Classifications

• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/02—Diffusing elements; Afocal elements
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor

Definitions

• the present invention relates to a photosensitive composition containing particles containing rare earth elements, and a film and optical sensor using the same.
• Titanium oxide is a particle with a high refractive index. Attempts are being made to use such particles with a high refractive index in light scattering films and the like.
• Patent Document 1 describes an invention relating to a paint for forming a light diffusion layer of a projection screen, which contains 100 parts by mass of a base resin and 0.1 to 50 parts by mass of rare earth phosphate fine particles.
• Titanium oxide has conventionally been used as particles with a high refractive index, but when a composition containing titanium oxide is used and patterned by photolithography to produce a patterned light scattering film, etc. Development residues were likely to occur between patterns, and there was room for improvement in developability.
• an object of the present invention is to provide a photosensitive composition with excellent storage stability and developability, and a film and optical sensor using the same.
• the present invention provides the following.
• ⁇ 1> Contains particles A containing a rare earth element, a photopolymerization initiator B, and a resin C,
• the resin C is a photosensitive composition containing a resin having at least one selected from acid value and base value.
• ⁇ 4> The photosensitive composition according to any one of ⁇ 1> to ⁇ 3>, wherein the particles A have an average primary particle diameter of 30 to 200 nm.
• the resin C includes a resin having a repeating unit of a poly(meth)acrylic structure and a resin having a repeating unit of a polyester structure, At least one of the resin having a repeating unit having a poly(meth)acrylic structure and the resin having a repeating unit having a polyester structure has at least one selected from acid value and base value ⁇ 1> to ⁇ 5>
• ⁇ 7> The photosensitive composition according to any one of ⁇ 1> to ⁇ 6>, further comprising a polyalkyleneimine.
• the resin C includes a resin having an acid value
• ⁇ 11> When a film with a thickness of 4 ⁇ m was formed by heating at 200° C. for 5 minutes using the photosensitive composition, the film contained the first phase containing the particles A and the first phase.
• the photosensitive composition according to any one of ⁇ 1> to ⁇ 10> which has a phase-separated structure with a second phase having a lower content of particles A than the first phase.
• ⁇ 12> The photosensitive composition according to ⁇ 11>, wherein the phase separation structure is a sea-island structure or a co-continuous phase structure.
• ⁇ 13> A film obtained using the photosensitive composition according to any one of ⁇ 1> to ⁇ 12>.
• An optical sensor comprising the film according to ⁇ 13>.
• the present invention it is possible to provide a photosensitive composition with excellent storage stability and developability, as well as a film and a photosensor using the same.
• FIG. 1 is a schematic diagram showing an embodiment of the optical sensor of the present invention. It is a schematic diagram showing other embodiments of the optical sensor of the present invention.
• a numerical range expressed using " ⁇ " means a range that includes the numerical values written before and after " ⁇ " as lower and upper limits.
• a group (atomic group) in this specification the description that does not indicate substituted or unsubstituted includes a group having a substituent (atomic group) as well as a group having no substituent (atomic group).
• alkyl group includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• (meth)acrylate represents acrylate and methacrylate
• (meth)acrylic represents acrylic and methacryl
• (meth)allyl represents allyl and methallyl
• (meth)acrylic represents allyl and methallyl
• acryloyl represents acryloyl and methacryloyl.
• Me in the chemical formula represents a methyl group
• Et represents an ethyl group
• Pr represents a propyl group
• Bu represents a butyl group
• Ph represents a phenyl group.
• exposure includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
• the light used for exposure include actinic rays or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV light), X-rays, and electron beams.
• the weight average molecular weight and number average molecular weight are defined as polystyrene equivalent values measured by gel permeation chromatography (GPC).
• the weight average molecular weight (Mw) and number average molecular weight (Mn) are expressed using, for example, HLC-8220GPC (manufactured by Tosoh Corporation) and columns such as TOSOH TSKgel Super HZM-H and TOSOH TSKgel Super HZ4000. It can be determined by using a column connected to TOSOH TSKgel Super HZ2000 and using tetrahydrofuran as a developing solvent.
• the refractive index value is the refractive index value for light with a wavelength of 589 nm at 23° C. unless otherwise specified.
• the photosensitive composition of the present invention is Contains particles A containing a rare earth element, a photopolymerization initiator B, and a resin C,
• the resin C is characterized by containing a resin having at least one selected from acid value and base value.
• the photosensitive composition of the present invention has excellent storage stability and developability. It is presumed that the reason why such an effect is obtained is as follows. That is, the photosensitive composition of the present invention includes particles A containing a rare earth element and a resin having at least one selected from an acid value and a base value, so that the particles A and the resin interact, It is presumed that the above-mentioned resin was able to suppress the agglomeration of particles A in the photosensitive composition and to suppress the sedimentation of particles A, and as a result, the storage stability of the photosensitive composition could be improved. Ru. It is also presumed that the particles A and the resin interact during film formation, and the resin tends to exist near the particles A in the film.
• the particles A existing in the unexposed area are easily removed by development together with the resin, and development residues derived from the particles A are less likely to remain between the patterns.As a result, the developability of the photosensitive composition is reduced. It is assumed that it was possible to improve the
• the film When a film with a thickness of 4 ⁇ m was formed by heating at 200° C. for 5 minutes using the photosensitive composition of the present invention, the film contained a first phase containing the particles A and a first phase containing the particles A. It is preferable that a phase-separated structure is formed with a second phase having a smaller content of particles A than the second phase. By forming such a phase-separated structure in the film, light scattering properties are improved, and the angular dependence of scattered light can also be reduced.
• the base material of the first phase and the second phase is a film-forming component such as a resin or a cured product derived from a film-forming component.
• the mere aggregate of the particles A is one form of particles, and the mere aggregate of the particles A itself is not the first phase.
• the film-forming component or the cured product derived from the film-forming component in which the particles A are present is the first phase.
• the second phase may have a lower content of the particles A than the first phase, and may not substantially contain the particles A.
• the content of the particles A is preferably 30% by mass or less of the total amount of the particles contained in the photosensitive composition, and 20% by mass or less of the total amount of the particles contained in the photosensitive composition.
• the amount is preferably at most 10% by mass, even more preferably at most 5% by mass, and the second phase does not substantially contain the particles A.
• phase-separated structure of the first phase and the second phase in the film can be observed using a scanning electron microscope (SEM), a transmission electron microscope (TEM), or an optical microscope. I can do it. For example, after coating a photosensitive composition on a support such as a glass substrate and heating it at 200°C for 5 minutes to form a film with a thickness of 4 ⁇ m, the cross section of the resulting film in the thickness direction is scanned. Examining whether a phase-separated structure of the first phase and the second phase is formed in the film by observing using a SEM, a transmission electron microscope, or an optical microscope. I can do it.
• phase-separated structure In order to form the above-mentioned phase-separated structure, it can be achieved by appropriately changing the type of resin, etc.
• One embodiment includes a method using a resin containing a first resin and a second resin that has low compatibility with the first resin.
• a phase-separated structure of a phase containing the first resin as a main component and a phase containing the second resin as a main component can be formed during film formation.
• one of the first resin and the second resin is a resin as a dispersant for particles A, and the other is a binder resin A
• a phase containing the resin as a dispersant as a main component is used.
• a large number of particles A can be unevenly distributed.
• it is preferable that at least one of the first resin and the second resin is a resin having at least one selected from acid value and base value.
• the phase separation structure in the membrane is such that phase interfaces exist isotropically in the membrane, and for example, a sea-island structure or a co-continuous phase structure is more preferable.
• a sea-island structure is a structure formed by a sea region that is a continuous region and an island region that is a discontinuous region.
• the second phase may be the ocean and the first phase may form an island, or the first phase may be the ocean and the second phase may form an island. It is preferable from the viewpoint of transmittance that the first phase is sea and the second phase forms islands.
• the co-continuous phase structure is a network structure in which the first phase and the second phase form a continuous phase structure in an interpenetrating manner.
• the transmittance of this film to light at a wavelength of 365 nm is preferably 15% or more. , more preferably 25% or more, and even more preferably 35% or more.
• the maximum value of the transmittance of light in the wavelength range of 400 to 700 nm is determined by light scattering. From the viewpoint of reducing the wavelength dependence of The following is particularly preferable.
• the lower limit of the maximum transmittance value is preferably 15% or more, more preferably 20% or more, even more preferably 30% or more, even more preferably 40% or more, and 45% or more. % or more is particularly preferable.
• the maximum value of the transmittance of light in the range of 400 to 1000 nm of the above film is preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, and 75% or less.
• the lower limit of the maximum transmittance is preferably 20% or more, more preferably 25% or more, even more preferably 35% or more, even more preferably 45% or more, and 50% or more. % or more is particularly preferable.
• the average value of the interphase refractive index difference in the film is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.3 or more, and 0.4 or more. It is particularly preferable that there be.
• the haze of the above film based on JIS K 7136 is preferably 30 to 100%.
• the upper limit is preferably 99% or less, more preferably 95% or less, and even more preferably 90% or less.
• the lower limit is preferably 35% or more, more preferably 40% or more, and even more preferably 50% or more.
• Formation of a film having such spectral characteristics can be achieved by appropriately adjusting the shape of the phase separation structure, the refractive index of the particles, the amount and uneven distribution of the particles in the film, etc. At this time, the higher the refractive index of the particles, the amount of particles present, and the degree of uneven distribution of particles, the better.
• the solid content concentration of the photosensitive composition of the present invention is preferably 5 to 90% by mass.
• the upper limit is preferably 85% by mass or more, more preferably 80% by mass or more, even more preferably 75% by mass or less, even more preferably 70% by mass or less, and even more preferably 60% by mass or less. It is even more preferable.
• the lower limit is preferably 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more.
• the photosensitive composition of the present invention includes particles A (hereinafter also referred to as specific particles) containing a rare earth element.
• the specific particles are materials that have a high refractive index and Abbe number (vd) in the wavelength range from ultraviolet light to infrared light, including the wavelength range of visible light. Therefore, by using specific particles, the light scattering properties of the resulting film can be further improved. Furthermore, the angular dependence of scattered light can also be reduced.
• the rare earth elements contained in the specific particles include scandium element, yttrium element, lanthanum element, cerium element, praseodymium element, neodymium element, promethium element, samarium element, europium element, gadolinium element, terbium element, dysprosium element, holmium element, Examples include erbium element, thulium element, ytterbium element and lutetium element.
• the above-mentioned specific particles can further improve storage stability and developability, further enhance the light scattering properties of the obtained film, and reduce the angle dependence of scattered light. , yttrium, gadolinium, dysprosium, ytterbium, and lutetium, and more preferably yttrium.
• Specific particles include rare earth phosphate particles, rare earth oxide particles, rare earth titanate particles, etc., which can further improve the storage stability and developability, and further improve the photoresist properties of the resulting film.
• Rare earth phosphate particles are preferred because they can further enhance scattering properties and reduce the angle dependence of scattered light.
• specific particles include YPO 4 , GdPO 4 , LuPO 4 , YbPO 4 , DyPO 4 and the like.
• the specific particles may be crystalline or amorphous.
• examples of the crystal system include monoclinic, tetragonal, cubic, and the like.
• the average primary particle diameter of the specific particles is preferably 300 nm or less, more preferably 250 nm or less, even more preferably 200 nm or less, and even more preferably 150 nm or less.
• the lower limit is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 20 nm or more, and even more preferably 30 nm or more, from the viewpoint of light scattering properties of the resulting film.
• the average primary particle diameter of the specific particles is preferably 30 to 200 nm, more preferably 30 to 150 nm.
• the average primary particle diameter of particles is a value measured by the following method. That is, the primary particle diameter of the particles can be determined by observing the particles with a transmission electron microscope (TEM) and observing the portions where the particles are not aggregated (primary particles). The particle size distribution of the particles can be determined by taking a transmission electron micrograph of the primary particles using a transmission electron microscope, and then measuring the particle size distribution using an image processing device using the photograph.
• the average primary particle diameter of particles is the number-based arithmetic mean diameter calculated from the particle size distribution.
• an electron microscope (H-7000) manufactured by Hitachi, Ltd. is used as a transmission electron microscope
• Luzex AP manufactured by Nireco Co., Ltd. is used as an image processing device.
• the refractive index of the specific particles is preferably 1.70 or more, more preferably 1.75 or more.
• the upper limit of the refractive index of the specific particles is not particularly limited, but can be 5.0 or less, and can also be 4.0 or less.
• the refractive index of the particles is a value measured by the following method.
• a dispersion liquid is prepared using particles, a resin (dispersant) having a known refractive index, and propylene glycol monomethyl ether acetate.
• the prepared dispersion liquid and a resin with a known refractive index were mixed to prepare coating liquids with particle concentrations of 10% by mass, 20% by mass, 30% by mass, and 40% by mass in the total solid content of the coating liquid. do.
• the refractive index of the resulting film is measured using ellipsometry (Lambda Ace RE-3300, manufactured by SCREEN Holdings, Inc.). Thereafter, the refractive index corresponding to the concentration of particles is plotted on a graph to derive the refractive index of the particles.
• the specific gravity of the specific particles is preferably 3.0 to 8.0 g/cm 3 .
• the upper limit is preferably 7.5 g/cm 3 or less, more preferably 7.0 g/cm 3 or less.
• the lower limit of the specific gravity is not particularly limited, but can be 3.2 g/cm 3 or more, and can also be 3.5 g/cm 3 or more.
• the specific surface area of the specific particles is preferably 1 to 100 m 2 /g as measured by the BET (Brunauer, Emmett, Teller) method.
• the upper limit is preferably 95 m 2 /g or less, more preferably 90 m 2 /g or less.
• the lower limit is preferably 2 m 2 /g or more, more preferably 3 m 2 /g or more.
• the content of the specific particles in the total solid content of the photosensitive composition is preferably 10% by mass or more, more preferably 20% by mass or more, even more preferably 30% by mass or more, 35% by mass or more. It is even more preferable that the amount is % by mass or more.
• the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.
• the photosensitive composition of the present invention may contain only one type of specific particles, or may contain two or more types of specific particles.
• the photosensitive composition of the present invention contains photopolymerization initiator B (hereinafter also referred to as photopolymerization initiator).
• the photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, compounds having photosensitivity to light in the ultraviolet to visible range are preferred.
• the photopolymerization initiator is preferably a radical photopolymerization initiator.
• photopolymerization initiators include halogenated hydrocarbon derivatives (e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and the like.
• halogenated hydrocarbon derivatives e.g., compounds with a triazine skeleton, compounds with an oxadiazole skeleton, etc.
• acylphosphine compounds e.g., acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, and the like.
• photopolymerization initiators include trihalomethyltriazine compounds, benzyl dimethyl ketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, and hexaarylbylene compounds.
• imidazole compounds onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds, cyclopentadiene-benzene-iron complexes, halomethyloxadiazole compounds and 3-aryl substituted coumarin compounds, oxime compounds, ⁇ -hydroxyketones
• the compound is more preferably a compound selected from a compound, an ⁇ -aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.
• photopolymerization initiators compounds described in paragraphs 0065 to 0111 of JP-A-2014-130173, compounds described in Japanese Patent No. 6301489, MATERIAL STAGE 37 to 60p, vol. 19, No.
• ⁇ -hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (manufactured by IGM Resins B.V.), Irgacure 184, and Irgacure 117. 3, Irgacure 2959, Irgacure 127 (all BASF (manufactured by a company).
• Commercially available ⁇ -aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (manufactured by IGM Resins B.V.), Irgacure 907, and Irgacure 36.
• Irgacure 369E Irgacure 379EG (all manufactured by BASF) (manufactured by).
• Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO H (manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (manufactured by BASF), and the like.
• Examples of oxime compounds include the compound described in paragraph 0142 of International Publication No. 2022/085485, the compound described in Patent No. 5430746, the compound described in Patent No. 5647738, and the general formula (1 ) and the compounds described in paragraphs 0022 to 0024, and the compounds represented by the general formula (1) and the compounds described in paragraphs 0117 to 0120 of JP-A-2021-170089.
• oxime compounds include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino -1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like.
• photopolymerization initiators include oxime compounds having a fluorene ring, oxime compounds having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring, oxime compounds having a fluorine atom, oxime compounds having a nitro group, and benzofuran skeleton.
• An oxime compound having a carbazole skeleton bonded with a substituent having a hydroxy group, and compounds described in paragraphs 0143 to 0149 of International Publication No. 2022/085485 can also be used.
• oxime compounds include compounds with the structures shown below.
• the oxime compound is preferably a compound having a maximum absorption wavelength in a wavelength range of 350 to 500 nm, more preferably a compound having a maximum absorption wavelength in a wavelength range of 360 to 480 nm.
• the molar extinction coefficient of the oxime compound at a wavelength of 365 nm or 405 nm is preferably high, more preferably from 1000 to 300,000, even more preferably from 2000 to 300,000, and even more preferably from 5000 to 200,000. It is particularly preferable that there be.
• the molar extinction coefficient of a compound can be measured using a known method. For example, it is preferable to measure with a spectrophotometer (Cary-5 spectrophotometer manufactured by Varian) using ethyl acetate at a concentration of 0.01 g/L.
• a difunctional, trifunctional or more functional photoradical polymerization initiator may be used as the photopolymerization initiator.
• a radical photopolymerization initiator two or more radicals are generated from one molecule of the radical photopolymerization initiator, so that good sensitivity can be obtained.
• the crystallinity decreases and the solubility in solvents improves, making it difficult to precipitate over time, thereby improving the stability of the photosensitive composition over time.
• Specific examples of bifunctional or trifunctional or more functional photoradical polymerization initiators include those listed in Japanese Patent Publication No. 2010-527339, Japanese Patent Publication No. 2011-524436, International Publication No.
• the content of the photopolymerization initiator in the total solid content of the photosensitive composition is preferably 0.1 to 30% by mass.
• the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and even more preferably 3% by mass or more.
• the upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.
• the photosensitive composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types of photopolymerization initiators. When two or more types of photopolymerization initiators are included, the total amount thereof is preferably within the above range.
• the photosensitive composition of the present invention contains resin C (hereinafter also referred to as resin).
• resin is blended, for example, for dispersing particles in a photosensitive composition or for use as a binder.
• a resin used mainly for dispersing particles and the like in a photosensitive composition is also referred to as a dispersant.
• this use of the resin is just an example, and the resin can also be used for purposes other than this use.
• any known resin can be used.
• examples include resins, polyimide resins, polyamide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, silicone resins, and urethane resins.
• the weight average molecular weight of the resin is preferably 3,000 to 2,000,000.
• the upper limit is preferably 1,000,000 or less, more preferably 500,000 or less.
• the lower limit is preferably 3000 or more, more preferably 4000 or more, and even more preferably 5000 or more.
• the photosensitive composition of the present invention preferably contains a resin as a dispersant for the specific particles and a resin as a binder. Further, the resin used as the binder preferably has low compatibility with the resin used as the dispersant. By using such resins in combination, the above-mentioned phase separation structure is easily formed in the film during film formation, and the light scattering properties of the resulting film can be further improved. Examples of combinations of resins with low compatibility include a combination of a resin having a repeating unit of a poly(meth)acrylic structure and a resin having a repeating unit of a polyester structure.
• the photosensitive composition of the present invention preferably contains at least one type selected from a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher linking group and a resin having a repeating unit having a graft chain.
• aggregation of particles in the photosensitive composition can be more effectively suppressed, and better storage stability can be obtained.
• the above-mentioned phase separation structure is easily formed in the film during film formation, and the light scattering properties of the resulting film can be further improved. It is more preferable to include a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher-valent linking group, and a resin having a repeating unit having a graft chain.
• the photosensitive composition of the present invention may each contain a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher-valent linking group, and a resin having a repeating unit having a graft chain. Details of the resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher-valent linking group and the resin having a repeating unit having a graft chain will be described later.
• the photosensitive composition of the present invention contains a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher linking group and a resin containing a repeating unit having a graft chain
• one of the resins is a dispersant.
• the other resin is a binder.
• the polymer chain in a resin with a structure in which multiple polymer chains are bonded to a trivalent or higher linking group is a polymer chain composed of repeating units with a different structure from the graft chain in a resin containing a repeating unit with a graft chain.
• a polymer chain in a resin with a structure in which multiple polymer chains are bonded to a trivalent or higher linking group is a polymer chain composed of repeating units of a polyether structure, a polyester structure, a poly(meth)acrylic structure, or a polystyrene structure.
• the graft chain in the resin containing a repeating unit having a graft chain is a repeating unit with a structure different from the above polymer chain, and the repeating unit has a polyether structure, a polyester structure, a poly(meth)acrylic structure, or a polystyrene structure.
• the polymer chain in the resin has a structure in which multiple polymer chains are bonded to a trivalent or higher linking group, and the polymer chain is composed of repeating units of a polyester structure or a poly(meth)acrylic structure.
• the graft chain in the resin containing a repeating unit having a graft chain is a repeating unit having a structure different from that of the polymer chain, and is composed of a repeating unit having a polyester structure or a poly(meth)acrylic structure.
• the combination is a grafted chain.
• the photosensitive composition of the present invention preferably contains 40 to 300 parts by mass of a resin as a binder per 100 parts by mass of the resin as a dispersant.
• the upper limit is preferably 250 parts by mass or less, more preferably 200 parts by mass or less.
• the lower limit is preferably 50 parts by mass or more, more preferably 100 parts by mass or more.
• the photosensitive composition of the present invention preferably contains 5 to 150 parts by mass of a resin as a dispersant per 100 parts by mass of the above-mentioned specific particles.
• the upper limit is preferably 140 parts by mass or less, more preferably 125 parts by mass or less, and even more preferably 100 parts by mass or less.
• the lower limit is preferably 10 parts by mass or more, more preferably 15 parts by mass or more, and even more preferably 25 parts by mass or more.
• the resin as a dispersant and the resin as a binder can be appropriately selected from the resins described below.
• dispersants are also available as commercial products, and specific examples include the Disperbyk series (for example, Disperbyk-111, 2001, etc.) manufactured by Byk Chemie, and Solsperse manufactured by Nippon Lubrizol Co., Ltd. series (for example, Solsperse 20000, 76500, etc.), Ajisperse series manufactured by Ajinomoto Fine Techno, Inc., and the like.
• the product described in paragraph number 0129 of JP 2012-137564A and the product described in paragraph number 0235 of JP 2017-194662A can also be used as a dispersant.
• a resin having an acid group can be used as the resin.
• resins having acid groups include resins having repeating units having acid groups.
• the acid group include a carboxy group, a phosphoric acid group, a sulfo group, and a phenolic hydroxy group.
• a resin having a basic group can be used as the resin.
• the resin having a basic group include resins having repeating units having a basic group.
• the basic group include an amino group and a pyridyl group.
• the basic group is preferably an amino group.
• the amino group include a group represented by -NR am1 Ram2 and a cyclic amino group, and a group represented by -NR am1 Ram2 is preferred.
• Ram1 and Ram2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, and are preferably an alkyl group.
• the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, even more preferably 1 to 3, particularly preferably 1 or 2.
• the alkyl group may be straight chain, branched, or cyclic, but straight chain or branched is preferable, and straight chain is more preferable.
• the number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
• Examples of the cyclic amino group include a pyrrolidine group, a piperidine group, a piperazine group, and a morpholine group. These groups may further have a substituent. Examples of the substituent include an alkyl group and an aryl group.
• a resin having an acid group and a basic group can be used.
• the resin having an acid group and a basic group include a resin having a repeating unit having an acid group and a repeating unit having a basic group.
• the resin includes a repeating unit derived from a compound represented by the following formula (ED1) and/or a compound represented by the following formula (ED2) (hereinafter, these compounds may be referred to as "ether dimer”). Resin can be used.
• R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
• R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
• the description in JP-A No. 2010-168539 can be referred to.
• paragraph number 0317 of JP-A-2013-029760 can be referred to, the contents of which are incorporated herein.
• a resin containing a repeating unit derived from a compound represented by the following formula (X) can be used as the resin.
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents an alkylene group having 2 to 10 carbon atoms
• R 3 represents a hydrogen atom or an alkylene group having 1 to 20 carbon atoms that may contain a benzene ring.
• n represents an integer from 1 to 15.
• a resin containing a repeating unit having a graft chain can also be used.
• the resin contains a repeating unit having a graft chain, aggregation of particles in the photosensitive composition can be more effectively suppressed due to steric hindrance caused by the graft chain, and excellent storage stability can be obtained. Moreover, it is easy to form the above-mentioned phase separation structure in the film during film formation, and the light scattering properties of the obtained film can be more easily improved.
• a resin containing a repeating unit having a graft chain may be used as a dispersant or as a binder.
• the graft chain preferably contains a repeating unit of at least one type of structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure; It is more preferable to contain a repeating unit having at least one type of structure selected from a polyester structure, a poly(meth)acrylic structure, and a polystyrene structure. It is even more preferable to contain a repeating unit having a polyether structure or a polyester structure. It is particularly preferable to include units.
• repeating units having a polyester structure include repeating units having a structure represented by formula (G-1), formula (G-4), or formula (G-5).
• Examples of repeating units having a polyether structure include repeating units having a structure represented by formula (G-2).
• Examples of the repeating unit of the poly(meth)acrylic structure include a repeating unit of the structure represented by formula (G-3).
• Examples of the repeating unit of the polystyrene structure include a repeating unit of the structure represented by formula (G-6).
• R G1 and R G2 each independently represent an alkylene group.
• the alkylene groups represented by R G1 and R G2 are not particularly limited, but are preferably linear or branched alkylene groups having 1 to 20 carbon atoms, and linear or branched alkylene groups having 2 to 16 carbon atoms. More preferred are linear or branched alkylene groups having 3 to 12 carbon atoms.
• R G3 represents a hydrogen atom or a methyl group
• Q G1 represents -O- or -NH-
• L G1 represents a single bond or a divalent linking group
• R G4 represents hydrogen Represents an atom or substituent.
• the divalent linking group represented by L G1 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an alkyleneoxy group (preferably an alkyleneoxy group having 1 to 12 carbon atoms), and an oxyalkylenecarbonyl group (preferably an alkylene group having 1 to 12 carbon atoms).
• oxyalkylenecarbonyl group having 1 to 12 carbon atoms is an oxyalkylenecarbonyl group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, -SO 2 -, -CO-, -O-, - Examples include COO-, OCO-, -S-, and groups formed by combining two or more of these.
• the substituents represented by R G4 include hydroxy group, carboxy group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthioether group, arylthioether group, heterocyclic thioether group, Examples include ethylenically unsaturated bond-containing groups, epoxy groups, oxetanyl groups, and blocked isocyanate groups.
• R G5 represents a hydrogen atom or a methyl group
• R G6 represents an aryl group.
• the number of carbon atoms in the aryl group represented by R G6 is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 12.
• the aryl group represented by R G6 may have a substituent.
• Substituents include hydroxy group, carboxy group, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthioether group, arylthioether group, heterocyclic thioether group, ethylenically unsaturated. Examples include bond-containing groups, epoxy groups, oxetanyl groups, and blocked isocyanate groups.
• the terminal structure of the graft chain is not particularly limited. It may be a hydrogen atom or a substituent.
• substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
• groups having a steric repulsion effect are preferred, and alkyl groups or alkoxy groups having 5 to 24 carbon atoms are preferred.
• the alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
• the graft chain is represented by the following formula (G-1a), formula (G-2a), formula (G-3a), formula (G-4a), formula (G-5a) or formula (G-6a). It is preferable to have a structure represented by formula (G-1a), formula (G-4a) or formula (G-5a).
• R G1 and R G2 each represent an alkylene group
• R G3 represents a hydrogen atom or a methyl group
• Q G1 represents -O- or -NH-
• L G1 represents a single bond or Represents a divalent linking group
• R G4 represents a hydrogen atom or a substituent
• R G5 represents a hydrogen atom or a methyl group
• R G6 represents an aryl group
• W 100 represents a hydrogen atom or a substituent.
• n1 to n6 each independently represent an integer of 2 or more.
• R G1 to R G6 , Q G1 , and L G1 have the same meanings as R G1 to R G6 , Q G1 , and L G1 explained in formulas (G-1) to (G-6 ) , and the preferred ranges are also the same. be.
• W 100 is preferably a substituent.
• the substituent include an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkylthioether group, an arylthioether group, and a heteroarylthioether group.
• groups having a steric repulsion effect are preferred, and alkyl groups or alkoxy groups having 5 to 24 carbon atoms are preferred.
• the alkyl group and the alkoxy group may be linear, branched, or cyclic, and preferably linear or branched.
• n1 to n6 are each preferably an integer of 2 to 100, more preferably an integer of 2 to 80, and even more preferably an integer of 8 to 60.
• R G1 in each repeating unit may be the same or different.
• R G1 contains two or more types of different repeating units
• the arrangement of each repeating unit is not particularly limited and may be random, alternating, or block. The same applies to formulas (G-2a) to (G-6a).
• the graft chain has a structure represented by formula (G-1a), formula (G-4a), or formula (G-5a), and has a structure containing two or more types of repeating units in which R G1 is different. is also preferable.
• repeating unit having a graft chain examples include a repeating unit represented by the following formula (A-1-2).
• X 2 represents a valent linking group
• L 2 represents a single bond or a divalent linking group
• W 1 represents a graft chain.
• the trivalent linking group represented by X 2 includes a poly(meth)acrylic linking group, a polyalkyleneimine linking group, a polyester linking group, a polyurethane linking group, a polyurea linking group, a polyamide linking group, and a polyether linking group.
• Examples include a poly(meth)acrylic coupling group and a polystyrene coupling group, preferably a poly(meth)acrylic coupling group and a polyalkyleneimine coupling group, and more preferably a poly(meth)acrylic coupling group.
• the divalent linking group represented by L 2 includes an alkylene group (preferably an alkylene group having 1 to 12 carbon atoms), an arylene group (preferably an arylene group having 6 to 20 carbon atoms), -NH-, -SO-, Examples thereof include -SO 2 -, -CO-, -O-, -COO-, OCO-, -S-, and groups formed by combining two or more of these.
• Examples of the graft chain represented by W 1 include the above-mentioned graft chains.
• repeating unit represented by the formula (A-1-2) include a repeating unit represented by the following formula (A-1-2a) and a repeating unit represented by the following formula (A-1-2b). Examples include units.
• R b1 to R b3 each independently represent a hydrogen atom or an alkyl group
• Q b1 is -CO-, -COO-, -OCO-, -CONH-, or phenylene.
• L 2 represents a single bond or a divalent linking group
• W 1 represents a graft chain.
• the number of carbon atoms in the alkyl group represented by R b1 to R b3 is preferably 1 to 10, more preferably 1 to 3, and even more preferably 1.
• Q b1 is preferably -COO- or -CONH-, more preferably -COO-.
• R b10 and R b11 each independently represent a hydrogen atom or an alkyl group
• m2 represents an integer of 1 to 5
• L 2 represents a single bond or a divalent linkage. group
• W 1 represents a graft chain.
• the number of carbon atoms in the alkyl group represented by R b10 and R b11 is preferably 1 to 10, more preferably 1 to 3.
• the weight average molecular weight (Mw) of the repeating unit having a graft chain is preferably 1,000 or more, more preferably 1,000 to 10,000, and even more preferably 1,000 to 7,500.
• the weight average molecular weight of a repeating unit having a graft chain is a value calculated from the weight average molecular weight of a raw material monomer used for polymerization of the same repeating unit.
• a repeating unit having a graft chain can be formed by polymerizing a macromonomer.
• the macromonomer refers to a polymer compound having a polymerizable group introduced at the end of the polymer.
• the weight average molecular weight of the macromonomer corresponds to the repeating unit having a graft chain.
• the content of repeating units having graft chains in the resin containing repeating units having graft chains is preferably 3 to 70 mol%.
• the lower limit is preferably 4 mol% or more, more preferably 5 mol% or more.
• the upper limit is preferably 60 mol% or less, more preferably 50 mol% or less.
• the resin containing a repeating unit having a graft chain may further contain a repeating unit having an acid group.
• the acid group include the acid groups mentioned above, and a carboxy group is preferable.
• the content of the repeating unit having an acid group in the resin containing the repeating unit having a graft chain is preferably 10 to 90 mol%.
• the lower limit is preferably 15 mol% or more, more preferably 20 mol% or more.
• the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less.
• the resin containing a repeating unit having a graft chain may further contain a repeating unit having a basic group.
• the basic group include the basic groups mentioned above, and an amino group is preferable.
• the content of the repeating unit having a basic group in the resin containing the repeating unit having a graft chain is preferably 20 to 80 mol%.
• the lower limit is preferably 25 mol% or more, more preferably 30 mol% or more.
• the upper limit is preferably 75 mol% or less, more preferably 70 mol% or less.
• the resin containing a repeating unit having a graft chain may further contain a repeating unit having an ethylenically unsaturated bond-containing group.
• the ethylenically unsaturated bond-containing group include a vinyl group, styrene group, maleimide group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, etc. It is preferably a meth)acryloyl group, a (meth)acryloyloxy group or a (meth)acryloylamide group, more preferably a (meth)acryloyloxy group, and even more preferably an acryloyloxy group.
• the content of the repeating unit having an ethylenically unsaturated bond-containing group in the resin containing the repeating unit having a graft chain is preferably 1 to 50 mol%.
• the lower limit is preferably 3 mol% or more, more preferably 5 mol% or more.
• the upper limit is preferably 40 mol% or less, more preferably 30 mol% or less.
• the weight average molecular weight of the resin containing repeating units having graft chains is preferably 10,000 to 50,000.
• the lower limit is preferably 12,000 or more, more preferably 13,000 or more.
• the upper limit is preferably 45,000 or less, more preferably 40,000 or less.
• the resin it is also preferable to use a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher-valent linking group.
• a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher-valent linking group By using such a resin, aggregation of particles in the photosensitive composition can be more effectively suppressed due to steric hindrance caused by the polymer chains, and excellent storage stability can be obtained.
• the weight average molecular weight of the resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher linking group is preferably 5,000 to 20,000.
• the lower limit is preferably 6,000 or more, more preferably 7,000 or more.
• the upper limit is preferably 18,000 or less, more preferably 15,000 or less.
• resin (SP-1) As a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher linking group, for example, a resin having a structure represented by the following formula (SP-1) (hereinafter also referred to as resin (SP-1)) is Can be mentioned.
• Z 1 represents a (m+n)-valent linking group
• Y 1 and Y 2 each independently represent a single bond or a linking group
• A1 is a heterocyclic group, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group
• P 1 represents a polymer chain
• n represents 1 to 20
• m represents 2 to 20
• m+n represents 3 to 21
• n Y 1 and A 1 may be the same or different
• the m pieces of Y 2 and P 1 may be the same or different.
• a 1 in formula (SP-1) represents a group containing the above-mentioned functional group.
• the functional group that A 1 has is preferably a heterocyclic group, an acid group, a group having a basic nitrogen atom, a hydrocarbon group having 4 or more carbon atoms, and a hydroxy group, and more preferably an acid group.
• the acid group include the acid groups mentioned above, and a carboxy group is preferable.
• At least one of the above-mentioned functional groups may be contained in one A1 , and two or more may be contained in one A1.
• a 1 preferably contains 1 to 10 substituents, more preferably 1 to 6 substituents.
• the group containing the above-mentioned functional group represented by A1 includes the above-mentioned functional group, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to 100 oxygen atoms, and 1 to 400 oxygen atoms. and a linking group consisting of 0 to 40 sulfur atoms.
• one or more acid groups may be connected via a chain saturated hydrocarbon group having 1 to 10 carbon atoms, a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms, or an aromatic hydrocarbon group having 5 to 10 carbon atoms.
• chain saturated hydrocarbon group having 1 to 10 carbon atoms a chain saturated hydrocarbon group having 1 to 10 carbon atoms
• a cyclic saturated hydrocarbon group having 3 to 10 carbon atoms or an aromatic hydrocarbon group having 5 to 10 carbon atoms.
• Examples include groups formed by bonding.
• the above-mentioned chain saturated hydrocarbon group, cyclic saturated hydrocarbon group and aromatic hydrocarbon group may further have a substituent.
• Substituents include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 16 carbon atoms, hydroxy groups, carboxy groups, amino groups, sulfonamide groups, N-sulfonylamide groups, acyloxy groups having 1 to 6 carbon atoms, Examples include an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate group, and an ethylenically unsaturated bond-containing group. Further, the above functional group itself may be A1 .
• the chemical formula weight of A 1 is preferably 30 to 2,000.
• the upper limit is preferably 1000 or less, more preferably 800 or less.
• the lower limit is preferably 50 or more, more preferably 100 or more.
• the (m+n)-valent linking group represented by Z 1 in formula (SP-1) includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, and 1 to 200 carbon atoms. Mention may be made of groups consisting of hydrogen atoms and 0 to 20 sulfur atoms. Examples of the (m+n)-valent linking group include the following structural units or groups formed by combining two or more of the following structural units (which may form a ring structure). * in the formula below represents a bond.
• the (m+n)-valent linking group may have a substituent.
• substituents include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 16 carbon atoms, hydroxy groups, amino groups, carboxy groups, sulfonamide groups, N-sulfonylamide groups, and acyloxy groups having 1 to 6 carbon atoms. , an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an alkoxycarbonyl group having 2 to 7 carbon atoms, a cyano group, a carbonate ester group, a group containing an ethylenically unsaturated bond, and the like.
• the (m+n)-valent linking group represented by Z 1 is preferably a group represented by any one of formulas (Z-1) to (Z-4).
• Lz 3 represents a trivalent group
• Tz 3 represents a single bond or a divalent linking group
• the three Tz 3s may be the same or different from each other.
• Lz 4 represents a tetravalent group
• Tz 4 represents a single bond or a divalent linking group
• the four Tz 4s present may be the same or different from each other.
• Lz 5 represents a pentavalent group
• Tz 5 represents a single bond or a divalent linking group
• the five Tz 5s may be the same or different from each other.
• Lz 6 represents a hexavalent group
• Tz 6 represents a single bond or a divalent linking group
• the six Tz 6s may be the same or different from each other.
• * represents a bond.
• the divalent linking group represented by Tz 3 to Tz 6 includes an alkylene group, an arylene group, a heterocyclic group, -O-, -CO-, -COO-, -OCO-, -NR-, -CONR-, - Examples include NRCO-, -S-, -SO-, -SO 2 -, and a linking group formed by linking two or more of these.
• R each independently represents a hydrogen atom, an alkyl group, or an aryl group.
• the number of carbon atoms in the alkyl group and alkylene group is preferably 1 to 30.
• the upper limit is more preferably 25 or less, and even more preferably 20 or less.
• the lower limit is more preferably 2 or more, and even more preferably 3 or more.
• the alkyl group and alkylene group may be linear, branched, or cyclic.
• the number of carbon atoms in the aryl group and arylene group is preferably 6 to 20, more preferably 6 to 12.
• the heterocyclic group preferably has a 5-membered ring or a 6-membered ring.
• the heteroatom contained in the heterocyclic group is preferably an oxygen atom, a nitrogen atom, or a sulfur atom.
• the number of heteroatoms that the heterocyclic group has is preferably 1 to 3.
• the alkylene group, arylene group, heterocyclic group, alkyl group, and aryl group may be unsubstituted or may have the above-mentioned substituents.
• Examples of the trivalent group represented by Lz 3 include a group obtained by removing one hydrogen atom from the above divalent linking group.
• Examples of the tetravalent group represented by Lz 4 include a group obtained by removing two hydrogen atoms from the above divalent linking group.
• the pentavalent group represented by Lz 5 includes a group obtained by removing three hydrogen atoms from the above divalent linking group.
• Examples of the hexavalent group represented by Lz 6 include a group obtained by removing four hydrogen atoms from the above divalent linking group.
• the trivalent to hexavalent groups represented by Lz 3 to Lz 6 may have the above-mentioned substituents.
• the chemical formula weight of Z 1 is preferably 20 to 3,000.
• the upper limit is preferably 2000 or less, more preferably 1500 or less.
• the lower limit is preferably 50 or more, more preferably 100 or more. Note that the chemical formula weight of Z 1 is a value calculated from the structural formula.
• Y 1 and Y 2 each independently represent a single bond or a linking group.
• the linking group include groups consisting of 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to 20 sulfur atoms. It will be done. The above-mentioned group may further have the above-mentioned substituent.
• Examples of the linking group represented by Y 1 and Y 2 include the following structural units or groups constituted by a combination of two or more of the following structural units. * in the formula below represents a bond.
• P 1 represents a polymer chain.
• the polymer chain represented by P 1 preferably contains a repeating unit of at least one type of structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure, It is more preferable to contain a repeating unit of at least one type of structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, and a polystyrene structure, and even more preferably a repeating unit of a poly(meth)acrylic structure.
• Examples of the repeating unit of the polyester structure include repeating units of the structure represented by the above-mentioned formula (G-1), formula (G-4), or formula (G-5).
• Examples of the repeating unit of the polyether structure include the repeating unit of the structure represented by the above-mentioned formula (G-2).
• Examples of the repeating unit of the poly(meth)acrylic structure include the repeating unit of the structure represented by the above-mentioned formula (G-3).
• Examples of the repeating unit of the polystyrene structure include the repeating unit of the structure represented by the above-mentioned formula (G-6).
• the polymer chain represented by P 1 may include a repeating unit having an acid group.
• the acid group contained in the repeating unit having an acid group include the acid groups mentioned above, and a carboxy group is preferable.
• the content of the repeating unit having an acid group in all the repeating units constituting P 1 is preferably 5 to 50 mol%.
• the lower limit is preferably 7 mol% or more, more preferably 10 mol% or more.
• the upper limit is preferably 45 mol% or less, more preferably 40 mol% or less.
• the polymer chain represented by P 1 may include a repeating unit having a basic group.
• Examples of the basic group contained in the repeating unit having a basic group include the above-mentioned basic groups, and an amino group is preferable.
• the content of repeating units having a basic group in all repeating units constituting P 1 is preferably 5 to 50 mol%.
• the lower limit is preferably 7 mol% or more, more preferably 10 mol% or more.
• the upper limit is preferably 45 mol% or less, more preferably 40 mol% or less.
• the polymer chain represented by P 1 may further include a repeating unit having an ethylenically unsaturated bond-containing group.
• the ethylenically unsaturated bond-containing group include a vinyl group, styrene group, maleimide group, (meth)allyl group, (meth)acryloyl group, (meth)acryloyloxy group, (meth)acryloylamide group, etc. It is preferably a meth)acryloyl group, a (meth)acryloyloxy group or a (meth)acryloylamide group, more preferably a (meth)acryloyloxy group, and even more preferably an acryloyloxy group.
• the content of the repeating unit having an ethylenically unsaturated bond-containing group in all the repeating units constituting P 1 is preferably 1 to 65 mol%.
• the lower limit is preferably 3 mol% or more, more preferably 5 mol% or more.
• the upper limit is preferably 60 mol% or less, more preferably 55 mol% or less.
• the weight average molecular weight of the polymer chain represented by P 1 is preferably 1,000 or more, more preferably 1,000 to 10,000.
• the upper limit is preferably 9,000 or less, more preferably 6,000 or less, and even more preferably 3,000 or less.
• the lower limit is preferably 1200 or more, more preferably 1400 or more.
• the weight average molecular weight of P1 is a value calculated from the weight average molecular weight of the raw material used to introduce the polymer chain.
• resin (SP-1) examples include polymer compounds C-1 to C-31 described in paragraph numbers 0196 to 0209 of JP-A No. 2013-043962, and paragraph numbers of JP-A No. 2014-177613.
• examples include polymer compounds (C-1) to (C-61) described in No. 0256 to 0269, and resins having the structure described in paragraph number 0061 of International Publication No. 2018/163668, the contents of which are included in this specification. incorporated into the book.
• a random polymer or a block polymer can also be used as the resin.
• the resin used in the present invention includes a resin having at least one selected from acid value and base value.
• a resin having at least one selected from acid value and base value is also referred to as a specific resin.
• the specific resin may be used as a dispersant or as a binder.
• the acid value of the resin is a value representing the mass of potassium hydroxide required to neutralize the acidic component per gram of the solid content of the resin
• the base value is the value representing the mass of potassium hydroxide required to neutralize the acidic component per gram of the solid content of the resin. This value represents the mass of potassium hydroxide equivalent to the amount of hydrochloric acid required to neutralize the basic component per gram.
• Examples of the resin having an acid value used as the specific resin include resins having an acid group.
• One embodiment of the resin having an acid value includes a resin having a repeating unit having an acid group.
• the resin having a basic value used as the specific resin includes a resin having a basic group.
• One embodiment of the resin having a basic value includes a resin having a repeating unit having a basic group.
• Examples of the resin having an acid value and a base value used as the specific resin include resins having an acid value and a basic group, respectively.
• One embodiment of the resin having an acid value and a base value includes a resin having a repeating unit having an acid group and a repeating unit having a basic group.
• the specific resin is preferably a resin containing a repeating unit having a graft chain or a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher valent linking group.
• the specific resin preferably contains a repeating unit having at least one type of structure selected from a polyether structure, a polyester structure, a poly(meth)acrylic structure, a polystyrene structure, a polyurethane structure, a polyurea structure, and a polyamide structure; It is more preferable to include a repeating unit having at least one type of structure selected from a polyester structure and a poly(meth)acrylic structure, and preferably a repeating unit having at least one type of structure selected from a polyester structure and a poly(meth)acrylic structure. is even more preferable.
• the resin contained in the photosensitive composition of the present invention includes a resin having a repeating unit of a poly(meth)acrylic structure, a resin having a repeating unit of a polyester structure, and a resin having a repeating unit of a poly(meth)acrylic structure. It is also preferable that at least one of the resin and the resin having a repeating unit of a polyester structure is the above-mentioned specific resin. According to this aspect, the above-mentioned phase separation structure is easily formed in the film during film formation, and the light scattering properties of the obtained film can be further improved.
• the content of the resin having a repeating unit of a polyester structure is equal to or less than the repeating unit of a poly(meth)acrylic structure.
• the amount is preferably 20 to 250 parts by mass per 100 parts by mass of the resin.
• the upper limit is preferably 230 parts by mass or less, more preferably 200 parts by mass or less.
• the lower limit is preferably 30 parts by mass or more, and more preferably 50 parts by mass or more.
• the acid value of the specific resin is preferably 30 to 250 mgKOH/g.
• the upper limit is preferably 230 mgKOH/g or less, more preferably 200 mgKOH/g or less.
• the lower limit is preferably 35 mgKOH/g or more, more preferably 40 mgKOH/g or more.
• the base number of the specific resin is preferably 20 to 150 mgKOH/g.
• the upper limit is preferably 140 mgKOH/g or less, more preferably 130 mgKOH/g or less.
• the lower limit is preferably 25 mgKOH/g or more, more preferably 30 mgKOH/g or more.
• the ratio of the acid value to the base value (acid value/base value) of the specific resin is preferably 0.5 to 1.5.
• the lower limit is preferably 0.6 or more, more preferably 0.7 or more.
• the upper limit is preferably 1.4 or less, more preferably 1.3 or less, and even more preferably 1.2 or less.
• the specific resin has an acid value of 30 to 120 mgKOH/g and a base value of 20 to 130 mgKOH/g.
• the upper limit of the acid value is preferably 115 mgKOH/g or less, more preferably 110 mgKOH/g or less.
• the lower limit of the acid value is preferably 35 mgKOH/g or more, more preferably 40 mgKOH/g or more.
• the upper limit of the base value is preferably 125 mgKOH/g or less, more preferably 120 mgKOH/g or less.
• the lower limit of the base value is preferably 25 mgKOH/g or more, more preferably 30 mgKOH/g or more.
• the weight average molecular weight of the specific resin is preferably 4,000 to 50,000.
• the upper limit is preferably 45,000 or less, more preferably 40,000 or less.
• the lower limit is preferably 4,500 or more, more preferably 5,000 or more.
• the resin used in the present invention includes a resin having an acid value and a base value. That is, an embodiment may be mentioned in which the specific resin includes a resin having an acid value and a base value. According to this aspect, the storage stability of the photosensitive composition can be further improved, and furthermore, the developability is also good.
• the resin having an acid value and a base value may be a dispersant or a binder, but the resin having an acid value and a base value may be a dispersant or a binder.
• the resin used as the agent preferably contains a resin having an acid value and a base value.
• the photosensitive composition preferably contains a resin as a dispersant, and the resin as a dispersant preferably contains a resin having an acid value and a base value.
• the resin having an acid value and a base value is preferably a resin containing a repeating unit having a graft chain or a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher valent linking group.
• the photosensitive composition in this embodiment may further contain a resin as a binder.
• the resin used as the binder preferably contains a resin having an acid value because the developability can be further improved.
• the resin used in the present invention includes one or more resins having an acid value and one or more resins having a base value. That is, examples include an embodiment in which the specific resin includes one or more resins having an acid value and one or more resins having a base value. According to this aspect, the storage stability of the photosensitive composition can be further improved, and furthermore, the developability is also good.
• the resin having an acid value used in this embodiment may be a resin having an acid value and no base value.
• the resin having a base value may be a resin having a base value and no acid value.
• the resin having an acid value and the resin having a base value may be a dispersant or a binder.
• the resin used as the dispersant preferably contains a resin having a basic value. Furthermore, the resin used as the binder preferably contains a resin having an acid value because the developability can be further improved. That is, in this embodiment, the photosensitive composition contains a resin as a dispersant and a resin as a binder, the resin as a dispersant contains a resin having a base value, and the resin as a binder contains a resin having a base value. It is preferable that the resin contains a resin having an acid value. Further, the resin used as the dispersant is preferably a resin containing a repeating unit having a graft chain or a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher valent linking group.
• the resin used in the present invention includes a resin having an acid value. That is, the specific resin may include a resin having an acid value. In this embodiment, it is preferable to further include a polyalkylene imine, which will be described later, because the storage stability of the photosensitive composition can be further improved.
• the resin having an acid value used in this embodiment may not contain a base value.
• the resin having an acid value may be a dispersant or a binder. Since the storage stability and developability of the photosensitive composition can be further improved, it is preferable to use a resin having an acid value as the resin as a dispersant and as the resin as a binder.
• the photosensitive composition preferably contains a resin as a dispersant and a resin as a binder, and the resin as a dispersant and the resin as a binder preferably contain a resin having an acid value.
• the resin used as the dispersant is preferably a resin containing a repeating unit having a graft chain or a resin having a structure in which a plurality of polymer chains are bonded to a trivalent or higher valent linking group.
• the content of the resin in the total solid content of the photosensitive composition is preferably 1 to 50% by mass.
• the lower limit is preferably 5% by mass or more, more preferably 10% by mass or more.
• the upper limit is preferably 45% by mass or less, more preferably 40% by mass or less, and even more preferably 35% by mass or less.
• the content of the above-mentioned specific resin in the resin contained in the photosensitive composition is preferably 10 to 100% by mass.
• the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more.
• the content of the resin having an acid value and a base value in the resin contained in the photosensitive composition is preferably 10 to 100% by mass. .
• the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more.
• the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
• the content of the resin having a base value in the resin contained in the photosensitive composition is preferably 10 to 100% by mass.
• the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more.
• the upper limit is preferably 90% by mass or less, more preferably 80% by mass or less.
• the content of the resin having an acid value in the resin contained in the photosensitive composition is preferably 10 to 100% by mass.
• the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more.
• One type of resin may be used alone, or two or more types may be used in combination. When two or more resins are used in combination, the total amount thereof is preferably within the above range.
• the photosensitive composition of the present invention preferably contains a polymerizable monomer.
• the polymerizable monomer include compounds having an ethylenically unsaturated bond-containing group.
• examples of the ethylenically unsaturated bond-containing group include a vinyl group, (meth)allyl group, and (meth)acryloyl group.
• the polymerizable monomer is preferably a radically polymerizable monomer.
• the polymerizable monomer is preferably a compound containing two or more ethylenically unsaturated bond-containing groups, more preferably a compound containing three or more ethylenically unsaturated bond-containing groups, and is more preferably a compound containing three or more ethylenically unsaturated bond-containing groups. More preferably, it is a compound containing four or more groups.
• the upper limit of the ethylenically unsaturated bond-containing groups is preferably 15 or less, more preferably 10 or less, and even more preferably 6 or less.
• the polymerizable monomer is preferably a trifunctional or more functional (meth)acrylate compound, more preferably a 3-15 functional (meth)acrylate compound, and a 3-10 functional (meth)acrylate compound. are more preferred, and tri- to hexa-functional (meth)acrylate compounds are particularly preferred.
• the molecular weight of the polymerizable monomer is preferably 200 to 3,000.
• the upper limit of the molecular weight is preferably 2,500 or less, more preferably 2,000 or less.
• the lower limit of the molecular weight is preferably 250 or more, more preferably 300 or more.
• the polymerizable monomer is a compound having at least one addition-polymerizable ethylene group and an ethylenically unsaturated bond-containing group having a boiling point of 100° C. or higher under normal pressure.
• monofunctional acrylates and methacrylates such as polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, phenoxyethyl(meth)acrylate; polyethylene glycol di(meth)acrylate, trimethylolethane tri(meth)acrylate; ) acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, hexanediol(meth)
• n is 0-14 and m is 1-8.
• a plurality of R's and T's in the same molecule may be the same or different.
• Specific examples of compounds represented by formulas (MO-1) to (MO-5) include compounds described in paragraph numbers 0248 to 0251 of JP-A No. 2007-269779, the content of which is incorporated herein by reference. Incorporated into the specification.
• polymerizable monomers examples include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320) ; made by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (as a commercial product KAYARAD D-310; made by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a commercial product KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.; NK ester A-DPH-12E; manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), and these (meth)acryloyl groups via ethylene glycol and/or propylene glycol residues.
• Polymerizable monomers include trimethylolpropane tri(meth)acrylate, trimethylolpropane propylene oxide-modified tri(meth)acrylate, trimethylolpropane ethylene oxide-modified tri(meth)acrylate, isocyanuric acid ethylene oxide-modified tri(meth)acrylate, and pentaerythritol tri(meth)acrylate. It is also preferable to use trifunctional (meth)acrylate compounds such as (meth)acrylate. Commercially available trifunctional (meth)acrylate compounds include Aronix M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, M-305.
• M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Examples include.
• the polymerizable monomer may be a compound having an acid group such as a carboxy group, a sulfo group, or a phosphoric acid group.
• examples of the polymerizable monomer having an acid group include esters of aliphatic polyhydroxy compounds and unsaturated carboxylic acids.
• Commercially available products include, for example, Aronix series M-305, M-510, and M-520 manufactured by Toagosei Co., Ltd.
• the acid value of the polymerizable monomer having an acid group is preferably 0.1 to 40 mgKOH/g.
• the lower limit is preferably 5 mgKOH/g or more.
• the upper limit is preferably 30 mgKOH/g or less.
• the polymerizable monomer may be a compound containing a ring structure.
• a phase separation structure can be easily formed in the film during film formation, and a film with better light scattering properties can be formed.
• the ring structure contained in the polymerizable monomer is preferably an aliphatic ring because the above effects are more likely to be obtained.
• the aliphatic ring is preferably an aliphatic bridged ring.
• An aliphatic bridged ring is an aliphatic ring having a structure in which two or more atoms that are not adjacent to each other are connected in one aliphatic ring.
• the aliphatic bridged ring examples include a tricyclodecane ring and an adamantane ring, with a tricyclodecane ring being preferred.
• the number of ring structures contained in the polymerizable monomer is preferably 1 to 5, more preferably 1 to 3, and most preferably 1.
• Specific examples of the polymerizable monomer containing a ring structure include dimethylol-tricyclodecane diacrylate, 1,3-adamantanediol diacrylate, and the like.
• the content of the polymerizable monomer in the total solid content of the photosensitive composition is preferably 0.1 to 40% by mass.
• the lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more.
• the upper limit is preferably 35% by mass or less, more preferably 33% by mass or less, and even more preferably 30% by mass or less.
• the polymerizable monomers may be used alone or in combination of two or more. When two or more types of polymerizable monomers are used in combination, the total amount thereof is preferably within the above range.
• the content of the polymerizable monomer is preferably 10 to 400 parts by mass based on 100 parts by mass of the resin.
• the lower limit is preferably 15 parts by mass or more, more preferably 20 parts by mass or more.
• the upper limit is preferably 380 parts by mass or less, more preferably 350 parts by mass or less.
• the total content of the polymerizable monomer and resin in the total solid content of the photosensitive composition is preferably 10 to 80% by mass.
• the upper limit is preferably 70% by mass or less, more preferably 65% by mass or less, and even more preferably 60% by mass or less.
• the lower limit is preferably 20% by mass or more, more preferably 30% by mass or more.
• the photosensitive composition of the present invention can also contain polyalkyleneimine.
• the photosensitive composition of the present invention when a resin having an acid value (more preferably a resin having an acid value but no base value) is used as the resin, the photosensitive composition of the present invention further contains a polyalkylene imine. It is preferable. According to this aspect, the storage stability of the photosensitive composition can be further improved.
• Polyalkyleneimine is a polymer obtained by ring-opening polymerization of alkyleneimine.
• Polyalkyleneimine is a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group, respectively.
• the alkylene imine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.
• the molecular weight of the polyalkylene imine is preferably 200 or more, more preferably 250 or more.
• the upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less.
• the molecular weight of the polyalkylene imine if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkylene imine is the value calculated from the structural formula.
• the molecular weight of a specific amine compound cannot be calculated from the structural formula or is difficult to calculate, the value of the number average molecular weight measured by the boiling point elevation method is used.
• the value of the number average molecular weight measured by the viscosity method is used. If the viscosity method cannot be used or it is difficult to measure, the number average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography) is used.
• the amine value of the polyalkyleneimine is preferably 5 mmol/g or more, more preferably 10 mmol/g or more, and even more preferably 15 mmol/g or more.
• alkyleneimine examples include ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, etc. Ethyleneimine or propyleneimine is preferable, and ethyleneimine is more preferable. preferable. It is particularly preferred that the polyalkyleneimine is polyethyleneimine. Further, the polyethyleneimine preferably contains 10 mol% or more, more preferably 20 mol% or more of primary amino groups based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. , more preferably 30 mol% or more.
• Commercial products of polyethyleneimine include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).
• the content of polyalkyleneimine in the total solid content of the photosensitive composition is preferably 0.05 to 5% by mass.
• the lower limit is preferably 0.10% by mass or more, more preferably 0.15% by mass or more.
• the upper limit is preferably 4% by mass or less, more preferably 3% by mass or less.
• the content of polyalkyleneimine is preferably 0.5 to 10 parts by mass based on 100 parts by mass of the specific particles.
• the lower limit is preferably 0.7 parts by mass or more, more preferably 1.0 parts by mass or more.
• the upper limit is preferably 5 parts by mass or less, more preferably 3 parts by mass or less. Only one type of polyalkylene imine may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.
• the photosensitive composition of the present invention preferably contains a solvent.
• the solvent include organic solvents. There are basically no particular restrictions on the solvent as long as it satisfies the solubility of each component and the coatability of the photosensitive composition.
• the organic solvent include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. For these details, the description in paragraph number 0223 of International Publication No. 2015/166779 can be referred to, and the contents thereof are incorporated herein. Ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used.
• organic solvents include acetone, methyl ethyl ketone, cyclohexane, cyclohexanone, cyclopentanone, ethyl acetate, butyl acetate, cyclohexyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol dimethyl ether.
• an organic solvent with a low metal content it is preferable to use an organic solvent with a low metal content, and the metal content of the organic solvent is preferably 10 mass ppb (parts per billion) or less, for example. If necessary, an organic solvent at a mass ppt (parts per trillion) level may be used, and such an organic solvent is provided by Toyo Gosei Co., Ltd. (Kagaku Kogyo Nippo, November 13, 2015).
• Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) and filtration using a filter.
• the filter pore diameter of the filter used for filtration is preferably 10 ⁇ m or less, more preferably 5 ⁇ m or less, and even more preferably 3 ⁇ m or less.
• the material of the filter is preferably polytetrafluoroethylene, polyethylene, or nylon.
• the organic solvent may contain isomers (compounds with the same number of atoms but different structures). Moreover, only one type of isomer may be included, or multiple types may be included.
• the content of peroxide in the organic solvent is preferably 0.8 mmol/L or less, and more preferably substantially free of peroxide.
• the content of the solvent in the photosensitive composition is preferably 10 to 95% by mass.
• the lower limit is preferably 15% by mass or more, more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 30% by mass or more, and 40% by mass. It is even more preferable that it is the above.
• the upper limit is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less. Only one type of solvent may be used, or two or more types may be used in combination. When two or more types of solvents are used in combination, it is preferable that the total amount is within the above range.
• the photosensitive composition of the present invention can further contain a pigment derivative.
• the pigment derivative include compounds having a structure in which a portion of the chromophore is substituted with an acidic group, a basic group, or a phthalimidomethyl group.
• the acid group include a sulfo group, a carboxy group, and their quaternary ammonium bases.
• the basic group include an amino group.
• the content of the pigment derivative is preferably 1 to 30 parts by weight, more preferably 3 to 20 parts by weight, based on 100 parts by weight of the pigment. Only one type of pigment derivative may be used, or two or more types may be used in combination. When two or more types of pigment derivatives are used in combination, it is preferable that the total amount is within the above range.
• the photosensitive composition of the present invention can contain a coloring inhibitor.
• the coloring inhibitor include phenol compounds, phosphite compounds, thioether compounds, etc., and preferably phenol compounds with a molecular weight of 500 or more, phosphite compounds with a molecular weight of 500 or more, or thioether compounds with a molecular weight of 500 or more.
• the coloring inhibitor is preferably a phenol compound, more preferably a phenol compound having a molecular weight of 500 or more.
• phenol compound examples include hindered phenol compounds.
• compounds having a substituent at the site adjacent to the phenolic hydroxy group (ortho position) are preferred.
• the above-mentioned substituents are preferably substituted or unsubstituted alkyl groups having 1 to 22 carbon atoms.
• compounds having a phenol group and a phosphite group in the same molecule are also preferred.
• polysubstituted phenolic compounds are preferably used as the phenolic hydroxy group-containing compounds.
• polysubstituted phenolic compounds There are three types of polysubstituted phenol compounds (formula (A) hindered type, formula (B) semi There are two types: hindered type and formula (C) less hindered type).
• R is a hydrogen atom or a substituent.
• R is a hydrogen atom, a halogen atom, an amino group that may have a substituent, an alkyl group that may have a substituent, an aryl group that may have a substituent, or a substituent.
• Alkoxy group, aryloxy group which may have a substituent, alkylamino group which may have a substituent, arylamino group which may have a substituent, alkylsulfonyl group which may have a substituent , an arylsulfonyl group which may have a substituent is preferable, an amino group which may have a substituent, an alkyl group which may have a substituent, an aryl group which may have a substituent, a substituent More preferred are an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, and an arylamino group which may have a substituent.
• a more preferable form is a complex coloring inhibitor in which a plurality of structures exhibiting antioxidant functions represented by the above formulas (A) to (C) exist in the same molecule, and specifically, the above formula (A) Compounds in which 2 to 4 structures exhibiting an antioxidant function represented by (C) are present in the same molecule are preferred.
• the semi-hindered type of formula (B) is more preferred.
• Typical examples available as commercial products include (A) Sumilizer BHT (manufactured by Sumitomo Chemical), Irganox 1010, 1222 (manufactured by BASF), ADEKA STAB AO-20, AO-50, AO-60 (ADEKA Corporation). (manufactured by).
• Examples of (B) include Sumilizer BBM-S (manufactured by Sumitomo Chemical Co., Ltd.), Irganox 245 (manufactured by BASF Corporation), and ADEKA STAB AO-80 (manufactured by ADEKA Corporation).
• Examples of (C) include ADEKA STAB AO-30 and AO-40 (manufactured by ADEKA Co., Ltd.).
• Examples of the phosphite compound and thioether compound include the compounds described in paragraphs 0213 to 0214 of International Publication No. 2017/159910 and commercially available products.
• commercially available coloring inhibitors include ADEKA STAB AO-50F, ADEKA STAB AO-60G, ADEKA STAB AO-330 (ADEKA Corporation), and the like.
• compounds described in paragraphs 0211 to 0223 of JP-A-2015-034961 can also be used as the coloring inhibitor.
• the content of the coloring inhibitor in the total solid content of the photosensitive composition is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and 0.3 to 5% by mass. % is more preferable. Only one type of coloring inhibitor may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention can contain an ultraviolet absorber.
• the ultraviolet absorber include conjugated diene compounds, aminobutadiene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, and the like. Specific examples of such compounds include paragraph numbers 0038 to 0052 of JP2009-217221A, paragraphs 0052 to 0072 of JP2012-208374A, and paragraphs 0317 to 0317 of JP2013-068814A.
• UV absorbers examples include UV-503 (manufactured by Daito Kagaku Co., Ltd.), Tinuvin series and Uvinul series manufactured by BASF, and Sumisorb series manufactured by Sumika Chemtex Co., Ltd. .
• examples of the benzotriazole compound include the MYUA series manufactured by Miyoshi Yushi (Kagaku Kogyo Nippo, February 1, 2016).
• the ultraviolet absorbers include compounds described in paragraph numbers 0049 to 0059 of Patent No.
• the maximum absorption wavelength of the ultraviolet absorber is preferably in the wavelength range of 200 to 340 nm, more preferably in the wavelength range of 210 to 320 nm, and even more preferably in the wavelength range of 220 to 300 nm.
• the content of the ultraviolet absorber in the total solid content of the photosensitive composition is preferably 0.1 to 10% by mass, more preferably 0.1 to 7% by mass, and 0.1 to 5% by mass. %, particularly preferably 0.1 to 3% by mass. Only one type of ultraviolet absorber may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that their total amount falls within the above range. It is also preferable that the photosensitive composition of the present invention does not substantially contain an ultraviolet absorber.
• "containing substantially no ultraviolet absorber” means that the content of the ultraviolet absorber in the total solid content of the photosensitive composition is 0.05% by mass or less, and 0. It is preferably .01% by mass or less, and more preferably contains no ultraviolet absorber.
• the photosensitive composition of the present invention can contain a silane coupling agent.
• a silane coupling agent means a silane compound having a hydrolyzable group and other functional groups.
• hydrolyzable group refers to a substituent that is directly bonded to a silicon atom and can form a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of the hydrolyzable group include a halogen atom, an alkoxy group, an acyloxy group, and an alkoxy group is preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.
• Examples of functional groups other than hydrolyzable groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, (meth)acryloyloxy groups, mercapto groups, epoxy groups, oxetanyl groups, amino groups, and ureido groups. group, sulfide group, isocyanate group, phenyl group, etc., and amino group, (meth)acryloyl group, (meth)acryloyloxy group, and epoxy group are preferable.
• Specific examples of the silane coupling agent include compounds described in paragraph 0177 of International Publication No. 2022/085485.
• the content of the silane coupling agent in the total solid content of the photosensitive composition is preferably 0.01 to 10% by mass, more preferably 0.1 to 7% by mass, and 1 to 5% by mass. % is more preferable. Only one type of silane coupling agent may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention can contain a polymerization inhibitor.
• polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, 1,4-benzoquinone, 4,4'-thiobis(3-methyl-6-tert -butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.), with p-methoxyphenol being preferred.
• the content of the polymerization inhibitor in the total solid content of the photosensitive composition is preferably 0.0001 to 5% by mass, more preferably 0.0001 to 1% by mass.
• the photosensitive composition of the present invention can contain a chain transfer agent.
• a chain transfer agent a compound described in paragraph 0225 of International Publication No. 2017/159190 can be used.
• the content of the chain transfer agent is preferably 0.2 to 5.0% by mass, more preferably 0.4 to 3.0% by mass based on the total solid content of the photosensitive composition. Further, the content of the chain transfer agent is preferably 1 to 40 parts by weight, more preferably 2 to 20 parts by weight, based on 100 parts by weight of the polymerizable monomer. Only one type of chain transfer agent may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention can further contain a sensitizer.
• the sensitizer is preferably a compound that sensitizes the photopolymerization initiator using an electron transfer mechanism or an energy transfer mechanism.
• Examples of the sensitizer include compounds having absorption in the range of 300 to 450 nm.
• the content of the sensitizer in the total solid content of the photosensitive composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 15% by mass. Only one type of sensitizer may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention can further contain a co-sensitizer.
• the co-sensitizer is preferably a compound that has the effect of further improving the sensitivity of the photopolymerization initiator or sensitizer to actinic radiation, or suppressing inhibition of polymerization of polymerizable monomers by oxygen.
• the description in paragraphs 0254 to 0257 of JP 2010-106268A (corresponding paragraphs 0277 to 0279 of US Patent Application Publication No. 2011/0124824) can be referred to. The contents are incorporated herein.
• the content of the co-sensitizer is preferably 0.1 to 30% by mass, more preferably 1 to 25% by mass, and 1.5 to 20% by mass based on the total solid content of the photosensitive composition. It is more preferable that Only one type of co-sensitizer may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention can contain a surfactant.
• a surfactant various surfactants such as fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants can be used.
• the surfactant is preferably a silicone surfactant or a fluorine surfactant.
• fluorosurfactant compounds described in paragraph numbers 0167 to 0173 of International Publication No. 2022/085485 can be used.
• nonionic surfactants examples include compounds described in paragraph 0174 of International Publication No. 2022/085485.
• silicone surfactants examples include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, SF 8419 OIL (manufactured by Dow Toray Industries, Inc.), and TSF- 4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (manufactured by Shin-Etsu Chemical Co., Ltd.) , BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (manufactured by BYK Chemie), and the like.
• the content of the surfactant in the total solid content of the photosensitive composition is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass. Only one type of surfactant may be used, or two or more types may be used in combination. When two or more types are used together, it is preferable that their total amount falls within the above range.
• the photosensitive composition of the present invention can contain known additives such as plasticizers and fat-sensitizing agents.
• plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, triacetylglycerin, and the like.
• the container for storing the photosensitive composition of the present invention is not particularly limited, and any known container can be used. Further, as the storage container, the container described in paragraph number 0187 of International Publication No. 2022/085485 can be used.
• the photosensitive composition of the present invention can be prepared by mixing the above-mentioned components.
• each component may be blended all at once, or may be blended sequentially after at least one of dissolving and dispersing each component in a solvent. Furthermore, there are no particular restrictions on the order of addition or working conditions when blending.
• the preparation of the photosensitive composition includes a process of dispersing particles.
• mechanical forces used for dispersing particles include compression, squeezing, impact, shearing, cavitation, and the like.
• Specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion, and the like.
• pulverizing particles in a sand mill (bead mill) it is preferable to use small-diameter beads or increase the filling rate of beads, thereby increasing the pulverizing efficiency.
• the process and dispersion machine for dispersing particles are described in ⁇ Encyclopedia of Dispersion Technology, Published by Information Technology Corporation, July 15, 2005'' and ⁇ Dispersion Technology and Industrial Applications Focusing on Suspension (Solid/Liquid Dispersion Systems)''.
• the process and dispersion machine described in Paragraph No. 0022 of JP2015-157893A, ⁇ Comprehensive Data Collection, Published by Management Development Center Publishing Department, October 10, 1978'' can be suitably used.
• the particles may be refined in a salt milling step.
• the descriptions in JP-A No. 2015-194521 and JP-A No. 2012-046629 can be referred to, for example.
• any filter that has been conventionally used for filtration and the like can be used without particular limitation.
• fluororesins such as polytetrafluoroethylene (PTFE), polyamide resins such as nylon (e.g. nylon-6, nylon-6,6), polyolefin resins (high density, ultra-high molecular weight) such as polyethylene, polypropylene (PP), etc.
• PTFE polytetrafluoroethylene
• nylon e.g. nylon-6, nylon-6,6)
• polyolefin resins high density, ultra-high molecular weight
• polyethylene polypropylene
• PP polypropylene
• filters using materials such as polyolefin resin (including polyolefin resin).
• polypropylene (including high-density polypropylene) and nylon are preferred.
• the pore diameter of the filter is preferably 0.01 to 10.0 ⁇ m, more preferably 0.05 to 3.0 ⁇ m, and even more preferably about 0.1 to 2.0 ⁇ m.
• various filters provided by Nippon Pole Co., Ltd. (DFA4201NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. (formerly Nippon Microlith Co., Ltd.), Kitz Microfilter Co., Ltd., etc. can be used.
• a fiber filter medium as the filter.
• the fibrous filter medium include polypropylene fiber, nylon fiber, and glass fiber.
• Commercially available products include the SBP type series (SBP008, etc.), the TPR type series (TPR002, TPR005, etc.), and the SHPX type series (SHPX003, etc.) manufactured by Loki Techno.
• filters When using filters, different filters (for example, a first filter and a second filter, etc.) may be combined. At that time, filtration with each filter may be performed only once, or may be performed two or more times. Further, filters having different pore diameters within the above-mentioned range may be combined. Alternatively, only the dispersion liquid may be filtered with the first filter, and then filtered with the second filter after other components are mixed.
• filters for example, a first filter and a second filter, etc.
• the film of the present invention is a film obtained using the photosensitive composition of the present invention described above.
• the maximum value of the transmittance of light in the wavelength range of 400 to 700 nm of the film of the present invention is preferably 80% or less, more preferably 70% or less, even more preferably 60% or less, Particularly preferably, it is 50% or less.
• the lower limit of the maximum transmittance value is preferably 1% or more, more preferably 5% or more, even more preferably 10% or more, even more preferably 15% or more, and 20% or more. % or more is particularly preferable.
• the transmittance of the film of the present invention for light at a wavelength of 365 nm is preferably 15% or more, more preferably 25% or more, even more preferably 35% or more, particularly 45% or more. preferable.
• the maximum value of the transmittance of light in the wavelength range of 400 to 700 nm of the film of the present invention is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, It is even more preferably 75% or less, particularly preferably 70% or less.
• the lower limit of the maximum transmittance value is preferably 15% or more, more preferably 20% or more, even more preferably 30% or more, even more preferably 40% or more, and 45% or more. % or more is particularly preferable.
• the maximum value of the transmittance of light in the wavelength range of 400 to 1000 nm of the film of the present invention is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, It is even more preferably 75% or less, particularly preferably 70% or less.
• the lower limit of the maximum transmittance is preferably 20% or more, more preferably 25% or more, even more preferably 35% or more, even more preferably 45% or more, and 50% or more. % or more is particularly preferable.
• the film of the present invention has a phase-separated structure of a first phase containing the particles A described above and a second phase containing less particles A than the first phase. It is preferable that it is formed. Moreover, it is preferable that the phase separation structure is a sea-island structure or a co-continuous phase structure. By forming these phase separation structures, light can be effectively scattered between the first phase and the second phase, and particularly excellent light scattering properties are likely to be obtained.
• the second phase may be the ocean and the first phase may form an island, or the first phase may be the ocean and the second phase may form an island. It is preferable from the viewpoint of transmittance that the first phase is sea and the second phase forms islands. It is preferable from the viewpoint of angular dependence that the first phase forms an island and the second phase forms an ocean.
• the haze of the film of the present invention based on JIS K 7136 is preferably 30 to 100%.
• the upper limit is preferably 99% or less, more preferably 95% or less, and even more preferably 90% or less.
• the lower limit is preferably 35% or more, more preferably 40% or more, and even more preferably 50% or more. If the haze of the film is within the above range, sufficient light scattering ability can be obtained while ensuring a sufficient amount of light transmission.
• the value of L* in the CIE1976 L*a*b* color system of the film of the present invention is preferably 35 to 100.
• the value of L* is preferably 40 or more, more preferably 50 or more, and even more preferably 60 or more. According to this aspect, a film with excellent whiteness can be obtained. Further, the value of L* is preferably 95 or less, more preferably 90 or less, and even more preferably 85 or less. According to this aspect, a film having appropriate visible transparency can be obtained.
• the value of a* is preferably -15 or more, more preferably -10 or more, and even more preferably -5 or more. Further, the value of a* is preferably 10 or less, more preferably 5 or less, and even more preferably 0 or less. According to this aspect, a film with excellent whiteness can be obtained.
• the value of b* is preferably -35 or more, more preferably -30 or more, and even more preferably -25 or more. Moreover, the value of b* is preferably 20 or less, more preferably 10 or less, and even more preferably 0 or less. According to this aspect, a film with excellent whiteness can be obtained.
• the thickness of the film of the present invention is preferably 1 to 50 ⁇ m.
• the upper limit of the film thickness is preferably 40 ⁇ m or less, more preferably 35 ⁇ m or less, and even more preferably 30 ⁇ m or less.
• the lower limit of the film thickness is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and even more preferably 3 ⁇ m or more. If the film thickness is within the above range, sufficient light scattering ability can be obtained. Furthermore, it is expected that the optical sensitivity of the device will be improved by making the sensor thinner and suppressing crosstalk.
• the film of the present invention has high light scattering properties and is preferably used as a light scattering film.
• the film of the present invention can be suitably used as a scattering layer for light emitting devices, a scattering layer for display devices, a scattering layer for environmental light sensors, and the like.
• the film of the present invention can also be suitably used for head-mounted displays.
• a head-mounted display consists of a display element, an eyepiece, a light source, a projection part, etc., and can be used either inside or between the display elements.
• Examples of head-mounted displays include JP 2019-061199, JP 2021-032975, JP 2019-032434, JP 2018-018077, JP 2016-139112, and U.S. patents.
• Application Publication No. 2021/0063745, China Patent Application Publication No. 112394509, US Patent No. 10921499, Korean Publication No. 10-2018-0061467, JP 2018-101034, JP Examples include head-mounted displays described in Publication No. 2020-101671, Taiwan Patent Application Publication No. 202028805, and the like.
• the film of the present invention can be manufactured through a step of applying the photosensitive composition of the present invention onto a support.
• the film manufacturing method may further include a step of forming a pattern.
• Examples of the pattern forming method include a pattern forming method using a photolithography method.
• the pattern forming method using the photolithography method includes a step of exposing the composition layer formed by applying the photosensitive composition of the present invention on a support in a pattern (exposure step), and exposing the composition layer of the unexposed area to light. It is preferable to include a step (developing step) of developing and forming a pattern by removing the layer. If necessary, a step of baking the developed pattern (post-bake step) may be provided. Each step will be explained below.
• the support to which the photosensitive composition is applied examples include substrates made of materials such as silicon, non-alkali glass, soda glass, Pyrex (registered trademark) glass, and quartz glass.
• An organic film, an inorganic film, or the like may be formed on these substrates.
• the material for the organic film include resin.
• a substrate made of resin can also be used as the support.
• a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. may be formed on the support.
• CMOS complementary metal oxide semiconductor
• a black matrix that isolates each pixel may be formed on the support.
• an undercoat layer may be provided on the support for improving adhesion with the upper layer, preventing substance diffusion, or flattening the substrate surface. Further, when a glass substrate is used as a support, it is preferable to form an inorganic film on the glass substrate or to use the glass substrate after dealkalization treatment.
• a known method can be used to apply the photosensitive composition to the support.
• drop casting method for example, drop casting method; slit coating method; spray method; roll coating method; spin coating method; casting coating method; slit and spin method;
• Various methods such as inkjet (for example, on-demand method, piezo method, thermal method), ejection printing such as nozzle jet, flexo printing, screen printing, gravure printing, reverse offset printing, metal mask printing, etc. Examples include printing method; transfer method using a mold etc.; nanoimprint method.
• the application method for inkjet is not particularly limited, and for example, the method described in the patent publication "Expanding and Usable Inkjet - Infinite Possibilities Seen in Patents," Published February 2005, Sumibe Techno Research.
• spin coating is preferably carried out in the range of 300 to 6000 rpm, and more preferably spin coating is carried out in the range of 400 to 3000 rpm.
• the temperature of the support during spin coating is preferably 10 to 100°C, more preferably 20 to 70°C. Within the above range, it is easy to produce a film with excellent coating uniformity.
• the dropping method (drop casting) it is preferable to form a dropping area of the photosensitive composition on the support using a photoresist as a partition so that a uniform film with a predetermined thickness can be obtained.
• a desired film thickness can be obtained by controlling the amount of the photosensitive composition dropped, the solid content concentration, and the area of the dropping area.
• the composition layer formed on the support may be dried (prebaked).
• the prebaking conditions are preferably, for example, at a temperature of 60 to 150° C. for 30 seconds to 15 minutes.
• the composition layer is exposed in a pattern.
• the composition layer can be pattern-exposed by exposing the composition layer to light through a mask having a predetermined mask pattern using an exposure device such as a stepper. This allows the exposed portion to be cured.
• radiation (light) that can be used for exposure include g-line and i-line.
• light with a wavelength of 300 nm or less preferably light with a wavelength of 180 to 300 nm
• Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm), ArF rays (wavelength 193 nm), and KrF rays (wavelength 248 nm).
• pulse exposure is an exposure method in which exposure is performed by repeating light irradiation and pauses in short cycles (for example, on the millisecond level or less).
• the pulse width is preferably 100 nanoseconds (ns) or less, more preferably 50 nanoseconds or less, and even more preferably 30 nanoseconds or less.
• the lower limit of the pulse width is not particularly limited, but can be 1 femtosecond (fs) or more, and can also be 10 femtoseconds or more.
• the frequency is preferably 1 kHz or more, more preferably 2 kHz or more, and even more preferably 4 kHz or more.
• the upper limit of the frequency is preferably 50 kHz or less, more preferably 20 kHz or less, and even more preferably 10 kHz or less.
• the maximum instantaneous illuminance is preferably 500000000 W/m 2 or more, more preferably 100000000 W/m 2 or more, and even more preferably 200000000 W/m 2 or more.
• the upper limit of the maximum instantaneous illuminance is preferably 1000000000 W/m 2 or less, more preferably 800000000 W/m 2 or less, and even more preferably 500000000 W/m 2 or less.
• the pulse width refers to the time during which light is irradiated in a pulse period.
• frequency refers to the number of pulse periods per second.
• the maximum instantaneous illuminance is the average illuminance within the time period during which light is irradiated in the pulse period.
• the pulse period is a period in which one cycle includes light irradiation and a pause in pulse exposure.
• the irradiation amount is preferably 0.03 to 2.5 J/cm 2 , more preferably 0.05 to 1.0 J/cm 2 , and even more preferably 0.08 to 0.5 J/cm 2 .
• the oxygen concentration during exposure can be selected as appropriate. For example, exposure may be carried out in the atmosphere, or in a low oxygen atmosphere with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, substantially oxygen-free); Exposure may be performed under a high oxygen atmosphere of more than 21% by volume (eg, 22% by volume, 30% by volume, 50% by volume). Further, the exposure illuminance can be set as appropriate, and is preferably selected from the range of 1,000 to 100,000 W/m 2 .
• the oxygen concentration and the exposure illuminance may be appropriately combined.
• the illumination intensity may be 10,000 W/m 2 at an oxygen concentration of 10% by volume, or 20,000 W/m 2 at an oxygen concentration of 35% by volume.
• the unexposed portions of the composition layer after exposure are developed and removed to form a pattern.
• the composition layer in the unexposed area can be removed by development using a developer.
• the temperature of the developer is preferably, for example, 20 to 30°C.
• the development time is preferably 20 to 180 seconds.
• the process of shaking off the developer every 60 seconds and supplying a new developer may be repeated several times.
• Examples of the developer include organic solvents, alkaline developers, and alkaline developers are preferably used.
• an alkaline aqueous solution (alkaline developer) prepared by diluting an alkaline agent with pure water is preferable.
• alkaline agents include ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide.
• alkaline compounds examples include alkaline compounds and inorganic alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, sodium silicate, and sodium metasilicate.
• alkali agent compounds with a large molecular weight are preferable from the environmental and safety standpoints.
• the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
• the developer may contain a surfactant.
• the surfactant include the above-mentioned surfactants, with nonionic surfactants being preferred.
• the developing solution may be manufactured as a concentrated solution and then diluted to a required concentration before use.
• the dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times.
• wash (rinse) with pure water after development.
• rinsing is preferably performed by supplying a rinsing liquid to the developed composition layer while rotating the support on which the developed composition layer is formed. It is also preferable to move the nozzle that discharges the rinsing liquid from the center of the support to the peripheral edge of the support. At this time, when moving the nozzle from the center of the support to the peripheral edge, the nozzle may be moved while gradually decreasing its moving speed. By performing rinsing in this manner, in-plane variations in rinsing can be suppressed. The same effect can also be obtained by gradually reducing the rotational speed of the support while moving the nozzle from the center of the support to the peripheral edge.
• post-bake After development, it is preferable to perform additional exposure treatment or heat treatment (post-bake) after drying. Additional exposure processing and post-bake are post-development curing processing to complete curing.
• the heating temperature in post-baking is preferably 100 to 260°C, for example.
• the lower limit of the heating temperature is preferably 120°C or higher, more preferably 160°C or higher.
• the upper limit of the heating temperature is preferably 240°C or lower, more preferably 220°C or lower.
• Post-baking can be carried out in a continuous or batch manner using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to maintain the developed film under the above conditions.
• the light used for exposure is preferably light with a wavelength of 400 nm or less. Further, the additional exposure process may be performed by the method described in Korean Patent Publication No. 10-2017-0122130.
• the optical sensor of the present invention has the film of the present invention.
• Types of optical sensors include environmental light sensors, illuminance sensors, etc., which are preferably used as environmental light sensors.
• An environmental light sensor is a sensor that detects the hue of surrounding light (environmental light).
• the optical sensor of the present invention also preferably has an optical filter having at least one type of pixel selected from colored pixels and pixels of an infrared transmission filter.
• colored pixels include red pixels, blue pixels, green pixels, yellow pixels, cyan pixels, magenta pixels, and the like.
• the film of the present invention is provided on the light incident side of the optical filter. By providing the film of the present invention on the light incident side of the optical filter, the angular dependence of each pixel can be further reduced.
• an optical filter 110 having pixels 111 to 114 is provided on a photoelectric conversion element 101.
• a film 121 of the present invention is then formed on the optical filter 110.
• An example of the pixels 111 to 114 constituting the optical filter 110 is a combination in which the pixel 111 is a red pixel, the pixel 112 is a blue pixel, the pixel 113 is a green pixel, and the pixel 114 is an infrared transmission filter pixel.
• an optical filter 110 having four types of pixels pixels 111 to 114
• the number of types of pixels may be one to three, or five types. It may be more than that. It can be selected as appropriate depending on the purpose.
• a flattening layer may be interposed between the photoelectric conversion element 101 and the optical filter 110 or between the optical filter 110 and the film 121 of the present invention.
• FIG. 2 shows another embodiment of the optical sensor.
• an optical filter 110 having pixels 111 to 114 is provided on the photoelectric conversion element 101.
• the optical filter 110 has the same configuration as the embodiment described above.
• a member in which the film 122 of the present invention is formed on the surface of a transparent support 130 is placed on the optical filter 110.
• Examples of the transparent support 130 include a glass substrate, a resin substrate, and the like.
• a member in which the film 122 of the present invention is formed on the surface of a transparent support 130 is arranged at a predetermined interval on the optical filter 110.
• the transparent support 130 may be in contact with the member on which the film 122 of the present invention is formed. Further, in the optical sensor 2 shown in FIG.
• the film 122 of the present invention is formed only on one side of the transparent support 130, but the film 122 of the present invention may be formed on both sides of the transparent support 130. .
• the film 122 of the present invention is formed on the surface of the transparent support 130 on the optical filter 110 side, but the film 122 of the present invention is formed on the surface of the transparent support 130 on the opposite side to the optical filter 110.
• the film 122 of the present invention may be formed thereon.
• a flattening layer may be interposed between the photoelectric conversion element 101 and the optical filter 110 or between the film 122 of the present invention and the transparent support 130.
• the primary particle diameter of the particles was determined by observing the particles using a transmission electron microscope (TEM) and observing the portions where the particles were not aggregated (primary particles). Specifically, after taking a transmission electron micrograph of the primary particles using a transmission microscope, the particle size distribution was determined using the photograph using an image processing device. The average primary particle diameter of the particles was the number-based arithmetic mean diameter calculated from the particle size distribution.
• An electron microscope (H-7000) manufactured by Hitachi, Ltd. was used as a transmission electron microscope, and Luzex AP manufactured by Nireco Co., Ltd. was used as an image processing device.
• the acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content of the resin.
• the acid value was calculated using the following formula, with the inflection point of the titration pH curve as the titration end point.
• A 56.11 ⁇ Vs ⁇ 0.5 ⁇ f/w
• w Mass (g) of measurement sample (solid content conversion)
• the base value represents the mass of potassium hydroxide equivalent to hydrochloric acid required to neutralize the basic component per gram of solid content of the resin.
• the base number was calculated using the following formula, with the inflection point of the titration pH curve as the titration end point.
• A 56.11 ⁇ Vs ⁇ 0.5 ⁇ f/w
• f Titer of 0.1 mol/L hydrochloric acid
• w Mass of measurement sample (g) (solid content equivalent)
• Synthesis of Particles P1 Weighed 300 g of water into a glass container 1, added 30.8 g of 60% nitric acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.), and Gd 2 O 3 (Yttrium Nippon) as a rare earth oxide. Co., Ltd.) was added thereto, and the mixture was heated to 80°C to dissolve. Into another glass container 2 were added 300 g of water and 9.4 g of 85% phosphoric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). After adding the contents of glass container 2 to glass container 1, aging was performed at 75° C. for 30 minutes.
• the obtained precipitate was washed by decantation until the conductivity of the supernatant became 200 ⁇ S/cm or less. After washing, solid-liquid separation was performed by vacuum filtration, dried in the air at 120°C for 5 hours, and then calcined in the air at 600°C for 5 hours to obtain particles P1.
• the crystal system of the particles P1 was measured using an X-ray diffraction device, it was confirmed that the particles were monoclinic GdPO4 . Further, the average primary particle diameter of the particles P1 was 127 nm.
• the solid content concentration, weight average molecular weight, acid value and base value of each resin are as follows.
• Ad-1 Epomin SP-003 (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine)
• Ad-2 Epomin SP-006 (manufactured by Nippon Shokubai Co., Ltd., polyethyleneimine)
• a photosensitive composition was produced by mixing the raw materials listed in the table below.
• I-1 Omnirad 369 (manufactured by IGM Resins B.V.)
• I-2 Omnirad 819 (manufactured by IGM Resins B.V.)
• I-3 Omnirad TPO H (manufactured by IGM Resins B.V.)
• I-4 Irgacure OXE03 (manufactured by BASF Japan Co., Ltd.)
• I-5 to I-7 Compounds with the following structure
• Ad-3 ADEKA STAB AO-80 (manufactured by ADEKA Co., Ltd., coloring prevention agent)
• Ad-4 Irganox 1010 (manufactured by BASF, anti-coloring agent)
• Ad-5 Compound with the following structure (silane coupling agent)
• (surfactant) Su-1 1% by mass propylene glycol monomethyl ether acetate solution of a compound with the following structure
• Su-2 A solution prepared by diluting KF-6001 (manufactured by Shin-Etsu Chemical Co., Ltd., a silicone surfactant) with propylene glycol monomethyl ether acetate to adjust the solid content concentration to 1% by mass
• Su-3 SH8400 (Dow.
• a solution prepared by diluting silicone surfactant manufactured by Toray Industries, Inc.
• propylene glycol monomethyl ether acetate to a solid concentration of 1% by mass.
• i-line stepper exposure device FPA-3000i5+ manufactured by Canon Inc.
• exposure was performed by irradiating light with a wavelength of 365 nm at an exposure dose of 1000 mJ/cm 2 , and then using a hot plate at 200°C.
• a heat treatment post-bake was performed for 5 minutes to form a film.
• the transmittance of the obtained film in the wavelength range of 400 to 1000 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technology Co., Ltd.).
• heat treatment prebaking
• FPA-3000i5+ manufactured by Canon Inc.
• light with a wavelength of 365 nm was irradiated through a patterned mask at an exposure dose of 1000 mj/cm 2 for exposure.
• a mask having an island pattern of 100 ⁇ m ⁇ 100 ⁇ m was used.
• the glass wafer on which the irradiated coating film has been formed is placed on the horizontal rotary table of a spin shower developer (Model DW-30, manufactured by Chemitronics Co., Ltd.), and an alkaline developer (CD-2060 , manufactured by Fujifilm Electronics Materials Co., Ltd.), paddle development was performed at room temperature for 60 seconds.
• the glass wafer after paddle development was fixed on a horizontal rotary table using a vacuum chuck method, and while the glass wafer was rotated at a rotation speed of 50 rpm by a rotating device, pure water was sprayed from above the center of rotation from a nozzle in the form of a shower.
• FPA-3000i5+ manufactured by Canon Inc.
• a heat treatment (post-bake) was performed for 5 minutes to form a film.
• the transmittance of the obtained film for light in the wavelength range of 400 to 1000 nm was measured using a spectrophotometer (U-4100, manufactured by Hitachi High-Technology Co., Ltd.), and the maximum value of transmittance in the above range (T max ) and the absolute value of the difference between the transmittance of light with a wavelength of 940 nm (T 940 ) and the transmittance of light with a wavelength of 450 nm (T 450 ) (transmittance difference ⁇ T) was calculated.
• Transmittance difference ⁇ T
• Transmittance difference ⁇ T is less than 15%.
• B Transmittance difference ⁇ T is 15% or more and less than 25%.
• C Transmittance difference ⁇ T is 25% or more and less than 30%.
• D Transmittance difference ⁇ T is 30% or more and less than 35%.
• E Transmittance difference ⁇ T is 35% or more.
• the photosensitive compositions of Examples had good storage stability and developability.
• FPA-3000i5+ manufactured by Canon Inc.
• a heat treatment (post-bake) was performed for 5 minutes using a 4- ⁇ m-thick film.
• a cross section of the obtained film in the thickness direction was observed using a scanning electron microscope (SEM) (S-4800H, manufactured by Hitachi High-Tech Corporation) (magnification: 10,000 times) to confirm the uneven distribution of particles.
• SEM scanning electron microscope
• Pigment dispersion liquid 1 C. I. Pigment Blue 15:6 and 88.80 parts by mass of C. I. A mixed solution of 23.20 parts by mass of Pigment Violet 23, 152.00 parts by mass of a 30 mass% PGMEA solution of a dispersant (Solsperse 36000; manufactured by Lubrizol), and 536.00 parts by mass of PGMEA was heated in a circulating type. A dispersion treatment was performed under the above-mentioned dispersion conditions using an Ultra Apex Mill manufactured by Kotobuki Kogyo Co., Ltd. as a dispersion device (bead mill) to produce Pigment Dispersion 1.
• a dispersant Solsperse 36000
• Optical sensor 101 Photoelectric conversion elements 111 to 114: Pixel 110: Optical filters 121, 122: Film 130: Transparent support

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• 2023
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