Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
  • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
  • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
• • H—ELECTRICITY
  • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
  • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
  • H05B33/00—Electroluminescent light sources
  • H05B33/12—Light sources with substantially two-dimensional radiating surfaces

Definitions

• the present invention relates to a photosensitive resin composition containing a specific photopolymerization initiator and a pyromethene derivative, a cured film thereof, a color conversion substrate and an image display device using the same, and a method for producing the cured film.
• organic EL (electroluminescence) displays have attracted attention as one of the new thin displays, and have begun to appear on the market as displays for mobile phones, mobile devices, televisions, and the like.
• a composition for forming a color conversion layer comprising a fluorescent dye, a highly refractive material, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent, and a self-luminous photosensitivity Resin compositions (see, for example, Patent Document 1) and curable compositions containing quantum dots and a binder resin (for example, see Patent Document 2) have been proposed.
• Patent Documents 1 and 2 Although a color conversion layer having a luminance higher than that of a color conversion layer using a pigment or dye having no light emission characteristics can be formed, the luminance obtained is It was still insufficient.
• Patent Document 3 does not disclose any method for forming a patterned color conversion film, and has not studied the improvement of luminance, which is a problem of conventional organic EL displays.
• the present invention has been made in view of the above circumstances, and is a photosensitive resin composition capable of forming a fine pattern with high brightness, a cured film thereof, a color conversion substrate using the same, and an image display device
• An object of the present invention is to provide a method for producing a cured film.
• the photosensitive resin composition according to the present invention includes at least a photopolymerization initiator, a pyromethene derivative, a light having an absorption coefficient of h-ray of 100 mL / g ⁇ cm or more. It contains a polymerizable compound and an alkali-soluble resin.
• the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the photopolymerization initiator is a phosphine oxide compound.
• the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the photopolymerization initiator has an extinction coefficient of 20 mL / g ⁇ cm or less at the absorption maximum wavelength of the pyromethene derivative. .
• the photosensitive resin composition according to the present invention is characterized in that, in the above-mentioned invention, further contains fine particles having a refractive index of 1.40 or more and 3.00 or less.
• the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the number average particle diameter of the fine particles is 10 nm or more and 300 nm or less.
• the photosensitive resin composition according to the present invention is characterized in that, in the above invention, a weight ratio of the content of the fine particles to the content of the pyromethene derivative is 5/1 or more and 100/1 or less. .
• the photosensitive resin composition according to the present invention is characterized in that, in the above invention, the pyromethene derivative is a compound represented by the following general formula (1).
• R 1 to R 9 may be the same or different and each represents hydrogen, an alkyl group, a cycloalkyl group, a heterocyclic group, alkenyl. Group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester Selected from a fused ring and an aliphatic ring formed between a group, a carbamoyl group, an amino group, a nitro group, a silyl group, a siloxanyl group, a boryl group, a sulfo group, a phosphine oxide group, and an adjacent substituent.
• R 1 to R 9 may be the same or different and each represents hydrogen, an alkyl group, a
• X is C—R 7 and R 7 is a group represented by the following general formula (2). It is characterized by that.
• r is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl Thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, sulfo group, phosphine oxide Selected from the group consisting of groups, k is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
• the photosensitive resin composition according to the present invention is characterized in that, in the above-described invention, the pyromethene derivative exhibits light emission observed in a region having a peak wavelength of 500 nm or more and less than 580 nm by excitation light.
• the photosensitive resin composition according to the present invention is characterized in that, in the above-described invention, the pyromethene derivative exhibits light emission observed in a region having a peak wavelength of 580 nm or more and less than 750 nm by excitation light.
• the photosensitive resin composition according to the present invention is characterized in that, in the above-mentioned invention, further contains an ultraviolet absorber having an absorption maximum wavelength in a wavelength region of 360 nm or less.
• the cured film according to the present invention is characterized by comprising a cured product of the photosensitive resin composition according to any one of the above inventions.
• the cured film according to the present invention is characterized in that, in the above-mentioned invention, the film thickness is 5 ⁇ m or more and 50 ⁇ m or less.
• the method for producing a cured film according to the present invention is a method for producing a cured film comprising a cured product of the photosensitive resin composition, and the photosensitive resin composition according to any one of the above inventions, Including an exposure step of exposing using an ultra-high pressure mercury lamp, wherein the exposure amount of the photosensitive resin composition in the exposure step is 60 mJ / cm 2 or more and 250 mJ / cm 2 or less in terms of i-line. To do.
• a color conversion substrate according to the present invention is characterized by including the cured film according to any one of the above inventions.
• an image display device includes the color conversion substrate described in the above invention.
• the photosensitive resin composition according to the present invention has an effect that a fine pattern with high luminance can be formed. Further, by using the photosensitive resin composition according to the present invention, there is an effect that a high-brightness cured film, a color conversion substrate, and an image display device can be realized.
• the photosensitive resin composition which concerns on embodiment of this invention is demonstrated in detail.
• the photosensitive resin composition according to the embodiment of the present invention contains at least a photopolymerization initiator having a h-ray extinction coefficient of 100 mL / g ⁇ cm or more, a pyromethene derivative, a photopolymerizable compound, and an alkali-soluble resin.
• the photosensitive resin composition according to the present embodiment contains the photopolymerization initiator, the photopolymerizable compound, and the alkali-soluble resin, radicals are generated by ultraviolet irradiation to cure the photosensitive resin composition, Pattern workability can be imparted to the photosensitive resin composition by the difference in alkali solubility between the ultraviolet irradiation part and the ultraviolet non-irradiation part of the photosensitive resin composition.
• the pyromethene derivative has a color conversion function for converting incident light into light having a longer wavelength than the incident light.
• the photosensitive resin composition contains a photopolymerization initiator having an absorption coefficient of h-line of 100 mL / g ⁇ cm or more together with such a pyromethene derivative.
• the h-line extinction coefficient is used as a photopolymerization initiator contained in the photosensitive resin composition by focusing on h-line that reaches the bottom more linearly. Is selected from photopolymerization initiators having an A of 100 mL / g ⁇ cm or more. Thereby, the sclerosis
• the photosensitive resin composition further comprises a photopolymerization initiator, an ultraviolet absorber, fine particles, an organic solvent, an adhesion improver, a surfactant, and a dispersant having an h-ray absorption coefficient of less than 100 mL / g ⁇ cm. Further, it may contain a polymerization inhibitor and the like.
• the fine particles contained in the photosensitive resin composition are preferably fine particles having a refractive index of 1.40 to 3.00. Such fine particles appropriately scatter incident light and light emission from the pyromethene derivative and improve the light conversion efficiency, so that the luminance can be further improved.
• the “photopolymerization initiator” refers to a compound that decomposes or reacts with light (including ultraviolet rays or electron beams) or decomposes and reacts to generate radicals.
• the photopolymerization initiator has an h-ray absorption coefficient of 100 mL / g ⁇ cm or more. When the h-ray extinction coefficient is less than 100 mL / g ⁇ cm, the h-ray absorption is reduced, and the curability of the bottom due to exposure of the thick film becomes insufficient. As a result, it becomes difficult to form a fine pattern on the thick film.
• the h-ray extinction coefficient of the photopolymerization initiator needs to be 100 mL / g ⁇ cm or more.
• the h-ray extinction coefficient of the photopolymerization initiator is preferably 200 mL / g ⁇ cm or more from the viewpoint of forming a finer pattern.
• the h-ray absorption coefficient of the photopolymerization initiator is preferably 1000 mL / g ⁇ cm or less from the viewpoint of ease of handling.
• the extinction coefficient refers to the value of absorbance when the optical path length is 1 cm and the concentration is converted to a 1 g / mL solution for the photopolymerization initiator solution.
• the extinction coefficient of the photopolymerization initiator was determined by preparing a diluted solution obtained by diluting the photopolymerization initiator with PGMEA (propylene glycol monomethyl ether acetate), and using a cell having an optical path length of 1 cm, an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation). , MultiSpec-1500), the absorbance at h-line (405 nm) is measured, and the measured value is converted to a 1 g / mL solution.
• Examples of the photopolymerization initiator having an h-ray absorption coefficient of 100 mL / g ⁇ cm or more include phosphine oxide compounds, benzophenone compounds, acetophenone compounds, oxime ester compounds, thioxanthene compounds, and the like.
• the photosensitive resin composition which concerns on this embodiment may contain 2 or more types of these as a photoinitiator.
• phosphine oxide compounds include bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (“IRGACURE” (registered trademark) 819), 1800, 1870, “DAROCUR” (registered trademark) 4265 ( BASF).
• IRGACURE 819 which is an example of a phosphine oxide compound, is abbreviated as IC819 as appropriate.
• benzophenone compounds include 4,4 '-(bis) dimethylaminobenzophenone.
• Examples of the acetophenone compound include 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone (“IRGACURE” (registered trademark) 369, manufactured by BASF).
• Examples of the oxime ester compound include “ADEKA ARKLES” (registered trademark) NCI-831 (manufactured by ADEKA).
• Examples of the thioxanthene compound include 2,4-diethylthioxanthen-9-one.
• the structure of the photopolymerization initiator having an h-ray extinction coefficient of 100 mL / g ⁇ cm or more is not particularly limited.
• the photopolymerization initiator is preferably a phosphine oxide compound from the viewpoint of bottom curability and transparency, more preferably a compound represented by the following general formula (8), and more preferably “IRGACURE” 819.
• R 16 to R 18 may be the same as or different from each other, and hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol Group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group A fused ring and an aliphatic ring formed between a group, a siloxanyl group, a boryl group, a sulfo group, a phosphine oxide group, and an adjacent substituent.
• an aryl group is preferable.
• the substituent include an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, Hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro Group, silyl group, siloxanyl group, boryl group, sulfo group and phosphine oxide group are preferable.
• the number of carbon atoms of R 16 to R 18 including the substituent is preferably 0 to 20, respectively.
• the photosensitive resin composition contains a pyromethene derivative as described above.
• the photopolymerization initiator in the photosensitive resin composition (having a h-ray extinction coefficient of 100 mL / g ⁇ cm or more) It is preferable that the extinction coefficient at the absorption maximum wavelength of the pyromethene derivative described later is low.
• the extinction coefficient of the photopolymerization initiator at the absorption maximum wavelength of the pyromethene derivative is preferably 20 mL / g ⁇ cm or less.
• the pyromethene derivative When the extinction coefficient of the photopolymerization initiator at the absorption maximum wavelength of the pyromethene derivative is 20 mL / g ⁇ cm or less, the pyromethene derivative can efficiently absorb light, so that the light emission characteristics of the pyromethene derivative are sufficiently exhibited. , The luminance can be further improved.
• the absorption maximum wavelength of the pyromethene derivative means a wavelength at which the absorption spectrum in the wavelength region of 300 nm to 800 nm is maximized.
• the absorption maximum wavelength of this pyromethene derivative can be measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, MultiSpec-1500).
• the content of the photopolymerization initiator contained in the photosensitive resin composition is the solid content of the photosensitive resin composition (other components excluding the organic solvent) from the viewpoint of suppressing surface roughness during development. It is preferable that it is 1 weight% or more in 100 weight% of this. Moreover, it is preferable that content of the said photoinitiator is 10 weight% or less in 100 weight% of the said solid content from a compatible viewpoint.
• the photosensitive resin composition may contain a chain transfer agent with the said photoinitiator.
• the pyromethene derivative contained in the photosensitive resin composition is preferably a compound represented by the following general formula (1).
• R 1 to R 9 may be the same or different and each represents hydrogen, an alkyl group, a cycloalkyl group, a heterocyclic group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a hydroxyl group, a thiol group, an alkoxy group, an alkylthio group, Aryl ether group, aryl thioether group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, It is selected from a fused ring and an aliphatic ring formed between a sulfo group, a phosphine oxide group, and an adjacent substituent.
• hydrogen may be deuterium.
• a substituted or unsubstituted aryl group having 6 to 40 carbon atoms includes 6 to 40 carbon atoms including the number of carbon atoms contained in the substituent group substituted on the aryl group.
• An aryl group The same applies to other substituents that define the number of carbon atoms.
• the substituents in the case of substitution include alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, hydroxyl groups, thiol groups, alkoxy groups, alkylthio groups.
• substituted means that a hydrogen atom or a deuterium atom is substituted.
• substituted or unsubstituted means that a hydrogen atom or a deuterium atom is substituted.
• substituted or unsubstituted is the same as described above.
• the alkyl group is, for example, a saturated aliphatic hydrocarbon such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group.
• substituents There are no particular limitations on the additional substituent when it is substituted, and examples thereof include an alkyl group, a halogen, an aryl group, a heteroaryl group, and the like, and this point is common to the following description.
• the number of carbon atoms of the alkyl group is not particularly limited, but is preferably in the range of 1 to 20 and more preferably 1 to 8 from the viewpoint of availability and cost.
• the cycloalkyl group represents, for example, a saturated alicyclic hydrocarbon group such as a cyclopropyl group, a cyclohexyl group, a norbornyl group, an adamantyl group, etc., which may or may not have a substituent.
• carbon number of an alkyl group part is not specifically limited, Preferably it is the range of 3-20.
• the heterocyclic group refers to, for example, an aliphatic ring having atoms other than carbon such as a pyran ring, piperidine ring, and cyclic amide in the ring, which may or may not have a substituent. Good. Although carbon number of a heterocyclic group is not specifically limited, Preferably it is the range of 2-20.
• alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group or a butadienyl group, which may or may not have a substituent. .
• carbon number of an alkenyl group is not specifically limited, Preferably it is the range of 2-20.
• the cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, a cyclohexenyl group, and the like. It may not have.
• the alkynyl group refers to, for example, an unsaturated aliphatic hydrocarbon group containing a triple bond such as an ethynyl group, which may or may not have a substituent.
• carbon number of an alkynyl group is not specifically limited, Preferably it is the range of 2-20.
• the alkoxy group refers to, for example, a functional group having an aliphatic hydrocarbon group bonded through an ether bond such as a methoxy group, an ethoxy group, or a propoxy group, and the aliphatic hydrocarbon group has a substituent. May not be included.
• carbon number of an alkoxy group is not specifically limited, Preferably it is the range of 1-20.
• the alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom.
• the hydrocarbon group of the alkylthio group may or may not have a substituent. Although carbon number of an alkylthio group is not specifically limited, Preferably it is the range of 1-20.
• An aryl ether group refers to a functional group to which an aromatic hydrocarbon group is bonded via an ether bond, such as a phenoxy group, and the aromatic hydrocarbon group may or may not have a substituent. Also good. Although carbon number of an aryl ether group is not specifically limited, Preferably, it is the range of 6-40.
• the aryl thioether group is a group in which an oxygen atom of an ether bond of an aryl ether group is substituted with a sulfur atom.
• the aromatic hydrocarbon group in the aryl thioether group may or may not have a substituent.
• the number of carbon atoms of the arylthioether group is not particularly limited, but is preferably in the range of 6 or more and 40 or less.
• the aryl group is, for example, phenyl group, biphenyl group, terphenyl group, naphthyl group, fluorenyl group, benzofluorenyl group, dibenzofluorenyl group, phenanthryl group, anthracenyl group, benzophenanthryl group, benzoanthracene group.
• An aromatic hydrocarbon group such as a nyl group, a chrycenyl group, a pyrenyl group, a fluoranthenyl group, a triphenylenyl group, a benzofluoranthenyl group, a dibenzoanthracenyl group, a perylenyl group, or a helicenyl group.
• a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, an anthracenyl group, a pyrenyl group, a fluoranthenyl group, and a triphenylenyl group are preferable.
• the aryl group may or may not have a substituent. Although carbon number of an aryl group is not specifically limited, Preferably it is 6-40, More preferably, it is the range of 6-30.
• the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, or an anthracenyl group, and a phenyl group, biphenyl group, Group, terphenyl group, and naphthyl group are more preferable. More preferred are a phenyl group, a biphenyl group, and a terphenyl group, and a phenyl group is particularly preferred.
• the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, or an anthracenyl group.
• a phenyl group and a naphthyl group are more preferable. Particularly preferred is a phenyl group.
• Heteroaryl group is, for example, pyridyl group, furanyl group, thienyl group, quinolinyl group, isoquinolinyl group, pyrazinyl group, pyrimidyl group, pyridazinyl group, triazinyl group, naphthyridinyl group, cinnolinyl group, phthalazinyl group, quinoxalinyl group, quinazolinyl group, Benzofuranyl group, benzothienyl group, indolyl group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzocarbazolyl group, carbolinyl group, indolocarbazolyl group, benzofurocarbazolyl group, benzothienocarbazolyl Group, dihydroindenocarbazolyl group, benzoquinolinyl group, acridinyl group, dibenzoacridinyl
• Atoms other than carbon shows a cyclic aromatic group having a single or a plurality of rings.
• the naphthyridinyl group is any of 1,5-naphthyridinyl group, 1,6-naphthyridinyl group, 1,7-naphthyridinyl group, 1,8-naphthyridinyl group, 2,6-naphthyridinyl group, and 2,7-naphthyridinyl group.
• the heteroaryl group may or may not have a substituent. Although carbon number of a heteroaryl group is not specifically limited, Preferably it is 2-40, More preferably, it is the range of 2-30.
• heteroaryl group examples include pyridyl, furanyl, thienyl, quinolinyl, pyrimidyl, triazinyl, benzofuranyl, benzothienyl, indolyl Group, dibenzofuranyl group, dibenzothienyl group, carbazolyl group, benzimidazolyl group, imidazopyridyl group, benzoxazolyl group, benzothiazolyl group and phenanthrolinyl group are preferable, and pyridyl group, furanyl group, thienyl group and quinolinyl group are preferable. More preferred. Particularly preferred is a pyridyl group.
• the heteroaryl group includes pyridyl, furanyl, thienyl, quinolinyl, pyrimidyl, triazinyl, benzofuranyl, benzothienyl, indolyl, dibenzo A furanyl group, a dibenzothienyl group, a carbazolyl group, a benzimidazolyl group, an imidazopyridyl group, a benzoxazolyl group, a benzothiazolyl group, and a phenanthrolinyl group are preferable, and a pyridyl group, a furanyl group, a thienyl group, and a quinolinyl group are more preferable. Particularly preferred is a pyridyl group.
• Halogen refers to an atom selected from fluorine, chlorine, bromine and iodine.
• the carbonyl group, carboxyl group, ester group, and carbamoyl group may or may not have a substituent.
• substituents include an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, and the like, and these substituents may be further substituted.
• An amino group is a substituted or unsubstituted amino group.
• substituent in the case of substitution include an aryl group, a heteroaryl group, a linear alkyl group, and a branched alkyl group.
• aryl group and heteroaryl group a phenyl group, a naphthyl group, a pyridyl group, and a quinolinyl group are preferable. These substituents may be further substituted.
• carbon number is not specifically limited, Preferably it is 2-50, More preferably, it is 6-40, Most preferably, it is the range of 6-30.
• silyl groups include trimethylsilyl groups, triethylsilyl groups, tert-butyldimethylsilyl groups, propyldimethylsilyl groups, vinyldimethylsilyl groups, and other alkylsilyl groups, phenyldimethylsilyl groups, tert-butyldiphenylsilyl groups, An arylsilyl group such as a phenylsilyl group or a trinaphthylsilyl group is shown. Substituents on silicon may be further substituted. Although carbon number of a silyl group is not specifically limited, Preferably it is the range of 1-30.
• a siloxanyl group refers to a silicon compound group via an ether bond such as a trimethylsiloxanyl group. Substituents on silicon may be further substituted.
• the boryl group is a substituted or unsubstituted boryl group. Examples of the substituent when the boryl group is substituted include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, an aryl ether group, an alkoxy group, and a hydroxyl group. Of these, an aryl group and an aryl ether group are preferable.
• the sulfo group is a substituted or unsubstituted sulfo group.
• Examples of the substituent when the sulfo group is substituted include an aryl group, a heteroaryl group, a linear alkyl group, a branched alkyl group, an aryl ether group, and an alkoxy group. Of these, a linear alkyl group and an aryl group are preferable.
• the phosphine oxide group is a group represented by —P ( ⁇ O) R 10 R 11 .
• R 10 and R 11 are selected from the same group as R 1 to R 9 .
• a condensed ring and an aliphatic ring formed between adjacent substituents are any two adjacent substituents (for example, R 1 and R 2 in the general formula (1)) bonded to each other to be conjugated or non-conjugated. Forming a cyclic skeleton.
• a constituent element of such a condensed ring and an aliphatic ring in addition to carbon, an element selected from nitrogen, oxygen, sulfur, phosphorus and silicon may be included.
• these condensed rings and aliphatic rings may be condensed with another ring.
• the compound represented by the general formula (1) exhibits a high emission quantum yield and has a small half-value width of the emission spectrum, it is possible to achieve both efficient color conversion and high color purity. Furthermore, the compound represented by the general formula (1) has various properties such as luminous efficiency, color purity, thermal stability, light stability and dispersibility by introducing an appropriate substituent at an appropriate position. And physical properties can be adjusted. For example, as compared to the case where R 1 , R 3 , R 4 and R 6 are all hydrogen, at least one of R 1 , R 3 , R 4 and R 6 is a substituted or unsubstituted alkyl group or substituted or unsubstituted. When the aryl group is a substituted or unsubstituted heteroaryl group, better thermal stability and light stability are exhibited.
• the alkyl group includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and n-butyl.
• Group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, and other alkyl groups having 1 to 6 carbon atoms are preferable.
• the alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, or a tert-butyl group from the viewpoint of excellent thermal stability. Further, from the viewpoint of preventing concentration quenching and improving the emission quantum yield, this alkyl group is more preferably a sterically bulky tert-butyl group. Further, from the viewpoint of ease of synthesis and availability of raw materials, a methyl group is also preferably used as this alkyl group.
• the aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group or a naphthyl group, more preferably Is a phenyl group or a biphenyl group.
• the aryl group is particularly preferably a phenyl group.
• the heteroaryl group is preferably a pyridyl group, a quinolinyl group or a thienyl group, more preferably A pyridyl group and a quinolinyl group; Particularly preferred as this heteroaryl group is a pyridyl group.
• R 1 , R 3 , R 4 and R 6 may be the same or different, and when they are substituted or unsubstituted alkyl groups, the solubility in alkali-soluble resins and solvents is improved.
• the alkyl group is preferably a methyl group from the viewpoints of ease of synthesis and availability of raw materials.
• R 1 , R 3 , R 4 and R 6 may be the same or different and each is a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group And light stability is preferable.
• all of R 1 , R 3 , R 4 and R 6 may be the same or different, and more preferably a substituted or unsubstituted aryl group.
• R 1 , R 3 , R 4 and R 6 may be the same or different and are substituted or unsubstituted aryl groups, for example, R 1 ⁇ R 4 , R 3 ⁇ R 6 , R 1 ⁇ R 3 or R 4 ⁇ R 6 etc. It is preferable to introduce a plurality of types of substituents.
• “ ⁇ ” indicates a group having a different structure.
• R 1 ⁇ R 4 indicates that R 1 and R 4 are groups having different structures.
• R 1 ⁇ R 3 or R 4 ⁇ R 6 is preferable from the viewpoint of improving the light emission efficiency and the color purity in a balanced manner.
• one or more aryl groups that affect the color purity are introduced into the pyrrole rings on both sides, and the aryl that affects the luminous efficiency at other positions. Since groups can be introduced, both of these properties can be maximized.
• an aryl group substituted with an electron donating group is preferable.
• the electron donating group is an atomic group that donates electrons to a substituted atomic group by an induced effect or a resonance effect in organic electronic theory.
• Examples of the electron donating group include those having a negative value as the Hammett's rule substituent constant ( ⁇ p (para)).
• the Hammett's rule substituent constant ( ⁇ p (para)) can be cited from the Chemical Handbook, Basic Revision 5 (II-380).
• electron donating groups for example, an alkyl group (.sigma.p methyl group: -0.17) and alkoxy groups (.sigma.p methoxy groups: -0.27), .sigma.p amino group (-NH 2: - 0.66).
• an alkyl group having 1 to 8 carbon atoms or an alkoxy group having 1 to 8 carbon atoms is preferable, and a methyl group, an ethyl group, a tert-butyl group, or a methoxy group is more preferable. From the viewpoint of dispersibility, a tert-butyl group and a methoxy group are particularly preferable.
• the substitution position of the substituent is not particularly limited, it is necessary to suppress the twisting of the bond in order to increase the light stability of the compound represented by the general formula (1). It is preferable to bond to the position or para position.
• the aryl group that mainly affects the luminous efficiency an aryl group having a bulky substituent such as a tert-butyl group, an adamantyl group, or a methoxy group is preferable.
• R 1 , R 3 , R 4 and R 6 may be the same or different, and when they are substituted or unsubstituted aryl groups, R 1 , R 3 , R 4 and R 6 are the same or different. It may be a substituted or unsubstituted phenyl group.
• R 1 , R 3 , R 4 and R 6 are more preferably selected from the following Ar-1 to Ar-6, respectively.
• preferred combinations of R 1 , R 3 , R 4 and R 6 include those shown in Table 1-1 to Table 1-11, but are not limited thereto.
• R 2 and R 5 are preferably any one of hydrogen, an alkyl group, and an aryl group.
• R 2 and R 5 hydrogen or an alkyl group is preferable from the viewpoint of thermal stability of the compound represented by the general formula (1), and hydrogen is preferable from the viewpoint that a narrow half-value width is easily obtained in the emission spectrum. Is more preferable.
• R 8 and R 9 are preferably an alkyl group, an aryl group, a heteroaryl group, fluorine, a fluorine-containing alkyl group, a fluorine-containing heteroaryl group, or a fluorine-containing aryl group.
• R 8 and R 9 are more preferably fluorine or a fluorine-containing aryl group because a higher emission quantum yield is obtained with respect to excitation light.
• R 8 and R 9 are more preferably fluorine for ease of synthesis.
• the fluorine-containing aryl group is an aryl group containing fluorine.
• the fluorine-containing aryl group include a fluorophenyl group, a trifluoromethylphenyl group, and a pentafluorophenyl group.
• the fluorine-containing heteroaryl group is a heteroaryl group containing fluorine.
• the fluorine-containing heteroaryl group include a fluoropyridyl group, a trifluoromethylpyridyl group, and a trifluoropyridyl group.
• the fluorine-containing alkyl group is an alkyl group containing fluorine. Examples of the fluorine-containing alkyl group include a trifluoromethyl group and a pentafluoroethyl group.
• X is preferably C—R 7 from the viewpoint of light stability.
• R 7 is hydrogen
• R 7 is a substituent having a high degree of freedom of movement of the molecular chain such as an alkyl group
• R 7 is preferably a group that is rigid and has a low degree of freedom of movement and hardly causes aggregation.
• R 7 is preferably either a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.
• X is C—R 7 and R 7 is a substituted or unsubstituted aryl group.
• aryl group a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a fluorenyl group, a phenanthryl group, and an anthracenyl group are preferable from the viewpoint of not impairing the emission wavelength.
• R 7 is preferably a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, or a substituted or unsubstituted naphthyl group.
• a phenyl group, a substituted or unsubstituted biphenyl group, and a substituted or unsubstituted terphenyl group are more preferred.
• R 7 is particularly preferably a substituted or unsubstituted phenyl group.
• R 7 is preferably a moderately bulky substituent. Since R 7 has a certain amount of bulkiness, aggregation of molecules can be prevented. As a result, the luminous efficiency and durability of the compound represented by the general formula (1) are further improved.
• R 7 which is such a bulky substituent includes a group having a structure represented by the following general formula (2). That is, in the general formula (1), when X is C—R 7 , R 7 is preferably a group represented by the following general formula (2).
• r is hydrogen, alkyl group, cycloalkyl group, heterocyclic group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, thiol group, alkoxy group, alkylthio group, aryl ether group, aryl thioether Group, aryl group, heteroaryl group, halogen, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, boryl group, sulfo group, phosphine oxide group Selected from the group consisting of k is an integer of 1 to 3. When k is 2 or more, r may be the same or different.
• r is preferably a substituted or unsubstituted aryl group.
• aryl groups a phenyl group and a naphthyl group are particularly preferable examples.
• k in the general formula (2) is preferably 1 or 2, and more preferably 2 from the viewpoint of further preventing aggregation of molecules.
• k is 2 or more, it is preferable that at least one of the plurality of r is substituted with an alkyl group.
• the alkyl group in this case, a methyl group, an ethyl group, and a tert-butyl group are particularly preferable from the viewpoint of thermal stability.
• r is a substituted or unsubstituted alkyl group, substituted or unsubstituted.
• a substituted alkoxy group or a halogen is preferable, and a methyl group, an ethyl group, a tert-butyl group, or a methoxy group is more preferable.
• r is particularly preferably a tert-butyl group or a methoxy group. When r is a tert-butyl group or a methoxy group, it is more effective for preventing quenching due to aggregation between molecules.
• At least one of R 1 to R 7 is an electron withdrawing group.
• the following first to third embodiments are preferable.
• at least one of R 1 to R 6 is an electron withdrawing group.
• R 7 is an electron withdrawing group.
• at least one of R 1 to R 6 is an electron withdrawing group, and R 7 is an electron withdrawing group.
• the electron-withdrawing group is also called an electron-accepting group, and is an atomic group that attracts electrons from a substituted atomic group by an induced effect or a resonance effect in organic electron theory.
• Examples of the electron withdrawing group include those having a positive value as the Hammett's rule substituent constant ( ⁇ p (para)).
• the Hammett's rule substituent constant ( ⁇ p (para)) can be cited from the Chemical Handbook, Basic Revision 5 (II-380).
• a phenyl group also has the example which takes the above positive values, in this invention, a phenyl group is not contained in an electron withdrawing group.
• electron withdrawing groups include, for example, -F ( ⁇ p: +0.06), -Cl ( ⁇ p: +0.23), -Br ( ⁇ p: +0.23), -I ( ⁇ p: +0.18), -CO 2 R 12 ( ⁇ p: when R 12 is an ethyl group +0.45), -CONH 2 ( ⁇ p: +0.38), -COR 12 ( ⁇ p: when R 12 is a methyl group +0.49),- Examples include CF 3 ( ⁇ p: +0.50), —SO 2 R 12 ( ⁇ p: +0.69 when R 12 is a methyl group), —NO 2 ( ⁇ p: +0.81), and the like.
• R 12 represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms, a substituted or unsubstituted carbon number. It represents a 1-30 alkyl group, a substituted or unsubstituted cycloalkyl group having 1-30 carbon atoms. Specific examples of these groups include the same examples as described above.
• Preferred electron withdrawing groups include fluorine, fluorine-containing aryl groups, fluorine-containing heteroaryl groups, fluorine-containing alkyl groups, substituted or unsubstituted acyl groups, substituted or unsubstituted ester groups, substituted or unsubstituted amide groups, Examples thereof include a substituted or unsubstituted sulfonyl group or a cyano group. This is because they are difficult to decompose chemically.
• More preferred electron withdrawing groups include a fluorine-containing alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted ester group, or a cyano group. This is because these lead to effects of preventing concentration quenching and improving the emission quantum yield. Particularly preferred electron withdrawing groups are substituted or unsubstituted ester groups.
• R 1 , R 3 , R 4 and R 6 may be the same or different and each may be a substituted or unsubstituted alkyl group.
• X is C—R 7 and R 7 is a group represented by the general formula (2).
• R 7 is particularly preferably a group represented by the general formula (2) in which r is included as a substituted or unsubstituted phenyl group.
• R 1 , R 3 , R 4 and R 6 may be the same or different, and the above-mentioned Ar-1 to Ar
• X is C—R 7 and R 7 is a group represented by the general formula (2).
• R 7 is more preferably a group represented by the general formula (2) in which r is a tert-butyl group or a methoxy group, and represented by the general formula (2) in which r is a methoxy group. It is particularly preferred that
• R 1 , R 3 , R 4 and R 6 may be the same or different, and the above-mentioned Ar-1 to Ar -6, and R 2 and R 5 may be the same or different and each is a substituted or unsubstituted ester group, X is C—R 7 , and R 7 is represented by the general formula The case where it is group represented by (2) is mentioned.
• R 7 is more preferably a group represented by the general formula (2) in which r is a tert-butyl group or a methoxy group, and represented by the general formula (2) in which r is a methoxy group. It is particularly preferred that
• Examples of the compound represented by the general formula (1) include compounds having the structure shown below.
• the compound represented by the general formula (1) can be synthesized, for example, by the methods described in JP-T-8-509471 and JP-A-2000-208262. That is, the target pyromethene metal complex is obtained by reacting a pyromethene compound and a metal salt in the presence of a base.
• a method of generating a carbon-carbon bond by using a coupling reaction between a halogenated derivative and a boronic acid or a boronic acid esterified derivative can be mentioned.
• the present invention is not limited to this.
• introducing an amino group or a carbazolyl group for example, there is a method of generating a carbon-nitrogen bond by using a coupling reaction between a halogenated derivative and an amine or a carbazole derivative under a metal catalyst such as palladium.
• the present invention is not limited to this.
• the pyromethene derivative in the present invention when used in a green photosensitive resin composition, it preferably exhibits light emission observed in an area where the emission maximum wavelength (peak wavelength) is 500 nm or more and less than 580 nm by excitation light.
• the emission maximum wavelength can be measured, for example, using an F-2500 type spectrofluorometer (manufactured by Hitachi, Ltd.).
• the pyromethene derivative in the present invention when used in a green photosensitive resin composition, it preferably emits green light by excitation light in a wavelength range of 430 nm or more and less than 500 nm.
• the excitation light tends to cause decomposition of the material as its energy increases.
• the excitation light in the wavelength range of 430 nm or more and less than 500 nm is of relatively low excitation energy.
• disassembly of the pyromethene derivative in the photosensitive resin composition can be suppressed by using the excitation light of the said wavelength range as light which a pyromethene derivative absorbs.
• green light emission with good color purity can be obtained from the pyromethene derivative.
• the pyromethene derivative in the present invention when used in a red photosensitive resin composition, it preferably exhibits light emission observed in an area where the emission maximum wavelength (peak wavelength) is 580 nm or more and less than 750 nm by excitation light.
• the emission maximum wavelength peak wavelength
• red light emission light emission observed in a region where the light emission maximum wavelength is not less than 580 nm and less than 750 nm.
• the pyromethene derivative in the present invention when used for a red photosensitive resin composition, it preferably emits red light by excitation light in a wavelength range of 430 nm or more and less than 580 nm or less.
• the excitation light tends to cause decomposition of the material as its energy increases.
• the excitation light in the wavelength range of 430 nm or more and less than 580 nm is of relatively low excitation energy.
• disassembly of the pyromethene derivative in the photosensitive resin composition can be suppressed by using the excitation light of the said wavelength range as light which a pyromethene derivative absorbs. As a result, red light emission with good color purity can be obtained from the pyromethene derivative.
• the content of the pyromethene derivative in the photosensitive resin composition can be appropriately set according to the molar extinction coefficient of the compound, the emission quantum yield and the absorption intensity at the excitation wavelength, and the thickness and transmittance of the cured film to be produced. .
• the content of the pyromethene derivative is preferably 0.1% by weight or more and 10% by weight or less in 100% by weight of the solid content of the photosensitive resin composition.
• the content of the pyromethene derivative in the photosensitive resin composition is more preferably 0.3% by weight or more in the solid content.
• the content of the pyromethene derivative in the photosensitive resin composition is more preferably 1.5% by weight or less in the solid content.
• alkali-soluble resin refers to a resin having an acidic group.
• the acidic group a carboxyl group, a hydroxyl group and the like are preferable.
• the alkali-soluble resin include acrylic resin, epoxy resin, polyimide resin, urethane resin, urea resin, polyvinyl alcohol resin, polyamide resin, polyamideimide resin, and polyester resin.
• the photosensitive resin composition may contain two or more of these as an alkali-soluble resin. Among these, an acrylic resin is more preferable from the viewpoint of stability.
• the acrylic resin has an alicyclic hydrocarbon group. Since the acrylic resin has an alicyclic hydrocarbon group, chemical resistance against an alkali developer, an organic solvent, or the like can be improved.
• the acrylic resin has a structural unit represented by the following general formula (3) having a carboxyl group in the side chain and a structural unit represented by the following general formula (4) having an alicyclic hydrocarbon group in the side chain. It is more preferable to have.
• the acrylic resin can further improve the solubility in an alkaline developer.
• the acrylic resin can further improve chemical resistance and brightness against an alkali developer, an organic solvent, and the like by having a structural unit represented by the following general formula (4).
• R 13 represents a hydrogen atom or a methyl group.
• R 14 represents a hydrogen atom or a methyl group
• R 15 represents an organic group having 1 to 6 carbon atoms.
• n is an integer of 1 to 3.
• the plurality of R 15 may be the same or different from each other.
• the organic group represented by R 15 include alkyl groups, cycloalkyl groups, heterocyclic groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, alkoxy groups, alkylthio groups, aryl ether groups, aryl thioether groups, aryl groups, and heteroaryls.
• the acrylic resin having the structural unit represented by the general formula (3) and the structural unit represented by the general formula (4) is, for example, a copolymer constituting the structural unit represented by the general formula (3). It can be obtained by copolymerizing the component and a copolymerization component constituting the structural unit represented by the general formula (4). For these copolymer components, other copolymer components may be further copolymerized.
• Examples of the copolymer component constituting the structural unit represented by the general formula (3) include (meth) acrylic acid.
• (meth) acrylic acid refers to acrylic acid or methacrylic acid. Two or more of these may be used as the copolymerization component. Among these, methacrylic acid is preferable.
• Examples of the copolymer component constituting the structural unit represented by the general formula (4) include dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and dicyclopentanyloxyethyl (meth). Acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decan-8-yl (meth) acrylate, tricyclo [5.2. 1.0 2,6 ] decan-8-yloxyethyl (meth) acrylate and the like. Two or more of these may be used as the copolymerization component. Among these, dicyclopentanyl (meth) acrylate is preferable.
• an ethylenically unsaturated compound is preferable. This is because the sensitivity of the photosensitive resin composition can be improved.
• the ethylenically unsaturated compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) Unsaturated carboxylic acid alkyl esters such as acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate; styrene Aromatic vinyl compounds such as p-methylstyrene, o-methylstyrene, m
• the content of the structural unit represented by the general formula (3) in the acrylic resin is preferably 5% by weight or more in 100% by weight of the acrylic resin from the viewpoint of further improving alkali solubility.
• the content of the structural unit represented by the general formula (3) in the acrylic resin is 60% by weight or less in 100% by weight of the acrylic resin from the viewpoint of forming a finer pattern. preferable.
• the content of the structural unit represented by the general formula (4) in the acrylic resin is preferably 5% by weight or more in 100% by weight of the acrylic resin from the viewpoint of further improving the luminance. More preferably, it is 15% by weight or more.
• the content of the structural unit represented by the general formula (4) in the acrylic resin is 60% by weight or less in 100% by weight of the acrylic resin from the viewpoint of forming a finer pattern. Preferably, it is 45% by weight or less.
• the glass transition temperature (Tg) of the alkali-soluble resin in the present invention is preferably 30 ° C. or higher and 180 ° C. or lower.
• the Tg of the alkali-soluble resin is more preferably 50 ° C. or higher, and further preferably 90 ° C. or higher.
• the flexibility of the cured film described later can be improved by setting the Tg of the alkali-soluble resin to 180 ° C. or lower.
• the Tg of the alkali-soluble resin is more preferably 150 ° C. or less, and further preferably 140 ° C. or less.
• the weight average molecular weight of the alkali-soluble resin in the present invention is preferably 10,000 to 800,000.
• the weight average molecular weight of the alkali-soluble resin is preferably 10,000 to 800,000.
• the strength of the alkali-soluble resin can be improved.
• a finer pattern of the photosensitive resin composition containing the alkali-soluble resin can be formed.
• the weight average molecular weight of the alkali-soluble resin can be measured by GPC (gel permeation chromatography).
• the acid value of the alkali-soluble resin in the present invention is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more, from the viewpoint of forming a finer pattern while suppressing residues.
• the acid value of the alkali-soluble resin is preferably 200 mgKOH / g or less, and more preferably 150 mgKOH / g or less, from the viewpoint of further improving alkali solubility.
• the acid value of the alkali-soluble resin can be determined by titrating a solution obtained by dissolving the alkali-soluble resin in ortho-cresol at 25 ° C. using a 0.1 mol / L potassium hydroxide / ethanol aqueous solution. .
• the content of the alkali-soluble resin in the photosensitive resin composition is 20 parts by weight or more and 80 parts by weight or less with respect to a total of 100 parts by weight of the alkali-soluble resin and the photopolymerizable compound described later. Is preferred.
• the content of the alkali-soluble resin is more preferably 30 parts by weight or more.
• the sensitivity and alkali solubility of the photosensitive resin composition can be improved by controlling the content of the alkali-soluble resin to 80 parts by weight or less.
• the content of the alkali-soluble resin is more preferably 60 parts by weight or less.
• the “photopolymerizable compound” refers to a compound having an ethylenically unsaturated group.
• the photopolymerizable compound include bisphenol A diglycidyl ether (meth) acrylate, poly (meth) acrylate carbamate, modified bisphenol A epoxy (meth) acrylate, adipic acid 1,6-hexanediol (meth) acrylic acid ester, Phthalic anhydride propylene oxide (meth) acrylic acid ester, trimellitic acid diethylene glycol (meth) acrylic acid ester, rosin modified epoxy di (meth) acrylate, alkyd modified (meth) acrylate and other oligomers, tripropylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, trimethylolpropane tri (meth) acrylate, te
• the photosensitive resin composition according to the embodiment of the present invention may further contain fine particles in addition to the above-described photopolymerization initiator, pyromethene derivative, photopolymerizable compound and alkali-soluble resin.
• the photosensitive resin composition contains fine particles, incident light from a light source and light emission from a pyromethene derivative can be appropriately scattered to improve light conversion efficiency and to further improve luminance.
• the fine particles contained in the photosensitive resin composition according to the embodiment of the present invention are abbreviated as fine particles as appropriate.
• the fine particles contained in the photosensitive resin composition are preferably white fine particles.
• white refers to a color whose lightness of the Munsell display system measured in accordance with JIS Z 8717 (1989) is 8.0 to 10.0.
• the white fine particles include minerals such as talc, mica and kaolin clay; metal oxides such as titania (titanium oxide), zirconia (zirconium dioxide), alumina (aluminum oxide), silica (silicon oxide), and zinc oxide; sulfuric acid Metal sulfates such as barium and calcium sulfate; metal carbonates such as barium carbonate, calcium carbonate, magnesium carbonate and strontium carbonate; sodium metasilicate; sodium stearate and the like.
• the photosensitive resin composition may contain two or more of these as fine particles.
• fine particles of titanium oxide, zirconium dioxide, aluminum oxide, silicon oxide, barium sulfate, calcium sulfate, barium carbonate, calcium carbonate, magnesium carbonate, strontium carbonate, sodium metasilicate are preferable.
• titanium oxide, zirconium dioxide, and aluminum oxide are more preferable.
• Commercially available titanium oxide fine particles include, for example, JR-301, JR-600A (manufactured by Teika).
• zirconia dioxide fine particles examples include “UEP” (registered trademark) 100 (manufactured by Daiichi Rare Element Chemical Industries, Ltd.).
• aluminum oxide examples include “AEROXIDE” (registered trademark) Alu C (Nippon Aerosil Co., Ltd.).
• the refractive index of the fine particles contained in the photosensitive resin composition is preferably 1.40 or more and 3.00 or less.
• the refractive index of the fine particles is more preferably 1.60 or more.
• the refractive index of the fine particles is more preferably 1.80 or less, whereby the fine pattern processability of the photosensitive resin composition can be further improved.
• the refractive index of the fine particles in the present invention is the Abbe refractometer (DR-M2, DR) for 30 fine particles selected at random at a temperature of 25 ° C. using a sodium D-line (589 nm) as a light source. The number average value of the refractive index measured by the immersion method (Becke line method) is used.
• Examples of the shape of the fine particles in the present invention include a spherical shape, an ellipsoidal shape, a needle shape, a polygonal shape, and a star shape. Further, the shape of the fine particles may have irregularities or pores on the surface, or may be a hollow shape.
• the particle diameter of the fine particles in the present invention is preferably 5 nm to 300 nm.
• the particle diameter of the fine particles is more preferably 10 nm or more.
• the particle diameter of the fine particles is more preferably 100 nm or less.
• the particle diameter of the fine particles in the present invention refers to the number average value of primary particle diameters (that is, the number average particle diameter), and the primary particle diameter refers to the average value of the maximum diameter and the minimum diameter of the primary particles. .
• the particle size of the fine particles can be determined by the following method. For example, 100 particles randomly selected from particles whose whole image is observed in a field of view magnified at a magnification of 10,000 using an electron microscope (S-4800, manufactured by Hitachi High-Technologies Corporation) The primary particle diameter of each is measured. When the cross-sectional shape of the particles is not a circle, the maximum diameter and the minimum diameter of the particles are measured, and the average value is taken as the primary particle diameter. It is not necessary to measure the primary particle size of 100 particles in one measurement, and a total of 100 particles may be selected from a plurality of fields of view. The particle diameter of the fine particles can be obtained by calculating the number average value of the primary particle diameters of the 100 particles measured.
• Examples of the method for producing fine particles include a pulverization method in which a raw material mineral is pulverized and refined; a chemical method in a gas phase, a liquid phase or a solid layer; a physical method, and the like.
• Examples of the pulverization method include a jet method, a hammer method, and a mill method.
• Examples of the chemical method in the gas phase include a chemical vapor deposition method (CVD method), an electric furnace method, a chemical flame method, and a plasma method.
• Examples of the chemical method in the liquid phase include a precipitation method, an alkoxide method, and a hydrothermal method.
• Examples of the chemical method in the solid phase include a crystallization method.
• Examples of the physical method include a spray method, a solution combustion method, and a freeze-drying method. Among these, the precipitation method is preferable because the particle diameter of the fine particles can be easily adjusted to a desired range.
• the content of fine particles contained in the photosensitive resin composition is defined by the weight ratio with respect to the content of the pyromethene derivative contained in the photosensitive resin composition.
• the content of the fine particles is the amount of fine particles relative to the content of the pyromethene derivative.
• the weight ratio of the content (Ma / Mb) is adjusted to be within a predetermined range.
• the weight ratio (Ma / Mb) of the content of the fine particles to the content of the pyromethene derivative in the photosensitive resin composition is preferably 5/1 or more and 100/1 or less.
• the weight ratio (Ma / Mb) By setting the weight ratio (Ma / Mb) to 5/1 or more, the light scattering intensity by the fine particles can be improved, and the luminance of the photosensitive resin composition can be further improved.
• the weight ratio (Ma / Mb) is more preferably 20/1 or more.
• the weight ratio (Ma / Mb) by setting the weight ratio (Ma / Mb) to 100/1 or less, the light scattering intensity by the fine particles can be moderately suppressed, and a finer pattern of the photosensitive resin composition can be formed.
• the weight ratio (Ma / Mb) is more preferably 80/1 or less.
• the photosensitive resin composition according to the embodiment of the present invention may further contain an ultraviolet absorber in addition to the above-described photopolymerization initiator, pyromethene derivative, photopolymerizable compound and alkali-soluble resin.
• the photosensitive resin composition absorbs light in the wavelength region of j-ray by containing an ultraviolet absorber. For this reason, the line width thickening of the bottom part of the photosensitive resin composition can be suppressed, and a finer pattern can be formed.
• the ultraviolet absorbent contained in the photosensitive resin composition preferably has an absorption maximum wavelength in a wavelength region of 360 nm or less.
• the absorption maximum wavelength can be measured using an ultraviolet-visible spectrophotometer (manufactured by Shimadzu Corporation, MultiSpec-1500).
• Examples of the ultraviolet absorber include benzotriazole compounds, benzophenone compounds, and triazine compounds.
• the photosensitive resin composition may contain two or more of these as an ultraviolet absorber.
• benzotriazole compound examples include 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4-6-bis (1-methyl-1) -Phenylethyl) phenol, 2- [5chloro (2H) -benzotriazol-2-yl] -4-methyl-6- (tert-butylphenol), 2,4 di-tert-butyl-6- (5-chloro Benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) phenol, 2- (2H-benzotriazol-2-yl) -4,6-tert-pentylphenol, 2- (2H- Benzotriazol-2-yl-4- (1,1,3,3-tetramethylbutyl) phenol, 2 (2H-benzotriazol-2-y ) -6-dodecyl-4-methylphenol, 2 [2-hydroxy-3- (3,4,5,6 te
• Examples of benzophenone compounds examples include octabenzone, 2-hydroxy-4-n-octoxybenzophenone, etc.
• Examples of triazine compounds include 2- (4,6-diphenyl-1,3,5triazin-2-yl)- Examples include 5-[(hexyl) oxy] -phenol, “Tinuvin” (registered trademark) 400, 405 manufactured by BASF Corporation.
• the content of the ultraviolet absorber contained in the photosensitive resin composition is preferably 0.05% by weight or more and 10% by weight or less in 100% by weight of the solid content of the photosensitive resin composition.
• the line width of the photosensitive resin composition is further suppressed and the fine pattern processability is further improved.
• Can do As for content of a ultraviolet absorber, it is more preferable that it is 0.1 weight% or more in 100 weight% of the said solid content.
• the sensitivity of the photosensitive resin composition can be improved by setting the content of the ultraviolet absorber to 10% by weight or less in 100% by weight of the solid content.
• content of a ultraviolet absorber it is more preferable that it is 5.0 weight% or less in 100 weight% of the said solid content.
• the photosensitive resin composition according to the embodiment of the present invention may further contain an organic solvent in addition to the above-described photopolymerization initiator, pyromethene derivative, photopolymerizable compound and alkali-soluble resin.
• organic solvent include diethylene glycol monobutyl ether acetate, benzyl acetate, ethyl benzoate, methyl benzoate, diethyl malonate, 2-ethylhexyl acetate, 2-butoxyethyl acetate, ethylene glycol monobutyl ether acetate, diethyl oxalate, ethyl acetoacetate.
• the content of the organic solvent contained in the photosensitive resin composition is preferably 40% by weight or more in 100% by weight of the photosensitive resin composition from the viewpoint of improving coatability. More preferably, it is at least wt%.
• the content of the organic solvent is preferably 90% by weight or less and preferably 80% by weight or less in 100% by weight of the photosensitive resin composition from the viewpoint of applying a resist to a thick film. More preferred.
• the photosensitive resin composition according to the embodiment of the present invention contains an adhesion improving agent in addition to the above-described photopolymerization initiator, pyromethene derivative, photopolymerizable compound, and alkali-soluble resin, thereby allowing the cured film to be described later. Adhesion to the substrate can be improved.
• adhesion improving agent examples include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2- Aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl)
• Examples include silane coupling agents such as ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-mercaptopropyltrimethoxysilane.
• the photosensitive resin composition according to the embodiment of the present invention includes a surfactant in addition to the above-described photopolymerization initiator, pyromethene derivative, photopolymerizable compound, and alkali-soluble resin, thereby providing coating properties and a coating surface. Can improve the uniformity.
• the surfactant examples include anionic surfactants such as ammonium lauryl sulfate and polyoxyethylene alkyl ether sulfate triethanolamine; cationic surfactants such as stearylamine acetate and lauryltrimethylammonium chloride; lauryldimethylamine oxide, Amphoteric surfactants such as lauryl carboxymethyl hydroxyethyl imidazolium betaine; Nonionic surfactants such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, sorbitan monostearate; Fluorosurfactant; Silicone surfactant Etc.
• the photosensitive resin composition may contain two or more of these as a surfactant.
• the content of the surfactant contained in the photosensitive resin composition is 0.001% by weight or more and 10% by weight in 100% by weight of the photosensitive resin composition from the viewpoint of in-plane uniformity of the coating film. % Or less is preferable.
• the photosensitive resin composition according to the embodiment of the present invention may further contain a dispersant in addition to the above-described photopolymerization initiator, pyromethene derivative, photopolymerizable compound, and alkali-soluble resin.
• a dispersant include low molecular dispersants such as pigment intermediates and pigment derivatives, and polymer dispersants.
• the photosensitive resin composition may contain two or more of these as a dispersant.
• the pigment derivative include a modified alkylamine of a pigment skeleton, a carboxylic acid derivative, and a sulfonic acid derivative that contribute to appropriate wetting and stabilization of the pigment.
• a sulfonic acid derivative having a pigment skeleton, which has a remarkable effect on stabilizing a fine pigment is preferable.
• the polymer dispersant include polymers such as polyester, polyalkylamine, polyallylamine, polyimine, polyamide, polyurethane, polyacrylate, polyimide, polyamideimide, and copolymers thereof.
• these polymer dispersants those having an amine value in terms of solid content of 5 to 200 mgKOH / g and an acid value of 1 to 100 mgKOH / g are preferable.
• a polymer dispersant having a basic group is more preferable. This is because the storage stability of the photosensitive resin composition can be improved.
• polymer dispersant having a basic group for example, “Solsperse” (registered trademark) 24000 (manufactured by Avicia), “EFKA” (registered trademark) 4300, 4330 (manufactured by Efka), 4340 ( Efka), “Ajisper” (registered trademark) PB821, PB822 (Ajinomoto Fine Techno), “BYK” (registered trademark) 161-163, 2000, 2001, 6919, 21116 (Bic Chemie) .
• the photosensitive resin composition according to the embodiment of the present invention improves stability by further including a polymerization inhibitor in addition to the above-described photopolymerization initiator, pyromethene derivative, photopolymerization compound, and alkali-soluble resin.
• a polymerization inhibitor generally inhibit or stop polymerization due to radicals generated by heat, light, radical initiators, etc., and are used to prevent gelation of thermosetting resins or to stop polymerization during polymer production. Is done.
• Examples of the polymerization inhibitor in the present invention include hydroquinone, tert-butylhydroquinone, 2,5-bis (1,1,3,3-tetramethylbutyl) hydroquinone, 2,5-bis (1,1-dimethylbutyl). ) Hydroquinone, catechol, tert-butylcatechol and the like.
• the photosensitive resin composition may contain two or more of these as a polymerization inhibitor.
• the photosensitive resin composition of the present invention is, for example, mixing the above-mentioned photopolymerization initiator, pyromethene derivative, photopolymerizable compound and alkali-soluble resin, and if necessary, mixing the above-described other components, Obtainable.
• the cured film which concerns on embodiment of this invention is a film
• the cured film means a film made of a cured product of the photosensitive resin composition according to the embodiment of the present invention.
• the thickness of the cured film is preferably 5 ⁇ m or more and more preferably 10 ⁇ m or more from the viewpoint of sufficiently exhibiting the color conversion function of the pyromethene derivative and further improving the luminance.
• the thickness of the cured film is preferably 50 ⁇ m or less.
• the film thickness of such a cured film can be calculated by measuring the height of the step using a stylus type film thickness measuring device. More specifically, a part of the cured film is scratched with a needle or the like to expose a lower layer such as a substrate, and the film thickness is observed by using a stylus type thickness meter vertically from above the cured film. Can be requested.
• the line width of the cured film is preferably 30 ⁇ m or more.
• the line width of the cured film refers to the width of the bottom of the narrowest portion of the width of the cured film processed into a desired pattern on the substrate. Since pixel defects in the image display device are less likely to occur when the stripe pattern is thicker, pixel defects in the image display device can be suppressed by setting the line width of the cured film to 30 ⁇ m or more. Further, from the viewpoint of definition when the cured film is incorporated in an image display device or the like, the line width of the cured film is preferably 400 ⁇ m or less. The line width of such a cured film can be measured by magnifying and observing the cured film pattern at a magnification of 50 times using an optical microscope.
• the components contained in the cured film are obtained by collecting a sample of the cured film with a manipulator and analyzing the laser Raman (for example, HOLIBA Jobin, Raman T-64000 manufactured by YON) or FT-IR (for example, SPECTR-TECH manufactured by FT).
• -IR MICROSCOPE
• analysis can be performed and identified by comparison with the sample. Moreover, it can identify with high precision by combining centrifugation, filtration, collection methods, such as GPC fractionation, NMR, etc. as needed.
• the metal can be detected by ICP emission spectroscopic analysis or LDI-MS analysis.
• a color conversion substrate includes a cured film made of a cured product of the above-described photosensitive resin composition, and color conversion that converts incident light into light having a longer wavelength than the incident light. It has a function.
• Such a color conversion substrate is preferably formed by a combination of the substrate and the cured film described above.
• the substrate used for the color conversion substrate is preferably a transparent substrate.
• transparent in the present invention means that the light transmittances at wavelengths of 400 nm, 550 nm, 633 nm, and 800 nm are all 90% or more. Examples of the transparent substrate include a glass plate, a resin plate, and a resin film.
• the material of the glass plate alkali-free glass is preferable.
• polyester resin, acrylic resin, transparent polyimide resin, polyether sulfone resin, and the like are preferable.
• the thickness of the glass plate and the resin plate is preferably 1 mm or less, and more preferably 0.6 mm or less.
• the thickness of the resin film is preferably 100 ⁇ m or less.
• a coating process for applying the photosensitive resin composition according to the present embodiment on the substrate is performed.
• a coating method of the photosensitive resin composition in this coating step for example, the photosensitive resin composition is applied to the substrate using a spin coater, a bar coater, a blade coater, a roll coater, a die coater, an inkjet printing method, a screen printing method, or the like.
• substrate, etc. are mentioned.
• this coating step it is preferable to form a coating film of the photosensitive resin composition by drying the photosensitive resin composition coated on the substrate.
• drying method include air drying, heat drying, and vacuum drying.
• an exposure process is performed in which the photosensitive resin composition on the substrate is exposed using a predetermined light source.
• the coating film of the photosensitive resin composition is selectively exposed by irradiating the coating film of the photosensitive resin composition formed on the substrate with light such as ultraviolet rays through a mask.
• the light source used in this exposure step include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, and a chemical lamp. Among these, from the viewpoint of exposure wavelength, an ultrahigh pressure mercury lamp or a high pressure mercury lamp is preferable, and an ultrahigh pressure mercury lamp is more preferable.
• the exposure machine include an exposure machine that employs a system such as proximity, mirror projection, and lens scanning. Among these, a lens scanning type exposure machine is preferable from the viewpoint of accuracy.
• the exposure amount of the photosensitive resin composition in this exposure process is 60 mJ / cm 2 or more 250 mJ / cm 2 or less.
• the exposure amount is 60 mJ / cm 2 or more, a finer pattern of the photosensitive resin composition can be formed.
• the exposure amount is 250 mJ / cm 2 or less, decomposition of the pyromethene derivative in the photosensitive resin composition due to exposure can be suppressed, and the luminance of the photosensitive resin composition can be further improved.
• an alkaline developer is preferable.
• the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia; primary amines such as ethylamine and n-propylamine Secondary amines such as diethylamine and di-n-propylamine; tertiary amines such as triethylamine and methyldiethylamine; alkaline substances such as organic alkalis such as tetramethylammonium hydroxide; and aqueous solutions thereof.
• the alkaline developer may use two or more of these.
• a curing step is performed in which the exposed photosensitive resin composition is cured to form a cured film.
• the patterned photosensitive resin composition obtained by the exposure step described above is cured by heat treatment, thereby forming a cured film made of a cured product of the photosensitive resin composition.
• the heat treatment can be performed in air, in a nitrogen atmosphere, or in a vacuum.
• the heating temperature is preferably 100 ° C. or higher, and more preferably 120 ° C. or higher, from the viewpoint of adhesion of the cured film to the substrate.
• the heating temperature is preferably 200 ° C. or less, and more preferably 180 ° C. or less, from the viewpoint of heat resistance of the pyromethene derivative.
• the heating time is preferably 0.5 hours or more and 5 hours or less.
• a cured film made of a cured product of the photosensitive resin composition is produced. That is, the manufacturing method of the cured film which concerns on embodiment of this invention includes the exposure process mentioned above. Moreover, the color conversion board
• the color conversion substrate thus manufactured can be suitably used for, for example, electronic materials, automobile lamps, various illumination devices, various displays, and the like. Since the color conversion substrate according to the embodiment of the present invention has high luminance and high definition, it can be suitably used for an image display device such as an organic EL display, a micro LED display device, a liquid crystal display, and electronic paper.
• An image display apparatus includes the color conversion substrate described above.
• the image display device preferably includes a color conversion substrate having a cured film of the above-described photosensitive resin composition, a color filter substrate, and a light emitting element.
• the color conversion substrate is preferably disposed between the color filter substrate and the light emitting element.
• the organic EL display preferably includes a partially-driven blue organic electroluminescent element light source, a color conversion substrate, and a color filter substrate. This organic EL display may have an organic protective layer or an inorganic oxide film between the color filter substrate and the partially driven blue organic electroluminescent light source.
• this organic EL display may be a passive drive system or an active drive system.
• the micro LED display preferably includes a partially driven blue LED light source, a color conversion substrate, and a color filter substrate.
• the acid value of the alkali-soluble resin in Synthesis Examples 3 and 4 is determined by titrating a solution obtained by dissolving the alkali-soluble resin in ortho-cresol at 25 ° C. using a 0.1 mol / L potassium hydroxide / ethanol aqueous solution. It was.
• ⁇ Measurement of absorption maximum wavelength> In the measurement of the absorption maximum wavelength, a diluted solution obtained by diluting the luminescent material used in each Example and Comparative Example with PGMEA (propylene glycol monomethyl ether acetate) was prepared, and UV-visible spectrophotometry was used using a cell having an optical path length of 1 cm. An absorption spectrum of 300 nm to 800 nm was measured with a meter (manufactured by Shimadzu Corporation, MultiSpec-1500), and the wavelength at which the absorbance was maximum was read as the absorption maximum wavelength.
• PGMEA propylene glycol monomethyl ether acetate
• ⁇ Measurement of extinction coefficient> In the measurement of the extinction coefficient, a diluted solution obtained by diluting the photopolymerization initiator used in each Example and Comparative Example with PGMEA (propylene glycol monomethyl ether acetate) was prepared, and UV-visible spectroscopy was performed using a cell having an optical path length of 1 cm. The absorption spectrum at 300 nm to 800 nm was measured with a photometer (manufactured by Shimadzu Corporation, MultiSpec-1500), and the absorbance at the absorption maximum wavelength of the h-ray (405 nm) and the luminescent material was converted into a 1 g / mL solution. The coefficient was obtained.
• the surface of the cured film of the color conversion substrate prepared in each example and comparative example was irradiated with light having a wavelength of 460 nm using an F-2500 type spectrofluorometer (manufactured by Hitachi, Ltd.). Then, the fluorescence spectrum when excited was measured, and the wavelength at which the fluorescence emission intensity was maximum was read as the emission maximum wavelength.
• a planar light emitting device equipped with a commercially available blue LED (maximum light emission wavelength of 450 nm) is mounted with a color conversion substrate prepared according to each example and comparative example and a yellow color filter substrate that transmits a wavelength of 500 nm or more. I put it.
• a blue LED was turned on by passing a current of 10 mA through the planar light emitting device, and the luminance (unit: cd / m 2 ) was measured using a spectral radiance meter (SR-LEDW, manufactured by Topcon Technohouse).
• Synthesis Example 1 a method for synthesizing Compound G1, which is an example of a pyromethene derivative in the present invention, will be described.
• 3,5-dibromobenzaldehyde (3.0 g) 4-t-butylphenylboronic acid (5.3 g), tetrakis (triphenylphosphine) palladium (0) (0.4 g), and Potassium carbonate (2.0 g) was placed in the flask and purged with nitrogen. To this was added degassed toluene (30 mL) and degassed water (10 mL), and the mixture was refluxed for 4 hours.
• reaction product was purified by silica gel chromatography to obtain 3,5-bis (4-tert-butylphenyl) benzaldehyde (3.5 g) as a white solid.
• Synthesis Example 2 a method for synthesizing Compound R1, which is an example of a pyromethene derivative in the present invention, will be described.
• a mixed solution of 4- (4-t-butylphenyl) -2- (4-methoxyphenyl) pyrrole (300 mg), 2-methoxybenzoyl chloride (201 mg) and toluene (10 mL) was used.
• the mixture was heated at 120 ° C. for 6 hours under a nitrogen stream. Subsequently, the mixed solution was cooled to room temperature and then evaporated.
• diisopropylethylamine (305 mg) and boron trifluoride diethyl ether complex (670 mg) were added to a mixed solution of the obtained pyromethene and toluene (10 mL) under a nitrogen stream, and the mixture was stirred at room temperature for 3 hours. . Thereafter, water (20 mL) was injected, and the organic layer was extracted with dichloromethane (30 mL). This organic layer was washed twice with water (20 mL), dried over magnesium sulfate and evaporated. The obtained product was purified by silica gel column chromatography and vacuum dried to obtain a reddish purple powder (0.27 g) (yield 70%).
• Synthesis Example 3 a method for synthesizing Resin A, which is an example of the alkali-soluble resin in the present invention, will be described.
• a synthesis method of Resin A propylene glycol monomethyl ether acetate (202 g) was introduced into a 1 L flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a gas introduction tube. Thereafter, nitrogen gas was introduced into the flask through the gas introduction tube, and the atmosphere in the flask was replaced with nitrogen gas.
• Synthesis Example 4 a method for synthesizing Resin B, which is an example of the alkali-soluble resin in the present invention, will be described.
• a styrene / methyl methacrylate / methacrylic acid copolymer (weight ratio 33/33/34) was synthesized by the same method as in Synthesis Example 3 except that the raw material monomer and the composition ratio were changed.
• glycidyl methacrylate 33 parts by weight
• an alkali-soluble resin (resin B) solution having a weight average molecular weight of 23,000, an acid value of 75 mgKOH / g, and a resin solid content of 45.0% by weight was obtained.
• Example 1 (Preparation of fine particle dispersion) A method for producing the fine particle dispersion of Example 1 will be described.
• fine particles of barium sulfate (BF-20, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 30 nm, refractive index: 1.64) (96 g) and resin A obtained in Synthesis Example 3 as an alkali-soluble resin Solution (60 g), ⁇ -butyrolactone (114 g), N-methyl-2pyrrolidone (598 g), and 3 methyl-3-methoxybutyl acetate (132 g) were charged into a tank and stirred for 1 hour with a homomixer.
• Example 1 (Preparation of photosensitive resin composition) A method for producing the photosensitive resin composition of Example 1 will be described.
• Example 1 5.0 parts by weight of “IRGACURE” (registered trademark) 819 manufactured by BASF as photopolymerization initiator, 0.5 part by weight of pyromethene derivative (compound G1) obtained in Synthesis Example 1, 36.8 parts by weight of “Kayarad” (registered trademark) DPHA (dipentaerythritol hexaacrylate) manufactured by Nippon Kayaku Co., Ltd. as a polymerizable compound, and 81.
• a solution of Resin A obtained in Synthesis Example 3 as an alkali-soluble resin were obtained.
• Example 1 A method for manufacturing the color conversion substrate of Example 1 will be described.
• non-alkali glass Arsahi Glass Co., Ltd., AN100
• the photosensitivity of Example 1 was such that the film thickness after curing was 20 ⁇ m on this glass substrate.
• the resin composition was applied and vacuum dried.
• the photosensitive resin composition of Example 1 was applied onto a glass substrate similar to the above glass substrate (non-alkali glass having a thickness of 0.5 mm) so that the film thickness after curing was 20 ⁇ m. Vacuum dried. Using a mask aligner (PLA-501F, manufactured by Canon Inc.), an ultrahigh pressure mercury lamp as a light source, and a photomask designed to be exposed to a line pattern of 10 ⁇ m to 50 ⁇ m, an exposure amount of 100 mJ / cm 2 (i Line) and developed with 0.3 wt% tetramethylammonium aqueous solution for 50 seconds. Thereafter, heat curing was performed at 170 ° C. for 30 minutes, and a cured film pattern of the photosensitive resin composition of Example 1 was formed on the glass substrate. As described above, the color conversion substrate of Example 1 was obtained.
• PPA-501F mask aligner
• an ultrahigh pressure mercury lamp as a light source
• a photomask designed to be exposed to a line pattern of
• Example 1 Each evaluation by the above-mentioned method was performed about the photosensitive resin composition of Example 1, and a color conversion board
• the evaluation results of Example 1 are shown in Table 2 described later.
• Example 2 a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 1 except that “ADEKA ARKLES” (registered trademark) NCI-831 manufactured by ADEKA was used as a photopolymerization initiator. Produced. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 2, and a color conversion board
• Example 3 a photosensitive resin composition and a photosensitive resin composition were prepared in the same manner as in Example 1 except that titanium oxide (JR-600A, manufactured by Teica, particle size: 250 nm, refractive index: 2.40) was used as the fine particles. A color conversion substrate was produced. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 3, and a color conversion board
• Example 4 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 3 except that no ultraviolet absorber was added. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 4, and a color conversion board
• Example 5 In Example 5, aluminum oxide (“AEROXIDE” (registered trademark) Alu C, manufactured by Nippon Aerosil Co., Ltd., particle size: 13 nm, refractive index: 1.76) was used as the fine particles, and no ultraviolet absorber was added. Produced a photosensitive resin composition and a color conversion substrate in the same manner as in Example 1. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 5, and a color conversion board
• AEROXIDE registered trademark
• Example 6 is the same as Example 1 except that barium sulfate (BF-40, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 10 nm, refractive index: 1.64) was used as the fine particles, and no ultraviolet absorber was added. Similarly, a photosensitive resin composition and a color conversion substrate were produced. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 6, and a color conversion board
• barium sulfate BF-40, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 10 nm, refractive index: 1.64
• Example 7 is the same as Example 1 except that barium sulfate (B-30, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 300 nm, refractive index: 1.64) was used as the fine particles, and no ultraviolet absorber was added. Similarly, a photosensitive resin composition and a color conversion substrate were produced. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 7, and a color conversion board
• Example 1 was different from Example 1 except that the addition amount of fine particles (content of fine particles in the photosensitive resin composition) was changed as shown in Tables 2 and 3 and no ultraviolet absorber was added. Similarly, a photosensitive resin composition and a color conversion substrate were produced. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 8, 9 and the color conversion board
• Example 10 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 1 except that fine particles and an ultraviolet absorber were not added. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 10, and a color conversion board
• Example 11 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 1 except that no ultraviolet absorber was added. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 11, and a color conversion board
• Example 12 and 13 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 1 except that the exposure amount was changed as shown in Table 3. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Examples 12 and 13, and a color conversion board
• Example 14 and 15 the same procedure as in Example 1 was conducted except that the photosensitive resin composition of Example 1 was applied onto a glass substrate so that the film thickness after curing was as shown in Table 3. A photosensitive resin composition and a color conversion substrate were prepared. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 14, 15 and the color conversion board
• Example 16 a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 11 except that the resin B synthesized in Synthesis Example 4 was used as the alkali-soluble resin and no ultraviolet absorber was added. did. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 16, and a color conversion board
• Example 17 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 1 except that Compound R1 was used as a pyromethene derivative. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 17, and a color conversion board
• Example 18 a photosensitive resin composition was prepared in the same manner as in Example 17 except that NCI-831 was used as an initiator and no ultraviolet absorber was added. Further, a color conversion substrate was produced in the same manner as in Example 17 except that the produced photosensitive resin composition was applied onto a glass substrate so that the film thickness after curing was 2.5 ⁇ m. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 18, and a color conversion board
• Example 19 aluminum oxide (“AEROXIDE” (registered trademark) Alu C, manufactured by Nippon Aerosil Co., Ltd., particle size: 13 nm, refractive index: 1.76) was used as the fine particles in the same manner as in Example 18. A photosensitive resin composition and a color conversion substrate were prepared. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 19, and a color conversion board
• AEROXIDE registered trademark
• Alu C manufactured by Nippon Aerosil Co., Ltd., particle size: 13 nm, refractive index: 1.76
• Example 20 a photosensitive resin composition was prepared in the same manner as in Example 18 except that barium sulfate (BF-40, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 10 nm, refractive index: 1.64) was used as the fine particles. And a color conversion substrate were prepared. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 20, and a color conversion board
• barium sulfate BF-40, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 10 nm, refractive index: 1.64
• Example 21 a photosensitive resin composition was prepared in the same manner as in Example 18 except that barium sulfate (B-30, manufactured by Sakai Chemical Industry Co., Ltd., particle size: 300 nm, refractive index: 1.64) was used as the fine particles. And a color conversion substrate were prepared. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 21, and a color conversion board
• Examples 22 and 23 In Examples 22 and 23, in the same manner as in Example 18 except that the photosensitive resin composition of Example 18 was applied onto a glass substrate so that the film thickness after curing was as shown in Table 4, A photosensitive resin composition and a color conversion substrate were prepared. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Examples 22 and 23, and a color conversion board
• Example 24 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 18 except that the resin B synthesized in Synthesis Example 4 was used as the alkali-soluble resin. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Example 24, and the color conversion board
• Comparative Example 1 a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 1 except that “IRGACURE” (registered trademark) OXE02 manufactured by BASF was used as a photopolymerization initiator. Then, each evaluation was performed like Example 1 about the photosensitive resin composition of the comparative example 1, and the color conversion board
• Comparative Example 2 the photosensitive resin composition was the same as Comparative Example 1 except that the photosensitive resin composition of Comparative Example 1 was applied onto a glass substrate so that the film thickness after curing was 3 ⁇ m. And a color conversion substrate was produced. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Comparative Example 2, and the color conversion board
• Comparative Example 3 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 10 except that Compound G2 was used as the light emitting material. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of Comparative Example 3, and a color conversion board
• Comparative Example 4 a photosensitive resin composition and a color conversion substrate were prepared in the same manner as in Example 10 except that quantum dots (CdSeS / ZnS: dot diameter 6 nm, manufactured by Sigma-Aldrich) were used as the luminescent material G3. did. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of the comparative example 4, and the color conversion board
• Comparative Example 5 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Comparative Example 1 except that Compound R1 was used as the light emitting material. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition and color conversion board
• FIG. The evaluation results of Comparative Example 5 are shown in Table 6 described later.
• Comparative Example 6 the photosensitive resin composition was the same as Comparative Example 5 except that the photosensitive resin composition of Comparative Example 1 was applied onto a glass substrate so that the film thickness after curing was 3 ⁇ m. And a color conversion substrate was produced. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition of the comparative example 6, and the color conversion board
• Comparative Example 7 a photosensitive resin composition and a color conversion substrate were produced in the same manner as in Example 18 except that Compound R2 was used as the light emitting material. Then, each evaluation was performed similarly to Example 1 about the photosensitive resin composition and color conversion board
• the photosensitive resin composition, the cured film, the color conversion substrate, the image display device, and the method for producing the cured film according to the present invention are capable of forming a fine pattern with high brightness. It is suitable for an object, a cured film thereof, a color conversion substrate using the same, and an image display device.

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