KBM-903 manufactured by Shin-Etsu Chemical Co., Ltd.), ⁇ -aminopropyl-triethoxysilane (trade name KBE-903 manufactured by Shin-Etsu Chemical Co., Ltd.), 3-methacryloxypropyltrimethoxysilane (trade name KBM-602 manufactured by Shin
- a silane coupling agent Y having at least a silicon atom, a nitrogen atom and a curable functional group in the molecule and having a hydrolyzable group bonded to the silicon atom is provided.
- the silane coupling agent Y only needs to have at least one silicon atom in the molecule, and the silicon atom can be bonded to the following atoms and substituents. They may be the same atom, substituent or different.
- Atoms and substituents that can be bonded are a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group having 1 to 20 carbon atoms, an alkenyl group, an alkynyl group, an aryl group, an alkyl group, and / or an amino group that can be substituted with an aryl group, silyl Group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group, and the like.
- substituents further include an amino group, a halogen atom, a sulfonamide group, a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an alkyl group and / or an aryl group. It may be substituted with an alkoxycarbonyl group, an amide group, a urea group, an ammonium group, an alkylammonium group, a carboxyl group, or a salt thereof, a sulfo group, or a salt thereof.
- at least one hydrolyzable group is bonded to the silicon atom.
- the definition of the hydrolyzable group is as described above.
- the silane coupling agent Y may contain a group represented by the formula (Z).
- the silane coupling agent Y has at least one nitrogen atom in the molecule, and the nitrogen atom is preferably present in the form of a secondary amino group or a tertiary amino group, that is, the nitrogen atom is used as a substituent. It preferably has at least one organic group.
- the amino group structure may exist in the molecule in the form of a partial structure of a nitrogen-containing heterocycle, or may exist as a substituted amino group such as aniline.
- examples of the organic group include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a combination thereof.
- substituents may further have a substituent
- substituents that can be introduced include a silyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a thioalkoxy group, an amino group, a halogen atom, and a sulfonamide.
- the nitrogen atom is couple
- Preferred examples of the organic linking group include the above-described nitrogen atom and a substituent that can be introduced into the organic group bonded thereto.
- the definition of the curable functional group contained in the silane coupling agent Y is as described above, and the preferred range is also as described above.
- the silane coupling agent Y only needs to have at least one curable functional group in one molecule, but it is also possible to adopt an embodiment having two or more curable functional groups, sensitivity, stability. From this viewpoint, it is preferable to have 2 to 20 curable functional groups, more preferably 4 to 15, and most preferably 6 to 10 curable functional groups in the molecule.
- the molecular weights of the silane coupling agent X and the silane coupling agent Y are not particularly limited, but include the above-described ranges (preferably 270 or more).
- the content of the silane coupling agent in the composition of the present invention is preferably 0.1 to 10% by mass, more preferably 0.5 to 8% by mass, based on the total solid content in the composition. More preferably, it is 0 to 6% by mass.
- composition of the present invention may contain one silane coupling agent or two or more silane coupling agents.
- silane coupling agents When a composition contains 2 or more types of silane coupling agents, the sum should just be in the said range.
- the composition of the present invention may contain an ultraviolet absorber. Thereby, the shape of a pattern can be made more excellent (fine).
- an ultraviolet absorber salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, and triazine-based ultraviolet absorbers can be used.
- compounds of paragraphs 0137 to 0142 corresponding to paragraphs 0251 to 0254 of US2012 / 0068292) of JP2012-068418A can be used, and the contents thereof can be incorporated and incorporated in the present specification. .
- a diethylamino-phenylsulfonyl ultraviolet absorber (trade name: UV-503, manufactured by Daito Chemical Co., Ltd.) is also preferably used.
- the ultraviolet absorber include compounds exemplified in paragraphs 0134 to 0148 of JP2012-32556A.
- the composition of the present invention may or may not contain an ultraviolet absorber, but when it is included, the content of the ultraviolet absorber is preferably 0.001 to 15% by mass relative to the total solid content of the composition. 0.01 to 10% by mass is more preferable, and 0.1 to 5% by mass is more preferable.
- the composition of the present invention may contain various surfactants from the viewpoint of further 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.
- liquid properties (particularly fluidity) when prepared as a coating liquid are further improved, and uniformity of coating thickness and liquid-saving properties are further improved. be able to. That is, in the case of forming a film using a coating liquid to which a composition containing a fluorosurfactant is applied, the interfacial tension between the coated surface and the coating liquid decreases, and the wettability to the coated surface is reduced. It improves and the applicability
- 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 MegaFuck F171, F172, F173, 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, S-393, KH-40 (above, manufactured by Asahi Glass Co., Ltd.) PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), and the like.
- fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A No. 2015-117327 can also be used.
- a block polymer can also be used as the fluorosurfactant, and specific examples thereof include compounds described in JP-A-2011-89090.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and 2 or more (preferably 5 or more) alkyleneoxy groups (preferably ethyleneoxy group or propyleneoxy group) (meth).
- 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.
- the fluoropolymer which has an ethylenically unsaturated group in a side chain can also be used as a fluorine-type surfactant.
- Specific examples thereof include compounds described in JP-A 2010-164965, paragraphs 0050 to 0090 and 0289 to 0295, such as MegaFac RS-101, RS-102, RS-718K, and RS-72- manufactured by DIC. K etc. are mentioned.
- nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62 manufactured by BASF, 10R5, 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1, Rusupasu 20000 (Nippon Lubrizol Co. tetrazole Co.) and the like. Further, the product of Wako Pure Chemical Industries, Ltd., may be used NCW-101,
- cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.), 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.
- phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo Co., Ltd.
- 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.
- anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei 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 BYK Chemie) and the like.
- the content of the surfactant is preferably from 0.001 to 2.0% by mass, more preferably from 0.005 to 1.0% by mass, based on the total solid content of the composition of the present invention.
- the composition of the present invention may contain a polymerization inhibitor.
- Polymerization inhibitors include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
- the content of the polymerization inhibitor is preferably 0.01 to 5% by mass relative to the total solid content of the composition.
- the composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range. If necessary, higher fatty acid derivatives such as behenic acid and behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and may be unevenly distributed on the surface of the coating film during the drying process after coating. . When the amount of the higher fatty acid derivative is added, the content of the higher fatty acid derivative is preferably 0.5 to 10% by mass with respect to the total solid content of the composition.
- the following components may be further added to the composition of the present invention.
- examples include sensitizers, co-sensitizers, crosslinking agents, curing accelerators, fillers, thermosetting accelerators, plasticizers, diluents, and sensitizers, and further adhesion promoters to the substrate surface.
- auxiliaries for example, conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, peeling accelerators, antioxidants, perfumes, surface tension modifiers, chain transfer agents, etc. You may add a well-known additive as needed.
- paragraph numbers 0183 to 0228 of JP2012-003225A (corresponding ⁇ 0237> to ⁇ 0309> of US Patent Application Publication No. 2013/0034812) and JP2008-250074.
- Paragraph numbers 0101 to 0102, paragraph numbers 0103 to 0104, paragraph numbers 0107 to 0109, paragraph numbers 0159 to 0184 in JP 2013-195480 A, and the like can be referred to, and the contents thereof are incorporated in this specification. .
- the solid content of the composition of the present invention is preferably 10 to 40% by mass, more preferably 12 to 30% by mass.
- the light shielding property of a cured film improves because the solid content of the composition is 10% by mass or more.
- the temporal stability of the composition becomes good.
- the composition of the present invention can be produced by mixing the above-described various components by a known mixing method (for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser).
- a known mixing method for example, a stirrer, a homogenizer, a high-pressure emulsifier, a wet pulverizer, a wet disperser.
- various components constituting the composition may be mixed at once, or may be sequentially mixed after various components are dissolved or dispersed in an organic solvent.
- the charging order and working conditions when blending are not particularly limited.
- the mechanical force used for dispersing the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
- the manufacturing method of the composition of this invention includes the process of obtaining the said titanium nitride containing particle
- the step of obtaining titanium nitride-containing particles is performed before mixing the various components described above. Since the specific manufacturing process of the titanium nitride-containing fine particles by the thermal plasma method is as described in the above-mentioned section of titanium nitride-containing particles, the description thereof is omitted.
- the titanium nitride-containing particles obtained by the thermal plasma method are not exposed to the atmosphere immediately after the titanium nitride-containing particles are produced (that is, after the thermal plasma treatment), and in a sealed container in which the oxygen concentration is controlled. It is preferably obtained after standing for a predetermined time (preferably 12 to 72 hours, more preferably 12 to 48 hours, still more preferably 12 to 24 hours). In addition, it is more preferable that the moisture content in the sealed container is controlled, which stabilizes the surface and crystal grain boundaries of the titanium nitride-containing particles subjected to the thermal plasma treatment, and improves the performance of the composition. It is guessed. Specifically, the generation of pinholes in a cured film obtained using the composition of the present invention can be suppressed.
- the oxygen (O 2 ) concentration and water content in the sealed container are each preferably 100 ppm or less, more preferably 10 ppm or less, and even more preferably 1 ppm or less.
- the oxygen (O 2 ) concentration and moisture content in the sealed container can be adjusted by adjusting the oxygen concentration and moisture content in the inert gas supplied into the sealed container.
- the inert gas nitrogen gas and argon gas are preferably used, and among these, it is more preferable to use nitrogen gas.
- the composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects.
- a filter for the purpose of removing foreign substances or reducing defects.
- Any filter can be used without particular limitation as long as it has been conventionally used for filtration.
- a filter made of fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like can be given.
- fluorine resin such as PTFE (polytetrafluoroethylene), polyamide resin such as nylon, polyolefin resin (including high density and ultra high molecular weight) such as polyethylene and polypropylene (PP), and the like
- PP polypropylene
- nylon are preferable.
- the pore size of the filter is suitably about 0.1 to 7.0 ⁇ m, preferably about 0.2 to 2.5 ⁇ m, more preferably about 0.2 to 1.5 ⁇ m, and still more preferably 0.3 to 0.0 ⁇ m. 7 ⁇ m. By setting it within this range, it is possible to reliably remove fine foreign matters such as impurities and aggregates contained in the pigment while suppressing filtration clogging of the pigment.
- different filters may be combined. At that time, the filtering by the first filter may be performed only once or may be performed twice or more. When filtering two or more times by combining different filters, it is preferable that the second and subsequent pore diameters are the same or larger than the pore diameter of the first filtering.
- the pore diameter here can refer to the nominal value of the filter manufacturer.
- a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
- the second filter a filter formed of the same material as the first filter described above can be used.
- the pore size of the second filter is suitably about 0.2 to 10.0 ⁇ m, preferably about 0.2 to 7.0 ⁇ m, more preferably about 0.3 to 6.0 ⁇ m.
- the cured film of this invention is obtained using the composition mentioned above.
- the cured film of the present invention mainly contains the titanium nitride-containing particles described above.
- the cured film of the present invention is preferably used as a light-shielding film, and specifically, is preferably used for light-shielding the periphery of the light-receiving part of the image sensor.
- the light-shielding film of the present invention is formed using the above-described composition (in particular, the above-described photosensitive composition).
- the light-shielding film obtained by using the composition of the present invention is excellent in patterning properties and electrode corrosion resistance.
- the thickness of the light-shielding film is not particularly limited, but from the viewpoint of obtaining the effect of the present invention more effectively, the thickness after drying is preferably 0.2 ⁇ m or more and 50 ⁇ m or less, and 0.3 ⁇ m or more and 10 ⁇ m or less. More preferably, it is 0.3 ⁇ m or more and 5 ⁇ m or less. Since the composition of the present invention has a high optical density per unit volume, the film thickness can be reduced as compared with a composition using a conventional black pigment.
- the size of the light-shielding film (the length of one side of the light-shielding film provided around the sensor light-receiving portion) is preferably 0.001 mm or more and 10 mm or less from the viewpoint of obtaining the effect of the present invention more effectively.
- the thickness is more preferably 7 mm or less and further preferably 0.1 mm or more and 3.5 mm or less. Since the composition of the present invention has a high optical density per unit volume, it is advantageous for microfabrication, such as being able to reduce the coating amount, and is excellent in patterning properties and anticorrosion properties of the electrode, and thus is particularly preferably used within the above range. be able to.
- a color filter having a black matrix has a cured film (black matrix) obtained by using the above-described composition on a substrate.
- the color filter having the black matrix of the present invention will be described in detail through its manufacturing method.
- the method for producing a color filter having a black matrix of the present invention comprises a step of applying a composition of the present invention on a substrate to form a composition layer (coating film) (hereinafter referred to as “composition layer forming step” as appropriate). Abbreviated), a step of exposing the composition layer through a mask (hereinafter abbreviated as “exposure step” where appropriate), and developing the exposed composition layer to form a patterned cured film. And a forming step (hereinafter, abbreviated as “development step” as appropriate).
- composition of the present invention is applied on a substrate directly or via another layer to form a composition layer (composition layer forming step), and exposed through a predetermined mask pattern. Only the coating film portion irradiated with light is cured (exposure process) and developed with a developer (development process) to form a patterned cured film composed of pixels to produce the color filter of the present invention. Can do.
- exposure process Exposure process
- development process developer
- each process in the manufacturing method of the color filter which has a black matrix of this invention is demonstrated.
- composition layer forming step In the composition layer forming step, the composition of the present invention is applied on a substrate to form a composition layer (coating film).
- the substrate examples include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display devices and the like, and those obtained by attaching a transparent conductive film to them, photoelectric sensors used for solid-state imaging devices, and the like.
- Examples include a conversion element substrate (for example, a silicon substrate), a CCD (Charge Coupled Device) substrate, and a CMOS (Complementary Metal-Oxide Semiconductor) substrate.
- an undercoat layer may be provided on these substrates in order to improve adhesion with the upper layer, prevent diffusion of substances, or planarize the substrate surface.
- various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.
- the coating film thickness of the composition is preferably 0.35 ⁇ m or more and 1.5 ⁇ m or less, preferably 0.40 ⁇ m or more, from the viewpoint of resolution and developability. 1.0 ⁇ m or less is more preferable.
- composition coated on the substrate is usually dried at 70 ° C. or higher and 110 ° C. or lower for 2 minutes or longer and 4 minutes or shorter. Thereby, a composition layer can be formed.
- the composition layer (coating film) formed in the composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
- the exposure is preferably performed by irradiation with actinic rays or radiation.
- actinic rays or radiation In particular, ultraviolet rays such as g-line, h-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable.
- the irradiation intensity 5 ⁇ 1500mJ / cm 2 is more preferably preferably 10 ⁇ 1000mJ / cm 2. Further, from the viewpoint of improving the resolution, exposure with an i-line stepper is preferable in forming a light-shielding film for a solid-state imaging device.
- an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part (the coating film part irradiated with light) remains.
- the developer when producing a light-shielding color filter having a black matrix for a solid-state imaging device, an organic alkali developer that does not cause damage to the underlying circuit or the like is desirable.
- the development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
- Examples of the alkaline aqueous solution include an inorganic developer and an organic developer.
- As the inorganic developer sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium oxalate, sodium metasuccinate having a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass. %, An alkaline aqueous solution dissolved so as to be%.
- Examples of the organic developer include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5.4.0] -7.
- An alkaline aqueous solution in which an alkaline compound such as undecene is dissolved so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass.
- An appropriate amount of a water-soluble organic solvent such as methanol and ethanol and / or a surfactant can be added to the alkaline aqueous solution.
- a developer composed of such an alkaline aqueous solution it is generally washed (rinsed) with pure water after development.
- the developing method for example, a paddle developing method and a shower developing method can be used.
- the cured film formed as needed is used.
- a curing step of curing by heating and / or exposure may be included.
- the color filter having the cured film (black matrix) of the present invention uses the composition of the present invention, the formed cured film is excellent in patterning property and anticorrosive property of the electrode. Therefore, it can be suitably used for a liquid crystal display device and a solid-state imaging device such as a CCD, and is particularly suitable for a high-resolution CCD device, CMOS, etc. exceeding 1 million pixels. That is, the color filter provided with the cured film of the present invention is preferably applied to a solid-state imaging device.
- the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
- the cured film (black matrix) of this invention is arrange
- the solid-state imaging device of the present invention has the above-described cured film (black matrix) according to the present invention.
- the solid-state imaging device of the present invention is preferably configured to include a color filter having a black matrix and, if necessary, a patterned film composed of pixels of other colors (three colors or four colors).
- the configuration of the solid-state imaging device of the present invention is a configuration provided with the black matrix of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device.
- the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
- the partition in this case preferably has a low refractive index for each color pixel. Examples of the image sensor having such a structure include apparatuses described in Japanese Patent Application Laid-Open Nos. 2012-227478 and 2014-177977.
- the cured film described above can be suitably applied as a so-called light shielding film.
- a light shielding film can be suitably applied to an infrared light cut filter with a light shielding film and a solid-state imaging device.
- Examples of such a solid-state imaging device include the individual imaging devices described in paragraphs 0011 to 0033 and paragraphs 0125 to 0127 described in JP-A-2015-034983.
- the cured film described above can be used in image display devices such as liquid crystal display devices and organic electroluminescence display devices.
- the cured film can be used for a color filter.
- the image display device For the definition of the image display device and details of each image display device, for example, “electronic display device (Akio Sasaki, published by Industrial Research Institute, Inc., 1990)”, “display device (written by Junichiro Ibuki, Sangyo Tosho Co., Ltd.) ) "Issued in 1989”).
- the liquid crystal display device is described, for example, in “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 liquid crystal display device of the present invention has the above-described cured film.
- a color filter, a liquid crystal layer, and a liquid crystal driving means are included between a pair of light-transmitting substrates.
- a color filter having a plurality of pixel groups and each pixel constituting the pixel group being separated from each other by the black matrix of the present invention is used. .
- At least one includes at least a color filter, a liquid crystal layer, and liquid crystal driving means between a pair of light transmissive substrates, and the liquid crystal driving means is an active element (
- a color filter obtained by using the composition of the present invention is provided between each active element, and has a TFT (Thin Film Transistor).
- the color filter using the composition of the present invention may be used for a color TFT (Thin Film Transistor) type liquid crystal display device.
- the color TFT liquid crystal display device is described in, for example, “Color TFT liquid crystal display (issued in 1996 by Kyoritsu Publishing Co., Ltd.)”.
- the present invention relates to a liquid crystal display device with a wide viewing angle, such as a horizontal electric field driving method such as IPS (In Plane Switching), a pixel division method such as MVA (Multi-domain Vertical Alignment), and a super-twist neutral (STN).
- IPS In Plane Switching
- MVA Multi-domain Vertical Alignment
- STN super-twist neutral
- TN Transmission Nematic
- VA Very Alignment
- OCS On-chip spacer
- FFS Feringe field switching
- R-OCB Reflective Optical Compensated
- the color filter in the present invention can be used for a bright and high-definition COA (Color-filter On Array) system.
- the required characteristics for the color filter may require the required characteristics for the interlayer insulating film, that is, the low dielectric constant and the stripping solution resistance, in addition to the normal required characteristics.
- the color filter of the present invention can provide a COA liquid crystal display device with high resolution and excellent long-term durability.
- a resin film may be provided on the color filter layer.
- the color filter may have a structure in which a cured film that forms each color pixel is embedded in a space partitioned by a partition, for example, in a lattice shape.
- the partition in this case preferably has a low refractive index for each color 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 liquid crystal display device of the present invention includes various members such as an electrode substrate, a polarizing film, a retardation film, a backlight, a spacer, and a viewing angle guarantee film.
- the color filter of the present invention can be applied to a liquid crystal display device composed of these known members.
- these components for example, “'94 Liquid Crystal Display Peripheral Materials / Chemicals Market (Kentaro Shima CMC 1994)”, “2003 Liquid Crystal Related Markets Current Status and Future Prospects (Volume 2)” Fuji Chimera Research Institute, Ltd., published in 2003) ”.
- backlights SID meeting Digest 1380 (2005) (A. Konno et.al), Monthly Display December 2005, pages 18-24 (Yasuhiro Shima), pages 25-30 (Takaaki Yagi), etc. Are listed.
- the cured film of the present invention is a portable device such as a personal computer, a tablet, a mobile phone, a smartphone, and a digital camera; an office automation (OA) device such as a printer multifunction device and a scanner; a monitoring camera, a barcode reader, and a cash automatic Industrial equipment such as personal identification using ATMs, high-speed cameras and face image authentication; in-vehicle camera equipment; medical camera equipment such as endoscopes, capsule endoscopes and catheters; biosensors, Optical filters and devices used in space equipment such as biosensors, military reconnaissance cameras, stereoscopic map cameras, weather and ocean observation cameras, land resource exploration cameras, and exploration cameras for space astronomy and deep space targets Module shading member Preliminary light shielding layer, and further can be used for anti-reflection member and the anti-reflection layer.
- OA office automation
- the cured film of this invention can be used also for uses, such as a micro LED (Light Emitting Diode) and a micro OLED (Organic Light Emitting Diode).
- a micro LED Light Emitting Diode
- a micro OLED Organic Light Emitting Diode
- it does not specifically limit,
- the optical filter and optical film which are used for micro LED and micro OLED it uses suitably with respect to the member which provides a light-shielding function or an antireflection function.
- the micro LED and the micro OLED include those described in JP-T-2015-500562 and JP-T-2014-533890.
- curing the composition of this invention can be used also for uses, such as a quantum dot display.
- a quantum dot display In addition to the optical and optical film which are used for a quantum dot display, it uses suitably with respect to the member which provides a light-shielding function and an antireflection function.
- quantum dot displays include U.S. Patent Application Publication No. 2013/0335677, U.S. Patent Application Publication No. 2014/0036536, U.S. Patent Application Publication No. 2014/0036203, and U.S. Patent Application Publication No. 2014/0035960. What has been described.
- composition Hereinafter, in preparing the compositions of Examples and Comparative Examples, each component contained in the composition will be described first.
- titanium nitride-containing particles TiN-1 to TiN-19 produced as follows were used. Table 1 shows the components and addition amounts used in the production of each titanium nitride-containing particle. In Table 1, among the addition amount of titanium particles (Ti particles), “residue” indicates an amount excluding the content of the addition particles. “Wt%” means mass%.
- TiN-1 titanium nitride-containing particles TiN-1
- Ti nanoparticles described in Table 1 were formed into Ti nanoparticles by plasma treatment in Ar gas.
- the Ti nanoparticles after the plasma treatment were allowed to stand for 24 hours under an Ar gas atmosphere at an O 2 concentration of 50 ppm or less and 30 ° C., and then O 2 gas was introduced into the Ar atmosphere so that the O 2 concentration was 100 ppm. In the state, it was left to stand at 30 ° C. for 24 hours (pretreatment of Ti particles).
- the obtained Ti nanoparticles were classified using a TTSP separator manufactured by Hosokawa Micron under the condition of a yield of 10% to obtain Ti nanoparticles powder.
- the primary particle diameter of the obtained powder was 120 nm when the average particle diameter of 100 particles was determined by arithmetic average by TEM observation.
- the titanium nitride-containing particles TiN-1 were produced using an apparatus according to the black composite fine particle production apparatus described in FIG. 1 of International Publication No. 2010/147098. Specifically, in the black composite particle manufacturing apparatus, a high frequency voltage of about 4 MHz and about 80 kVA is applied to the high frequency oscillation coil of the plasma torch, and an argon gas of 50 L / min and nitrogen as plasma gases are supplied from the plasma gas supply source.
- a mixed gas of 50 L / min was supplied to generate an argon-nitrogen thermal plasma flame in the plasma torch.
- 10 L / min carrier gas was supplied from the spray gas supply source of the material supply apparatus.
- the titanium particles obtained as described above and the additive particles described in Table 1 are added as the additive amount described in Table 1, and together with the argon gas as the carrier gas, in the thermal plasma flame in the plasma torch , Evaporated in a thermal plasma flame, and highly dispersed in the gas phase.
- nitrogen was used as a gas supplied into the chamber by the gas supply device.
- the flow rate in the chamber at this time was 5 m / sec, and the supply amount was 1000 L / min.
- the pressure in the cyclone was 50 kPa, and the supply rate of each raw material from the chamber to the cyclone was 10 m / s (average value). In this way, titanium nitride-containing particles TiN-1 were obtained.
- the obtained titanium nitride-containing particles TiN-1 were measured for the content of titanium (Ti) atoms, Fe (iron) atoms, and silicon (Si) atoms by ICP emission spectroscopy. The results are shown in Table 1.
- ICP emission spectroscopic analysis an ICP emission spectroscopic analyzer “SPS3000” (trade name) manufactured by Seiko Instruments Inc. was used.
- the nitrogen atom content was measured using an oxygen / nitrogen analyzer “EMGA-620W / C” (trade name) manufactured by Horiba, Ltd., and was calculated by an inert gas melting-thermal conductivity method. The results are shown in Table 1.
- X-ray diffraction of titanium nitride-containing particles TiN-1 was measured by a wide-angle X-ray diffraction method (trade name “RU-200R” manufactured by Rigaku Corporation) with a powder sample placed in an aluminum standard sample holder.
- the X-ray source is CuK ⁇ ray
- the output is 50 kV / 200 mA
- the slit system is 1 ° -1 ° -0.15 mm-0.45 mm
- the measurement step (2 ⁇ ) is 0.02 °
- the scan speed is It was 2 ° / min.
- the diffraction angle 2 ⁇ of the peak derived from the TiN (200) plane observed near the diffraction angle 2 ⁇ (42.6 °) was measured.
- the crystallite size constituting the particle was determined using Scherrer's equation. The results are shown in Table 1. Note that no X-ray diffraction peak due to TiO 2 was observed. For the following titanium nitride-containing particles TiN-2 to TiN-19, the diffraction angle 2 ⁇ and crystallite size were measured in the same manner as the titanium nitride-containing particles TiN-1. The results are shown in Table 1. For any titanium nitride-containing particles, no X-ray diffraction peak due to TiO 2 was observed.
- Titanium nitride-containing particles TiN-2 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- Titanium nitride-containing particles TiN-3 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used in the production of TiN-1 particles were as shown in Table 1. .
- Titanium nitride-containing particles TiN-4 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- Titanium nitride-containing particles TiN-5 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- Titanium nitride-containing particles TiN-6 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- TiN-7 (Titanium nitride-containing particles TiN-7) Contains titanium nitride in the same manner as the production of titanium nitride-containing particles TiN-6, except that the feed rate of each raw material from the chamber to the cyclone in the production of TiN-6 particles is changed to 8 m / s (average value). Particle TiN-7 was produced.
- Titanium nitride-containing particles TiN-8 Contains titanium nitride except that the raw materials used in the production of TiN-1 particles and the amount added were as shown in Table 1 and the feed rate of each raw material from the chamber to the cyclone was changed to 15 m / s (average value). Titanium nitride-containing particles TiN-8 were produced in the same manner as in the production of particles TiN-1.
- Titanium nitride-containing particles TiN-9 Contains titanium nitride except that the raw materials used in the production of TiN-1 particles and the amount added were as shown in Table 1 and the feed rate of each raw material from the chamber to the cyclone was changed to 20 m / s (average value). Titanium nitride-containing particles TiN-9 were produced in the same manner as in the production of particles TiN-1.
- Titanium nitride-containing particles TiN-10 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- TiN-11 titanium nitride-containing particles TiN-11
- Table 1 The raw materials and addition amounts used for the production of TiN-1 particles are as shown in Table 1, and the same as the production of titanium nitride-containing particles TiN-1 except that the Ti particle pretreatment and stationary treatment were not performed. Thus, titanium nitride-containing particles TiN-11 were produced.
- Titanium nitride-containing particles TiN-12 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used in the production of TiN-1 particles were as shown in Table 1. .
- Titanium nitride-containing particles TiN-13 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- Titanium nitride-containing particles TiN-14 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- Titanium nitride-containing particles TiN-15 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- Titanium nitride-containing particles TiN-16 were produced in the same manner as the production of titanium nitride-containing particles TiN-1, except that the raw materials and addition amounts used for the production of TiN-1 particles were as shown in Table 1. .
- TiN-4 particles In the production of TiN-4 particles, the same as the titanium nitride-containing particles TiN-4 except that the standing time under the control of oxygen (O 2 ) concentration after the production of titanium nitride-containing particles described later is as shown in Table 1. Thus, titanium nitride-containing particles TiN-17, TiN-18 and TiN-19 were produced.
- Dispersants A to G having the following structures were used as the dispersants.
- the numerical value described in each structural unit intends the mass% of each structural unit with respect to all the structural units.
- resin A which is a binder resin
- ACRYCURE RD-F8 (trade name, manufactured by Nippon Shokubai Co., Ltd.) was used.
- the structure of resin A is shown below.
- Polymerizable compound M1 (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD DPHA”, see formula below)
- Polymerizable compound M2 (manufactured by Nippon Kayaku Co., Ltd., trade name “KAYARAD RP-1040”, see formula below)
- OXE-01 Irgacure OXE01 (trade name, manufactured by BASF Japan)
- OXE-02 Irgacure OXE02 (trade name, manufactured by BASF Japan)
- I-1 polymerization initiator of the following formula (I-1)
- I-2 polymerization initiator of the following formula (I-2) (trade name “B-CIM”, manufactured by Hodogaya Chemical Co., Ltd.)
- I-3 polymerization initiator of the following formula (I-3)
- I-4 polymerization initiator of the following formula (I-4)
- I-5 polymerization initiator of the following formula (I-5)
- NCI -831 Adeka Arcles NCI-831 (trade name, manufactured by Adeka) ⁇ N-1919: Product name, manufactured by ADEKA
- Test solutions were prepared by diluting the compositions of Examples and Comparative Examples 100 times with PGMEA, and the obtained test solutions were stored in an environment of 45 ° C. for 3 days. Then, the average particle diameter (D90) of the titanium nitride-containing particles contained in the test solution before and after storage was measured with a particle size distribution measuring device (product name “Nanotrack UPA-150EX” manufactured by Microtrack). Based on the value of the average particle size (D90) of the test solution before and after storage, the particle size variation during preparation was evaluated according to the following criteria.
- ⁇ Number of particles> A sample solution in which the above composition was diluted 500 times with PGMEA was prepared, and the number of titanium nitride-containing particles having a size of 10 ⁇ m or more contained in 10 ml of this sample solution was determined by a flow type particle image analyzer (trade name “FPIA”). , Manufactured by Malvern).
- Electrode patterns (copper copper) formed on the surface of the silicon wafer so that the dry film thickness of the coating film of each composition was 0.7 ⁇ m.
- a spine coater was applied on top. 10 minutes after coating, the film was left as it was, and then a silicon wafer coated with each composition was subjected to heat treatment (pre-baking) for 120 seconds using a hot plate at 100 ° C. to form a coating film.
- each composition of an Example and a comparative example is a negative photosensitive resin composition with which an exposure part hardens
- the silicon wafer on which the exposed coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics), and CD-2000 (Fuji Film Electronics Material). Paddle development was performed at 23 ° C.
- the silicon wafer after the paddle development is fixed to the horizontal rotating table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is sprayed from the upper part of the rotation center into a shower-like shape. The rinsing process was performed. Thereafter, the silicon wafer was spray-dried to produce a wafer having a frame-like black matrix. A wafer having a frame-like black matrix is stored for 3 months in an environment of a temperature of 25 ° C.
- the anticorrosion property of the electrode was evaluated according to the following criteria based on the number of occurrences of rust. A: 0 to 5 locations where rust occurs B: 6 to 10 locations where rust occurs C: 11 to 20 locations where rust occurs D: 21 or more locations where rust occurs
- ⁇ Appearance during moisture resistance test> A wafer having a frame-like black matrix similar to the wafer used for evaluating the corrosion resistance of the electrode was exposed to an environment of 90 ° C. and humidity of 85% RH for 1000 hours. About the wafer after exposure, the external appearance change of the black matrix was observed with the optical microscope (The Olympus company make, brand name "LEXT OLS4500"), and the external appearance at the time of a moisture resistance test was evaluated based on the following evaluation criteria. A: No difference is observed before and after the moisture resistance test, or surface roughness with an unevenness difference of 10 nm or less is observed after the moisture resistance test.
- B Surface roughness with an unevenness difference of more than 10 nm and 50 nm or less is observed after the moisture resistance test.
- C Surface roughness with an unevenness difference of more than 50 nm and less than 100 nm is observed after the moisture resistance test.
- D Surface roughness with an unevenness difference of more than 100 nm is observed after the moisture resistance test.
- Example 1 a composition was prepared in the same manner except that the polymerizable compound M1 used for preparing the composition was changed to a polymerizable compound U15HA (manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “U15HA”). went. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.
- Example 1 a composition was prepared and evaluated in the same manner except that the polymerizable compound M1 used for preparation of the composition was changed to a cardo monomer (trade name “Ogsol” manufactured by Osaka Gas Chemical Co., Ltd.). . As a result of the evaluation, it was found that the same result as in Example 1 was obtained except that the evaluation result of the patterning property was “A”.
- Example 1 a composition was prepared in the same manner except that the composition was prepared without using a polymerization inhibitor, and each evaluation was performed. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.
- a composition was prepared in the same manner as in Example 1 except that the composition was prepared without using the surfactant F-1, and each evaluation was performed. As a result of the evaluation, it was found that the same result as in Example 1 was obtained.
- CB dispersion ⁇ Preparation of carbon black dispersion (CB dispersion)>
- carbon black trade name “Color Black S170”, manufactured by Degussa, average primary particle diameter of 17 nm, BET specific surface area of 200 m 2 / g, gas black method, instead of titanium nitride-containing particles, was used.
- a pigment dispersion was prepared in the same manner except that the carbon black produced by the above method was used to obtain a carbon black dispersion.
- titanium nitride-containing particles TiN-1 are contained instead of the pigment dispersion added so that the titanium nitride-containing particles TiN-1 are contained in the composition in an amount of 16% by mass.
- a composition was prepared in the same manner except that the total content of the particles TiN-1 and carbon black was 16% by mass)], and each evaluation was performed. As a result of the evaluation, it was found that the same light shielding property as in Example 1 was obtained.
- titanium nitride-containing particles TiN-1 are contained instead of the pigment dispersion added so that the titanium nitride-containing particles TiN-1 are contained in the composition in an amount of 16% by mass.
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Abstract
Description
具体的には、液晶表示装置に用いられるカラーフィルタには着色画素間の光を遮蔽し、コントラストを向上させる等の目的で、ブラックマトリクスと呼ばれる遮光膜が備えられている。
また、固体撮像素子においてもノイズ発生防止、画質の向上等を目的としてブラックマトリクスが設けられている。現在、携帯電話およびPDA(Personal Digital Assistant)などの電子機器の携帯端末には、小型で薄型な撮像ユニットが搭載されている。このような撮像ユニットは、一般に、CCD(Charge Coupled Device)イメージセンサおよびCMOS(Complementary Metal-Oxide Semiconductor)イメージセンサなどの固体撮像素子と、固体撮像素子上に被写体像を形成するためのレンズと、を備えている。
そこで、本発明者らが、電極パターンが形成された基板上にチタン窒化物含有粒子を含有する組成物を塗布して、パターン状に形成された硬化膜を作製したところ、チタン窒化物含有粒子の種類によっては、電極パターンの劣化(腐食)が起こったり、所望のパターンが得られなかったりすること(パターニング性の低下)が明らかになった。
すなわち、本発明者は、以下の構成により上記課題が解決できることを見出した。
Fe原子を含むチタン窒化物含有粒子を含有し、
上記チタン窒化物含有粒子中における上記Fe原子の含有量が、0.001質量%超0.4質量%未満である、組成物。
[2]
上記チタン窒化物含有粒子の(200)面に由来するピークの回折角2θが、CuKα線をX線源とした場合において、42.6°超43.5°以下である、上記[1]に記載の組成物。
[3]
上記チタン窒化物含有粒子が、さらにSi原子を含有し、
上記チタン窒化物含有粒子中における上記Si原子の含有量が、0.002質量%超0.3質量%未満である、上記[1]または[2]に記載の組成物。
[4]
以下の粒子数測定方法によって求められる10μm以上のサイズの上記チタン窒化物含有粒子の数が、100個以下である、上記[1]~[3]のいずれか1つに記載の組成物。
粒子数測定方法:プロピレングリコールモノメチルエーテルアセテートによって上記組成物を500倍に希釈した試料溶液を調製し、上記試料溶液10ml中に含まれる10μm以上のサイズの上記チタン窒化物含有粒子の数をフロー式粒子像分析装置によって測定する。
[5]
さらに、2種以上の有機溶剤を含有する、上記[1]~[4]のいずれか1つに記載の組成物。
[6]
さらに、バインダー樹脂を含有する、上記[1]~[5]のいずれか1つに記載の組成物。
[7]
さらに、重合性化合物を含有する、上記[1]~[6]のいずれか1つに記載の組成物。
[8]
さらに、重合開始剤を含有する、上記[1]~[7]のいずれか1つに記載の組成物。
[9]
上記組成物中の固形分が10~40質量%である、上記[1]~[8]のいずれか1つに記載の組成物。
[10]
上記チタン窒化物含有粒子の含有量が、上記組成物の全固形分に対して、20~70質量%である、上記[1]~[9]のいずれか1つに記載の組成物。
[11]
さらに、水を含有し、
上記水の含有量が、上記組成物全質量に対して、0.1~1質量%である、上記[1]~[10]のいずれか1つに記載の組成物。
[12]
さらに、分散剤を含有し、
上記分散剤が、ポリアクリル酸メチル、ポリメタクリル酸メチルおよび環状または鎖状のポリエステルからなる群より選択される少なくとも1種の構造を有する、上記[1]~[11]のいずれか1つに記載の組成物。
[13]
上記チタン窒化物含有粒子に対する上記分散剤の含有割合が、質量比で0.05~0.30である、上記[12]に記載の組成物。
[14]
上記[1]~[13]のいずれか1つに記載の組成物の製造方法であって、
熱プラズマ法によって上記チタン窒化物含有粒子を得る工程を含む、組成物の製造方法。
[15]
上記[1]~[13]のいずれか1つに記載の組成物を用いて得られる、硬化膜。
[16]
上記[15]に記載の硬化膜を有する、カラーフィルタ。
[17]
上記[15]に記載の硬化膜を有する、遮光膜。
[18]
上記[15]に記載の硬化膜を有する、固体撮像素子。
[19]
上記[15]に記載の硬化膜を有する、画像表示装置。
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。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さないものと共に置換基を有するものをも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含する。
本明細書中における「活性光線」または「放射線」とは、例えば、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、および、電子線等を意味する。また本発明において光とは、活性光線または放射線を意味する。本明細書中における「露光」とは、特に断らない限り、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、X線、および、EUV光などによる露光のみならず、電子線およびイオンビーム等の粒子線による描画も露光に含める。
本明細書において、“(メタ)アクリレート”はアクリレートおよびメタアクリレートを表し、“(メタ)アクリル”はアクリルおよびメタアクリルを表し、“(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を表し、“(メタ)アクリルアミド”は、アクリルアミドおよびメタアクリルアミドを表す。また、本明細書中において、“単量体”と“モノマー”とは同義である。本発明における単量体は、オリゴマーおよびポリマーと区別され、重量平均分子量が2,000以下の化合物をいう。本明細書中において、重合性化合物とは、重合性基を有する化合物のことをいい、単量体であっても、ポリマーであってもよい。重合性基とは、重合反応に関与する基をいう。
本発明の組成物は、Fe原子を含むチタン窒化物含有粒子を含有し、上記チタン窒化物含有粒子中における上記Fe原子の含有量が、0.001質量%超0.4質量%未満である。
本発明の組成物によれば、パターニング性および電極の防食性に優れた硬化膜を作製できる。
本発明者らは、鋭意検討の結果、チタン窒化物含有粒子中のFe原子の含有量がパターニング性および電極の防食性に関連することを知見している。
チタン窒化物含有粒子中に含まれるFe原子は、電極および基板に対する密着性に優れており、チタン窒化物含有粒子中のチタン窒化物は、Fe原子を介して、電極および基板に付着していたと考えられる。そのため、現像処理などの硬化膜のパターニング後において、Fe原子が電極および基板上に残留し、チタン窒化物が除去されやすくなったと考えられる。そのため、チタン窒化物含有粒子中のFe原子の含有量を所定量以上にすることで、硬化膜のパターニング性が向上したと推測される。
一方で、チタン窒化物含有粒子中に含まれるFe原子の含有量が多すぎると、電極および基板上に残留するFe原子の量が増加して、電極の腐食の原因となると考えられる。そのため、チタン窒化物含有粒子中のFe原子の含有量を所定量以下にすることで、電極の防食性が優れたものになったと推測される。
本発明の組成物は、Fe原子を含むチタン窒化物含有粒子を含有する。チタン窒化物含有粒子は、黒色顔料として使用することが好適である。
チタン窒化物含有粒子の製造には、通常、気相反応法が用いられ、具体的には電気炉法および熱プラズマ法等が挙げられる。これらの製法の中でも、不純物の混入が少ない点、粒子径が揃いやすい点、および、生産性が高い点などの理由から、熱プラズマ法が好ましい。
熱プラズマの発生方法としては、直流アーク放電、多相アーク放電、高周波(RF)プラズマ、および、ハイブリッドプラズマ等が挙げられ、電極からの不純物の混入が少ない高周波プラズマが好ましい。熱プラズマ法によるチタン窒化物含有微粒子の具体的な製造方法としては、例えば、チタン粉末を高周波熱プラズマにより蒸発させ、窒素をキャリアガスとして装置内に導入し、冷却過程にてチタン粉末を窒化させ、チタン窒化物含有粒子を合成する方法等が挙げられる。なお、熱プラズマ法は、上記に限定されない。
チタン粉末材料がFe原子を含有する場合には、Fe原子の含有量は、チタン粉末材料の全質量に対して、0.001質量%超であることが好ましい。これにより、硬化膜のパターニング性がより優れる。また、チタン粉末材料がFe原子を含有する場合には、Fe原子の含有量は、チタン粉末材料の全量に対して、0.4質量%未満であることが好ましい。これにより、硬化膜による電極の防食性がより優れる(硬化膜が電極を腐食することをより抑制できる)。すなわち、チタン窒化物含有粒子の製造に使用するチタン粉末材料に含まれるFe原子が上記範囲内(0.001質量超、0.4質量%未満)にあることで、本発明の効果をより顕著に得ることができる。
チタン粉末材料がSi原子を含有する場合には、Si原子の含有量が、チタン粉末材料全質量に対して、0.002質量%超0.3質量%未満であることが好ましく、0.01~0.15質量%であることがより好ましく、0.02~0.1質量%であることがさらに好ましい。Si原子の含有量が0.002質量%超であることで、硬化膜のパターニング性がより向上する。また、Si原子の含有量が0.3質量%未満であることで、得られるチタン窒化物含有粒子の最表層の極性が安定し、チタン窒化物含有粒子を分散させる際におけるチタン窒化物含有粒子への分散剤の吸着性が良化して、チタン窒化物含有粒子の未分散物が低減することで、パーティクル発生を抑制する効果があると考えられる。すなわち、チタン窒化物含有粒子の製造に使用するチタン粉末材料に含まれるSi原子が上記範囲内であることで、本発明の効果がより顕著に得ることができる。
また、チタン窒化物含有粒子の製造に使用するチタン粉末材料(チタン粒子)中の水分は、チタン粉末材料の全質量に対して、1質量%未満であることが好ましく、0.1質量%未満であることがより好ましく、実質的に含まないことがさらに好ましい。チタン窒化物含有粒子の製造に使用するチタン粉末材料中の水分が上記範囲にあることで、本発明の効果がより顕著に得ることができる。
また、チタン窒化物含有粒子の製造において熱プラズマ法を用いる場合には、原料であるチタン粒子の他に、Fe粒子、Fe酸化物などの成分を添加して、これらを熱プラズマ法によって窒化することによって、チタン窒化物含有粒子にFe原子を含有させることができる。
なお、チタン窒化物含有粒子中に含まれているFe原子は、イオン、金属化合物(錯化合物も含む)、金属間化合物、合金、酸化物、複合酸化物、窒化物、酸窒化物、硫化物および酸硫化物など、いずれの形態で含まれていてもよい。また、チタン窒化物含有粒子中に含まれているFe原子は、結晶格子間位置の不純物として存在していてもよいし、結晶粒界にアモルファス状態で不純物として存在していてもよい。
すなわち、チタン窒化物含有粒子中におけるFe原子の含有量が上記範囲内にあることで、本発明の効果(硬化膜のパターニング性および電極の防食性)が顕著に発揮される。
ここで、チタン窒化物含有粒子中におけるFe原子の含有量は、ICP(高周波誘導結合プラズマ)発光分光分析法により測定される。
チタン窒化物含有粒子中におけるSi原子の含有量は、チタン窒化物含有粒子全質量に対して、0.002質量%超0.3質量%未満であることが好ましく、0.01~0.15質量%であることがより好ましく、0.02~0.1質量%であることがさらに好ましい。Si原子の含有量が0.002質量%超であることで、硬化膜のパターニング性がより向上する。また、0.3質量%未満であることで、チタン窒化物含有粒子の最表層の極性が安定し、チタン窒化物含有粒子を分散させる際におけるチタン窒化物含有粒子への分散剤の吸着性が良化して、チタン窒化物含有粒子の未分散物が低減することで、パーティクル発生を抑制する効果があると考えられる。
チタン窒化物含有粒子中におけるSi原子の含有量は、上述したFe原子と同様の方法によって測定される。
また、チタン窒化物含有粒子の製造において熱プラズマ法を用いる場合には、原料であるチタン粒子の他に、Si粒子、Si酸化物などの成分を添加して、これらを熱プラズマ法によって窒化することによって、チタン窒化物含有粒子にSi原子を含有させることができる。
なお、チタン窒化物含有粒子中に含まれるSi原子は、イオン、金属化合物(錯化合物も含む)、金属間化合物、合金、酸化物、複合酸化物、窒化物、酸窒化物、硫化物および酸硫化物など、いずれの形態で含まれていてもよい。また、チタン窒化物含有粒子中に含まれているSi原子は、結晶格子間位置の不純物として存在していてもよいし、結晶粒界にアモルファス状態で不純物として存在していてもよい。
チタン窒化物含有粒子中の窒素原子(N原子)の含有量は、チタン窒化物含有粒子の全質量に対して、3~60質量%であることが好ましく、5~50質量%であることがより好ましく、10~40質量%であることがさらに好ましい。窒素原子の含有量は不活性ガス融解-熱伝導度法により分析することができる。
チタン窒化物含有粒子は主成分としてチタン窒化物(TiN)を含み、通常、その合成時に酸素が混入する場合、および、粒子径が小さい場合などに顕著になるが、粒子表面の酸化などにより、一部酸素原子を含有してもよい。
チタン窒化物含有粒子中の酸素原子の含有量は、チタン窒化物含有粒子の全質量に対して、1~40質量%であることが好ましく、1~35質量%であることがより好ましく、5~30質量%であることがさらに好ましい。酸素原子の含有量は、不活性ガス融解-赤外線吸収法により分析することができる。
複合微粒子とは、チタン窒化物粒子と金属微粒子が複合化しているか、高度に分散した状態にある粒子のことをいう。ここで、「複合化している」とは、チタン窒化物と金属の両成分によって粒子が構成されていることを意味し、「高度に分散した状態」とは、チタン窒化物粒子と金属粒子がそれぞれ個別で存在し、かつ少量成分の粒子が凝集せず均一、一様に分散していることを意味する。
金属微粒子としては特に限定されず、例えば、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウム、イリジウム、ルテニウム、オスミウム、マンガン、モリブデン、タングステン、ニオブ、タンタル、カルシウム、チタン、ビスマス、アンチモンおよび鉛、並びにこれらの合金、から選ばれる少なくとも一種が挙げられる。中でも、銅、銀、金、白金、パラジウム、ニッケル、錫、コバルト、ロジウムおよびイリジウム、並びにこれらの合金から選ばれる少なくとも1種であることが好ましく、銅、銀、金、白金および錫、並びにこれらの合金から選ばれる少なくとも一種であることがより好ましい。耐湿性により優れる観点から、銀であることが好ましい。
チタン窒化物含有粒子における金属微粒子の含有量としては、チタン窒化物含有粒子の全質量に対して5質量%以上50質量%以下であることが好ましく、10質量%以上30質量%以下であることがより好ましい。
なお、本明細書において、固形分とは、組成物により形成される硬化膜を構成する成分を意図し、溶媒は含まれない。例えば、後述する重合性化合物は硬化膜を構成する成分であるため、液体(液状)であっても固形分に含まれる。
粒子数測定方法:プロピレングリコールモノメチルエーテルアセテートによって本発明の組成物を500倍に希釈した試料溶液を調製し、試料溶液10ml中に含まれる10μm以上のサイズのチタン窒化物含有粒子の数をフロー式粒子像分析装置によって測定する。
チタン窒化物含有粒子のサイズは、フロー式粒子像分析装置の、フラットで偏平な透明フローセル(厚み約200μm)の流路(流れ方向に沿って広がる流路)に、有機溶剤や水などの溶媒によって組成物を希釈した試料溶液を通過させて測定される。
フロー式粒子像分析装置は、フローセルの厚み方向と交差する方向に通過する光路を形成するために、ストロボとCCDカメラとが、フローセルに対して、相互に反対側に位置するように装着される。ストロボは、試料溶液が流路を流れている間に1/60秒間隔でストロボ光を照射する。その結果、フローセルを流れるそれぞれの粒子が、フローセルに平行な一定範囲を有する2次元画像として撮影される。それぞれの粒子の2次元画像の面積から、同一の面積を有する円の直径を本発明の「サイズ」として算出する。
測定に用いる試料は、有機溶剤や水などの溶媒によって組成物を希釈して調製されることが好ましい。試料は、チタン窒化物含有粒子を分散状態で含有した分散液であることがより好ましい。試料の調製方法は、チタン窒化物含有粒子を含む組成物を、固形分が10~40質量%になるように有機溶剤や水などの溶媒によって希釈することが好ましく、チタン窒化物含有粒子以外の成分を溶媒に溶解させたのち、チタン窒化物含有粒子を再分散させることがより好ましい。
試料は、チタン窒化物含有粒子を再分散させた分散液を、さらに10~2000倍に希釈することがさらに好ましい。チタン窒化物含有粒子を分散させた分散液の状態としては、動的光散乱法により分散液を測定したチタン窒化物含有粒子の平均粒子径(D90)が1μm以下である状態が好ましい。
動的光散乱法による測定装置としては、特に限定されないが、マイクロトラック社製、製品名「ナノトラックUPA-150EX」などが挙げられる。
本発明の組成物は、分散剤を含有することが好ましい。分散剤は、上述したチタン窒化物含有粒子などの顔料の分散性向上に寄与する。本発明において、分散剤と、後述するバインダー樹脂とは、異なる成分である。
分散剤としては、例えば、公知の顔料分散剤を適宜選択して用いることができる。なかでも、高分子化合物が好ましい。
分散剤としては、高分子分散剤〔例えば、ポリアミドアミンとその塩、ポリカルボン酸とその塩、高分子量不飽和酸エステル、変性ポリウレタン、変性ポリエステル、変性ポリ(メタ)アクリレート、(メタ)アクリル系共重合体、ナフタレンスルホン酸ホルマリン縮合物〕、ポリオキシエチレンアルキルリン酸エステル、ポリオキシエチレンアルキルアミン、および、顔料誘導体等を挙げることができる。
高分子化合物は、その構造からさらに直鎖状高分子、末端変性型高分子、グラフト型高分子、およびブロック型高分子に分類することができる。
一方で、チタン窒化物含有粒子の表面を改質することにより、これに対する高分子化合物の吸着性を促進させることもできる。
このようなグラフト鎖を有する構造単位を有する高分子化合物は、グラフト鎖によって溶剤との親和性を有するために、黒色顔料等の着色顔料の分散性、および、経時後の分散安定性に優れるものである。また、グラフト鎖の存在により、グラフト鎖を有する構造単位を有する高分子化合物は重合性化合物またはその他の併用可能な樹脂などとの親和性を有する。結果として、アルカリ現像で残渣を生じにくくなる。
グラフト鎖が長くなると立体反発効果が高くなり顔料等の分散性は向上する。一方、グラフト鎖が長すぎると黒色顔料等の着色顔料への吸着力が低下して、顔料等の分散性は低下する傾向となる。このため、グラフト鎖は、水素原子を除いた原子数が40~10000であるものが好ましく、水素原子を除いた原子数が50~2000であるものがより好ましく、水素原子を除いた原子数が60~500であるものがさらに好ましい。
ここで、グラフト鎖とは、共重合体の主鎖の根元(主鎖から枝分かれしている基において主鎖に結合する原子)から、主鎖から枝分かれしている基の末端までを示す。
グラフト鎖と溶剤との相互作用性を向上させ、それにより分散性を高めるために、グラフト鎖は、ポリエステル構造、ポリエーテル構造およびポリ(メタ)アクリレート構造からなる群から選ばれた少なくとも1種を有するグラフト鎖であることが好ましく、ポリエステル構造およびポリエーテル構造の少なくともいずれかを有するグラフト鎖であることがより好ましい。
ここで、ポリカプロラクトン構造とは、ε-カプロラクトンを開環した構造を繰り返し単位として有するものをいう。ポリバレロラクトン構造とは、δ-バレロラクトンを開環した構造を繰り返し単位として有するものをいう。
ポリカプロラクトン構造を有する分散剤の具体例としては、下記式(1)および下記式(2)におけるjおよびkが5であるものが挙げられる。また、ポリバレロラクトン構造を有する分散剤の具体例としては、下記式(1)および下記式(2)におけるjおよびkが4であるものが挙げられる。
ポリアクリル酸メチル構造を有する分散剤の具体例としては、下記式(4)におけるX5が水素原子であり、R4がメチル基であるものが挙げられる。また、ポリメタクリル酸メチル構造を有する分散剤の具体例としては、下記式(4)におけるX5がメチル基であり、R4がメチル基であるものが挙げられる。
式(1)~式(4)において、X1、X2、X3、X4、およびX5は、それぞれ独立に、水素原子または1価の有機基を表す。X1、X2、X3、X4、およびX5としては、合成上の制約の観点からは、それぞれ独立に、水素原子または炭素数(炭素原子数)1~12のアルキル基であることが好ましく、それぞれ独立に、水素原子またはメチル基であることがより好ましく、メチル基がさらに好ましい。
また、式(1)および式(2)において、jおよびkは、それぞれ独立に、2~8の整数を表す。式(1)および式(2)におけるjおよびkは、組成物の分散安定性および現像性の観点から、4~6の整数が好ましく、5が最も好ましい。
式(4)中、R4は水素原子または1価の有機基を表し、この1価の有機基としては特に構造上限定はされない。R4として好ましくは、水素原子、アルキル基、アリール基、およびヘテロアリール基が挙げられ、より好ましくは、水素原子、またはアルキル基である。R4がアルキル基である場合、アルキル基としては、炭素数1~20の直鎖状アルキル基、炭素数3~20の分岐状アルキル基、または炭素数5~20の環状アルキル基が好ましく、炭素数1~20の直鎖状アルキル基がより好ましく、炭素数1~6の直鎖状アルキル基がさらに好ましい。式(4)において、qが2~500のとき、グラフト共重合体中に複数存在するX5およびR4は互いに同じであっても異なっていてもよい。
また、式(2)で表される構造単位としては、組成物の分散安定性および現像性の観点から、下記式(2A)で表される構造単位であることがより好ましい。
A. J. Leo, Comprehensive Medicinal Chemistry, Vol.4, C. Hansch, P. G. Sammnens, J. B. Taylor and C. A. Ramsden, Eds., p.295, Pergamon Press, 1990 C. Hansch & A. J. Leo. SUbstituent Constants For Correlation Analysis in Chemistry and Biology. John Wiley & Sons. A.J. Leo. Calculating logPoct from structure. Chem. Rev., 93, 1281-1306, 1993.
logP=log(Coil/Cwater)
式中、Coilは油相中の化合物のモル濃度を、Cwaterは水相中の化合物のモル濃度を表す。
logPの値が0をはさんでプラスに大きくなると油溶性が増し、マイナスで絶対値が大きくなると水溶性が増すことを意味し、有機化合物の水溶性と負の相関があり、有機化合物の親疎水性を見積るパラメータとして広く利用されている。
R1、R2、およびR3は、好ましくは水素原子、または炭素数が1~3のアルキル基であり、より好ましくは水素原子またはメチル基である。R2およびR3は、水素原子であることが特に好ましい。
Xは、酸素原子(-O-)またはイミノ基(-NH-)を表し、酸素原子であることが好ましい。
脂肪族基は不飽和脂肪族基よりも飽和脂肪族基の方が好ましい。また、脂肪族基は、置換基を有していてもよい。置換基の例は、ハロゲン原子、芳香族基および複素環基が挙げられる。ただし、脂肪族基は、置換基として酸基を有さない。
また、上記一般式(ii)で表される単量体として、R1が水素原子またはメチル基であって、Lがアルキレン基であって、Zが脂肪族基、複素環基または芳香族基である化合物が好ましい。また、上記一般式(iii)で表される単量体として、R4、R5、およびR6が水素原子またはメチル基であって、Zが脂肪族基、複素環基または芳香族基である化合物が好ましい。
なお、式(i)~(iii)で表される代表的な化合物の例としては、特開2013-249417号公報の段落0089~0093に記載の化合物を参照でき、これらの内容は本明細書に組み込まれる。
この黒色顔料等の着色顔料と相互作用を形成しうる官能基としては、例えば、酸基、塩基性基、配位性基、および、反応性を有する官能基等が挙げられる。
高分子化合物が、酸基、塩基性基、配位性基、または、反応性を有する官能基を有する場合、それぞれ、酸基を有する構造単位、塩基性基を有する構造単位、配位性基を有する構造単位、または、反応性を有する構造単位を有することが好ましい。
特に、高分子化合物が、さらに、酸基として、カルボン酸基などのアルカリ可溶性基を有することで、高分子化合物に、アルカリ現像によるパターン形成のための現像性を付与することができる。
すなわち、高分子化合物にアルカリ可溶性基を導入することで、本発明の組成物は、黒色顔料等の着色顔料の分散に寄与する分散剤としての高分子化合物がアルカリ可溶性を有することになる。このような高分子化合物を含有する組成物は、露光部の遮光性に優れたものとなり、且つ、未露光部のアルカリ現像性が向上される。
また、高分子化合物が酸基を有する構造単位を有することにより、高分子化合物が溶剤となじみやすくなり、塗布性も向上する傾向となる。
これは、酸基を有する構造単位における酸基が黒色顔料等の着色顔料と相互作用しやすく、高分子化合物が黒色顔料等の着色顔料を安定的に分散すると共に、黒色顔料等の着色顔料を分散する高分子化合物の粘度が低くなっており、高分子化合物自体も安定的に分散されやすいためであると推測される。
すなわち、高分子化合物は、カルボン酸基、スルホン酸基、および、リン酸基のうち少なくとも1種を有する構造単位をさらに有することが好ましい。
高分子化合物は、酸基を有する構造単位を含有してもしなくてもよいが、含有する場合、酸基を有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは5~80%であり、より好ましくは、アルカリ現像による画像強度のダメージ抑制という観点から、10~60%である。
高分子化合物は、塩基性基を有する構造単位を含有してもしなくてもよいが、含有する場合、塩基性基を有する構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは0.01%以上50%以下であり、より好ましくは、現像性阻害抑制という観点から、0.01%以上30%以下である。
高分子化合物は、配位性基を有する構造単位、または、反応性を有する官能基を有する構造単位を含有してもしなくてもよいが、含有する場合、これらの構造単位の含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは10%以上80%以下であり、より好ましくは、現像性阻害抑制という観点から、20%以上60%以下である。
一般式(iv)~一般式(vi)中、R11、R12、およびR13は、好ましくは、それぞれ独立に水素原子、または炭素数が1~3のアルキル基であり、より好ましくは、それぞれ独立に水素原子またはメチル基である。一般式(iv)中、R12およびR13は、それぞれ水素原子であることが特に好ましい。
また、一般式(v)中のYは、メチン基または窒素原子を表す。
また、一般式(v)で表される単量体として、R11が水素原子またはメチル基であって、L1がアルキレン基であって、Z1がカルボン酸基であって、Yがメチン基である化合物が好ましい。
さらに、一般式(vi)で表される単量体として、R14、R15、およびR16がそれぞれ独立に水素原子またはメチル基であって、L1が単結合またはアルキレン基であって、Zがカルボン酸基である化合物が好ましい。
単量体の例としては、メタクリル酸、クロトン酸、イソクロトン酸、分子内に付加重合性二重結合および水酸基を有する化合物(例えば、メタクリル酸2-ヒドロキシエチル)とコハク酸無水物との反応物、分子内に付加重合性二重結合および水酸基を有する化合物とフタル酸無水物との反応物、分子内に付加重合性二重結合および水酸基を有する化合物とテトラヒドロキシフタル酸無水物との反応物、分子内に付加重合性二重結合および水酸基を有する化合物と無水トリメリット酸との反応物、分子内に付加重合性二重結合および水酸基を有する化合物とピロメリット酸無水物との反応物、アクリル酸、アクリル酸ダイマー、アクリル酸オリゴマー、マレイン酸、イタコン酸、フマル酸、4-ビニル安息香酸、ビニルフェノール、および、4-ヒドロキシフェニルメタクリルアミドなどが挙げられる。
このような、他の構造単位としては、例えば、アクリロニトリル類、および、メタクリロニトリル類などから選ばれるラジカル重合性化合物に由来の構造単位が挙げられる。
高分子化合物は、これらの他の構造単位を1種或いは2種以上用いることができ、その含有量は、質量換算で、高分子化合物の総質量に対して、好ましくは0%以上80%以下であり、特に好ましくは、10%以上60%以下である。含有量が上記範囲において、十分なパターン形成性が維持される。
高分子化合物の酸価が160mgKOH/g以下であれば、硬化膜を形成する際の現像時におけるパターン剥離がより効果的に抑えられる。また、高分子化合物の酸価が10mgKOH/g以上であればアルカリ現像性がより良好となる。また、高分子化合物の酸価が20mgKOH/g以上であれば、黒色顔料等の着色顔料の沈降をより抑制でき、粗大粒子数をより少なくすることができ、組成物の経時安定性をより向上できる。
GPC法は、HLC-8020GPC(東ソー(株)製)を用い、カラムとしてTSKgel SuperHZM-H、TSKgel SuperHZ4000、TSKgel SuperHZ2000(東ソー(株)製、4.6mmID×15cm)を、溶離液としてTHF(テトラヒドロフラン)を用いる方法に基づく。
また、両性樹脂の市販品としては、例えば、ビックケミー社製のDISPERBYK-130、DISPERBYK-140、DISPERBYK-142、DISPERBYK-145、DISPERBYK-180、DISPERBYK-187、DISPERBYK-191、DISPERBYK-2001、DISPERBYK-2010、DISPERBYK-2012、DISPERBYK-2025、BYK-9076、味の素ファインテクノ社製のアジスパーPB821、アジスパーPB822、および、アジスパーPB881等が挙げられる。
これらの高分子化合物は、単独で使用してもよく、2種以上を組み合わせて使用してもよい。
また、上記以外にも、特開2011-153283号公報の段落0028~0084(対応するUS2011/0279759の段落0075~0133欄)の酸性基が連結基を介して結合してなる側鎖構造を有する構成成分を含む高分子化合物が使用でき、これらの内容は援用でき、本明細書に組み込まれる。
分散剤は、1種単独で用いてもよいし、2種以上併用してもよい。2種以上を併用する場合は、合計量が上記範囲となることが好ましい。
なお、組成物中のFe原子の含有量(質量%)は、上述したようにして求められたチタン窒化物含有粒子中のFe原子の含有量(質量%)に、組成物中に含まれるチタン窒化物含有粒子の含有量(質量%)を掛けることで算出できる。
Fe原子の含有量に対する分散剤の含有割合が上記範囲内にあることで、所望の効果が顕著に得られる。特に、上記含有割合が1.5~50の範囲内にあることで、所望の効果がより顕著に得られる。この理由としては、組成物中のFe原子と分散剤とが相互に作用し、パターニング性(硬化性および現像性)に影響を与えていることによると考えられる。
なお、組成物中のFe原子の含有量(質量%)の算出は、上記のように行うことができる。
Fe原子の含有量に対する重合性化合物の含有割合が上記範囲内にあることで、所望の効果が顕著に得られる。特に、上記含有割合が1.0~7.0の範囲内にあることで、所望の効果がより顕著に得られる。この理由としては、組成物中のFe原子と重合性化合物とが相互に作用し、パターニング性(硬化性および現像性)に影響を与えていることによると考えられる。
本発明の組成物は、バインダー樹脂を含有することが好ましい。
バインダー樹脂としては、線状有機ポリマーを用いることが好ましい。このような線状有機ポリマーとしては、公知のものを任意に使用することができる。好ましくは、水現像または弱アルカリ水現像を可能とするために、水または弱アルカリ水に可溶性または膨潤性である線状有機ポリマーが選択される。なかでも、バインダー樹脂としては、アルカリ可溶性樹脂(アルカリ可溶性を促進する基を有する樹脂)が特に好ましい。
バインダー樹脂としては、線状有機ポリマーであって、分子(好ましくは、(メタ)アクリル系共重合体、または、スチレン系共重合体を主鎖とする分子)中に少なくとも1つのアルカリ可溶性を促進する基を有するアルカリ可溶性樹脂の中から適宜選択することができる。耐熱性の観点からは、ポリヒドロキシスチレン系樹脂、ポリシロキサン系樹脂、(メタ)アクリル系樹脂、(メタ)アクリルアミド系樹脂、(メタ)アクリル/(メタ)アクリルアミド共重合体樹脂、エポキシ系樹脂およびポリイミド系樹脂が好ましく、現像性制御の観点からは、(メタ)アクリル系樹脂、(メタ)アクリルアミド系樹脂、(メタ)アクリル/(メタ)アクリルアミド共重合体樹脂およびポリイミド系樹脂が好ましい。
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、カルボキシル基、リン酸基、スルホン酸基、および、フェノール性水酸基などが挙げられる。なかでも、有機溶剤に可溶で弱アルカリ水溶液により現像可能なものが好ましく、(メタ)アクリル酸由来の構造単位を有するアルカリ可溶性樹脂がより好ましいものとして挙げられる。これら酸基は、1種のみであってもよいし、2種以上であってもよい。
また、欧州特許第993966号、欧州特許第1204000号、および、特開2001-318463号等の各公報に記載の酸基を有するアセタール変性ポリビニルアルコール系バインダー樹脂は、膜強度、および、現像性のバランスに優れており、好適である。
さらに、この他に水溶性線状有機ポリマーとして、ポリビニルピロリドンやポリエチレンオキサイド等が有用である。また、硬化皮膜の強度を上げるために、アルコール可溶性ナイロン、および、2,2-ビス-(4-ヒドロキシフェニル)-プロパンとエピクロロヒドリンとの反応物であるポリエーテル等も有用である。
また、国際公開第2008/123097号に記載のポリイミド樹脂も有用である。
市販品としては、例えばアクリベースFF-187、FF-426(藤倉化成社製)、アクリキュア-RD-F8(日本触媒(株))、および、ダイセルオルネクス(株)製サイクロマーP(ACA)230AAなどが挙げられる。
グラフト鎖を有する構造単位の定義は、上述した分散剤が有するグラフト鎖を有する構造単位と同義であり、また好適範囲も同様である。
酸基としては、例えば、カルボン酸基、スルホン酸基、リン酸基、または、フェノール性水酸基などがあり、好ましくは、カルボン酸基、スルホン酸基、および、リン酸基のうち少なくとも1種であり、より好ましいものは、カルボン酸基である。
一般式(vii)~一般式(ix)中、R21、R22、およびR23は、好ましくは、それぞれ独立に水素原子、または炭素数が1~3のアルキル基であり、より好ましくは、それぞれ独立に水素原子またはメチル基である。一般式(vii)中、R21およびR23は、それぞれ水素原子であることが特に好ましい。
また、一般式(viii)中のYは、メチン基または窒素原子を表す。
また、一般式(vii)で表される単量体として、R21が水素原子またはメチル基であって、L2がアルキレン基であって、Z2がカルボン酸基であって、Yがメチン基である化合物が好ましい。
さらに、一般式(ix)で表される単量体として、R24、R25、およびR26がそれぞれ独立に水素原子またはメチル基であって、Z2がカルボン酸基である化合物が好ましい。
酸基を有する構造単位の含有量は、質量換算で、上記バインダー樹脂の総質量に対して、好ましくは5~95%であり、より好ましくは、アルカリ現像による画像強度のダメージ抑制という観点から、10~90%である。
バインダー樹脂は、1種単独で用いてもよいし、2種以上併用してもよい。2種以上を併用する場合は、合計量が上記範囲となることが好ましい。
本発明の組成物は、重合性化合物を含有することが好ましい。
重合性化合物は、エチレン性不飽和結合を有する基を1個以上有する化合物が好ましく、2個以上有する化合物がより好ましく、3個以上有することがさらに好ましく、5個以上有することが特に好ましい。上限は、たとえば、15個以下である。エチレン性不飽和結合を有する基としては、例えば、ビニル基、(メタ)アリル基、および、(メタ)アクリロイル基などが挙げられる。
重合性化合物の分子量は、100~3000が好ましく、250~1500がより好ましい。
重合性化合物は、3~15官能の(メタ)アクリレート化合物であることが好ましく、3~6官能の(メタ)アクリレート化合物であることがより好ましい。
モノマー、プレポリマーの例としては、不飽和カルボン酸(例えば、アクリル酸、メタクリル酸、イタコン酸、クロトン酸、イソクロトン酸、マレイン酸など)やそのエステル類、アミド類、並びにこれらの多量体が挙げられ、好ましくは、不飽和カルボン酸と脂肪族多価アルコール化合物とのエステル、および不飽和カルボン酸と脂肪族多価アミン化合物とのアミド類、並びにこれらの多量体である。また、ヒドロキシル基、アミノ基、メルカプト基等の求核性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能イソシアネート類或いはエポキシ類との付加反応物や、上記不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のカルボン酸との脱水縮合反応物等も好適に使用される。また、イソシアネート基、エポキシ基等の親電子性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との反応物、ハロゲン基やトシルオキシ基等の脱離性置換基を有する不飽和カルボン酸エステル或いはアミド類と、単官能若しくは多官能のアルコール類、アミン類、チオール類との反応物も好適である。また、上記の不飽和カルボン酸の代わりに、不飽和ホスホン酸、スチレン等のビニルベンゼン誘導体、ビニルエーテル、アリルエーテル等に置き換えた化合物群を使用することも可能である。
これらの具体的な化合物としては、特開2009-288705号公報の段落〔0095〕~〔0108〕に記載されている化合物を本発明においても好適に用いることができる。
以下に好ましい重合性化合物の態様を示す。
カプロラクトン構造を有する化合物としては、分子内にカプロラクトン構造を有する限り特に限定されないが、例えば、トリメチロールエタン、ジトリメチロールエタン、トリメチロールプロパン、ジトリメチロールプロパン、ペンタエリスリトール、ジペンタエリスリトール、トリペンタエリスリトール、グリセリン、ジグリセロール、トリメチロールメラミン等の多価アルコールと、(メタ)アクリル酸およびε-カプロラクトンとをエステル化することにより得られる、ε-カプロラクトン変性多官能(メタ)アクリレートを挙げることができる。なかでも下記一般式(Z-1)で表されるカプロラクトン構造を有する化合物が好ましい。
-、または-((CH2)yCH(CH3)O)-を表し、yは、各々独立に0~10の整数を表し、Xは、各々独立に、(メタ)アクリロイル基、水素原子、またはカルボキシル基を表す。
一般式(Z-4)中、(メタ)アクリロイル基の合計は3個または4個であり、mは各々独立に0~10の整数を表し、各mの合計は0~40の整数である。
一般式(Z-5)中、(メタ)アクリロイル基の合計は5個または6個であり、nは各々独立に0~10の整数を表し、各nの合計は0~60の整数である。
また、各mの合計は、2~40の整数が好ましく、2~16の整数がより好ましく、4~8の整数がさらに好ましい。
一般式(Z-5)中、nは、0~6の整数が好ましく、0~4の整数がより好ましい。
また、各nの合計は、3~60の整数が好ましく、3~24の整数がより好ましく、6~12の整数がさらに好ましい。
また、一般式(Z-4)または一般式(Z-5)中の-((CH2)yCH2O)-または-((CH2)yCH(CH3)O)-は、酸素原子側の末端がXに結合する形態が好ましい。
具体的には、下記式(a)~(f)で表される化合物(以下、「例示化合物(a)~(f)」とも称する。)が挙げられ、中でも、例示化合物(a)、(b)、(e)、(f)が好ましい。
市販品としては、ウレタンオリゴマーUAS-10、UAB-140(山陽国策パルプ社製)、UA-7200(新中村化学社製)、DPHA-40H(日本化薬社製)、UA-306H、UA-306T、UA-306I、AH-600、T-600、および、AI-600(共栄社製)などが挙げられる。
なお、本明細書においてSP値は、特に断らない限り、Hoy法によって求める(H.L.Hoy Journal of Painting,1970,Vol.42,76-118)。また、SP値については単位を省略して示しているが、その単位はcal1/2cm-3/2である。
カルド骨格を有する重合性化合物としては、9,9-ビスアリールフルオレン骨格を有する重合性化合物が好ましく、下記式(Q3)で表される化合物がより好ましい。
X1~X4が表す重合性基を有する脂肪族基としては、特に制限はないが、重合性基以外における炭素数が1~12のアルキレン基であることが好ましく、炭素数2~10のアルキレン基であることがより好ましく、炭素数2~5のアルキレン基であることがさらに好ましい。
また、X1~X4が表す重合性基を有する脂肪族基において、上記脂肪族基がヘテロ原子によって置換される場合は、-NR-(Rは置換基)、酸素原子、硫黄原子によって置換されていることが好ましく、上記脂肪族基中の隣り合わない-CH2-が酸素原子または硫黄原子で置換されていることがより好ましく、上記脂肪族基中の隣り合わない-CH2-が酸素原子で置換されていることがさらに好ましい。X1~X4が表す重合性基を有する脂肪族基は、ヘテロ原子によって1~2箇所置換されていることが好ましく、ヘテロ原子によって1箇所置換されていることがより好ましく、Ar11~Ar14が表す破線で囲まれたベンゼン環を含むアリール基に隣接する1箇所がヘテロ原子によって置換されていることがさらに好ましい。
X1~X4が表す重合性基を有する脂肪族基に含まれる重合性基としては、ラジカル重合またはカチオン重合可能な重合性基(以下、それぞれラジカル重合性基およびカチオン重合性基とも言う)が好ましい。
ラジカル重合性基としては、一般に知られているラジカル重合性基を用いることができ、好適なものとしてラジカル重合可能なエチレン性不飽和結合を有する重合性基を挙げることができ、具体的にはビニル基、(メタ)アクリロイルオキシ基などを挙げることができる。中でも、(メタ)アクリロイルオキシ基が好ましく、アクリロイルオキシ基がより好ましい。
カチオン重合性基としては、一般に知られているカチオン重合性基を用いることができ、具体的には、脂環式エーテル基、環状アセタール基、環状ラクトン基、環状チオエーテル基、スピロオルソエステル基、ビニルオキシ基などを挙げることができる。中でも、脂環式エーテル基、ビニルオキシ基が好適であり、エポキシ基、オキセタニル基、ビニルオキシ基が特に好ましい。
Ar1~Ar4が含む置換基が有する上記重合性基は、ラジカル重合性基であることが好ましい。
Ar1~Ar4のうち2つ以上は重合性基を有する置換基を含み、Ar1~Ar4のうち2~4個が重合性基を有する置換基を含むことが好ましく、Ar1~Ar4のうち2または3個が重合性基を有する置換基を含むことがより好ましく、Ar1~Ar4のうち2個が重合性基を有する置換基を含むことがさらに好ましい。
Ar11~Ar14がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含む多環芳香族炭化水素基である場合は、X1~X4はそれぞれ独立に破線で囲まれたベンゼン環に置換していても、破線で囲まれたベンゼン環以外の環に置換していてもよい。
上記一般式(Q3)中、cおよびdはそれぞれ独立に0~5の整数を表し、0または1であることが好ましく、cおよびdがいずれも0であることがより好ましい。
上記一般式(Q3)中、Ar11~Ar14がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含む多環芳香族炭化水素基である場合は、R1~R4はそれぞれ独立に破線で囲まれたベンゼン環に置換していても、破線で囲まれたベンゼン環以外の環に置換していてもよい。
e、f、gおよびhはそれぞれ独立に0~8であることが好ましく、0~2であることがより好ましく、0であることがさらに好ましい。
Ar11~Ar14がそれぞれ独立に破線で囲まれたベンゼン環を縮合環のひとつとして含む多環芳香族炭化水素基である場合、e、f、gおよびhは0または1であることが好ましく、0であることがより好ましい。
重合性化合物は、1種単独であってもよいし、2種以上を併用してもよい。2種以上を併用する場合は、合計量が上記範囲となることが好ましい。
本発明の組成物は、重合開始剤を含有することが好ましい。
重合開始剤としては特に制限はなく、公知の重合開始剤の中から適宜選択することができ、例えば、感光性を有するもの(いわゆる、光重合開始剤)が好ましい。
本発明の組成物は、チタン窒化物含有粒子の他に、光重合開始剤および上述した重合性化合物を含有する場合には、活性光線または放射線の照射により硬化することから、「感光性組成物」と呼ばれることがある。
光重合開始剤としては、重合性化合物の重合を開始する能力を有する限り、特に制限はなく、公知の光重合開始剤の中から適宜選択することができる。例えば、紫外線領域から可視の光線に対して感光性を有するものが好ましい。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活性剤であってもよく、モノマーの種類に応じてカチオン重合を開始させるような開始剤であってもよい。
また、光重合開始剤は、約300nm~800nm(330nm~500nmがより好ましい。)の範囲内に少なくとも約50のモル吸光係数を有する化合物を、少なくとも1種含有していることが好ましい。
光重合開始剤の具体例としては、例えば、特開2013-29760号公報の段落0265~0268を参酌することができ、この内容は本明細書に組み込まれる。
ヒドロキシアセトフェノン系開始剤としては、IRGACURE-184、DAROCUR-1173、IRGACURE-500、IRGACURE-2959,IRGACURE-127(商品名:いずれもBASF社製)を用いることができる。
アミノアセトフェノン系開始剤としては、市販品であるIRGACURE-907、IRGACURE-369、および、IRGACURE-379EG(商品名:いずれもBASF社製)を用いることができる。アミノアセトフェノン系開始剤は、365nmまたは405nm等の長波光源に吸収波長がマッチングされた特開2009-191179公報に記載の化合物も用いることができる。
アシルホスフィン系開始剤としては、市販品であるIRGACURE-819やDAROCUR-TPO(商品名:いずれもBASF社製)を用いることができる。
オキシム化合物の具体例としては、特開2001-233842号公報記載の化合物、特開2000-80068号公報記載の化合物、特開2006-342166号公報記載の化合物を用いることができる。
本発明において、好適に用いることのできるオキシム化合物としては、例えば、3-ベンゾイロキシイミノブタン-2-オン、3-アセトキシイミノブタン-2-オン、3-プロピオニルオキシイミノブタン-2-オン、2-アセトキシイミノペンタン-3-オン、2-アセトキシイミノ-1-フェニルプロパン-1-オン、2-ベンゾイロキシイミノ-1-フェニルプロパン-1-オン、3-(4-トルエンスルホニルオキシ)イミノブタン-2-オン、および2-エトキシカルボニルオキシイミノ-1-フェニルプロパン-1-オンなどが挙げられる。
また、J.C.S.Perkin II(1979年)pp.1653-1660)、J.C.S.Perkin II(1979年)pp.156-162、Journal of Photopolymer Science and Technology(1995年)pp.202-232、特開2000-66385号公報記載の化合物、特開2000-80068号公報、特表2004-534797号公報、特開2006-342166号公報の各公報に記載の化合物等も挙げられる。
市販品ではIRGACURE-OXE01(BASF社製)、IRGACURE-OXE02(BASF社製)も好適に用いられる。また、TR-PBG-304(常州強力電子新材料有限公司社製)、アデカアークルズNCI-831およびアデカアークルズNCI-930(ADEKA社製)、N-1919(カルバゾール・オキシムエステル骨格含有光開始剤(ADEKA社製)も用いることができる。
好ましくは、例えば、特開2013-29760号公報の段落0274~0275を参酌することができ、この内容は本明細書に組み込まれる。
具体的には、オキシム化合物としては、下記式(OX-1)で表される化合物が好ましい。なお、オキシムのN-O結合が(E)体のオキシム化合物であっても、(Z)体のオキシム化合物であっても、(E)体と(Z)体との混合物であってもよい。
一般式(OX-1)中、Rで表される一価の置換基としては、一価の非金属原子団であることが好ましい。
一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または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。
一般式(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。
一般式(OX-1)中、Aで表される二価の有機基としては、炭素数1~12のアルキレン基、シクロアルキレン基、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。
式(1)および式(2)で表される化合物の具体例としては、例えば、特開2014-137466号公報の段落番号0076~0079に記載された化合物が挙げられる。この内容は本明細書に組み込まれることとする。
オキシム化合物は、365nmまたは405nmにおけるモル吸光係数は、感度の観点から、1,000~300,000であることが好ましく、2,000~300,000であることがより好ましく、5,000~200,000であることが特に好ましい。
化合物のモル吸光係数は、公知の方法を用いることができるが、例えば、紫外可視分光光度計(Varian社製Cary-5 spctrophotometer)にて、酢酸エチル溶媒を用い、0.01g/Lの濃度で測定することが好ましい。
本発明に用いられる光重合開始剤は、必要に応じて2種以上を組み合わせて使用してもよい。
本発明の組成物は、有機溶剤を含有することが好ましい。
有機溶剤の例としては、例えば、アセトン、メチルエチルケトン、シクロヘキサン、酢酸エチル、エチレンジクロライド、テトラヒドロフラン、トルエン、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、アセチルアセトン、シクロヘキサノン、シクロペンタノン、ジアセトンアルコール、エチレングリコールモノメチルエーテルアセテート、エチレングリコールエチルエーテルアセテート、エチレングリコールモノイソプロピルエーテル、エチレングリコールモノブチルエーテルアセテート、3-メトキシプロパノール、メトキシメトキシエタノール、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールジエチルエーテル、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、3-メトキシプロピルアセテート、N,N-ジメチルホルムアミド、ジメチルスルホキシド、γ-ブチロラクトン、酢酸エチル、酢酸ブチル、乳酸メチル、および、乳酸エチルなどが挙げられるが、これらに限定されない。
2種以上の有機溶剤を含有する場合には、上記の3-エトキシプロピオン酸メチル、3-エトキシプロピオン酸エチル、エチルセロソルブアセテート、乳酸エチル、ジエチレングリコールジメチルエーテル、酢酸ブチル、3-メトキシプロピオン酸メチル、2-ヘプタノン、シクロヘキサノン、シクロペンタノン、エチルカルビトールアセテート、ブチルカルビトールアセテート、プロピレングリコールモノメチルエーテル、およびプロピレングリコールモノメチルエーテルアセテートからなる群から選択される2種以上で構成されることが好ましい。
本発明の組成物は、水を含有してもよい。水は、意図的に添加されるものであってもよいし、本発明の組成物に含まれる各成分を添加することで不可避的に組成物中に含有されるものであってもよい。
水の含有量は、組成物100質量%に対して、0.01~1質量%であることが好ましく、0.05~0.8質量%であることがより好ましく、0.1~0.7質量%であることがさらに好ましい。水の含有量が上記範囲内にあることで、硬化膜を作製したときのピンホールの発生を抑制できたり、硬化膜の耐湿性が向上したりする。
本発明の組成物中には、上述した成分以外の他の成分が含まれていてもよい。
以下、各成分について詳述する。
本発明の組成物は、上述したチタン窒化物含有粒子以外の着色剤(以下、単に「着色剤」ともいう。)を用いることもできる。着色剤は、例えば、組成物の色度調整のために用いられ、OD値が低下しない範囲で、チタン窒化物の一部を着色剤に置き換えることが可能である。このような着色剤としては、顔料(黒色有機顔料および有彩色の有機顔料の有機顔料、ならびに、無機顔料)および染料などが挙げられる。
顔料としては、従来公知の種々の顔料を挙げることができる。
有彩色の有機顔料として、以下のものを挙げることができる。但し本発明は、これらに限定されない。
カラーインデックス(C.I.)ピグメントイエロー1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214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等、
C.I.ピグメントグリーン 7,10,36,37,58,59等
C.I.ピグメントバイオレット 1,19,23,27,32,37,42等
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等
これら有機顔料は、単独若しくは色純度を上げるため種々組合せて用いることができる。
チタンブラックの市販品の例としては、チタンブラック10S、12S、13R、13M、13M-C、13R、13R-N、13M-T(商品名:三菱マテリアル(株)製)、ティラック(Tilack)D(商品名:赤穂化成(株)製)などが挙げられる。
この形態において、チタンブラックは、組成物中において被分散体として含有されるものであり、被分散体中のSi原子とTi原子との含有比(Si/Ti)が質量換算で0.05以上が好ましく、0.05~0.5がより好ましく、0.07~0.4がさらに好ましい。
ここで、上記被分散体は、チタンブラックが一次粒子の状態であるもの、凝集体(二次粒子)の状態であるものの双方を包含する。
被分散体のSi/Tiを変更する(例えば、0.05以上とする)ためには、以下のような手段を用いることができる。
先ず、酸化チタンとシリカ粒子とを分散機を用いて分散することにより分散物を得て、この分散物を高温(例えば、850~1000℃)にて還元処理することにより、チタンブラック粒子を主成分とし、SiとTiとを含有する被分散体を得ることができる。上記還元処理は、アンモニアなどの還元性ガスの雰囲気下で行うこともできる。
酸化チタンとしては、TTO-51N(商品名:石原産業製)などが挙げられる。
プラズマ法によって作成された酸化チタンは、その粒径が市販の酸化チタン微粒子よりも小さいことから好適に使用できる(日本金属学会誌第63巻第1号(1999)74-81の記載を参照)。
シリカ粒子の市販品としては、AEROSIL(登録商標)90、130、150、200、255、300、380(商品名:エボニック製)などが挙げられる。
酸化チタンとシリカ粒子との分散は、分散剤を用いてもよい。分散剤としては、後述する分散剤の欄で説明するものが挙げられる。
上記の分散は溶剤中で行ってもよい。溶剤としては、水、有機溶剤が挙げられる。後述する有機溶剤の欄で説明するものが挙げられる。
Si/Tiが、例えば、0.05以上等に調整されたチタンブラックは、例えば、特開2008-266045号公報の段落番号〔0005〕および段落番号〔0016〕~〔0021〕に記載の方法により作製することができる。
残渣物が低減される理由は未だ明確ではないが、上記のような被分散体は小粒径となる傾向があり(例えば、粒径が30nm以下)、さらに、この被分散体のSi原子が含まれる成分が増すことにより、膜全体の下地との吸着性が低減され、これが、遮光膜の形成における未硬化の組成物(特に、チタンブラック)の現像除去性の向上に寄与すると推測している。
また、チタンブラックは、紫外光から赤外光までの広範囲に亘る波長領域の光に対する遮光性に優れることから、上記したチタンブラックおよびSi原子を含む被分散体(好ましくはSi/Tiが質量換算で0.05以上であるもの)を用いて形成された遮光膜は優れた遮光性を発揮する。
なお、被分散体中のSi原子とTi原子との含有比(Si/Ti)は、例えば、特開2013-249417号公報の段落0033に記載の方法(1-1)または方法(1-2)を用いて測定できる。
また、組成物を硬化して得られた遮光膜に含有される被分散体について、その被分散体中のSi原子とTi原子との含有比(Si/Ti)が0.05以上か否かを判断するには、特開2013-249417号公報の段落0035に記載の方法(2)を用いる。
また、この被分散体においては、チタンブラックと共に、分散性、着色性等を調整する目的で、Cu、Fe、Mn、V、Ni等の複合酸化物、酸化コバルト、酸化鉄、カーボンブラック、アニリンブラック等からなる黒色顔料を、1種または2種以上を組み合わせて、被分散体として併用してもよい。
この場合、全被分散体中の50質量%以上をチタンブラックからなる被分散体が占めることが好ましい。
また、この被分散体においては、遮光性の調整等を目的として、本発明の効果を損なわない限りにおいて、チタンブラックと共に、他の着色剤(有機顔料や染料など)を所望により併用してもよい。
以下、被分散体にSi原子を導入する際に用いられる材料について述べる。被分散体にSi原子を導入する際には、シリカなどのSi含有物質を用いればよい。
用いうるシリカとしては、沈降シリカ、フュームドシリカ、コロイダルシリカ、合成シリカなどを挙げることができ、これらを適宜選択して使用すればよい。
さらに、シリカ粒子の粒径が遮光膜を形成した際に膜厚よりも小さい粒径であると遮光性がより優れるため、シリカ粒子として微粒子タイプのシリカを用いることが好ましい。なお、微粒子タイプのシリカの例としては、例えば、特開2013-249417号公報の段落0039に記載のシリカが挙げられ、これらの内容は本明細書に組み込まれる。
タングステン化合物、および金属ホウ化物は、赤外線(波長が約800~1200nmの光)に対しては吸収が高く(すなわち、赤外線に対する遮光性(遮蔽性)が高く)、可視光に対しては吸収が低い赤外線遮蔽材である。このため、本発明の感光性組成物は、タングステン化合物、および/または金属ホウ化物を含有することで、赤外領域における遮光性が高く、可視光領域における透光性が高いパターンを形成できる。
また、タングステン化合物、および金属ホウ化物は、画像形成に用いられる、高圧水銀灯、KrFおよびArFなどの露光に用いられる可視域より短波の光に対しても吸収が小さい。
MxWyOz・・・(I)
Mは金属、Wはタングステン、Oは酸素を表す。
0.001≦x/y≦1.1
2.2≦z/y≦3.0
z/yが2.2以上であることにより、材料としての化学的安定性をより向上させることができ、3.0以下であることにより赤外線を十分に遮蔽することができる。
また、酸化タングステン系化合物は、例えば、住友金属鉱山株式会社製のYMF-02などのタングステン微粒子の分散物としても、入手可能である。
染料としては、例えば特開昭64-90403号公報、特開昭64-91102号公報、特開平1-94301号公報、特開平6-11614号公報、特登2592207号、米国特許4808501号明細書、米国特許5667920号明細書、米国特許505950号明細書、米国特許5667920号明細書、特開平5-333207号公報、特開平6-35183号公報、特開平6-51115号公報、特開平6-194828号公報等に開示されている色素を使用できる。化学構造として区分すると、ピラゾールアゾ化合物、ピロメテン化合物、アニリノアゾ化合物、トリフェニルメタン化合物、アントラキノン化合物、ベンジリデン化合物、オキソノール化合物、ピラゾロトリアゾールアゾ化合物、ピリドンアゾ化合物、シアニン化合物、フェノチアジン化合物、ピロロピラゾールアゾメチン化合物等を使用できる。また、染料としては色素多量体を用いてもよい。色素多量体としては、特開2011-213925号公報、特開2013-041097号公報に記載されている化合物が挙げられる。
本発明の組成物は、顔料誘導体を含有することができる。顔料誘導体としては、例えば、有機顔料の一部分を、酸性基、塩基性基又はフタルイミドメチル基で置換した構造を有する化合物が挙げられる。
顔料誘導体を構成するための有機顔料としては、ジケトピロロピロール系顔料、アゾ系顔料、フタロシアニン系顔料、アントラキノン系顔料、キナクリドン系顔料、ジオキサジン系顔料、ペリノン系顔料、ペリレン系顔料、チオインジゴ系顔料、イソインドリン系顔料、イソインドリノン系顔料、キノフタロン系顔料、スレン系顔料、金属錯体系顔料等が挙げられる。
また、顔料誘導体が有する酸性基としては、スルホン酸基、カルボン酸基及びその4級アンモニウム塩基が好ましく、カルボン酸基及びスルホン酸基がさらに好ましく、スルホン酸基が特に好ましい。顔料誘導体が有する塩基性基としては、アミノ基が好ましく、特に三級アミノ基が好ましい。
顔料誘導体の具体例としては、例えば下記化合物が挙げられる。また、特開2011-252065号公報の段落0162~0183の記載を参酌でき、この内容は本明細書に組み込まれる。
シランカップリング剤とは、分子中に加水分解性基とそれ以外の官能基を有する化合物である。なお、アルコキシ基等の加水分解性基は、珪素原子に結合している。
加水分解性基とは、珪素原子に直結し、加水分解反応および/または縮合反応によってシロキサン結合を生じ得る置換基をいう。加水分解性基としては、例えば、ハロゲン原子、アルコキシ基、アシルオキシ基、アルケニルオキシ基が挙げられる。加水分解性基が炭素原子を有する場合、その炭素数は6以下であることが好ましく、4以下であることがより好ましい。特に、炭素数4以下のアルコキシ基または炭素数4以下のアルケニルオキシ基が好ましい。
また、シランカップリング剤は基板と硬化膜間の密着性を向上させるため、フッ素原子および珪素原子(ただし、加水分解性基が結合した珪素原子は除く)を含まないことが好ましく、フッ素原子、珪素原子(ただし、加水分解性基が結合した珪素原子は除く)、珪素原子で置換されたアルキレン基、炭素数8以上の直鎖アルキル基、および、炭素数3以上の分鎖アルキル基は含まないことが望ましい。
式(Z) *-Si-(RZ1)3
式(Z)中、RZ1は加水分解性基を表し、その定義は上述の通りである。
なお、上記シランカップリング剤に含まれる硬化性官能基の好適態様としては、ラジカル重合性基も挙げられる。
式(W) RZ2-Lz-Si-(RZ1)3
Rz1は、加水分解性基を表し、定義は上述の通りである。
Rz2は、硬化性官能基を表し、定義は上述のとおりであり、好適範囲も上述の通りである。
Lzは、単結合または2価の連結基を表す。Lzが2価の連結基を表す場合、2価の連結基としては、ハロゲン原子が置換していてもよいアルキレン基、ハロゲン原子が置換していてもよいアリーレン基、-NR12-、-CONR12-、-CO-、-CO2-、SO2NR12-、-O-、-S-、-SO2-、または、これらの組み合わせが挙げられる。なかでも、炭素数2~10のハロゲン原子が置換していてもよいアルキレン基および炭素数6~12のハロゲン原子が置換していてもよいアリーレン基からなる群から選択される少なくとも1種、または、これらの基と-NR12-、-CONR12-、-CO-、-CO2-、SO2NR12-、-O-、-S-、およびSO2-からなる群から選択される少なくとも1種の基との組み合わせからなる基が好ましく、炭素数2~10のハロゲン原子が置換していてもよいアルキレン基、-CO2-、-O-、-CO-、-CONR12-、または、これらの基の組み合わせからなる基がより好ましい。ここで、上記R12は、水素原子またはメチル基を表す。
このシランカップリング剤Yは、分子内に少なくとも1つの珪素原子を有すればよく、珪素原子は、以下の原子、置換基と結合できる。それらは同じ原子、置換基であっても異なっていてもよい。結合しうる原子、置換基は、水素原子、ハロゲン原子、水酸基、炭素数1から20のアルキル基、アルケニル基、アルキニル基、アリール基、アルキル基および/またはアリール基で置換可能なアミノ基、シリル基、炭素数1から20のアルコキシ基、アリーロキシ基などが挙げられる。これらの置換基はさらに、シリル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、チオアルコキシ基、アルキル基および/またはアリール基で置換可能なアミノ基、ハロゲン原子、スルホンアミド基、アルコキシカルボニル基、アミド基、ウレア基、アンモニウム基、アルキルアンモニウム基、カルボキシル基、またはその塩、スルホ基、またはその塩などで置換されていてもよい。
なお、珪素原子には少なくとも一つの加水分解性基が結合している。加水分解性基の定義は、上述の通りである。
シランカップリング剤Yには、式(Z)で表される基が含まれていてもよい。
ここで、有機基としては、アルキル基、アルケニル基、アルキニル基、アリール基、または、これらの組み合わせなどが挙げられる。これらはさらに置換基を有してもよく、導入可能な置換基としては、シリル基、アルケニル基、アルキニル基、アリール基、アルコキシ基、アリーロキシ基、チオアルコキシ基、アミノ基、ハロゲン原子、スルホンアミド基、アルコキシカルボニル基、カルボニルオキシ基、アミド基、ウレア基、アルキレンオキシ基アンモニウム基、アルキルアンモニウム基、カルボキシル基、またはその塩、スルホ基などが挙げられる。
また、窒素原子は、任意の有機連結基を介して硬化性官能基と結合していることが好ましい。好ましい有機連結基としては、上述の窒素原子およびそれに結合する有機基に導入可能な置換基を挙げることができる。
シランカップリング剤Yには、硬化性官能基は一分子中に少なくとも一つ以上有していればよいが、硬化性官能基を2以上有する態様をとることも可能であり、感度、安定性の観点からは、硬化性官能基を2~20有することが好ましく、4~15有することがさらに好ましく、最も好ましくは分子内に硬化性官能基を6~10有する態様である。
本発明の組成物には、紫外線吸収剤が含まれていてもよい。これにより、パターンの形状をより優れた(精細な)ものにすることができる。
紫外線吸収剤としては、サリシレート系、ベンゾフェノン系、ベンゾトリアゾール系、置換アクリロニトリル系、トリアジン系の紫外線吸収剤を使用することができる。これらの具体例としては、特開2012-068418号公報の段落0137~0142(対応するUS2012/0068292の段落0251~0254)の化合物が使用でき、これらの内容が援用でき、本明細書に組み込まれる。
他にジエチルアミノ-フェニルスルホニル系紫外線吸収剤(大東化学製、商品名:UV-503)なども好適に用いられる。
紫外線吸収剤としては、特開2012-32556号公報の段落0134~0148に例示される化合物が挙げられる。
本発明の組成物は、紫外線吸収剤を含んでも含まなくてもよいが、含む場合、紫外線吸収剤の含有量は、組成物の全固形分に対して、0.001~15質量%が好ましく、0.01~10質量%がより好ましく、0.1~5質量%がさらに好ましい。
本発明の組成物は、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は、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。
また、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0050~0090段落および0289~0295段落に記載された化合物、例えばDIC社製のメガファックRS-101、RS-102、RS-718K、RS-72-K等が挙げられる。
本発明の組成物は、重合禁止剤を含有してもよい。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第一セリウム塩等が挙げられる。
本発明の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、組成物の全固形分に対して、0.01~5質量%が好ましい。本発明の組成物は、重合禁止剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
また必要に応じて、酸素による重合阻害を防止するためにベヘン酸やベヘン酸アミドのような高級脂肪酸誘導体等を添加して、塗布後の乾燥の過程で塗布膜の表面に偏在させてもよい。高級脂肪酸誘導体の添加量を含有する場合、高級脂肪酸誘導体の含有量は、組成物の全固形分に対して、0.5~10質量%が好ましい。
これらの成分は、例えば、特開2012-003225号公報の段落番号0183~0228(対応する米国特許出願公開第2013/0034812号明細書の<0237>~<0309>)、特開2008-250074号公報の段落番号0101~0102、段落番号0103~0104、段落番号0107~0109、特開2013-195480号公報の段落番号0159~0184等の記載を参酌でき、これらの内容は本明細書に組み込まれる。
本発明の組成物は、上述した各種成分を公知の混合方法(例えば、攪拌機、ホモジナイザー、高圧乳化装置、湿式粉砕機、湿式分散機)により混合して製造することができる。
組成物の製造に際しては、組成物を構成する各種成分を一括配合してもよいし、各種成分を有機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および作業条件は、特に制約を受けない。
また、顔料を分散させるプロセスにおいて、顔料の分散に用いる機械力としては、圧縮、圧搾、衝撃、剪断およびキャビテーションなどが挙げられる。これらプロセスの具体例としては、ビーズミル、サンドミル、ロールミル、高速インペラー、サンドグラインダー、フロージェットミキサー、高圧湿式微粒化および超音波分散などが挙げられる。また、「分散技術大全、株式会社情報機構発行、2005年7月15日」および「サスペンション(固/液分散系)を中心とした分散技術と工業的応用の実際 総合資料集、経営開発センター出版部発行、1978年10月10日」に記載のプロセスおよび分散機を好適に使用することができる。
また、顔料を分散させるプロセスにおいては、ソルトミリング工程による顔料の微細化処理を行ってもよい。ソルトミリング工程に用いられる素材、機器および処理条件等は、例えば、特開2015-194521号および特開2012-046629号に記載のものを使用することができる。
また、本発明の組成物の製造方法は、熱プラズマ法によって上記チタン窒化物含有粒子を得る工程を含むことが好ましい。チタン窒化物含有粒子を得る工程は、上述した各種成分を混合する前に実施される。熱プラズマ法によるチタン窒化物含有微粒子の具体的な製造工程は、上述のチタン窒化物含有粒子の項で説明した通りであるので、その説明を省略する。
さらに、熱プラズマ法によって得られた窒化チタン含有粒子は、窒化チタン含有粒子を製造した後(すなわち、熱プラズマ処理の後)に直ちに大気に曝すことなく、酸素濃度が制御された密閉容器内において、所定時間(好ましくは12~72時間、より好ましくは12~48時間、さらに好ましくは12~24時間)静置されて得られたものであることが好ましい。また、密閉容器内における水分の含有量が制御されているとより好ましく、これにより、熱プラズマ処理された窒化チタン含有粒子の表面および結晶粒界が安定となり、組成物の性能が良化するものと推測される。具体的には、本発明の組成物を用いて得られる硬化膜のピンホールの発生を抑制できる。
密閉容器内における酸素(O2)濃度および水分の含有量が、それぞれ100ppm以下であることが好ましく、10ppm以下であることがより好ましく、1ppm以下であることがさらに好ましい。
密閉容器内における酸素(O2)濃度および水分の含有量は、密閉容器内に供給する不活性ガス中の酸素濃度および水分量を調整することによって行うことができる。不活性ガスとしては、窒素ガスおよびアルゴンガスが好ましく用いられ、この中でも窒素ガスを用いることがより好ましい。これにより、熱プラズマ処理された窒化チタン含有粒子の表面および結晶粒界が安定となり、組成物の性能が良化するものと推測される。具体的には、本発明の組成物を用いて得られる硬化膜のピンホールの発生を抑制できる。
本発明の組成物は、異物の除去や欠陥の低減などの目的で、フィルタでろ過することが好ましい。フィルタとしては、従来からろ過用途等に用いられているものであれば特に限定されることなく用いることができる。例えば、PTFE(ポリテトラフルオロエチレン)等のフッ素樹脂、ナイロン等のポリアミド系樹脂、ポリエチレン、ポリプロピレン(PP)等のポリオレフィン樹脂(高密度、超高分子量を含む)等によるフィルタが挙げられる。これら素材の中でもポリプロピレン(高密度ポリプロピレンを含む)、ナイロンが好ましい。
フィルタの孔径は、0.1~7.0μm程度が適しており、好ましくは0.2~2.5μm程度、より好ましくは0.2~1.5μm程度、さらに好ましくは0.3~0.7μmである。この範囲とすることにより、顔料のろ過詰まりを抑えつつ、顔料に含まれる不純物や凝集物など、微細な異物を確実に除去することが可能となる。
フィルタを使用する際、異なるフィルタを組み合わせてもよい。その際、第1のフィルタでのフィルタリングは、1回のみでもよいし、2回以上行ってもよい。異なるフィルタを組み合わせて2回以上フィルタリングを行う場合は1回目のフィルタリングの孔径より2回目以降の孔径が同じ、または、大きい方が好ましい。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、日本ポール株式会社、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)または株式会社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。第2のフィルタの孔径は、0.2~10.0μm程度が適しており、好ましくは0.2~7.0μm程度、さらに好ましくは0.3~6.0μm程度である。
本発明の硬化膜は、上述した組成物を用いて得られる。本発明の硬化膜には、上述したチタン窒化物含有粒子が主に含まれる。本発明の硬化膜は、遮光膜として好適に用いられ、具体的にはイメージセンサの受光部周辺部分の遮光に好適に用いられる。
以下、硬化膜がイメージセンサの受光部周辺部分の遮光膜として使用された場合を一例として説明する。
本発明の遮光膜は、上述した組成物(特に、上述した感光性組成物)を用いて形成されたものである。本発明の組成物を用いて得られる遮光膜は、パターニング性および電極の防食性に優れる。
遮光膜のサイズ(センサー受光部周辺に設けられた遮光膜の一辺の長さ)としては、本発明による効果をより効果的に得る観点からは、0.001mm以上10mm以下が好ましく、0.05mm以上7mm以下がより好ましく、0.1mm以上3.5mm以下がさらに好ましい。本発明の組成物は単位体積あたりの光学濃度が高いため、塗布量が減らせるなど、微細加工に有利であり、かつ、パターニング性および電極の防食性に優れるため、上記の範囲で特に好ましく用いることができる。
次に、本発明の硬化膜(遮光膜)の製造方法の一例として、ブラックマトリクスを有するカラーフィルタおよびその製造方法を用いて説明する。
本発明のブラックマトリクスを有するカラーフィルタは、基板上に、上述した組成物を用いて得られる硬化膜(ブラックマトリクス)を有することを特徴とする。
以下、本発明のブラックマトリクスを有するカラーフィルタについて、その製造方法を通じて詳述する。
以下、本発明のブラックマトリクスを有するカラーフィルタの製造方法における各工程について説明する。
組成物層形成工程では、基板上に、本発明の組成物を塗布して組成物層(塗布膜)を形成する。
また、これらの基板上には、必要により、上部の層との密着改良、物質の拡散防止或いは基板表面の平坦化のために下塗り層を設けてもよい。
露光工程では、組成物層形成工程において形成された組成物層(塗布膜)を、マスクを介して露光し、光照射された塗布膜部分だけを硬化させる。
露光は、活性光線または放射線の照射により行うことが好ましく、特に、g線、h線、i線等の紫外線が好ましく用いられ、高圧水銀灯がより好まれる。照射強度は5~1500mJ/cm2が好ましく10~1000mJ/cm2がより好ましい。また、解像性向上の観点から固体撮像素子用の遮光膜形成では、i線ステッパーによる露光が好ましい。
露光工程に次いで、アルカリ現像処理(現像工程)を行い、露光工程における光未照射部分をアルカリ水溶液に溶出させる。これにより、光硬化した部分(光照射された塗布膜部分)だけが残る。
現像液としては、固体撮像素子用のブラックマトリクスを有する遮光性カラーフィルタを作製する場合には、下地の回路などにダメージを起さない、有機アルカリ現像液が望ましい。現像温度としては通常20~30℃であり、現像時間は20~90秒である。
したがって、液晶表示装置およびCCD等の固体撮像素子に好適に用いることができ、特に100万画素を超えるような高解像度のCCD素子やCMOS等に好適である。すなわち、本発明の硬化膜を備えたカラーフィルタは、固体撮像素子に適用されることが好ましい。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を有していてもよい。
本発明の硬化膜(ブラックマトリクス)は、例えば、CCDまたはCMOSを構成する各画素の受光部と集光するためのマイクロレンズとの間に配置される。
本発明の固体撮像素子は、上述した本発明に係る硬化膜(ブラックマトリクス)を有する。本発明の固体撮像素子は、ブラックマトリクスと、必要により他の色(3色あるいは4色)の画素からなるパターン状皮膜と、を有するカラーフィルタを備えて構成されることが好ましい。
本発明の固体撮像素子の構成としては、本発明のブラックマトリクスが備えられた構成であり、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、基板上に、固体撮像素子(CCDイメージセンサ、CMOSイメージセンサ等)の受光エリアを構成する複数のフォトダイオードおよびポリシリコン等からなる受光素子を有し、基板の受光素子形成面の反対側の面に本発明のブラックマトリクスが備えられた構成等が挙げられる。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を有していてもよい。この場合の隔壁は各色画素に対して低屈折率であることが好ましい。このような構造を有する撮像素子の例としては、特開2012-227478号公報および特開2014-179577号公報に記載の装置が挙げられる。
上述した硬化膜は、いわゆる遮光膜として好適に適用できる。また、このような遮光膜は、遮光膜付き赤外光カットフィルタおよび固体撮像装置に好適に適用することができる。このような固体撮像装置としては、例えば、特開2015-034983号公報に記載の段落0011~0033および段落0125~0127に記載の個体撮像装置が挙げられる。
上述した硬化膜は、液晶表示装置および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。また、硬化膜は、カラーフィルタに用いることができる。
本発明の液晶表示装置の一態様としては、例えば、少なくとも1つが光透過性の1対の基板の間にカラーフィルタ、液晶層および液晶駆動手段(単純マトリックス駆動方式、およびアクティブマトリックス駆動方式を含む)を少なくとも備えたものであり、カラーフィルタとして、複数の画素群を有し、この画素群を構成する各画素が、互いに本発明のブラックマトリクスにより離画されているカラーフィルタを用いるものである。
本発明の組成物を用いてられるカラーフィルタは、カラーTFT(Thin Film Transistor)方式の液晶表示装置に用いてもよい。カラーTFT方式の液晶表示装置については、例えば「カラーTFT液晶ディスプレイ(共立出版(株)1996年発行)」に記載されている。さらに、本発明はIPS(In Plane Switching)などの横電界駆動方式、MVA(Multi-domain Vertical Alignment)などの画素分割方式などの視野角が拡大された液晶表示装置、STN(Super-Twist Nematic)、TN(Twisted Nematic)、VA(Vertical Alignment)、OCS(on-chip spacer)、FFS(fringe field switching)、および、R-OCB(Reflective Optically Compensated Bend)等にも適用できる。
また、本発明におけるカラーフィルタは、明るく高精細なCOA(Color-filter On Array)方式にも供することが可能である。COA方式の液晶表示装置にあっては、カラーフィルタに対する要求特性は、通常の要求特性に加えて、層間絶縁膜に対する要求特性、すなわち低誘電率および剥離液耐性が必要とされることがある。本発明のカラーフィルタは、解像度が高く長期耐久性に優れたCOA方式の液晶表示装置を提供することができる。なお、低誘電率の要求特性を満足するためには、カラーフィルタ層の上に樹脂被膜を設けてもよい。
これらの画像表示方式については、例えば、「EL、PDP、LCDディスプレイ-技術と市場の最新動向-(東レリサーチセンター調査研究部門 2001年発行)」の43ページなどに記載されている。また、カラーフィルタは、隔壁により例えば格子状に仕切られた空間に、各色画素を形成する硬化膜が埋め込まれた構造を有していてもよい。
この場合の隔壁は各色画素に対して低屈折率であることが好ましい。このような構造を有する撮像装置の例としては、特開2012-227478号公報、特開2014-179577号公報に記載の装置が挙げられる。
バックライトに関しては、SID meeting Digest 1380(2005)(A.Konno et.al)や、月刊ディスプレイ 2005年12月号の18~24ページ(島 康裕)、同25~30ページ(八木隆明)などに記載されている。
マイクロLEDおよびマイクロOLEDの例としては、特表2015-500562号および特表2014-533890に記載されたものが挙げられる。
量子ドットディスプレイの例としては、米国特許出願公開第2013/0335677号、米国特許出願公開第2014/0036536号、米国特許出願公開第2014/0036203号、および、米国特許出願公開第2014/0035960号に記載されたものが挙げられる。
以下、実施例および比較例の組成物の調製にあたって、まず組成物に含まれる各成分について説明する。
チタン窒化物含有粒子として、次のようにして製造したチタン窒化物含有粒子TiN-1~TiN-19を用いた。
各チタン窒化物含有粒子の製造に用いた成分および添加量について、表1に示す。表1中、チタン粒子(Ti粒子)の添加量のうち、「残分」とは、添加粒子の含有量を除いた量を示す。また、「wt%」とは、質量%を意味する。
表1に記載の各成分を用いてチタン窒化物含有粒子TiN-1を製造した。
まず、表1に記載のTi粒子をArガス中においてプラズマ処理することにより、Tiナノ粒子化した。プラズマ処理後のTiナノ粒子を、Arガス雰囲気下でO2濃度50ppm以下、30℃の条件で24時間静置した後、O2濃度が100ppmとなるようにAr雰囲気にO2ガスを導入した状態において30℃、24時間静置した(Ti粒子の前処理)。
その後、得られたTiナノ粒子をホソカワミクロン製TTSPセパレータを用いて収率10%となる条件で分級を行い、Tiナノ粒子の粉末を得た。得られた粉末の一次粒径は、TEM観察よって100個の粒子の平均粒子径を算術平均により求めたところ、120nmであった。
チタン窒化物含有粒子TiN-1は、国際公開第2010/147098の図1に記載の黒色複合微粒子製造装置に準ずる装置を用いて製造した。
具体的には、黒色複合微粒子製造装置において、プラズマトーチの高周波発振用コイルには、約4MHzおよび約80kVAの高周波電圧を印加し、プラズマガス供給源からはプラズマガスとしてアルゴンガス50L/minおよび窒素50L/minの混合ガスを供給し、プラズマトーチ内にアルゴン-窒素熱プラズマ炎を発生させた。また、材料供給装置の噴霧ガス供給源からは10L/minのキャリアガスを供給した。
そして、上記のようにして得られたチタン粒子、および表1に記載の添加粒子を、表1に記載の添加量として加えて、キャリアガスであるアルゴンガスと共に、プラズマトーチ内の熱プラズマ炎中に供給し、熱プラズマ炎中で蒸発させ、気相状態で高度に分散させた。
また、気体供給装置によって、チャンバ内に供給される気体としては、窒素を使用した。このときのチャンバ内の流速は5m/secとして、供給量は1000L/minとした。また、サイクロン内の圧力は50kPaとし、また、チャンバからサイクロンへの各原料の供給速度は、10m/s(平均値)とした。
このようにして、チタン窒化物含有粒子TiN-1を得た。
また、窒素原子の含有量については、堀場製作所製の酸素/窒素分析装置「EMGA-620W/C」(商品名)を用いて測定し、不活性ガス融解-熱伝導度法により算出した。結果を表1に示す。
なお、後述するチタン窒化物含有粒子TiN-2~TiN-19についても、チタン窒化物含有粒子TiN-1と同様の方法によって、Ti原子、Fe原子、ケイ素原子、窒素原子の含有量を測定した。結果を表1に示す。
そして、回折角2θ(42.6°)付近に観察されるTiN(200)面に由来するピークの回折角2θを測定した。さらに、この(200)面に由来するピークの半値幅より、シェラーの式を用いて、粒子を構成する結晶子サイズを求めた。結果を表1に示す。なお、TiO2に起因するX線回折ピークは全く見られなかった。
なお、以下のチタン窒化物含有粒子TiN-2~TiN-19についても、チタン窒化物含有粒子TiN-1と同様の方法によって、回折角2θ、結晶子サイズを測定した。結果を表1に示す。なお、いずれのチタン窒化物含有粒子について、TiO2に起因するX線回折ピークは、全く見られなかった。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-2を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-3を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-4を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-5を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-6を製造した。
TiN-6粒子の製造におけるチャンバからサイクロンへの各原料の供給速度を8m/s(平均値)に変更した以外は、チタン窒化物含有粒子TiN-6の製造と同様にして、チタン窒化物含有粒子TiN-7を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにして、チャンバからサイクロンへの各原料の供給速度を15m/s(平均値)に変更した以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-8を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにして、チャンバからサイクロンへの各原料の供給速度を20m/s(平均値)に変更した以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-9を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-10を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにし、Ti粒子の前処理および静置処理を実施しなかった以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-11を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-12を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-13を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-14を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-15を製造した。
TiN-1粒子の製造に使用した原料および添加量を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-1の製造と同様にして、チタン窒化物含有粒子TiN-16を製造した。
TiN-4粒子の製造における、後述する窒化チタン含有粒子製造後の酸素(O2)濃度制御下における静置時間を表1に示す通りにした以外は、チタン窒化物含有粒子TiN-4と同様にして、チタン窒化物含有粒子TiN-17、TiN-18およびTiN-19を製造した。
上記のようにして得られたチタン窒化物含有粒子を表1~第5表に記載の期間、酸素(O2)濃度および水分の含有量をそれぞれ100ppm以下に制御した窒素(N2)ガスを導入した密閉容器内に静置した後、各組成物の調製を行った。
なお、表1~表5中、「なし」とは製造したチタン窒化物含有粒子を直ちに大気開放して使用したことを示す。また、12hr、24hr、48hrおよび72hrはそれぞれ、製造したチタン窒化物含有粒子を酸素(O2)濃度100ppm以下の容器内に静置した時間を示す。
分散剤として、以下の構造の分散剤A~Gを用いた。各構造単位に記載の数値は、全構造単位に対する、各構造単位の質量%を意図する。
バインダー樹脂である樹脂Aとしては、アクリキュアRD-F8(商品名、日本触媒社製)を用いた。以下に樹脂Aの構造を示す。
・重合性化合物M1(日本化薬社製、商品名「KAYARAD DPHA」、下記式参照)
・重合性化合物M2(日本化薬社製、商品名「KAYARAD RP-1040」、下記式参照)
・OXE-01:Irgacure OXE01(商品名、BASFジャパン社製)
・OXE-02:Irgacure OXE02(商品名、BASFジャパン社製)
・I-1:下記式(I-1)の重合開始剤
・I-2:下記式(I-2)の重合開始剤(商品名「B-CIM」、保土ヶ谷化学工業社製)
・I-3:下記式(I-3)の重合開始剤
・I-4:下記式(I-4)の重合開始剤
・I-5:下記式(I-5)の重合開始剤
・NCI-831:アデカアークルズ NCI-831(商品名、アデカ社製)
・N-1919:商品名、アデカ社製
・PGMEA:プロピレングリコールモノメチルエーテルアセテート
・シクロペンタノン
・酢酸ブチル
F-1:下記混合物(重量平均分子量(Mw)=14000)
p-メトキシフェノール
まず、チタン窒化物含有粒子、分散剤および有機溶剤を、攪拌機(IKA社製EUROSTAR)によって15分間混合し、分散物を得た。次に、得られた分散物に対して、(株)シンマルエンタープライゼス製のNPM-Pilotを使用して下記条件にて分散処理を行い、顔料分散物を得た。なお、チタン窒化物含有粒子に対する分散剤の比率(D/P)が第2表~第5表の各実施例および比較例に示す割合になるように添加した。
(分散条件)
・ビーズ径:φ0.05mm、(ニッカトー製ジルコニアビーズ、YTZ)
・ビーズ充填率:65体積%
・ミル周速:10m/sec
・セパレータ周速:13m/s
・分散処理する混合液量:15kg
・循環流量(ポンプ供給量):90kg/hour
・処理液温度:19~21℃
・冷却水:水
・処理時間:22時間程度
次に、上記顔料分散液、バインダー樹脂、重合性化合物、界面活性剤、重合禁止剤および有機溶剤を混合、攪拌して、下記第2表~第5表に示す実施例および比較例の各組成物を得た。
実施例および比較例の各組成物に含まれる各成分の含有量(質量%)を、第2表~第5表に示す。
実施例および比較例の各組成物の水分量について、カールフィッシャー法を測定原理とするMKV-710(商品名、京都電子工業社製)により測定した。結果を第2表~第5表に示す。
実施例および比較例の各組成物について、以下の各評価試験を行った。
実施例および比較例の各組成物をPGMEAによって100倍に希釈した試験溶液を調製し、得られた試験溶液を45℃の環境下で3日間保存した。そして、保存前後の試験溶液に含まれるチタン窒化物含有粒子の平均粒子径(D90)を粒度分布測定装置(マイクロトラック社製、製品名「ナノトラックUPA-150EX」)によって測定した。保存前後における試験溶液の平均粒子径(D90)の値に基づいて、以下の基準により調液時の粒径変動を評価した。
A:0≦(保存後のチタン窒化物含有粒子のD90)-(保存前のチタン窒化物含有粒子のD90)<0.010μm
B:0.010μm≦(保存後のチタン窒化物含有粒子のD90)-(保存前のチタン窒化物含有粒子のD90)<0.015μm
C:0.015μm≦(保存後のチタン窒化物含有粒子のD90)-(保存前のチタン窒化物含有粒子のD90)<0.020μm
D:0.020μm≦(保存後のチタン窒化物含有粒子のD90)-(保存前のチタン窒化物含有粒子のD90)
PGMEAによって上記組成物を500倍に希釈した試料溶液を調製し、この試料溶液10ml中に含まれる10μm以上のサイズのチタン窒化物含有粒子の数をフロー式粒子像分析装置(商品名「FPIA」、マルバーン社製)によって測定した。
実施例および比較例の各組成物について、カプセルフィルターDFA(日本ポール社製、ナイロン孔径0.45μm、2inch)を用いたろ過により、ろ過性を評価した。ろ過は、組成物16kgを0.05MPaの加圧条件で送液して行った。ろ過性は、以下の基準に基づいて評価した。
A:16kgすべてろ過できた。
B:10kg以上16kg未満においてろ過詰まりが発生した。
C:5kg以上10kg未満においてろ過詰まりが発生した。
D:5kg未満においてろ過詰まりが発生した。
実施例および比較例の各組成物を23℃において10日間保存した後、7℃において90日間保存した。その後、保存前後の各組成物の粘度を、E型粘度計(東機産業社製、商品名「R85形粘度計」)を用いて回転数10rpm、23℃の条件にて測定した。そして、[(組成物の保存後の粘度)-(組成物の保存前の粘度)/(組成物の保存前の粘度)]×100の値(%)を算出した。評価基準は以下の通りである。
A:±3%以内
B:±3%超、±5%以内
C:±5超%、±10%以内
D:±10%超
実施例および比較例の各組成物を感光性樹脂組成物として用いて、各組成物の塗布膜の乾燥膜厚が0.7μmになるように、シリコンウエハの表面に形成された電極パターン(銅)上に、スピーンコーター塗布した。塗布後10分間、そのままの状態にして、次いで、100℃のホットプレートを用いて、各組成物が塗布されたシリコンウエハに対して120秒間加熱処理(プリベーク)を行い、塗布膜を形成した
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、20μm四方のIslandパターンを有するパターンマスクを通して、365nmの波長および500mJ/cm2の露光量で塗布膜を露光した。
なお、実施例および比較例の各組成物は、露光部が硬化するネガ型の感光性樹脂組成物である。
その後、露光された塗布膜が形成されているシリコンウエハをスピンシャワー現像機(DW-30型、(株)ケミトロニクス製)の水平回転テーブル上に載置し、CD-2000(富士フイルムエレクトロニクスマテリアルズ(株)製、有機アルカリ液現像液)を用いて23℃で60秒間パドル現像を行った。
次いで、パドル現像後のシリコンウエハを真空チャック方式で上記水平回転テーブルに固定し、回転装置によってシリコンウエハを回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行った。その後シリコンウエハをスプレー乾燥し、額縁状のブラックマトリクスを有するウエハを作製した。
額縁状のブラックマトリクスを有するウエハを温度25℃、湿度65%RHの環境下で3ヶ月保存した後、ウエハ上に形成された電極パッド300個について電極パターンの錆の発生個所数を光学顕微鏡(オリンパス社製、商品名「LEXT OLS4500」)により観察した。電極の防食性は、錆の発生個所数に基づいて以下の基準により評価した。
A:錆の発生個所が0~5個
B:錆の発生個所が6~10個
C:錆の発生個所が11~20個
D:錆の発生個所が21個以上
上記の「電極の防食性」と同様にして得られた額縁状のブラックマトリクスを有するウエハについて、未露光部を走査型電子顕微鏡(日立ハイテクノロジーズ社製、商品名「SU8010」)を用いて、2万倍の倍率にて基板表面を観察し、得られた観察像に確認される粒子状の残渣の個数をカウントし、パターニング性(現像残渣)の評価を以下の基準により行った。
A:未露光部に現像残渣が観察されない
B:未露光部に粒子状の現像残渣が1~49個
C:未露光部に粒子状の現像残渣が50~100個
D:未露光部に粒子状の現像残渣が101個以上
電極の防食性の評価に用いたウエハと同様の、額縁状のブラックマトリクスを有するウエハを、85℃のTMAH(水酸化テトラメチルアンモニウム)25%水溶液に5時間浸漬し、次いで、2LのDIW(純水)槽に室温にて2分間浸漬することで、リンス処理した。得られたリンス処理後のウエハについて、額縁状のブラックマトリクスの除去状態を光学顕微鏡(オリンパス社製、商品名「LEXT OLS4500」)により観察し、以下の評価基準に基づいてリワーク性を評価した。
A:パターンが観察されない
B:パターン形成領域の5%以下に粒子状の除去残渣が観察される
C:パターン形成面積の5%超10%以下に粒子状の除去残渣が観察される
D:パターン形成面積の10%超に粒子状の除去残渣が観察されるか、もしくは、パターンもしくはパターンの一部が観察される
電極の防食性の評価に用いたウエハと同様の、額縁状のブラックマトリクスを有するウエハを、90℃、湿度85%RHの環境下に1000時間曝露した。曝露後のウエハについて、光学顕微鏡(オリンパス社製、商品名「LEXT OLS4500」)によりブラックマトリクスの外観変化を観察し、以下の評価基準に基づいて耐湿試験時の外観を評価した。
A:耐湿試験前後で差異が観察されない、又は、耐湿試験後に凹凸差10nm以下の表面荒れが観察される。
B:耐湿試験後に凹凸差10nm超50nm以下の表面荒れが観察される。
C:耐湿試験後に凹凸差50nm超100nm以下の表面荒れが観察される。
D:耐湿試験後に凹凸差100nm超の表面荒れが観察される。
電極の防食性の評価に用いたウエハの作製において、シリコンウエハに代えて10cm角のガラス基板を用い、Islandパターンを有するパターンマスクを使用せずに、ガラス基板の全面に塗布膜を形成した以外は、上記の電極の防食性の評価に用いたウエハの作製と同様にして、ガラス基板の一方の面の全面に、実施例および比較例の各組成物を用いて得られる硬化膜を形成した。
ガラス基板の硬化膜が設けられた側とは反対側に、光源を設置して、光源を設置した側から硬化膜の外観を目視にて観察し、ガラス基板に存在するピンホール(直径10μm以上)の数をカウントした。以下の基準により評価した。
A:ピンホールが0~1個
B:ピンホールが2~10個
C:ピンホールが11~20個
D:ピンホールが21個以上
厚さ0.7mm、10cm角のガラス板(EagleXG,Corning)上に、膜厚1.0μmとなる回転数にてスピンコートにより、実施例および比較例の各組成物を塗布して塗布膜を形成した。次いで、ホットプレートを用いて、塗布膜を100℃で、2分間加熱処理して乾燥膜を得た。得られた乾燥膜に対し、分光光度計U-4100(日立ハイテクノロジーズ製)によりOD(光学濃度)を測定した。波長400~1200nmにおける最低ODに基づいて、以下の基準により分光(遮光性)を評価した。
AA:最低OD>4.2
A:4.2≧最低OD>4.0
B:4.0≧最低OD>3.7
C:3.7≧最低OD>3.5
D:3.5≧最低OD
これに対して、チタン窒化物含有粒子中におけるFe原子の含有量が0.001質量%以下であると、パターニング性が劣ることが示された(比較例1および比較例3)。
また、チタン窒化物含有粒子中におけるFe原子の含有量が0.4質量%以上であると、電極の防食性が劣ることが示された(比較例2)。
上記の顔料分散物の調製において、チタン窒化物含有粒子に代えて、カーボンブラック(商品名「カラーブラック S170」、デグサ社製、平均一次粒子径17nm、BET比表面積200m2/g、ガスブラック方式により製造されたカーボンブラック)を用いた以外は同様にして、顔料分散物を調製し、カーボンブラック分散物を得た。
上記の顔料分散物の調製において、チタン窒化物含有粒子に代えて、ピグメントイエロー150(Hangzhou Star-up Pigment Co., Ltd.製、商品名6150顔料黄5GN)を使用した以外は同様の方法により、分散物を作製し、有彩色顔料分散物(PY分散液)を得た。
Claims (19)
- Fe原子を含むチタン窒化物含有粒子を含有し、
前記チタン窒化物含有粒子中における前記Fe原子の含有量が、0.001質量%超0.4質量%未満である、組成物。 - 前記チタン窒化物含有粒子の(200)面に由来するピークの回折角2θが、CuKα線をX線源とした場合において、42.6°超43.5°以下である、請求項1に記載の組成物。
- 前記チタン窒化物含有粒子が、さらにSi原子を含有し、
前記チタン窒化物含有粒子中における前記Si原子の含有量が、0.002質量%超0.3質量%未満である、請求項1または2に記載の組成物。 - 以下の粒子数測定方法によって求められる10μm以上のサイズの前記チタン窒化物含有粒子の数が、100個以下である、請求項1~3のいずれか1項に記載の組成物。
粒子数測定方法:プロピレングリコールモノメチルエーテルアセテートによって前記組成物を500倍に希釈した試料溶液を調製し、前記試料溶液10ml中に含まれる10μm以上のサイズの前記チタン窒化物含有粒子の数をフロー式粒子像分析装置によって測定する。 - さらに、2種以上の有機溶剤を含有する、請求項1~4のいずれか1項に記載の組成物。
- さらに、バインダー樹脂を含有する、請求項1~5のいずれか1項に記載の組成物。
- さらに、重合性化合物を含有する、請求項1~6のいずれか1項に記載の組成物。
- さらに、重合開始剤を含有する、請求項1~7のいずれか1項に記載の組成物。
- 前記組成物中の固形分が10~40質量%である、請求項1~8のいずれか1項に記載の組成物。
- 前記チタン窒化物含有粒子の含有量が、前記組成物の全固形分に対して、20~70質量%である、請求項1~9のいずれか1項に記載の組成物。
- さらに、水を含有し、
前記水の含有量が、前記組成物全質量に対して、0.1~1質量%である、請求項1~10のいずれか1項に記載の組成物。 - さらに、分散剤を含有し、
前記分散剤が、ポリアクリル酸メチル、ポリメタクリル酸メチルおよび環状または鎖状のポリエステルからなる群より選択される少なくとも1種の構造を有する、請求項1~11のいずれか1項に記載の組成物。 - 前記チタン窒化物含有粒子に対する前記分散剤の含有割合が、質量比で0.05~0.30である、請求項12に記載の組成物。
- 請求項1~13のいずれか1項に記載の組成物の製造方法であって、
熱プラズマ法によって前記チタン窒化物含有粒子を得る工程を含む、組成物の製造方法。 - 請求項1~13のいずれか1項に記載の組成物を用いて得られる、硬化膜。
- 請求項15に記載の硬化膜を有する、カラーフィルタ。
- 請求項15に記載の硬化膜を有する、遮光膜。
- 請求項15に記載の硬化膜を有する、固体撮像素子。
- 請求項15に記載の硬化膜を有する、画像表示装置。
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61227909A (ja) * | 1985-04-03 | 1986-10-11 | Toho Titanium Co Ltd | 窒化チタンの製造方法 |
JP2005179121A (ja) * | 2003-12-19 | 2005-07-07 | Sumitomo Metal Mining Co Ltd | 日射遮蔽用微粒子とこの微粒子が樹脂成分中に分散された日射遮蔽樹脂材料および日射遮蔽樹脂材料の製造に用いられる日射遮蔽用微粒子分散体と日射遮蔽樹脂材料を用いて得られる日射遮蔽樹脂基材並びに日射遮蔽複合基材 |
JP2009228085A (ja) * | 2008-03-25 | 2009-10-08 | Kyocera Corp | サーメット |
WO2010147098A1 (ja) * | 2009-06-15 | 2010-12-23 | 東レ株式会社 | 黒色複合微粒子、黒色樹脂組成物、カラーフィルター基板および液晶表示装置 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3717851A (en) | 1971-03-03 | 1973-02-20 | Ibm | Processing of compacted data |
KR100282952B1 (ko) * | 1997-06-18 | 2001-03-02 | 미다라이 후지오 | 토너, 2성분계 현상제 및 화상 형성 방법 |
JP2002241178A (ja) * | 2001-02-13 | 2002-08-28 | Ngk Spark Plug Co Ltd | 導電性セラミックベアリングボール、ボールベアリング、ベアリング付きモータ、ハードディスク装置及びポリゴンスキャナ |
EP2135900A4 (en) * | 2007-03-20 | 2010-04-28 | Toray Industries | BLACK RESIN COMPOSITION, RESIN BLACK MATRIX, COLOR FILTER AND LIQUID CRYSTAL DISPLAY |
TWI516450B (zh) * | 2009-10-19 | 2016-01-11 | 富士軟片股份有限公司 | 鈦黑分散物、感光性樹脂組成物、晶圓級透鏡、遮光膜及其製造方法、以及固態攝像元件 |
CN102351157A (zh) * | 2011-08-10 | 2012-02-15 | 河南大学 | 一种掺杂铁的新型氮化钛纳米颗粒 |
JP2013249417A (ja) * | 2012-06-01 | 2013-12-12 | Fujifilm Corp | 分散組成物、並びに、これを用いた、重合性組成物、遮光性カラーフィルタ、固体撮像素子、液晶表示装置、ウエハレベルレンズ、及び、撮像ユニット |
CN105378615B (zh) * | 2013-07-25 | 2019-05-31 | 东丽株式会社 | 触控面板用负型感光性白色组合物、触控面板及触控面板的制造方法 |
JP6438817B2 (ja) * | 2015-03-27 | 2018-12-19 | リンテック株式会社 | 粘着性組成物、粘着剤、粘着シートおよび粘着剤層付き光学フィルム |
JP2018124297A (ja) * | 2015-05-29 | 2018-08-09 | 富士フイルム株式会社 | 反転パターン形成方法、画像反転用組成物及び電子デバイスの製造方法 |
-
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Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS61227909A (ja) * | 1985-04-03 | 1986-10-11 | Toho Titanium Co Ltd | 窒化チタンの製造方法 |
JP2005179121A (ja) * | 2003-12-19 | 2005-07-07 | Sumitomo Metal Mining Co Ltd | 日射遮蔽用微粒子とこの微粒子が樹脂成分中に分散された日射遮蔽樹脂材料および日射遮蔽樹脂材料の製造に用いられる日射遮蔽用微粒子分散体と日射遮蔽樹脂材料を用いて得られる日射遮蔽樹脂基材並びに日射遮蔽複合基材 |
JP2009228085A (ja) * | 2008-03-25 | 2009-10-08 | Kyocera Corp | サーメット |
WO2010147098A1 (ja) * | 2009-06-15 | 2010-12-23 | 東レ株式会社 | 黒色複合微粒子、黒色樹脂組成物、カラーフィルター基板および液晶表示装置 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111511680A (zh) * | 2017-12-26 | 2020-08-07 | 三菱综合材料电子化成株式会社 | 黑色遮光膜形成用粉末及其制备方法 |
CN111511680B (zh) * | 2017-12-26 | 2023-10-24 | 三菱综合材料电子化成株式会社 | 黑色遮光膜形成用粉末及其制备方法 |
US11835679B2 (en) | 2017-12-26 | 2023-12-05 | Mitsubishi Materials Electronic Chemicals Co., Ltd. | Powder for forming black light-shielding film and method for manufacturing same |
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