WO2019065001A1 - 感光性着色組成物、硬化膜、パターンの形成方法、カラーフィルタ、固体撮像素子および画像表示装置 - Google Patents
感光性着色組成物、硬化膜、パターンの形成方法、カラーフィルタ、固体撮像素子および画像表示装置 Download PDFInfo
- Publication number
- WO2019065001A1 WO2019065001A1 PCT/JP2018/030863 JP2018030863W WO2019065001A1 WO 2019065001 A1 WO2019065001 A1 WO 2019065001A1 JP 2018030863 W JP2018030863 W JP 2018030863W WO 2019065001 A1 WO2019065001 A1 WO 2019065001A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- coloring composition
- mass
- photosensitive coloring
- compound
- Prior art date
Links
Classifications
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133514—Colour filters
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
- G03F7/2004—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image characterised by the use of a particular light source, e.g. fluorescent lamps or deep UV light
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
Definitions
- the present invention relates to photosensitive coloring compositions. More particularly, the present invention relates to a photosensitive coloring composition used to form colored pixels of a color filter. The invention also relates to a cured film using a photosensitive coloring composition, a method of forming a pattern, a color filter, a solid-state imaging device, and an image display device.
- a colored photosensitive composition for forming each color pixel is applied on a support, prebaked at about 100 ° C., a pattern subjected to exposure and development is then formed, and then post-baked.
- Post-baking is a heat treatment for accelerating the curing of the film after development, and is performed at a relatively high temperature.
- post-baking is performed on a film after development at a temperature of 200 ° C. or higher.
- organic electroluminescence (organic EL) conversion of the light emission light source in an image display apparatus and the organic material conversion of a photoelectric conversion film in an image sensor have been studied. Many of these members have low heat resistance. Therefore, it has been studied to manufacture color filters at low temperatures.
- Patent Document 2 (i) a step of forming a layer on a substrate using a photosensitive coloring composition, (ii) a step of exposing the photosensitive coloring composition layer to light having a wavelength of more than 350 nm and 380 nm or less (Iii) alkaline developing the photosensitive coloring composition layer and (iv) exposing the photosensitive coloring composition layer to light having a wavelength of 254 to 350 nm in this order, as a photosensitive coloring composition ( a) A polymerization initiator having an absorption coefficient of at least 1.0 ⁇ 10 3 mL / g cm at a wavelength of 365 nm in methanol, and (b) an absorption coefficient of at a wavelength of 365 nm in a methanol of 1.0 ⁇ 10 2 mL / g cm or less, a polymerization initiator having an absorption coefficient of 1.0 ⁇ 10 3 mL / g cm or more at a wavelength of 254 nm, (c)
- an object of this invention is to provide the photosensitive coloring composition which can form the cured film excellent in the decoloring resistance with respect to a developing solution. Moreover, this invention aims at providing a cured film, the formation method of a pattern, a color filter, a solid-state image sensor, and an image display apparatus.
- the photosensitive coloring composition containing a specific photopolymerization initiator described later and a coloring material having a polymerizable group is resistant to decoloring to a developer even when cured at a low temperature. It has been found that a cured film excellent in the above can be formed, and the present invention has been completed. That is, the present invention is as follows.
- Photopolymerization initiator a having an absorption coefficient of light with a wavelength of 365 nm in methanol exceeding 1.0 ⁇ 10 2 mL / g cm
- Photopolymerization initiator b having an absorption coefficient of light of wavelength 365 nm in methanol of not more than 1.0 ⁇ 10 2 mL / g cm and an absorption coefficient of light of wavelength 254 nm of not less than 1.0 ⁇ 10 3 mL / g cm
- Alkali-soluble resin It is a photosensitive coloring composition containing a coloring material having a polymerizable group, A photosensitive coloring material, wherein the content of the photopolymerization initiator a in the total solid content of the photosensitive coloring composition is 1.5% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more Composition.
- the absorption coefficient of light of wavelength 365nm in methanol of the photoinitiator a is is 1.0 ⁇ 10 3 mL / gcm or higher, the photosensitive coloring composition according to ⁇ 1>.
- the photosensitive coloring composition according to any one of ⁇ 1> to ⁇ 4> which contains 50 to 500 parts by mass of the photopolymerization initiator a with respect to 100 parts by mass of the ⁇ 5> photopolymerization initiator b.
- Any one of ⁇ 1>- ⁇ 5> whose content of the sum total of the photoinitiator a and the photoinitiator b in the total solid of a ⁇ 6> photosensitive coloring composition is 3-17 mass%.
- ⁇ 8> A cured film obtained by curing the photosensitive coloring composition according to any one of ⁇ 1> to ⁇ 7>.
- ⁇ 9> A process of forming a photosensitive coloring composition layer on a support using the photosensitive coloring composition according to any one of ⁇ 1> to ⁇ 7>, Irradiating the photosensitive coloring composition layer with light having a wavelength of more than 350 nm and 380 nm or less and exposing it in a pattern; Alkaline developing the photosensitive coloring composition layer after exposure; And irradiating the photosensitive coloring composition layer after development with light having a wavelength of 254 to 350 nm.
- the color filter which has a cured film as described in ⁇ 10> ⁇ 8>.
- the solid-state image sensor which has a cured film as described in ⁇ 11> ⁇ 8>.
- the image display apparatus which has a cured film as described in ⁇ 12> ⁇ 8>.
- the photosensitive coloring composition which can form the cured film excellent in the color-removing property with respect to a developing solution can be provided.
- a cured film, the formation method of a pattern, a color filter, and a solid-state image sensor can be provided.
- the notation not describing substitution and non-substitution includes a group (atomic group) having a substituent as well as a group (atomic group) having no substituent.
- the "alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
- “exposure” includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.
- a bright line spectrum of a mercury lamp far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light), actinic rays such as X-rays, electron beams and the like can be mentioned.
- EUV light extreme ultraviolet rays
- actinic rays such as X-rays, electron beams and the like
- a numerical range represented using “to” means a range including the numerical values described before and after “to” as the lower limit value and the upper limit value.
- total solids refers to the total mass of all components of the composition excluding the solvent.
- (meth) acrylate represents both or either of acrylate and methacrylate
- (meth) acryl represents both or either of acrylic and methacryl
- Allyl represents both or any of allyl and methallyl
- (meth) acryloyl represents both or any of acryloyl and methacryloyl.
- the term "process” is included in the term if the intended function of the process is achieved, even if it can not be clearly distinguished from other processes, not only the independent process.
- the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene conversion values measured by gel permeation chromatography (GPC).
- the photosensitive coloring composition of the present invention is A photopolymerization initiator a having an absorption coefficient of light of wavelength 365 nm in methanol of more than 1.0 ⁇ 10 2 mL / g cm, Photopolymerization initiator b having an absorption coefficient of light of wavelength 365 nm in methanol of not more than 1.0 ⁇ 10 2 mL / g cm and an absorption coefficient of light of wavelength 254 nm of not less than 1.0 ⁇ 10 3 mL / g cm
- Alkali-soluble resin It is a photosensitive coloring composition containing a coloring material having a polymerizable group,
- the content of the photopolymerization initiator a in the total solid content of the photosensitive coloring composition is 1.5% by mass or more, and the content of the photopolymerization initiator b is 1.5% by mass or more.
- the photosensitive coloring composition of the present invention contains the photopolymerization initiator a and the photopolymerization initiator b as the photopolymerization initiator in the above-mentioned predetermined ratio, it is possible to cure firmly to the deep part of the cured film by exposure. it can. And in this invention, since the coloring material which has a polymeric group is used, at the time of hardening of a photosensitive coloring composition, the polymeric group of a coloring material reacts with components other than the coloring material of a photosensitive coloring composition. The coloring material is easily taken into the cured film, and a cured film excellent in the decoloring resistance to the developer can be formed. Therefore, color loss after development can be effectively suppressed.
- the photosensitive coloring composition of the present invention can be appropriately cured in the first exposure (exposure before development). Therefore, it is possible to form a rectangular pattern.
- the entire photosensitive coloring composition can be substantially cured by the next exposure (exposure after development). For this reason, it is possible to form a pattern excellent in the decoloring resistance to the developer while having excellent pattern formability.
- the photosensitive coloring composition of the present invention can obtain particularly remarkable effects when a dye having a polymerizable group is used as a coloring material having a polymerizable group.
- a dye is used as the coloring material, the affinity to the developing solution tends to be high, and decoloring to the developing solution tends to easily occur. For this reason, in the conventional photosensitive coloring composition, it was necessary to heat-process at high temperature and to fully harden a film
- the photosensitive coloring composition of the present invention by using a dye having a polymerizable group, it is possible to form a cured film having excellent resistance to decoloring to a developer even when cured at low temperature. In particular, the effects of the present invention are remarkable. In addition, by using a dye, it is possible to form a clearer, high-colored cured film.
- the photosensitive coloring composition of the present invention contains a photopolymerization initiator.
- a photopolymerization initiator for example, a halogenated hydrocarbon derivative (for example, a compound having a triazine skeleton, a compound having an oxadiazole skeleton, etc.), an acylphosphine compound such as an acylphosphine oxide, a hexaarylbiimidazole compound, an oxime derivative And oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ether compounds, aminoacetophenone compounds, hydroxyacetophenone compounds, phenylglyoxylate compounds and the like.
- the photopolymerization initiator for example, the description in paragraph Nos. 0265 to 0268 of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
- a bifunctional or trifunctional or higher functional photopolymerization initiator may be used as the photopolymerization initiator.
- a photopolymerization initiator paragraph Nos. 0417 to 0412 of JP-A-2010-527339, JP-A-2011-524436, International Publication WO2015 / 004565, JP-A-2016-532675.
- the phenylglyoxylic acid methyl ester may, for example, be mentioned as the phenylglyoxylate compound.
- Examples of commercially available products include DAROCUR-MBF (manufactured by BASF).
- aminoacetophenone compound examples include aminoacetophenone compounds described in JP-A-10-291969. Further, as the aminoacetophenone compound, IRGACURE-907, IRGACURE-369, IRGACURE-379 (all manufactured by BASF Corporation) can also be used.
- acyl phosphine compound As an acyl phosphine compound, the acyl phosphine compound as described in patent 4225898 is mentioned. Specific examples include bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide and the like. As the acyl phosphine compound, IRGACURE-819 and DAROCUR-TPO (both manufactured by BASF Corporation) can also be used.
- Rv 1 represents a substituent
- Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent
- Rv 2 and Rv 3 may be mutually bonded to form a ring
- m represents an integer of 0 to 4;
- Examples of the substituent represented by Rv 1 include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms) and an alkoxy group (preferably an alkoxy group having 1 to 10 carbon atoms).
- the alkyl group and the alkoxy group are preferably linear or branched, and more preferably linear.
- the alkyl group and alkoxy group which Rv 1 represents may be unsubstituted and may have a substituent.
- Examples of the substituent include a hydroxyl group and a group having a hydroxyacetophenone structure.
- Examples of the group having a hydroxyacetophenone structure include a benzene ring to which Rv 1 is bonded in Formula (V) or a group having a structure in which one hydrogen atom is removed from Rv 1 .
- Rv 2 and Rv 3 each independently represent a hydrogen atom or a substituent.
- an alkyl group preferably an alkyl group having 1 to 10 carbon atoms
- Rv 2 and Rv 3 may be bonded to each other to form a ring (preferably a ring having 4 to 8 carbon atoms, more preferably an aliphatic ring having 4 to 8 carbon atoms).
- the alkyl group is preferably linear or branched, and more preferably linear.
- IRGACURE-184 As the hydroxyacetophenone compound, IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names: all manufactured by BASF Corp.) can also be used.
- a compound described in JP-A-2001-233842 a compound described in JP-A-2000-80068, or a compound described in JP-A-2006-342166 can be used.
- a compound described in JP-A-2001-233842 a compound described in JP-A-2000-80068, or a compound described in JP-A-2006-342166 can be used.
- an oxime compound J.I. C. S. Perkin II (1979) pp. 1653-1660, J.M. C. S. Perkin II (1979) pp. No. 156-162, Journal of Photopolymer Science and Technology (1995, pp. 202-232), JP-A 2000-66385, JP-A 2000-80068, JP-A-2004-534797, JP-A 2006-342166. It is also possible to use the compounds etc. described in Japanese Patent Application Publication No.
- oxime compound examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methyl) Benzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) and the like.
- IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03 and IRGACURE-OXE04 are preferably used.
- TRONLY TR-PBG-304 TRONLY TR-PBG-309, TRONLY TR-PBG-305 (made by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD.), Adeka ARKules NCI-930 Adeka Optomer N-1919 (photopolymerization initiator 2 in JP-A-2012-14052) (all manufactured by ADEKA Co., Ltd.) can be used.
- oxime compound a compound described in JP-A-2009-519904, in which an oxime is linked to the N-position of a carbazole ring
- a compound described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into a benzophenone moiety Compounds described in JP-A-2010-15025 and U.S. Patent Publication 2009-292039 in which a nitro group is introduced at a dye site, a ketoxime compound described in WO2009 / 131189, the same molecule having a triazine skeleton and an oxime skeleton
- the oxime compound which has a fluorene ring can also be used as an oxime compound.
- the oxime compound having a fluorene ring compounds described in JP-A-2014-137466 can be mentioned. This content is incorporated herein.
- an oxime compound having a benzofuran skeleton can also be used as the oxime compound.
- Specific examples thereof include the compounds OE-01 to OE-75 described in International Publication WO 2015/036910.
- an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is a naphthalene ring can also be used.
- an oxime compound the compound described in International Publication WO 2013/083505 can be mentioned.
- the oxime compound which has a fluorine atom can also be used as a photoinitiator.
- Specific examples of the oxime compound having a fluorine atom include the compounds described in JP-A-2010-262028, the compounds 24 and 36 to 40 described in JP-A-2014-500852, and JP-A-2013-164471. And the like (C-3) and the like. This content is incorporated herein.
- the oxime compound which has a nitro group can be used as an oxime compound.
- the oxime compound having a nitro group is also preferably a dimer.
- specific examples of the oxime compound having a nitro group compounds described in paragraphs 0031 to 0047 of JP 2013-114249 A, paragraphs 0008 to 0012 and 0070 to 0079 of JP 2014-137466 A, and patent 4223071 Compounds described in Paragraph Nos. 0007 to 0025 of the gazette, Adeka Arkles NCI-831 (manufactured by ADEKA Co., Ltd.), and the like.
- a photopolymerization initiator a (hereinafter, also referred to as a photopolymerization initiator a) having an absorption coefficient of light with a wavelength of 365 nm in methanol exceeding 1.0 ⁇ 10 2 mL / g cm as a photopolymerization initiator , Photopolymerization initiator b having an absorption coefficient of light of wavelength 365 nm in methanol of not more than 1.0 ⁇ 10 2 mL / g cm and an absorption coefficient of light of wavelength 254 nm of not less than 1.0 ⁇ 10 3 mL / g cm (Hereafter, it is also called a photoinitiator b.) And is used together.
- the photopolymerization initiator a and the photopolymerization initiator b compounds having the above-mentioned absorption coefficient can be selected and used from the above-mentioned compounds.
- the light absorption coefficient at the above-mentioned wavelength of the photopolymerization initiator is a value measured as follows. That is, the photopolymerization initiator was dissolved in methanol to prepare a measurement solution, and the absorbance was calculated by measuring the absorbance of the above-mentioned measurement solution. Specifically, the above-mentioned measurement solution is placed in a 1 cm wide glass cell, the absorbance is measured using a UV-Vis-NIR spectrometer (Cary 5000) manufactured by Agilent Technologies, and the wavelength is 365 nm and the wavelength The extinction coefficient at 254 nm (mL / g cm) was calculated. In the above formula, ⁇ represents the extinction coefficient (mL / g cm), A represents the absorbance, c represents the concentration of the photopolymerization initiator (g / mL), and l represents the optical path length (cm).
- the absorption coefficient of light with a wavelength of 365 nm in methanol of the photopolymerization initiator a is a value exceeding 1.0 ⁇ 10 2 mL / g cm, preferably 1.0 ⁇ 10 3 mL / g cm or more, It is more preferably 1.0 ⁇ 10 3 to 1.0 ⁇ 10 4 mL / g cm, still more preferably 2.0 ⁇ 10 3 to 9.0 ⁇ 10 3 mL / g cm, 3.0 ⁇ Particularly preferred is 10 3 to 8.0 ⁇ 10 3 mL / g cm.
- the light absorption coefficient of light of wavelength 254 nm in methanol of the photopolymerization initiator a is preferably 1.0 ⁇ 10 4 to 1.0 ⁇ 10 5 mL / g cm, and 1.5 ⁇ 10 4 to It is more preferably 9.5 ⁇ 10 4 mL / g cm, and still more preferably 3.0 ⁇ 10 4 to 8.0 ⁇ 10 4 mL / g cm.
- the photopolymerization initiator a is preferably an oxime compound, an aminoacetophenone compound or an acyl phosphine compound, more preferably an oxime compound and an acyl phosphine compound, still more preferably an oxime compound.
- the photopolymerization initiator a examples include 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (commercially available products include, for example, IRGACURE-OXE01, BASF (Trade name), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (commercially available products include, for example, IRGACURE- OXE02 (manufactured by BASF), bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (as a commercial product, for example, IRGACURE-819, manufactured by BASF), specific examples of the oxime compound described above C-13) and the like.
- IRGACURE-OXE01 BASF (Trade name)
- ethanone 1- [9-ethyl-6- (2-methylbenzoyl
- the light absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator b is 1.0 ⁇ 10 2 mL / g cm or less, preferably 10 to 1.0 ⁇ 10 2 mL / g cm, and 20 More preferably, it is -1.0 ⁇ 10 2 mL / g cm.
- the difference between the absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator a and the absorption coefficient of light having a wavelength of 365 nm in methanol of the photopolymerization initiator b is 9.0 ⁇ 10 2 mL / Gcm or more is preferable, 9.0 ⁇ 10 2 to 1.0 ⁇ 10 5 mL / g cm is more preferable, and 9.0 ⁇ 10 2 to 1.0 ⁇ 10 4 mL / g cm Is more preferred.
- the light absorption coefficient of light of wavelength 254 nm in methanol of the photopolymerization initiator b is 1.0 ⁇ 10 3 mL / g cm or more, and 1.0 ⁇ 10 3 to 1.0 ⁇ 10 6 mL / g cm Is preferably 5.0 ⁇ 10 3 to 1.0 ⁇ 10 5 mL / g cm, and more preferably 1.0 ⁇ 10 4 to 5.0 ⁇ 10 5 mL / g cm.
- the photopolymerization initiator b is preferably a hydroxyacetophenone compound, a phenylglyoxylate compound, an aminoacetophenone compound or an acylphosphine compound, more preferably a hydroxyacetophenone compound or a phenylglyoxylate compound, and still more preferably a hydroxyacetophenone compound.
- a hydroxyacetophenone compound the compound represented by Formula (V) mentioned above is preferable.
- photopolymerization initiator b examples include 1-hydroxy-cyclohexyl-phenyl-ketone (as a commercial product, for example, IRGACURE-184, manufactured by BASF), 1- [4- (2-hydroxyethoxy) -phenyl ] -2-hydroxy-2-methyl-1-propan-1-one (as a commercial product, for example, IRGACURE-2959, manufactured by BASF) and the like.
- the absorption coefficient of light with a wavelength of more than 350 nm and 380 nm or less and the absorption coefficient of light with a wavelength of 254 nm or more and 350 nm or less can be increased.
- a combination in which the photopolymerization initiator a is an oxime compound and the photopolymerization initiator b is a hydroxyacetophenone compound is preferable, the photopolymerization initiator a is an oxime compound, and the photopolymerization initiator b is the above-mentioned formula (V)
- the combination which is the compound represented is more preferable.
- the content of the photopolymerization initiator a is 1.5% by mass or more in the total solid content of the photosensitive coloring composition of the present invention, and preferably 1.5 to 15% by mass.
- the lower limit of the content of the photopolymerization initiator a is preferably 2% by mass or more, more preferably 3% by mass or more More preferably, it is 5% by mass or more.
- the upper limit of the content of the photopolymerization initiator a is preferably 14.5% by mass or less, more preferably 12.5% by mass or less, and 9% by mass or less from the viewpoint of miniaturization of the development pattern It is further preferred that The photopolymerization initiator a may contain only one type, or two or more types. When 2 or more types of photoinitiator a are included, it is preferable that those sum totals become said range.
- the content of the photopolymerization initiator b is 1.5% by mass or more in the total solid content of the photosensitive coloring composition of the present invention, and preferably 1.5 to 10% by mass.
- the lower limit of the content of the photopolymerization initiator b is preferably 1.6% by mass or more, more preferably 2% by mass or more, and 3% by mass from the viewpoint of the decoloring resistance of the obtained cured film. It is more preferable that it is more than.
- the upper limit of the content of the photopolymerization initiator b is preferably 9.5% by mass or less, more preferably 7.5% by mass or less, and 5% by mass or less from the viewpoint of miniaturization of the development pattern. It is further preferred that The photoinitiator b may contain only 1 type, and may contain 2 or more types. When 2 or more types of photoinitiator b are included, it is preferable that those sum totals become said range.
- the photosensitive coloring composition of the present invention preferably contains 50 to 500 parts by mass of the photopolymerization initiator a with respect to 100 parts by mass of the photopolymerization initiator b.
- the upper limit is preferably 400 parts by mass or less, and more preferably 350 parts by mass or less, because it is easy to form a cured film excellent in color fastness.
- the lower limit is preferably 100 parts by mass or more, and 150 parts by mass or more because the residual film ratio after development is high and a cured film having excellent adhesion to the support can be easily formed. More preferable.
- the total content of the photopolymerization initiator a and the photopolymerization initiator b in the total solid content of the photosensitive coloring composition of the present invention is preferably 3 to 17% by mass or more.
- the lower limit is preferably 3.2% by mass or more, more preferably 3.5% by mass or more, and still more preferably 4.5% by mass or more.
- the upper limit is preferably 16% by mass or less, more preferably 15% by mass or less, and still more preferably 14% by mass or less from the viewpoint of miniaturization of the development pattern.
- the photosensitive coloring composition of the present invention can also contain a photopolymerization initiator (hereinafter also referred to as another photopolymerization initiator) other than the photopolymerization initiator a and the photopolymerization initiator b as a photopolymerization initiator
- a photopolymerization initiator hereinafter also referred to as another photopolymerization initiator
- the content of the other photopolymerization initiator is 1 part by mass with respect to a total of 100 parts by mass of the photopolymerization initiator a and the photopolymerization initiator b. It is preferable that it is the following, It is more preferable that it is 0.5 mass part or less, It is still more preferable that it is 0.1 mass part or less, It is still more preferable that it does not contain another photoinitiator.
- the photosensitive coloring composition of the present invention contains a coloring material having a polymerizable group.
- the colorant having a polymerizable group may be a pigment or a dye, but is preferably a dye. That is, the colorant having a polymerizable group is preferably a dye having a polymerizable group.
- a cured film obtained using a photosensitive coloring composition containing a dye as a coloring material tends to be susceptible to color loss due to a developer, but it is cured at a low temperature by using a polymerizable group as the dye. Even in this case, a cured film having excellent resistance to color development to a developer can be formed. For this reason, the effect of the present invention is more remarkable.
- a dye refers to a dye compound that is soluble in water or an organic solvent.
- a dye compound which dissolves in an amount of 0.1% by mass or more in cyclohexanone or propylene glycol monomethyl ether acetate (PGMEA) at 25 ° C. is preferable.
- Color materials having a polymerizable group include triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, pyrazolo Triazole dye structure, dipyrromethene dye structure, isoindoline dye structure, thiazole dye structure, benzimidazolone dye structure, perinone dye structure, pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, diimmonium dye structure, naphthalocyanine dye structure, rylene It is preferable that it is a compound having a dye structure selected from a dye structure, a dibenzofuranone dye structure, a merocyanine dye structure, a croconium dye structure and an oxonol dye structure, and a triarylmethane dye structure Dyes selected from x
- Rtp 1 to Rtp 4 each independently represent a hydrogen atom, an alkyl group or an aryl group.
- Rtp 5 represents a hydrogen atom, an alkyl group, an aryl group or NRtp 9 Rtp 10 (Rtp 9 and Rtp 10 represents a hydrogen atom, an alkyl group or an aryl group).
- Rtp 6 , Rtp 7 and Rtp 8 represent substituents.
- a, b and c each represents an integer of 0 to 4; When a, b and c are 2 or more, Rtp 6 each other, Rtp 7 each other and Rtp 8 each may be linked to form a ring.
- X represents an anion. When X is absent, at least one of Rtp 1 to Rtp 8 contains an anion. At least one of Rtp 1 to Rtp 8 contains a polymerizable group.
- Rtp 1 to Rtp 4 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, and a phenyl group.
- Rtp 5 is preferably a hydrogen atom or NRtp 9 Rtp 10 , and particularly preferably NRtp 9 Rtp 10 .
- Rtp 9 and Rtp 10 are preferably a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, or a phenyl group.
- Examples of the substituent represented by Rtp 6 , Rtp 7 and Rtp 8 include the groups and polymerizable groups mentioned in the substituent T group described later.
- X represents a counter anion.
- the counter anion is not particularly limited. It may be an organic anion or an inorganic anion.
- the counter anion is preferably an organic anion.
- a fluorine anion, a chlorine anion, a bromine anion, an iodine anion, a cyanide ion, a perchlorate anion, a non-nucleophilic anion and the like can be mentioned. It is preferable that it is a non-nucleophilic anion from the viewpoint of heat resistance.
- non-nucleophilic means the property which does not carry out the nucleophilic attack of the pigment by heating.
- the counter anion is preferably an imide anion (eg, bis (sulfonyl) imide anion), a tris (sulfonyl) methyl anion, an anion having a boron atom, more preferably a bis (sulfonyl) imide anion and a tris (sulfonyl) methyl anion, and
- the sulfonyl) imide anion is more preferred.
- Examples of the anion having a boron atom include tetrafluoroborate anion, tetraphenylborate anion, and tetraperfluorophenylborate anion.
- the molecular weight of the counter anion is preferably 100 to 1,000, and more preferably 200 to 500.
- a, b or c each independently represents an integer of 0 to 4.
- a and c are each preferably 0 or 1, and more preferably 0.
- b is preferably an integer of 0 to 2, more preferably 0 or 2.
- TP if it contains at least one anion of Rtp 1 ⁇ Rtp 7, as the anion, -SO 3 -, -COO -, -PO 4 -, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion And tetraaryl borate anions are preferable, bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetra aryl borate anion are more preferable, and bis (sulfonyl) imide anion and tris (sulfonyl) methide anion are more preferable.
- Formula (P) In formula (P), L represents a single bond or a divalent linking group, and X 1 represents an anion.
- L represents a single bond or a divalent linking group.
- the divalent linking group is preferably a group consisting of —NR 10 —, —O—, —SO 2 —, an alkylene group containing a fluorine atom, an arylene group containing a fluorine atom, or a combination of these.
- a group consisting of a combination of -NR 10- , -SO 2 and an alkylene group containing a fluorine atom a group consisting of a combination of -O- and an arylene group containing a fluorine atom, or -NR 10 -and -SO
- the group which consists of a combination of 2 and the alkylene group containing a fluorine atom is preferable.
- R 10 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom.
- the carbon number of the alkylene group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
- alkylene groups are more preferably perfluoroalkylene groups.
- fluorine-substituted alkylene group include difluoromethylene group, tetrafluoroethylene group, hexafluoropropylene group and the like.
- the carbon number of the arylene group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.
- Specific examples of the arylene group containing a fluorine atom include tetrafluorophenylene group, hexafluoro-1-naphthylene group, hexafluoro-2-naphthylene group and the like.
- X 1 represents an anion, and one kind selected from —SO 3 ⁇ , —COO ⁇ , —PO 4 ⁇ , bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraaryl borate anion Is more preferably one selected from bis (sulfonyl) imide anion, tris (sulfonyl) methide anion and tetraaryl borate anion, and more preferably bis (sulfonyl) imide anion or tris (sulfonyl) methide anion.
- L 1 represents a single bond or a divalent linking group, and is preferably a single bond.
- the divalent linking group represented by L 1 include an alkylene group having 1 to 6 carbon atoms, an arylene group having 6 to 12 carbon atoms, a group consisting of —O—, —S—, or a combination thereof.
- L 2 represents -SO 2 -or -CO-.
- G represents a carbon atom or a nitrogen atom.
- n1 represents 2 when G is a carbon atom, and 1 when G is a nitrogen atom.
- R 6 represents an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom. When n1 is 2, two R 6 may be the same or different.
- the carbon number of the alkyl group containing a fluorine atom represented by R 6 is preferably 1 to 10, more preferably 1 to 6, and still more preferably 1 to 3.
- the carbon number of the aryl group containing a fluorine atom represented by R 6 is preferably 6 to 20, more preferably 6 to 14, and still more preferably 6 to 10.
- Examples of the compound having a xanthene dye structure include a compound represented by the following formula (J).
- R 81 , R 82 , R 83 and R 84 each independently represent a hydrogen atom or a monovalent substituent, and R 85 each independently represents a monovalent substituent, and m Represents an integer of 0 to 5.
- X represents a counter anion. When X is absent, at least one of R 81 to R 85 contains an anion. At least one of R 81 to R 85 contains a polymerizable group.
- R 81 to R 85 in the formula (J) examples include the groups listed as the substituent T described later, and a polymerizable group.
- R 81 and R 82 in the formula (J), R 83 and R 84 , and R 85 when m is 2 or more are each independently bonded to each other to be a 5-, 6- or 7-membered saturated ring Or a 5-, 6- or 7-membered unsaturated ring may be formed.
- ring to be formed for example, pyrrole ring, furan ring, thiophene ring, pyrazole ring, imidazole ring, triazole ring, oxazole ring, thiazole ring, pyrrolidine ring, piperidine ring, cyclopentene ring, cyclohexene ring, benzene ring, pyridine ring, Pyrazine ring and pyridazine ring can be mentioned, and preferably, benzene ring and pyridine ring can be mentioned.
- the ring formed is a further substitutable group, it may be substituted by the substituents described in R 81 to R 85 , and when substituted by two or more substituents, The substituents may be the same or different.
- X represents a counter anion.
- a counter anion the counter anion demonstrated by the formula (TP) mentioned above is mentioned.
- TP the counter anion demonstrated by the formula (TP) mentioned above is mentioned.
- X is absent, at least one of R 81 to R 85 contains an anion.
- examples of the anion include the anion described in the above-mentioned formula (TP).
- R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom or a substituent
- R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group Or a heterocyclic group.
- substituent T group mentioned later is mentioned.
- At least one of R 1 to R 7 contains a polymerizable group.
- the metal or metal compound which forms a dipyrromethene metal complex compound is demonstrated.
- the metal or metal compound may be any metal atom or metal compound capable of forming a complex, and is a divalent metal atom, a divalent metal oxide, a divalent metal hydroxide, or Contain metal chloride of For example, Zn, Mg, Si, Sn , Rh, Pt, Pd, Mo, Mn, Pb, Cu, Ni, Co, Fe, in addition to B, such as, AlCl, InCl, FeCl, TiCl 2, SnCl, SiCl 2, Also included are metal chlorides such as GeCl 2 , metal oxides such as TiO and VO, and metal hydroxides such as Si (OH) 2 .
- Fe, Zn, Mg, Si, Pt, Pd, Mo, Mn, Cu, Ni, Co, TiO, B from the viewpoints of stability of the complex, spectral characteristics, heat resistance, light resistance, manufacturing suitability, etc.
- Zn is particularly preferred.
- dipyrromethene dye structure can be referred to the description of paragraphs 0045 to 0095 of JP-A 2014-132348 and the description of paragraphs 0033 to 0136 of JP-A 2011-95732, the contents of which are incorporated herein by reference. Be incorporated.
- Substituent group T The following groups may be mentioned as the substituent T group.
- An alkyl group preferably an alkyl group having 1 to 30 carbon atoms
- an alkenyl group preferably an alkenyl group having 2 to 30 carbon atoms
- an alkynyl group preferably an alkynyl group having 2 to 30 carbon atoms
- an aryl group preferably An aryl group having 6 to 30 carbon atoms, an amino group (preferably an amino group having 0 to 30 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 30 carbon atoms), an aryloxy group (preferably 6 to carbon atoms 30) aryloxy group), heteroaryloxy group
- acyl group preferably having 1 to 30 carbon atoms
- alkoxycarbonyl group preferably having 2 to 30 carbon atoms
- aryloxycarbonyl group preferably having 2 to 30 carbon atoms
- an acylamino group (preferably an acylamino group having 2 to 30 carbon atoms), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 30 carbon atoms), an aryloxycarbonylamino group (preferably 7 to carbon atoms) 30) aryloxycarbonylamino group), sulfamoyl group (preferably sulfamoyl group having 0 to 30 carbon atoms), carbamoyl group (preferably carbamoyl group having 1 to 30 carbon atoms), alkylthio group (preferably having 1 to 30 carbon atoms) Alkylthio group), arylthio group (preferably arylthio group having 6 to 30 carbon atoms), heteroarylthio group (preferably 1 to 30 carbon atoms), alkylsulfonyl group (preferably 1 to 30 carbon atoms), arylsulfonyl group (preferably 1 to 30 carbon atoms) Preferably having 6 to 30 carbon
- Examples of the polymerizable group possessed by the color material include ethylenic unsaturated groups such as vinyl group, (meth) allyl group and (meth) acryloyl group.
- the coloring material having a polymerizable group is preferably a dye multimer because it is easy to form a cured film excellent in color fastness to a developer.
- the dye multimer is a dye compound having two or more dye structures in one molecule, and preferably has three or more dye structures.
- the upper limit is not particularly limited, but may be 100 or less.
- the dye structures in one molecule may be the same dye structure or different dye structures.
- different dye structures include not only dye structures having different dye skeletons but also dye structures having the same dye skeleton and different types of substituents bonded to the dye skeleton. I assume.
- the dye multimer a large amount of dye containing at least one of the repeating unit represented by the formula (A) described later, the repeating unit represented by the formula (B), and the repeating unit represented by the formula (C) A dye or a dye multimer represented by the formula (D) described later is preferred.
- the dye multimer is a dye multimer having a repeating unit represented by the formula (A) (also referred to as a dye multimer (A)), a dye multimer having a repeating unit represented by the formula (B) A multimer (also referred to as "B"), a dye multimer having a repeating unit represented by the formula (C) (also referred to as a dye multimer (C)), and a dye multimer represented according to the formula (D)
- the multimer (D) is also preferred, and the dye multimer (A) or the dye multimer (D) is more preferred.
- the dye multimer (A) preferably contains a repeating unit represented by formula (A).
- the proportion of the repeating unit represented by the formula (A) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more of all repeating units constituting the dye polymer (A). 50 mass% or more is especially preferable.
- the upper limit may be 100% by mass or less, and may be 95% by mass or less.
- X 1 represents a main chain of a repeating unit
- L 1 represents a single bond or a divalent linking group
- D 1 represents a dye structure.
- X 1 represents a main chain of a repeating unit.
- Examples of X 1 include a linking group formed by polymerization reaction, and a main chain derived from a compound having a (meth) acrylic group, a styrene group, a vinyl group and an ether group is preferable. Also preferred is an embodiment in which the main chain has a cyclic alkylene group.
- the X 1 is not particularly limited as long as it is a linking group formed from a known polymerizable monomer.
- linking groups represented by the following (XX-1) to (XX-25) are preferable, and (XX-1), (XX-2), (XX-10) to (XX-17), (XX-18) , (XX-19), (XX-24) and (XX-25), and more preferably (XX-1), (XX-2), (XX-10) to (XX-17) , (XX-24) and (XX-25).
- * is a binding site to L 1 of formula (A).
- Me represents a methyl group.
- R in (XX-18) and (XX-19) represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.
- L 1 represents a single bond or a divalent linking group.
- each R independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
- the carbon number of the alkylene group is preferably 1 to 30.
- the upper limit is more preferably 25 or less, still more preferably 20 or less.
- the lower limit is more preferably 2 or more, and still more preferably 3 or more.
- the alkylene group may be linear, branched or cyclic.
- the alkylene group may have a substituent or may be unsubstituted.
- the group demonstrated by the substituent T group is mentioned.
- the carbon number of the arylene group is preferably 6 to 20, and more preferably 6 to 12.
- the arylene group may have a substituent or may be unsubstituted.
- the heterocyclic linking group is preferably a 5- or 6-membered ring.
- the hetero atom that the hetero ring linking group has is preferably an oxygen atom, a nitrogen atom and a sulfur atom.
- the number of heteroatoms in the heterocyclic linking group is preferably 1 to 3.
- the hetero ring linking group may have a substituent or may be unsubstituted. As a substituent, the group demonstrated by the substituent T group is mentioned.
- D 1 represents a dye structure. It is not particularly limited as type of dye structures that D 1 represents. Triarylmethane dye structure, xanthene dye structure, anthraquinone dye structure, cyanine dye structure, squarylium dye structure, quinophthalone dye structure, phthalocyanine dye structure, subphthalocyanine dye structure, azo dye structure, pyrazolotriazole dye structure, dipyrromethene dye structure, iso Indoline dye structure, thiazole dye structure, benzimidazolone dye structure, perinone dye structure, pyrrolopyrrole dye structure, diketopyrrolopyrrole dye structure, diimmonium dye structure, naphthalocyanine dye structure, rylene dye structure, dibenzofuranone dye structure, merocyanine Dye structures, croconium dye structures, oxonol dye structures and the like can be mentioned.
- the dye structure represented by D 1 may contain a polymerizable group.
- the dye polymer (A) preferably further has a repeating unit having a polymerizable group, in addition to the repeating unit represented by the formula (A).
- the dye structure represented by D 1 of the formula (A) described above is, in the case where no polymerizable group, the dye multimer (A) has a repeating unit having a polymerizable group.
- the dye multimer (A) may contain other repeating units in addition to the repeating unit represented by the formula (A).
- the other repeating unit may contain a functional group such as a polymerizable group or an acid group. It may not contain a functional group.
- the dye structure represented by D 1 of the formula (A) described above is, in the case where no polymerizable group, the dye multimer (A) has a repeating unit having a polymerizable group.
- the proportion of repeating units having a polymerizable group is preferably 0 to 50% by mass of all repeating units constituting the dye multimer (A).
- the lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. 35 mass% or less is more preferable, and, as for an upper limit, 30 mass% or less is still more preferable.
- an acid group a carboxyl group, a sulfonic acid group, and a phosphoric acid group are illustrated. Only one type of acid group may be contained, or two or more types may be contained.
- the proportion of repeating units having an acid group is preferably 0 to 50% by mass of all repeating units constituting the dye multimer (A).
- the lower limit is more preferably 1% by mass or more, and still more preferably 3% by mass or more. 35 mass% or less is more preferable, and, as for an upper limit, 30 mass% or less is still more preferable.
- Other functional groups include groups consisting of repeating 2 to 20 unsubstituted alkyleneoxy chains, lactones, acid anhydrides, amides, development promoting groups such as cyano groups, long chain and cyclic alkyl groups, aralkyl groups, aryl Examples thereof include hydrophilic / hydrophobic adjusting groups such as a group, a polyalkylene oxide group, a hydroxyl group, a maleimide group and an amino group, and the like, which can be appropriately introduced.
- the number of repetitions of the alkyleneoxy chain is preferably 2 to 15, and more preferably 2 to 10.
- One alkyleneoxy chain is represented by — (CH 2 ) n O—, and n is an integer, but n is preferably 1 to 10, more preferably 1 to 5, and still more preferably 2 or 3.
- Me represents a methyl group
- Et represents an ethyl group
- Dye multimer (B) contains the repeating unit represented by Formula (B).
- the proportion of the repeating unit represented by the formula (B) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more of all repeating units constituting the dye polymer (B) 50 mass% or more is especially preferable.
- the upper limit may be 100% by mass or less, and may be 95% by mass or less.
- X 2 represents a main chain of a repeating unit
- L 2 represents a single bond or a divalent linking group
- D 2 has a dye structure having a group capable of ionically bonding or coordinating with Y 2
- Y 2 represents a group capable of forming an ionic bond or coordinate bond with D 2 ;
- X 2 has the same meaning as X 1 in formula (A), and the preferred range is also the same.
- L 2 represents a single bond or a divalent linking group.
- each R independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group.
- L 2 is preferably a single bond or an alkylene group, an arylene group, —NH—, —CO—, —O—, —COO—, —OCO— and a divalent linking group combining two or more of these.
- Y 2 may be a group capable of ionic bond or coordinate bond with D 2 .
- an anionic group, a cationic group etc. are mentioned.
- the anionic group -SO 3 -, -COO -, -PO 4 -, -PO 4 H -, bis (sulfonyl) imide anion, and tris (sulfonyl) methide anion and tetraarylborate anions.
- the cationic group include substituted or unsubstituted onium cations (eg, ammonium, pyridinium, imidazolium, phosphonium and the like), with ammonium cation being particularly preferable.
- Ammonium cations include —N (R) 3 + .
- Each R independently represents a hydrogen atom or an alkyl group, and at least one of R represents an alkyl group.
- the carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 5.
- the alkyl group may be linear, branched or cyclic, but is preferably linear.
- D 2 represents a dye structure having a group that can be ionically or coordinately bound to Y 2 .
- the type of dye structure There is no particular limitation on the type of dye structure, and the types of dye structures described in D 1 can be mentioned.
- the dye structure represented by D 2 may have a polymerizable group.
- the dye multimer (B) may contain, in addition to the repeating unit represented by the formula (B), other repeating units described in the dye multimer (A), and the like. Moreover, you may further include the repeating unit represented by Formula (A) mentioned above, and the repeating unit represented by Formula (C) mentioned later.
- the dye structure represented by D 2 of formula (B) described above is, in the case where no polymerizable group, the dye multimer (B) has a repeating unit having a polymerizable group.
- the dye multimer (C) preferably contains a repeating unit represented by the formula (C).
- the proportion of the repeating unit represented by the formula (C) is preferably 10% by mass or more, more preferably 20% by mass or more, and still more preferably 30% by mass or more of all the repeating units constituting the dye polymer (C). 50 mass% or more is especially preferable.
- the upper limit may be 100% by mass or less, and may be 95% by mass or less.
- L 3 represents a single bond or a divalent linking group
- D 3 represents a dye structure
- m represents 0 or 1.
- L 3 represents a single bond or a divalent linking group.
- each R independently represents a hydrogen atom, an alkyl group, an aryl group or a heterocyclic group.
- the carbon number of the alkyl group and the alkylene group is preferably 1 to 30.
- the upper limit is more preferably 25 or less, still more preferably 20 or less.
- the lower limit is more preferably 2 or more, and still more preferably 3 or more.
- the alkyl group and the alkylene group may be linear, branched or cyclic.
- the number of carbon atoms of the aryl group and arylene group is preferably 6 to 20, and more preferably 6 to 12.
- the heterocyclic linking group and the heterocyclic group are preferably a 5- or 6-membered ring.
- the hetero atom that the hetero ring linking group and the hetero ring group have is preferably an oxygen atom, a nitrogen atom and a sulfur atom.
- the number of hetero atoms contained in the heterocyclic linking group and the heterocyclic group is preferably 1 to 3.
- the alkylene group, the arylene group, the heterocyclic linking group, the alkyl group, the aryl group and the heterocyclic group may be unsubstituted or may have a substituent. Examples of the substituent include a polymerizable group and an acid group.
- a group consisting of a repetition of 2 to 20 unsubstituted alkyleneoxy chains a development accelerating group such as a lactone, an acid anhydride, an amide or a cyano group, a long chain and a cyclic alkyl group, an aralkyl group, an aryl group or a polyalkylene It may have a hydrophilic / hydrophobic adjusting group such as an oxide group, a hydroxyl group, a maleimide group or an amino group as a substituent.
- L 3 is preferably an alkylene group, an arylene group, —NH—, —CO—, —O—, —COO—, —OCO—, —S— and a linking group combining two or more of these.
- D 3 represents a dye structure. There is no particular limitation on the type of dye structure, and the types of dye structures described in D 1 can be mentioned.
- the dye structure represented by D 3 may have a polymerizable group.
- m represents 0 or 1, preferably 1.
- the dye multimer (C) may contain, in addition to the repeating unit represented by the general formula (C), other repeating units described in the dye multimer (A).
- the dye multimer (D) is preferably represented by formula (D).
- L 4 represents a (n + k) -valent linking group
- L 41 and L 42 each independently represent a single bond or a divalent linking group
- D 4 represents a dye structure
- P 4 represents a substituent
- n represents 2 to 15
- k represents 0 to 13
- n + k is 2 to 15.
- the n D 4 's may be different from or identical to one another. When k is 2 or more, the plurality of P 4 may be different from each other or may be the same.
- N is preferably 2 to 14, more preferably 2 to 8, particularly preferably 2 to 7, and even more preferably 2 to 6.
- k is preferably 1 to 13, more preferably 1 to 10, still more preferably 1 to 8, particularly preferably 1 to 7, and still more preferably 1 to 6.
- L 41 and L 42 each independently represent a single bond or a divalent linking group.
- the divalent linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 And a group consisting of up to 20 sulfur atoms, and may be unsubstituted or may further have a substituent.
- Specific examples of the divalent linking group can include the following structural units or a group formed by combining two or more of the following structural units.
- the (n + k) -valent linking group represented by L 4 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 Included are hydrogen atoms and groups consisting of from 0 to 20 sulfur atoms.
- Examples of the (n + k) -valent linking group can include a group formed by combining two or more of the following structural units or the following structural units (which may form a ring structure).
- (n + k) -valent linking group examples include the linking groups described in paragraphs 0071 to 0072 of JP-A 2008-222950, and the linking groups described in paragraph 0176 of JP-A 2013-029760. Can be mentioned.
- D 4 represents a dye structure. There is no particular limitation on the type of dye structure, and the types of dye structures described in D 1 can be mentioned.
- the dye structure represented by D 4 may contain a polymerizable group.
- substituent P 4 represents an acid group, such as a polymerizable group.
- the substituent represented by P 4 may be a monovalent polymer chain having a repeating unit.
- the monovalent polymer chain having a repeating unit is preferably a monovalent polymer chain having a repeating unit derived from a vinyl compound.
- k P 4 may be the same or different.
- the dye structure represented by D 4 does not contain a polymerizable group, one or more of k P 4 represent a polymerizable group.
- the dye multimer represented by the formula (D) preferably has a structure represented by the formula (D-1).
- L 4 represents a (n + k) -valent linking group.
- n represents 2 to 15, and k represents 0 to 13.
- D 4 represents a dye structure
- P 4 represents a substituent.
- B 41 and B 42 are each independently a single bond, -O -, - S -, - CO -, - NR -, - O 2 C -, - CO 2 -, - NROC-, or, -CONR- Represents R represents a hydrogen atom, an alkyl group or an aryl group.
- C 41 and C 42 each independently represent a single bond or a divalent linking group.
- S represents a sulfur atom.
- the n D 4 's may be different from or identical to one another. When k is 2 or more, the plurality of P 4 may be different from each other or may be the same. n + k is 2 to 15.
- L 4, D 4 and P 4 of formula (D-1) has the same meaning as L 4, D 4 and P 4 of the formula (D).
- B 41 and B 42 of formula (D-1) is a single bond, -O -, - CO -, - O 2 C -, - CO 2 -, - NROC-, or, -CONR- more preferably a single bond , -O-, -CO-, -O 2 C- or -CO 2 -is more preferable.
- R represents a hydrogen atom, an alkyl group or an aryl group.
- an alkylene group, an arylene group and a group combining these are preferable.
- the carbon number of the alkylene group is preferably 1 to 30, and more preferably 1 to 10.
- the alkylene group may be linear, branched or cyclic.
- the carbon number of the arylene group is preferably 6 to 30, and more preferably 6 to 12.
- the weight average molecular weight (Mw) of the dye multimer is preferably 2,000 to 50,000.
- the lower limit is more preferably 3000 or more, and still more preferably 6000 or more.
- the upper limit is more preferably 30000 or less, further preferably 20000 or less.
- the content of the coloring material having a polymerizable group is preferably 5 to 40% by mass based on the total solid content of the photosensitive coloring composition.
- the lower limit is more preferably 6% by mass or more, further preferably 10% by mass or more. 35 mass% or less is more preferable, and, as for an upper limit, 30 mass% or less is still more preferable.
- the content of the coloring material having a polymerizable group is preferably 25 to 500 parts by mass with respect to 100 parts by mass in total of the photopolymerization initiator a and the photopolymerization initiator b.
- the lower limit is more preferably 30 parts by mass or more, still more preferably 50 parts by mass or more, and particularly preferably 100 parts by mass or more.
- the upper limit is more preferably 450 parts by mass or less, still more preferably 400 parts by mass or less, and particularly preferably 350 parts by mass or less. Within this range, it is easy to obtain a cured film that is more excellent in the decoloring resistance to the developer.
- the photosensitive coloring composition of the present invention may further contain a coloring material having no polymerizable group (hereinafter, also referred to as another coloring material).
- Other coloring materials may be either pigments or dyes.
- the pigment include inorganic pigments and organic pigments, and organic pigments are preferable.
- the average particle size of the pigment is preferably 20 to 300 nm, more preferably 25 to 250 nm, and still more preferably 30 to 200 nm.
- the "average particle size" as used herein means the average particle size of secondary particles in which primary particles of the pigment are collected.
- the particle size distribution of the secondary particles of the pigment (hereinafter, also simply referred to as “particle size distribution”) is 70% by mass or more, preferably 80% by mass or more of the secondary particles entering (average particle size ⁇ 100) nm. It is preferable that it is mass% or more.
- the particle size distribution of the secondary particles can be measured using the scattering intensity distribution.
- TEM transmission electron microscope
- Examples of the organic pigment include those shown below.
- a green pigment a halogenated zinc phthalocyanine pigment having an average of 10 to 14 halogen atoms in one molecule, an average of 8 to 12 bromine atoms and an average of 2 to 5 chlorine atoms is used. It can also be done. Specific examples include the compounds described in International Publication WO 2015/118720. Moreover, the aluminum phthalocyanine compound which has a phosphorus atom can also be used as a blue pigment. Specific examples thereof include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.
- the dye is not particularly limited, and known dyes can be used.
- the chemical structure includes pyrazole azo, anilinoazo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Dyes such as xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyromethene dyes can be used.
- a thiazole compound described in JP-A-2012-158649, an azo compound described in JP-A-2011-184493, and an azo compound described in JP-A-2011-145540 can also be preferably used.
- a yellow dye a quinophthalone compound described in paragraph 0011 to 0034 of JP-A-2013-54339, a quinophthalone compound described in paragraph 0013 to 0058 of JP-A 2014-26228, or the like can be used.
- the content of the other coloring material is preferably 5 to 50% by mass in the total solid content of the photosensitive coloring composition.
- the lower limit is more preferably 6% by mass or more, further preferably 10% by mass or more.
- the upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less.
- the content of the pigment in the other colorant is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 80% by mass or more.
- the total amount of the coloring material having a polymerizable group and the other coloring material is preferably 20 to 70% by mass in the total solid content in the photosensitive coloring composition.
- the content of the dye in the colorant (total of the colorant having a polymerizable group and the other colorant) contained in the photosensitive coloring composition of the present invention is preferably 10% by mass or more.
- the content is more preferably 20% by mass or more, further preferably 30% by mass or more.
- the photosensitive coloring composition of the present invention contains a resin.
- the resin include alkali soluble resins.
- the resin is blended, for example, in applications of dispersing particles such as pigments in a composition and applications of a binder.
- grains, such as a pigment is also called a dispersing agent.
- such application of the resin is an example, and the resin can also be used for purposes other than such application.
- the content of the resin is preferably 1 to 80% by mass in the total solid content of the photosensitive coloring composition.
- the lower limit is more preferably 5% by mass or more, further preferably 10% by mass or more.
- the upper limit is more preferably 70% by mass or less and still more preferably 60% by mass or less.
- the photosensitive coloring composition of the present invention contains an alkali soluble resin.
- the alkali-soluble resin can be appropriately selected from resins having a group that promotes alkaline dissolution.
- Examples of the group promoting alkali dissolution include, for example, a carboxyl group, a phosphate group, a sulfo group, a phenolic hydroxyl group and the like, with a carboxyl group being preferable.
- the type of the acid group possessed by the alkali-soluble resin may be only one type, or two or more types.
- the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 100,000.
- the number average molecular weight (Mn) of the alkali-soluble resin is preferably 1000 to 20,000.
- the acid value of the alkali-soluble resin is preferably 25 to 200 mg KOH / g.
- the lower limit is more preferably 30 mg KOH / g or more, and still more preferably 40 mg KOH / g or more.
- the upper limit is more preferably 150 mg KOH / g or less, still more preferably 120 mg KOH / g or less, and particularly preferably 100 mg KOH / g or less.
- the alkali-soluble resin is preferably a polyhydroxystyrene resin, a polysiloxane resin, an acrylic resin, an acrylamide resin, or an acrylic / acrylamide copolymer resin. Further, from the viewpoint of control of developability, acrylic resins, acrylamide resins, and acrylic / acrylamide copolymer resins are preferable.
- the alkali soluble resin a polymer having a carboxyl group in a side chain is preferable.
- a copolymer having a repeating unit derived from a monomer such as methacrylic acid, acrylic acid, itaconic acid, crotonic acid, maleic acid, 2-carboxyethyl (meth) acrylic acid, vinylbenzoic acid, partially esterified maleic acid examples thereof include alkali-soluble phenol resins such as novolac resins, acid cellulose derivatives having a carboxyl group in a side chain, and polymers obtained by adding an acid anhydride to a polymer having a hydroxyl group.
- copolymers of (meth) acrylic acid and other monomers copolymerizable therewith are suitable as the alkali-soluble resin.
- Other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like.
- alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, etc.
- vinyl compound examples include styrene, ⁇ -methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like.
- vinyl compound examples include styrene, ⁇ -methylstyrene, vinyl toluene, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, polystyrene macromonomer, polymethyl methacrylate macromonomer and the like.
- These other monomers copolymerizable with (meth) acrylic acid may be only one type or two or more types.
- the alkali-soluble resin may have a repeating unit derived from a maleimide compound.
- a maleimide compound N-alkyl maleimide, N-aryl maleimide and the like can be mentioned.
- Examples of the repeating unit derived from the maleimide compound include repeating units represented by the formula (C-mi).
- Rmi represents an alkyl group or an aryl group.
- the carbon number of the alkyl group is preferably 1 to 20.
- the alkyl group may be linear, branched or cyclic.
- the carbon number of the aryl group is preferably 6 to 20, more preferably 6 to 15, and still more preferably 6 to 10.
- Rmi is preferably an aryl group.
- benzyl (meth) acrylate / (meth) acrylic acid copolymer As an alkali soluble resin, benzyl (meth) acrylate / (meth) acrylic acid copolymer, benzyl (meth) acrylate / (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, benzyl (meth) acrylate
- a multicomponent copolymer composed of / (meth) acrylic acid / other monomers can be preferably used.
- Methacrylic acid copolymer 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer and the like can also be preferably used.
- the alkali-soluble resin can also be an alkali-soluble resin having a polymerizable group.
- the polymerizable group include (meth) allyl group and (meth) acryloyl group.
- the alkali-soluble resin having a polymerizable group an alkali-soluble resin having a polymerizable group in a side chain is useful.
- Commercial products of the alkali-soluble resin having a polymerizable group include Dianal NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (carboxyl group-containing polyurethane acrylate oligomer, manufactured by Diamond Shamrock Co., Ltd.), Biscoat R-264.
- KS Resist 106 (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P series (for example, ACA 230 AA), Plaxcel CF 200 series (both manufactured by Daicel Co., Ltd.), Ebecryl 3800 (manufactured by Daicel UBC Co., Ltd.), Acrycure RD-F8 (manufactured by Nippon Shokubai Co., Ltd.), DP-1305 (manufactured by Fujifilm Fine Chemicals Co., Ltd.), and the like.
- Cyclomer P series for example, ACA 230 AA
- Plaxcel CF 200 series both manufactured by Daicel Co., Ltd.
- Ebecryl 3800 manufactured by Daicel UBC Co., Ltd.
- Acrycure RD-F8 manufactured by Nippon Shokubai Co., Ltd.
- DP-1305 manufactured by Fujifilm Fine Chemicals Co., Ltd.
- an alkali-soluble resin containing a repeating unit having a hydroxyl group is preferable. According to this aspect, affinity with the developer is improved, and a pattern having excellent rectangularity is easily formed.
- the hydroxyl group value of the alkali-soluble resin is preferably 30 to 100 mg KOH / g.
- the lower limit is more preferably 35 mg KOH / g or more, and still more preferably 40 mg KOH / g or more.
- the upper limit is more preferably 80 mg KOH / g or less.
- hydroxyl group value of the alkali-soluble resin is in the above range, it is easy to form a pattern excellent in rectangularity.
- alkali-soluble resin containing the repeating unit which has a hydroxyl group resin of the following structure is mentioned, for example.
- the alkali-soluble resin comprises at least one compound selected from a compound represented by the following formula (ED1) and a compound represented by formula (1) in JP-A-2010-168539 (hereinafter referred to as “ether dimer It is also preferable to include a polymer formed by polymerizing a monomer component including “sometimes referred to as
- R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
- ether dimer for example, paragraph “0317” of JP-A-2013-29760 can be referred to, and the contents thereof are incorporated in the present specification.
- the ether dimer may be only one type, or two or more types.
- a polymer formed by polymerizing a monomer component containing an ether dimer for example, a polymer of the following structure can be mentioned.
- the alkali-soluble resin may contain a repeating unit derived from a compound represented by the following formula (X).
- R 1 represents a hydrogen atom or a methyl group
- R 2 represents an alkylene group having 2 to 10 carbon atoms
- R 3 has a hydrogen atom or 1 to 20 carbon atoms which may contain a benzene ring.
- Represents an alkyl group of n represents an integer of 1 to 15.
- the alkali-soluble resin can be referred to the description in paragraphs 0558 to 0571 of JP 2012-208494 A (paragraph 0685 to 0700 in the corresponding US Patent Application Publication 2012/0235099), the contents of which are incorporated herein by reference. Incorporated into the book.
- Binder resin described and binder resin used in Examples Binder resin described in paragraphs 0022 to 0032 of JP 2012-137531 A and binder resin used in Examples, JP 2013-024934 Binder resins described in paragraphs 0132 to 0143 of the gazette and binder resins used in the examples, binder resins used in paragraphs 0092 to 0098 of JP 2011-242752 A and examples, JP 2012 Paragraph No. 0030 of Japanese Patent Application Publication No. 032770 0072 can also be used a binder resin according to. The contents of these are incorporated herein.
- the content of the alkali-soluble resin is preferably 1 to 50% by mass in the total solid content of the photosensitive coloring composition.
- the lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more.
- the upper limit is more preferably 40% by mass or less, and still more preferably 35% by mass or less.
- the photosensitive coloring composition of the present invention may contain only one alkali-soluble resin, or may contain two or more. When 2 or more types are included, it is preferable that the sum becomes said range.
- the photosensitive coloring composition of the present invention can contain a resin as a dispersant.
- a resin as a dispersing agent, an acidic dispersing agent (acidic resin) and a basic dispersing agent (basic resin) are mentioned.
- the acidic dispersant represents a resin in which the amount of acid groups is larger than the amount of basic groups.
- the acidic dispersant (acidic resin) when the total amount of the amount of acid groups and the amount of basic groups is 100 mol%, the resin in which the amount of acid groups occupies 70 mol% or more is preferable, Resins consisting only of acid groups are more preferred.
- the acid group of the acidic dispersant (acidic resin) is preferably a carboxyl group.
- the acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mg KOH / g.
- a basic dispersing agent (basic resin) represents resin whose quantity of a basic group is larger than the quantity of an acidic radical.
- basic dispersing agent (basic resin) when the total amount of the quantity of an acidic radical and the quantity of a basic group is made into 100 mol%, resin whose quantity of a basic group exceeds 50 mol% is preferable.
- the basic group possessed by the basic dispersant is preferably an amino group.
- polymer dispersing agents for example, polyamide amine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, modified polyurethane, modified polyester, modified poly (meth) acrylate, (meth) Acrylic copolymers, naphthalene sulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanolamines and the like.
- Polymer dispersants can be further classified into linear polymers, terminal modified polymers, graft polymers, and block polymers according to their structures. The polymeric dispersant adsorbs to the surface of the pigment and acts to prevent reaggregation.
- a terminal modified polymer, a graft polymer, and a block polymer having an anchor site on the pigment surface can be mentioned as a preferable structure.
- dispersants described in paragraphs 0028 to 0124 of JP-A-2011-070156 and dispersants described in JP-A-2007-277514 are preferably used. The contents of these are incorporated herein.
- a graft copolymer can also be used as the dispersant.
- the details of the graft copolymer can be referred to the description of paragraphs [0131] to [0160] of JP-A-2012-137564, the contents of which are incorporated herein.
- a resin containing a nitrogen atom in the main chain can also be used.
- Resins containing nitrogen atoms in the main chain are poly (lower alkyleneimine) based repeating units, polyallylamine based repeating units, polydiallylamine based repeating units, metaxylene diamine-epichlorohydrin polycondensate based system It is preferable to contain a repeating unit and at least one repeating unit having a nitrogen atom selected from polyvinylamine repeating units.
- the oligoimine resin can be referred to the description in paragraph Nos. 0102 to 0174 of JP-A-2012-255128, the contents of which are incorporated herein.
- a commercial item can also be used for a dispersing agent.
- the product described in paragraph No. 0129 of JP 2012-137564 A can also be used as a dispersant.
- DISPERBYK series eg, DISPERBYK-161 etc.
- the resin demonstrated as the said dispersing agent can also be used for uses other than a dispersing agent.
- it can also be used as a binder.
- the content of the dispersant is preferably 1 to 200 parts by mass with respect to 100 parts by mass of the pigment. 5 mass parts or more are preferable, and, as for a lower limit, 10 mass parts or more are more preferable. 150 parts by mass or less is preferable, and 100 parts by mass or less is more preferable as the upper limit.
- the photosensitive coloring composition of the present invention can contain the above-described dispersant as the resin and resins other than the alkali-soluble resin (also referred to as other resins).
- resins for example, (meth) acrylic resin, (meth) acrylamide resin, ene / thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyether sulfone resin, polyphenylene resin, polyarylene ether Phosphine oxide resin, polyimide resin, polyamide imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, siloxane resin, etc. may be mentioned.
- the other resins may be used singly or in combination of two or more of these resins.
- the photosensitive coloring composition of the present invention preferably further contains a polymerizable compound in addition to the coloring material having a polymerizable group.
- a polymeric compound the compound etc. which have an ethylenically unsaturated group are mentioned, for example.
- an ethylenically unsaturated group a vinyl group, a (meth) allyl group, a (meth) acryloyl group etc. are mentioned.
- the polymerizable compound is preferably a compound that can be polymerized by radicals (radically polymerizable compound).
- the polymerizable compound is a compound different from the coloring material having a polymerizable group.
- the polymerizable compound is preferably a compound having no dye structure.
- the polymerizable compound may be in any of chemical forms such as monomers, prepolymers and oligomers, but monomers are preferred.
- the molecular weight of the polymerizable compound is preferably 100 to 3,000.
- the upper limit is more preferably 2000 or less, still more preferably 1500 or less.
- the lower limit is more preferably 150 or more, and still more preferably 250 or more.
- the polymerizable compound is preferably a compound containing 3 or more ethylenically unsaturated groups, more preferably a compound containing 3 to 15 ethylenically unsaturated groups, and 3 to 6 ethylenically unsaturated groups. More preferably, it is a compound containing one.
- the radically polymerizable compound is preferably a 3 to 15 functional (meth) acrylate compound, and more preferably a 3 to 6 functional (meth) acrylate compound.
- the polymerizable compound is dipentaerythritol triacrylate (commercially available as KAYARAD D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320; Nippon Kayaku Co., Ltd.) Made, Dipentaerythritol penta (meth) acrylate (Commercial product: KAYARAD D-310; Nippon Kayaku Co., Ltd.), Dipentaerythritol hexa (meth) acrylate (Commercial product: KAYARAD DPHA; Nippon Kayaku ( Ltd.
- NK ester A-DPH-12E Shin-Nakamura Chemical Co., Ltd. product
- the compound of the structure where these (meth) acryloyl groups are linked via ethylene glycol and / or propylene glycol residue is preferable.
- These oligomer types can also be used.
- NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.
- KAYARAD RP-1040 KAYARAD RP-1040
- DPCA-20 manufactured by Nippon Kayaku Co., Ltd.
- trimethylolpropane tri (meth) acrylate trimethylolpropane propyleneoxy modified tri (meth) acrylate, trimethylolpropane ethyleneoxy modified tri (meth) acrylate, isocyanuric acid ethyleneoxy modified tri (meth)
- a trifunctional (meth) acrylate compound such as acrylate or pentaerythritol tri (meth) acrylate.
- Commercially available products of trifunctional (meth) acrylate compounds include Alonics M-309, M-310, M-321, M-350, M-360, M-313, M-315, M-306, and M-305.
- M-303, M-452, M-450 (manufactured by Toagosei Co., Ltd.), NK ester A9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A -TMM-3LM-N, A-TMPT, TMPT (manufactured by Shin-Nakamura Chemical Co., Ltd.), KAYARAD GPO-303, TMPTA, THE-330, TPA-330, PET-30 (manufactured by Nippon Kayaku Co., Ltd.) Etc.
- the polymerizable compound may have an acid group.
- an acid group a carboxyl group, a sulfo group, a phosphoric acid group etc. are mentioned, A carboxyl group is preferable.
- Commercially available products of the radically polymerizable compound having an acid group include Alonics M-510 and M-520, and Alonics TO-2349 (manufactured by Toagosei Co., Ltd.).
- the acid value of the polymerizable compound having an acid group is preferably 0.1 to 40 mg KOH / g, more preferably 5 to 30 mg KOH / g. If the acid value of the polymerizable compound is 0.1 mg KOH / g or more, the solubility in a developer is good, and if 40 mg KOH / g or less, it is advantageous in terms of production and handling.
- the polymerizable compound is also preferably a compound having a caprolactone structure.
- examples of the polymerizable compound having a caprolactone structure are commercially available from Nippon Kayaku Co., Ltd. as KAYARAD DPCA series, and include DPCA-20, DPCA-30, DPCA-60, DPCA-120 and the like.
- the polymerizable compound is also preferably a compound having an alkyleneoxy group.
- the polymerizable compound having an alkyleneoxy group is preferably a compound having an ethyleneoxy group and / or a propyleneoxy group, more preferably a compound having an ethyleneoxy group, and having 4 to 20 ethyleneoxy groups. More preferably, it is a 3- to 6-functional (meth) acrylate compound.
- SR-494 which is a tetrafunctional (meth) acrylate having four ethyleneoxy groups manufactured by Sartomer, a trifunctional (meth) having three isobutylene oxy groups
- examples thereof include KAYARAD TPA-330 which is an acrylate.
- urethane acrylates as described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293 and JP-B-2-16765
- the urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417 and JP-B-62-39418 are also suitable.
- the content of the polymerizable compound is preferably 0.1 to 50% by mass based on the total solid content of the photosensitive coloring composition. As for a minimum, 0.5 mass% or more is more preferable, and 1 mass% or more is still more preferable.
- the upper limit is more preferably 45% by mass or less, and still more preferably 40% by mass or less.
- the content of the polymerizable compound is preferably 25 to 500 parts by mass with respect to 100 parts by mass of the colorant having a polymerizable group.
- the lower limit is more preferably 30 parts by mass or more, and still more preferably 50 parts by mass or more.
- the upper limit is more preferably 450 parts by mass or less, and still more preferably 300 parts by mass or less.
- the total amount of the polymerizable compound and the colorant having a polymerizable group is preferably 20 to 80% by mass in the total solid content of the photosensitive coloring composition. As for a minimum, 25 mass% or more is more preferable, and 40 mass% or more is still more preferable. As for the upper limit, 75 mass% or less is more preferable, and 60 mass% or less is still more preferable. If the above-mentioned total amount is in the above-mentioned range, a cured film having more excellent adhesion to the support is easily obtained.
- the total amount of the polymerizable compound and the coloring material having a polymerizable group is preferably 25 to 500 parts by mass with respect to 100 parts by mass of the total of the photopolymerization initiator a and the photopolymerization initiator b.
- the lower limit is more preferably 30 parts by mass or more, and still more preferably 50 parts by mass or more.
- the upper limit is more preferably 450 parts by mass or less, and still more preferably 300 parts by mass or less. Within this range, it is easy to obtain a cured film which is more excellent in the color fastness to a developer and the adhesion with a support.
- the photosensitive coloring composition of the present invention preferably further contains a compound having an epoxy group. According to this aspect, the mechanical strength and the like of the obtained cured film can be improved.
- the compound having an epoxy group is preferably a compound having two or more epoxy groups in one molecule. It is preferable to have 2 to 100 epoxy groups in one molecule. The upper limit may be, for example, 10 or less, or 5 or less.
- the compound having an epoxy group may be a low molecular weight compound (for example, having a molecular weight of less than 1000) or a macromolecular compound (for example, having a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more).
- the molecular weight (weight average molecular weight in the case of a polymer) of the compound having an epoxy group is preferably 200 to 100,000, and more preferably 500 to 50,000. 3000 or less is preferable, as for the upper limit of molecular weight (in the case of a polymer, weight average molecular weight), 2000 or less is more preferable, and 1500 or less is still more preferable.
- the content of the compound having an epoxy group is preferably 0.1 to 40% by mass in the total solid content of the photosensitive coloring composition.
- the lower limit is, for example, more preferably 0.5% by mass or more, and still more preferably 1% by mass or more.
- the upper limit is, for example, more preferably 30% by mass or less, and still more preferably 20% by mass or less.
- the compound having an epoxy group may be used alone or in combination of two or more. When using 2 or more types together, it is preferable that a total amount becomes said range.
- the content of the compound having an epoxy group is preferably 1 to 400 parts by mass, more preferably 1 to 100 parts by mass, and more preferably 1 to 50 parts by mass with respect to 100 parts by mass of the polymerizable compound. It is further preferred that
- the photosensitive coloring composition of the present invention preferably contains a solvent.
- the solvent is preferably an organic solvent.
- the solvent is not particularly limited as long as the solubility of each component and the coatability of the photosensitive coloring composition are satisfied.
- organic solvent examples include, for example, the following organic solvents.
- esters for example, ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl alkyl oxyacetate alkylate (Eg, methyl alkyl oxyacetate, ethyl alkyl oxyacetate, butyl alkyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate etc.), alkyl 3-alkyloxypropionate Esters (eg, methyl 3-alkyloxypropionate,
- 2-alkyloxypropionic acid alkyl esters eg methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate etc.
- ethers for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol Monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate and the like can be mentioned.
- ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone and the like.
- Preferred examples of the aromatic hydrocarbons include toluene and xylene. However, it may be better to reduce aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene etc.) as a solvent due to environmental reasons etc. (For example, 50 mass ppm (parts per part of the total amount of organic solvent) or less, 10 mass ppm or less, or 1 mass ppm or less).
- the organic solvents may be used alone or in combination of two or more.
- methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate is particularly preferable.
- the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
- an organic solvent having a low metal content it is preferable to use an organic solvent having a low metal content.
- the metal content of the organic solvent is preferably 10 parts by weight or less (parts per billion).
- the metal content of the organic solvent may be of the mass ppt (parts per trillion) level, and such a high purity solvent is provided by, for example, Toyo Gosei Co., Ltd. (Chemical Industry Journal, 2015) November 13).
- the content of the solvent is preferably such that the total solid content of the photosensitive coloring composition is 5 to 80% by mass.
- the lower limit is preferably 10% by mass or more. 60 mass% or less is preferable, 50 mass% or less is more preferable, and 40 mass% or less is still more preferable.
- a curing accelerator may be added to the photosensitive coloring composition of the present invention in order to accelerate the reaction of the polymerizable compound or to lower the curing temperature.
- a hardening accelerator the polyfunctional thiol compound etc. which have a 2 or more mercapto group in a molecule
- the polyfunctional thiol compound may be added for the purpose of improving the stability, odor, resolution, developability, adhesion and the like.
- the polyfunctional thiol compound is preferably a secondary alkanethiol, and more preferably a compound represented by Formula (T1).
- Formula (T1) In the formula (T1), n represents an integer of 2 to 4 and L represents a divalent to tetravalent linking group.)
- the linking group L is preferably an aliphatic group having 2 to 12 carbon atoms, and it is particularly preferable that n is 2 and L is an alkylene group having 2 to 12 carbon atoms.
- Specific examples of the polyfunctional thiol compound include compounds represented by the following structural formulas (T2) to (T4), and a compound represented by formula (T2) is particularly preferable. These polyfunctional thiol compounds can be used alone or in combination.
- methylol compounds for example, compounds exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963
- amines for example, compounds exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963
- amines for example, compounds exemplified as a crosslinking agent in paragraph 0246 of JP-A-2015-34963
- amines for example, amines, phosphonium salts, amidine salts, amide compounds
- amide compounds above, for example, Curing agent described in paragraph [0186] of JP2013-41165A, base generator (for example, ionic compound described in JP2014-55114A), cyanate compound (for example, JP2012-150180A)
- alkoxysilane compounds eg, alkoxysilane compounds having an epoxy group described in JP-A-2011-25305
- onium salt compounds eg, JP-A-2015-34963
- the content of the curing accelerator is preferably 0.3 to 8.9% by mass in the total solid content of the photosensitive coloring composition, and 0.8 -6.4% by mass is more preferable.
- the photosensitive coloring composition of the present invention may contain various surfactants from the viewpoint of further improving the coatability.
- various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, a silicone surfactant and the like can be used.
- liquid properties when prepared as a coating liquid are improved, and uniformity of coating thickness and liquid saving property are further enhanced. It can be improved. That is, in the case of film formation using a coating liquid to which a photosensitive coloring composition containing a fluorine-based surfactant is applied, the interfacial tension between the surface to be coated and the coating liquid is reduced, and the coating surface is coated. The wettability is improved, and the coatability on the surface to be coated is improved. For this reason, film formation with small uniform thickness can be more suitably performed.
- the fluorine content in the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass.
- the fluorine-based surfactant having a fluorine content in the above range is effective in terms of uniformity of the thickness of the coating film and liquid saving property, and the solubility in the photosensitive coloring composition is also good.
- fluorine-based surfactants for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, R304, F437, F475, F479, F482, F554, F780 (all, DIC Corporation) , Florard FC430, FC431, FC171 (above, Sumitomo 3M Co., Ltd.), Surfron S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC -383, S-393, KH-40 (all, manufactured by Asahi Glass Co., Ltd.), PF636, PF656, PF6320, PF6520, PF7002 (all, manufactured by OMNOVA) and the like.
- fluorine-based surfactant compounds described in paragraphs 0015 to 0158 of JP-A-2015-117327, and compounds described in paragraphs 0117 to 0132 of JP-A-2011-132503 can also be used.
- the fluorine-based surfactant is a molecular structure having a functional group containing a fluorine atom, and an acrylic compound in which a portion of the functional group containing a fluorine atom is cleaved when heat is applied and the fluorine atom is volatilized can also be suitably used.
- a fluorochemical surfactant Megafuck DS series (Chemical Chemical Daily, February 22, 2016) manufactured by DIC Corporation (Nikkei Sangyo Shimbun, February 23, 2016), for example, Megafuck DS -21 can be mentioned.
- fluorinated surfactant it is also preferable to use a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound as the fluorinated surfactant.
- fluorine-based surfactants can be referred to the description of JP-A-2016-216602, the contents of which are incorporated herein.
- the fluorine-based surfactant a block polymer can also be used.
- the fluorine-based surfactant has a repeating unit derived from a (meth) acrylate compound having a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy and propyleneoxy) (meth)
- a fluorine-containing polymer compound containing a repeating unit derived from an acrylate compound can also be preferably used.
- the following compounds are also exemplified as the fluorinated surfactant used in the present invention. In the following formulas,% indicating the proportion of repeating units is mol%.
- the weight average molecular weight of the above-mentioned compounds is preferably 3,000 to 50,000, for example, 14,000.
- a fluorine-containing polymer having an ethylenically unsaturated group in the side chain can also be used as the fluorine-based surfactant.
- Specific examples thereof include compounds described in paragraph Nos. 0050 to 0090 and paragraphs 0289 to 0295 of JP-A-2010-164965.
- Examples of commercially available products include Megafac RS-101, RS-102, RS-718-K, RS-72-K and the like manufactured by DIC Corporation.
- nonionic surfactants glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (eg, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, Polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (BASF Company), Tetronics 304, 701, 704, 901, 904, 150R1 (BA).
- BA nonionic surfactants
- organosiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.
- (meth) acrylic acid (co) polymer polyflow No. 1 is used. 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical Co., Ltd.), W001 (manufactured by Yusho Co., Ltd.), and the like.
- anionic surfactant examples include W004, W005, W017 (manufactured by Yusho Co., Ltd.), Sandet BL (manufactured by Sanyo Kasei Co., Ltd.), and the like.
- silicone type surfactant for example, Toray silicone DC3PA, Toray silicone SH7PA, Toray silicone DC11PA, Toray silicone SH21PA, Toray silicone SH28PA, Toray silicone SH29PA, Toray silicone SH30PA, Toray silicone SH8400 (more than Toray Dow Corning ), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (above, Momentive Performance Materials Co., Ltd.), KP-341, KF-6001, KF-6002 (above, Shin-Etsu Silicone Co., Ltd.), BYK-307, BYK-323, BYK-330 (above, manufactured by Big Chemie Co., Ltd.) and the like.
- the content of the surfactant is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, in the total solid content of the photosensitive coloring composition. Only one surfactant may be used, or two or more surfactants may be combined. When two or more kinds are contained, the total amount is preferably in the above range.
- the photosensitive coloring composition of the present invention can contain a silane coupling agent.
- silane coupling agent silane compounds having at least two different functional groups having different reactivity in one molecule are preferable.
- the silane coupling agent includes at least one group selected from a vinyl group, an epoxy group, a styrene group, a methacryl group, an amino group, an isocyanurate group, an ureido group, a mercapto group, a sulfide group, and an isocyanate group, and an alkoxy group.
- the silane compound which has and is preferable.
- silane coupling agent examples include, for example, N- ⁇ -aminoethyl- ⁇ -aminopropylmethyl dimethoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-602), N- ⁇ -aminoethyl- ⁇ -aminopropyl tri- trile Methoxysilane (Shin-Etsu Chemical Co., Ltd., KBM-603), N- ⁇ -aminoethyl- ⁇ -aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-602), ⁇ -aminopropyltrimethoxysilane (Shin-Etsu Chemical) Manufactured by Kogyo Co., Ltd., KBM-903), ⁇ -aminopropyltriethoxysilane (Shin-Etsu Chemical Co., Ltd., KBE-903), 3-methacryloxypropyltrime
- the content of the silane coupling agent is preferably 0.001 to 20% by mass in the total solid content of the photosensitive coloring composition, and 0.01
- the content is more preferably 10% by mass, and particularly preferably 0.1% by mass to 5% by mass.
- the photosensitive coloring composition of the present invention may contain only one type of silane coupling agent, or may contain two or more types. When it contains two or more types, it is preferable that the total amount of them becomes the said range.
- the photosensitive coloring composition of the present invention preferably also contains a polymerization inhibitor.
- a polymerization inhibitor hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butyl catechol, benzoquinone, 4,4'-thiobis (3-methyl-6-t-butylphenol), Examples include 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts etc.) and the like.
- the content of the polymerization inhibitor is preferably 0.01 to 5% by mass in the total solid content of the photosensitive coloring composition.
- the photosensitive coloring composition of the present invention may contain only one type of polymerization inhibitor, or may contain two or more types. When it contains two or more types, it is preferable that the total amount becomes the said range.
- the photosensitive coloring composition of the present invention can contain an ultraviolet absorber.
- an ultraviolet absorber conjugated diene compounds, aminobutadiene compounds, methyldibenzoyl compounds, coumarin compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyl triazine compounds and the like can be used. The details of these can be referred to the descriptions of paragraphs 0052 to 0072 of JP 2012-208374 A and paragraphs 0317 to 0334 of JP 2013-68814 A, the contents of which are incorporated herein.
- Examples of commercially available ultraviolet light absorbers include UV-503 (manufactured by Daito Kagaku Co., Ltd.).
- MYUA series Carbonate, N-oshi Yushi may be used as the benzotriazole compound.
- the content of the ultraviolet absorber is preferably 0.1 to 10% by mass in the total solid content of the photosensitive coloring composition. % By mass is more preferable, and 0.1 to 3% by mass is particularly preferable.
- an ultraviolet absorber may use only 1 type and may use 2 or more types. When using 2 or more types, it is preferable that a total amount becomes said range.
- additives such as a filler, an adhesion promoter, an antioxidant, an aggregation inhibitor and the like can be blended, if necessary.
- these additives include the additives described in paragraphs [0155] to [0156] of JP-A-2004-295116, the contents of which are incorporated herein.
- the antioxidant for example, a phenol compound, a phosphorus compound (for example, a compound described in paragraph 0042 of JP-A-2011-90147), a thioether compound or the like can be used.
- Adekastab series (AO-20, AO-30, AO-40, AO-50, AO-50F, AO-60G, AO-60, AO-80, AO-A manufactured by ADEKA Co., Ltd.) 330).
- One type of antioxidant may be used or two or more types may be used.
- the coloring composition of the present invention can contain the sensitizer and the light stabilizer described in paragraph 0078 of JP-A-2004-295116, and the thermal polymerization inhibitor described in paragraph 0081 of the same publication.
- the metal element may be contained in the photosensitive coloring composition depending on the raw materials used, etc.
- the content of the Group 2 element (such as calcium and magnesium) in the coloring composition is 50 mass from the viewpoint of suppression of defect generation and the like. It is preferably at most ppm, and more preferably 0.01 to 10 ppm by weight. Further, the total amount of the inorganic metal salt in the photosensitive coloring composition is preferably 100 mass ppm or less, and more preferably 0.5 to 50 mass ppm.
- the moisture content of the photosensitive coloring composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. .
- the moisture content can be measured by the Karl Fischer method.
- the photosensitive coloring composition of the present invention can be used with its viscosity adjusted for the purpose of adjusting the film surface state (flatness and the like), adjusting the film thickness, and the like.
- the value of the viscosity can be appropriately selected as necessary, but for example, 0.3 mPa ⁇ s to 50 mPa ⁇ s at 25 ° C. is preferable, and 0.5 mPa ⁇ s to 20 mPa ⁇ s is more preferable.
- As a method of measuring the viscosity for example, using a Toki Sangyo viscometer RE85L (rotor: 1 ° 34 ′ ⁇ R24, measurement range 0.6 to 1200 mPa ⁇ s) and performing temperature control at 25 ° C. It can be measured.
- a storage container of the photosensitive coloring composition of this invention A well-known storage container can be used.
- a container for the purpose of suppressing the mixing of impurities into the raw materials and the composition, a multilayer bottle in which the inner wall of the container is composed of six types and six layers of resin or a bottle in which six types of resin are seven layers It is also preferred to use.
- a container for example, the container described in JP-A-2015-123351 can be mentioned.
- the photosensitive coloring composition of the present invention can be preferably used as a photosensitive coloring composition for forming colored pixels in a color filter.
- colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
- the conventional photosensitive coloring composition tends to be insufficient in curing upon exposure. For this reason, conventionally, post-baking at a high temperature has been required to form blue pixels.
- the voltage holding ratio of the liquid crystal display device provided with the color filter is preferably 70% or more, and 90% or more More preferable.
- Known means for obtaining high voltage holding ratio can be suitably incorporated, and typical means include use of a high purity material (for example, reduction of ionic impurities) and control of the amount of acidic functional groups in the composition Can be mentioned.
- the voltage holding ratio can be measured, for example, by the method described in paragraph 0243 of JP-A-2011-008004 and paragraph 0123 to 0129 of JP-A-2012-224847.
- the photosensitive coloring composition of the present invention can be prepared by mixing the above-mentioned components.
- all components may be simultaneously dissolved and / or dispersed in a solvent to prepare a photosensitive coloring composition, and each component may be appropriately mixed with two or more solutions as needed.
- the photosensitive coloring composition may be prepared by using them as a dispersion and mixing them at the time of use (at the time of application).
- the process of disperse distributing a pigment in preparation of a photosensitive coloring composition.
- mechanical force used to disperse the pigment includes compression, squeezing, impact, shearing, cavitation and the like.
- specific examples of these processes include bead mills, sand mills, roll mills, ball mills, paint shakers, microfluidizers, high speed impellers, sand grinders, flow jet mixers, high pressure wet atomization, ultrasonic dispersion and the like.
- the process and the dispersing machine for dispersing the pigment are the dispersion technology and industrial application centering on “Dispersion Technology Complete, Information Technology Co., Ltd. issued July 15, 2005” and “suspension (solid / liquid dispersion system)” The process and the dispersing machine described in Paragraph No.
- the particles may be subjected to a refinement treatment in a salt milling step.
- the materials, equipment, processing conditions and the like used in the salt milling step can be referred to, for example, the descriptions of JP-A-2015-194521 and JP-A-2012-04629.
- a filter for the purpose of removal of foreign matter and reduction of defects.
- a filter if it is a filter conventionally used for filtration applications etc., it can be used, without being limited in particular.
- a fluorine resin such as polytetrafluoroethylene (PTFE), a polyamide resin such as nylon (for example, nylon-6, nylon-6, 6), a polyolefin resin such as polyethylene or polypropylene (PP) (high density and / or super
- PP polypropylene
- nylon high density and / or super
- polypropylene including high density polypropylene
- nylon are preferable.
- the pore diameter of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, and more preferably about 0.05 to 0.5 ⁇ m.
- the filter using a fiber-like filter medium as a filter.
- the fibrous filter medium include polypropylene fiber, nylon fiber, glass fiber and the like.
- Specific examples of the filter using a fiber-like filter medium include filter cartridges of SBP type series (SBP 008, etc.), TPR type series (TPR 002, TPR 005, etc.), and SHPX type series (SHPX 003, etc.) manufactured by Loki Techno. .
- filters When using filters, different filters may be combined. In that case, filtration with each filter may be performed only once or may be performed twice or more. For example, filters of different pore sizes may be combined within the range described above.
- the pore size here can refer to the nominal value of the filter manufacturer.
- filters for example, it is possible to select from various filters provided by Nippon Pall Co., Ltd. (DFA 4201 NIEY, etc.), Advantech Toyo Co., Ltd., Nippon Entegris Co., Ltd. can do.
- filtration with a 1st filter may be performed only with a dispersion liquid, and you may filter with a 2nd filter, after mixing other components.
- the second filter one formed of the same material as the first filter can be used.
- the cured film of the present invention is a cured film obtained from the photosensitive coloring composition of the present invention described above.
- the cured film of the present invention can be preferably used as a colored pixel of a color filter. Examples of colored pixels include red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, and yellow pixels.
- the thickness of the cured film can be appropriately adjusted according to the purpose. For example, the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and still more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and still more preferably 0.3 ⁇ m or more.
- the pattern forming method of the present invention comprises the steps of forming a photosensitive coloring composition layer on a support using the above-described photosensitive coloring composition of the present invention; Irradiating the photosensitive coloring composition layer with light having a wavelength of more than 350 nm and 380 nm or less and exposing it in a pattern; Alkaline developing the photosensitive coloring composition layer after exposure; And irradiating the photosensitive coloring composition layer after alkali development with light having a wavelength of 254 to 350 nm.
- a step of baking after forming a photosensitive coloring composition layer on a support and before exposing (pre-baking step), and a step of baking an alkali-developed pattern (post-baking step) Step) may be provided.
- pre-baking step a step of baking after forming a photosensitive coloring composition layer on a support and before exposing
- post-baking step a step of baking an alkali-developed pattern
- a photosensitive coloring composition layer is formed on a support body using a photosensitive coloring composition.
- a support body there is no limitation in particular as a support body, According to a use, it can select suitably.
- a glass substrate a substrate for solid-state imaging device provided with a solid-state imaging device (light-receiving device), a silicon substrate and the like can be mentioned.
- a subbing layer may be provided to improve the adhesion with the upper layer, to prevent the diffusion of substances, or to planarize the surface.
- various methods such as slit coating, inkjet method, spin coating, cast coating, roll coating, screen printing method and the like can be used.
- the photosensitive coloring composition layer formed on the support may be dried (prebaked).
- the prebaking may not be performed.
- the prebaking temperature is preferably 120 ° C. or less, more preferably 110 ° C. or less, and still more preferably 105 ° C. or less.
- the lower limit may be, for example, 50 ° C. or more, and may be 80 ° C. or more.
- the prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and still more preferably 80 to 220 seconds. Prebaking can be performed with a hot plate, an oven, or the like.
- the photosensitive coloring composition layer is irradiated with light having a wavelength of more than 350 nm and 380 nm or less to be exposed in a pattern.
- the photosensitive coloring composition layer can be exposed in a pattern by exposing through a mask having a predetermined mask pattern using an exposure device such as a stepper. Thereby, the exposed part of the photosensitive coloring composition layer can be cured.
- Radiation (light) that can be used for exposure is light with a wavelength of more than 350 nm and 380 nm or less, light with a wavelength of 355 to 370 nm is preferable, and i-line is more preferable.
- the irradiation dose for example, preferably 30 ⁇ 1500mJ / cm 2, more preferably 50 ⁇ 1000mJ / cm 2.
- the oxygen concentration at the time of exposure can be appropriately selected, and in addition to being performed under the atmosphere, for example, under a low oxygen atmosphere having an oxygen concentration of 19% by volume or less (eg, 15% by volume, 5% by volume, substantially oxygen free , And may be exposed in a high oxygen atmosphere (for example, 22% by volume, 30% by volume, 50% by volume) in which the oxygen concentration exceeds 21% by volume.
- the exposure illuminance can be set appropriately, and can usually be selected from the range of 1000 W / m 2 to 100000 W / m 2 (for example, 5000 W / m 2 , 15000 W / m 2 , 35000 W / m 2 ) .
- Oxygen concentration and exposure illuminance may appropriately combined conditions, for example, illuminance 10000 W / m 2 at an oxygen concentration of 10 vol%, oxygen concentration of 35 vol% can be such illuminance 20000W / m 2.
- the reaction rate of the polymerizable compound in the photosensitive coloring composition layer after exposure is preferably more than 30% and less than 60%. By setting such a reaction rate, the polymerizable compound can be appropriately cured.
- the reaction rate of the polymerizable compound means the ratio of the reacted ethylenically unsaturated group in all the ethylenically unsaturated groups possessed by the polymerizable compound.
- the photosensitive coloring composition layer after exposure is subjected to alkali development. That is, the photosensitive coloring composition layer in the unexposed area is removed using an alkaline developer to form a pattern.
- the temperature of the alkaline developer is preferably, for example, 20 to 30.degree.
- the developing time is preferably 20 to 300 seconds.
- an alkaline aqueous solution obtained by diluting an alkaline agent with pure water is preferably used.
- the alkaline agent include aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, diglycolamine, diethanolamine, hydroxyamine, ethylenediamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
- Organic alkaline compounds such as benzyl, trimethyltrimethylammonium hydroxide, dimethylbis (2-hydroxyethyl) ammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo [5.4.0] -7-undecene, or water Inorganic materials such as sodium oxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium silicate, sodium metasilicate Potassium compounds may be mentioned.
- the concentration of the alkaline agent in the alkaline aqueous solution is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass.
- the alkaline developer may further contain a surfactant.
- the alkali developer may be prepared once as a concentrate and diluted to a concentration required for use, from the viewpoint of transfer and storage convenience and the like.
- the dilution ratio is not particularly limited, but can be set, for example, in the range of 1.5 to 100 times.
- the photosensitive coloring composition layer after alkali development is exposed to light by irradiation with light having a wavelength of 254 to 350 nm.
- exposure after alkali development is also referred to as post-exposure.
- the radiation (light) which can be used in the post-exposure ultraviolet rays having a wavelength of 254 to 300 nm are preferable, and ultraviolet rays having a wavelength of 254 nm are more preferable.
- Post-exposure can be performed using, for example, an ultraviolet photoresist curing apparatus. From the ultraviolet photoresist curing apparatus, for example, light of a wavelength of 254 to 350 nm may be irradiated with other light (eg, i-line).
- the difference between the wavelength of the light used in the exposure before the alkali development and the wavelength of the light used in the exposure (post-exposure) after the alkali development is preferably 200 nm or less, and more preferably 100 to 150 nm. preferable.
- Irradiation dose (exposure dose) is preferably 30 ⁇ 4000mJ / cm 2, more preferably 50 ⁇ 3500mJ / cm 2.
- the oxygen concentration at the time of exposure can be selected appropriately.
- the conditions described in the exposure step before the above-mentioned alkali development may be mentioned.
- the reaction rate of the polymerizable compound in the photosensitive coloring composition layer after the post-exposure is preferably 60% or more.
- the upper limit may be 100% or less, or 90% or less.
- the photosensitive coloring composition is appropriately cured by the first exposure (exposure before alkali development) by exposing the photosensitive coloring composition layer in two steps before and after alkali development.
- the entire photosensitive coloring composition can be almost completely cured in the next exposure (exposure after development).
- the photosensitive coloring composition can be sufficiently cured even under low temperature conditions, and a pattern (cured film) excellent in the decoloring resistance to the developer can be formed.
- post-baking may be further performed after post-exposure.
- post-baking when an organic electroluminescent element is used as a light emission light source of the image display device, or when the photoelectric conversion film of the image sensor is made of an organic material, 50 to 120 ° C. It is preferable to carry out heat treatment (post-baking) at a temperature of (° C., preferably 80 to 90 ° C.). Post-baking can be carried out continuously or batchwise using heating means such as a hot plate, a convection oven (hot air circulation type drier), a high frequency heater or the like. Further, in the case of forming a pattern by a low temperature process, post baking may not be performed.
- the thickness of a pattern (hereinafter also referred to as a pixel) after post-exposure is preferably 0.1 to 2.0 ⁇ m.
- the lower limit is preferably 0.2 ⁇ m or more, and more preferably 0.3 ⁇ m or more.
- the upper limit is preferably 1.7 ⁇ m or less, more preferably 1.5 ⁇ m or less.
- the width of the pixel is preferably 0.5 to 20.0 ⁇ m.
- the lower limit is preferably 1.0 ⁇ m or more, and more preferably 2.0 ⁇ m or more.
- the upper limit is preferably 15.0 ⁇ m or less, more preferably 10.0 ⁇ m or less.
- the Young's modulus of the pixel is preferably 0.5 to 20 GPa, more preferably 2.5 to 15 GPa.
- the pixels have high flatness.
- the surface roughness Ra of the pixel is preferably 100 nm or less, more preferably 40 nm or less, and still more preferably 15 nm or less.
- the lower limit is not defined, but is preferably, for example, 0.1 nm or more.
- the surface roughness can be measured, for example, using an AFM (atomic force microscope) Dimension 3100 manufactured by Veeco.
- the contact angle of water on the pixel can be set to a preferable value as appropriate, but is typically in the range of 50 to 110 °.
- the contact angle can be measured, for example, using a contact angle meter CV-DT ⁇ A type (manufactured by Kyowa Interface Science Co., Ltd.).
- the volume resistivity of the pixel is preferably 10 9 ⁇ ⁇ cm or more, and more preferably 10 11 ⁇ ⁇ cm or more.
- the upper limit is not specified, but is preferably 10 14 ⁇ ⁇ cm or less, for example.
- the volume resistance value of the pixel can be measured, for example, using an ultra-high resistance meter 5410 (manufactured by Advantest Corporation).
- the color filter of the present invention has the cured film of the present invention described above.
- the thickness of the cured film can be appropriately adjusted according to the purpose.
- the film thickness is preferably 20 ⁇ m or less, more preferably 10 ⁇ m or less, and still more preferably 5 ⁇ m or less.
- the lower limit of the film thickness is preferably 0.1 ⁇ m or more, more preferably 0.2 ⁇ m or more, and still more preferably 0.3 ⁇ m or more.
- the color filter of the present invention can be used for a solid-state imaging device such as a CCD (charge coupled device) or a CMOS (complementary metal oxide semiconductor) or an image display device.
- CCD charge coupled device
- CMOS complementary metal oxide semiconductor
- the solid-state imaging device of the present invention has the cured film of the present invention described above.
- the configuration of the solid-state imaging device of the present invention is not particularly limited as long as the cured film of the present invention is provided and functions as a solid-state imaging device, and examples thereof include the following configurations.
- the substrate there are a plurality of photodiodes forming the light receiving area of a solid-state imaging device (CCD (charge coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.) and transfer electrodes made of polysilicon etc.
- CCD charge coupled device
- CMOS complementary metal oxide semiconductor
- Device protective film formed of silicon nitride or the like formed on the light shielding film so as to cover the entire surface of the light shielding film and the photodiode light receiving portion. And has a color filter on the device protection film.
- the device has a light collecting means (for example, a micro lens etc., hereinafter the same) on the device protective film and under the color filter (closer to the substrate) or a structure having the light collecting means on the color filter It may be.
- the color filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned into, for example, a grid shape by partition walls.
- the partition walls in this case preferably have a low refractive index for each colored pixel.
- an imaging device having such a structure devices described in JP 2012-227478 A and JP 2014-179577 A can be mentioned.
- the imaging device provided with the solid-state imaging device according to the present invention can be used not only for digital cameras and electronic devices (such as mobile phones) having an imaging function, but also for in-vehicle cameras and surveillance cameras.
- the cured film of the present invention can be used in an image display device such as a liquid crystal display device or an organic electroluminescence display device.
- an image display device such as a liquid crystal display device or an organic electroluminescence display device.
- an image display device such as a liquid crystal display device or an organic electroluminescence display device.
- electroluminescence display device for the definition of the image display device and details of each image display device, for example, “Electronic display device (authored by Akio Sasaki, Inc., Industrial Research Association, published in 1990)”, “Display device (authored by Ibuki, industrial book ( Co., Ltd., published in Heisei 1973).
- the liquid crystal display device is described, for example, in "Next-generation liquid crystal display technology (edited by Tatsuo Uchida, Industrial Research Association, Inc., 1994)".
- Pigment dispersion liquid P1 C. I. Pigment Blue 15: 6, 20.0 parts by mass (average primary particle diameter 55 nm), 2.40 parts by mass of a pigment dispersant (DISPERBYK-161, manufactured by BYK Chemie), 2.40 parts by mass of dispersant 1; A mixture of 175.2 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was mixed and dispersed for 3 hours using a bead mill (zirconia beads of 0.3 mm in diameter).
- PGMEA propylene glycol monomethyl ether acetate
- dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high pressure disperser NANO-3000-10 (manufactured by Nippon Bei Co., Ltd.) with a pressure reducing mechanism.
- This dispersion process was repeated 10 times to obtain a pigment dispersion P1. It was 24 nm when the average primary particle diameter of the pigment was measured by the dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (made by Nikkiso Co., Ltd.)) about the obtained pigment dispersion liquid P1.
- Example 1 ⁇ Preparation of Photosensitive Colored Composition> Example 1 The following raw materials were mixed and stirred, and then filtered through a nylon filter (manufactured by Nippon Pall Co., Ltd.) having a pore size of 0.45 ⁇ m to prepare a photosensitive coloring composition.
- a nylon filter manufactured by Nippon Pall Co., Ltd.
- Examples 2 to 18, Comparative Examples 1 to 4 The same as Example 1, except that the type of pigment dispersion, the type and content of photopolymerization initiator, the type of alkali-soluble resin, the type of dye and the type of polymerizable compound are changed as described in the following table.
- a photosensitive coloring composition was prepared.
- the numerical value of content as described in the column of the photoinitiator of a following table is content in the total solid of a photosensitive coloring composition.
- Example 19 to 22 A photosensitive coloring composition was prepared in the same manner as Example 1, except that the content of the dye (V1) was changed as described in the following table.
- the mass ratio of the colorant having a polymerizable group and the photopolymerization initiator (the total amount of the initiator 1 and the initiator 4) is described in the following table.
- Initiator 1 IRGACURE-OXE01 (BASF, manufactured by BASF, having an absorption coefficient of light of wavelength 365 nm of 6969 mL / gcm)
- Initiator 2 IRGACURE-OXE02 (manufactured by BASF, the absorption coefficient of light of wavelength 365 nm in methanol is 7749 mL / g cm)
- Initiator 3 Compound of the following structure (the absorption coefficient of light of wavelength 365 nm in methanol is 18,900 mL / g cm)
- Initiator 4 IRGACURE 2959 (BASF, manufactured by BASF, the extinction coefficient of light having a wavelength of 365 nm is 48.93 mL / gcm, and the absorption coefficient of light having a wavelength of 254 nm is 3.0 ⁇ 10 4 mL / gcm .)
- Initiator 5 IRGACURE 2959 (BASF
- Resin C Alkali-soluble resin J5 described in paragraph 0573 of JP-A-2013-225112
- Resin D Resin B-1 described in paragraph 0150 of JP-A-2010-049161
- Dye V1 20% by mass cyclohexanone solution of dye multimer of the following structure (dye having a polymerizable group)
- Dye V4 20% by mass cyclohexanone solution of dye compound of the following structure (dye having a polymerizable group)
- the transmittance of light in the wavelength range of 300 to 800 nm was measured for the obtained cured film using a spectrophotometer (reference: glass substrate) of an ultraviolet visible near infrared spectrophotometer UV3600 (manufactured by Shimadzu Corporation).
- a differential interference image was observed by reflection observation (magnification of 50 times) using an optical microscope BX60 manufactured by OLYMPUS.
- the cured film is immersed for 5 minutes in an alkaline developer (FHD-5, manufactured by Fujifilm Electronics Materials Co., Ltd.) at 25 ° C., dried, and then again subjected to spectral measurement, and dipped in the alkaline developer.
- an alkaline developer FHD-5, manufactured by Fujifilm Electronics Materials Co., Ltd.
- the transmittance fluctuation before and after was calculated, and the color loss resistance was evaluated according to the following criteria.
- Transmittance fluctuation
- T0 is the transmittance of the cured film before immersion in the alkaline developer
- T1 is the transmittance of the cured film after immersion in the alkaline developer.
- AA The transmittance fluctuation in the entire wavelength range of 300 to 800 nm is less than 2%.
- B The transmittance fluctuation in the entire range of wavelengths 300 to 800 nm is less than 7.5%, and in a partial range, the transmittance fluctuation is 5% or more and less than 7.5%.
- C The transmittance fluctuation in the entire range of wavelengths 300 to 800 nm is less than 10%, and in a partial range, the transmittance fluctuation is 7.5% or more and less than 10%.
- D The transmittance fluctuation is 10% or more in at least a part of the wavelength range of 300 to 800 nm.
- a 40% diluted solution manufactured by Fujifilm Electronics Materials Co., Ltd.
- the glass substrate on which this colored pattern (pixel) is formed is fixed to a horizontal rotary table by a vacuum chuck method, and while rotating the glass substrate at a rotation speed of 50 rpm by a rotary device, pure water is jetted from above the rotation center It supplied in shower shape and performed rinse processing, and spin-drying was performed after that, and the coloring pattern (pixel) was formed.
- Residual film ratio (thickness before development / thickness after development) ⁇ 100 AA: Residual film rate 87.5% or more A: Residual film rate 82.5% or more, less than 87.5% B: Residual film rate 80% or more, less than 82.5% C: Residual film rate 80 %Less than
- the adhesion was evaluated by observing a colored pattern formed on a glass substrate using an optical microscope and based on the following criteria. AA: There is no peeling of the coloring pattern. A: Peeling of colored pattern is 1 to 5 in 100 pixels B: Peeling of colored pattern is 6 to 15 in 100 C C: Peeling of colored pattern is 16 or more in 100
- Comparative Example 1 in which the coloring material having a polymerizable group was not used
- Comparative Examples 2 and 3 in which only one of the photopolymerization initiator a and the photopolymerization initiator b was contained, the photopolymerization initiator a and the photopolymerization
- the comparative example 4 which contains the initiator b and whose content is less than 1.5 mass% was inferior in the decoloring resistance compared with the Example.
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Nonlinear Science (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Mathematical Physics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
Description
一方で、本発明者が、色材とアルカリ可溶性樹脂とを含む感光性着色組成物について検討を進めたところ、このような感光性着色組成物を低温で硬化して硬化膜を形成した場合、得られた硬化膜は現像液に対する耐色抜け性が低い傾向にあることが分かった。
<1> メタノール中での波長365nmの光の吸光係数が1.0×102mL/gcmを超える光重合開始剤aと、
メタノール中での波長365nmの光の吸光係数が1.0×102mL/gcm以下であり、波長254nmの光の吸光係数が1.0×103mL/gcm以上である光重合開始剤bと、
アルカリ可溶性樹脂と、
重合性基を有する色材と、を含有する感光性着色組成物であって、
感光性着色組成物の全固形分中における光重合開始剤aの含有量が1.5質量%以上であり、光重合開始剤bの含有量が1.5質量%以上である、感光性着色組成物。
<2> 光重合開始剤aのメタノール中での波長365nmの光の吸光係数が1.0×103mL/gcm以上である、<1>に記載の感光性着色組成物。
<3> 光重合開始剤aがオキシム化合物である、<1>または<2>に記載の感光性着色組成物。
<4> 光重合開始剤bがヒドロキシアセトフェノン化合物である、<1>~<3>のいずれかに記載の感光性着色組成物。
<5> 光重合開始剤bの100質量部に対して、光重合開始剤aを50~500質量部含有する、<1>~<4>のいずれかに記載の感光性着色組成物。
<6> 感光性着色組成物の全固形分中における光重合開始剤aと光重合開始剤bとの合計の含有量が3~17質量%である、<1>~<5>のいずれかに記載の感光性着色組成物。
<7> 色材は色素多量体である、<1>~<6>のいずれかに記載の感光性着色組成物。
<8> <1>~<7>のいずれかに記載の感光性着色組成物を硬化して得られる硬化膜。
<9> <1>~<7>のいずれかに記載の感光性着色組成物を用いて支持体上に感光性着色組成物層を形成する工程と、
感光性着色組成物層に対して、波長350nmを超え380nm以下の光を照射してパターン状に露光する工程と、
露光後の感光性着色組成物層をアルカリ現像する工程と、
現像後の感光性着色組成物層に対して、波長254~350nmの光を照射して露光する工程と、を有するパターンの形成方法。
<10> <8>に記載の硬化膜を有するカラーフィルタ。
<11> <8>に記載の硬化膜を有する固体撮像素子。
<12> <8>に記載の硬化膜を有する画像表示装置。
本明細書における基(原子団)の表記において、置換および無置換を記していない表記は、置換基を有さない基(原子団)と共に置換基を有する基(原子団)をも包含するものである。例えば、「アルキル基」とは、置換基を有さないアルキル基(無置換アルキル基)のみならず、置換基を有するアルキル基(置換アルキル基)をも包含するものである。
本明細書において「露光」とは、特に断らない限り、光を用いた露光のみならず、電子線、イオンビーム等の粒子線を用いた描画も露光に含める。また、露光に用いられる光としては、一般的に、水銀灯の輝線スペクトル、エキシマレーザーに代表される遠紫外線、極紫外線(EUV光)、X線、電子線等の活性光線または放射線が挙げられる。
本明細書において「~」を用いて表される数値範囲は、「~」の前後に記載される数値を下限値および上限値として含む範囲を意味する。
本明細書において、全固形分とは、組成物の全成分から溶剤を除いた成分の合計質量をいう。
本明細書において、「(メタ)アクリレート」は、アクリレートおよびメタクリレートの双方、または、いずれかを表し、「(メタ)アクリル」は、アクリルおよびメタクリルの双方、または、いずれかを表し、「(メタ)アリル」は、アリルおよびメタリルの双方、または、いずれかを表し、「(メタ)アクリロイル」は、アクリロイルおよびメタクリロイルの双方、または、いずれかを表す。
本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。
本明細書において、重量平均分子量(Mw)および数平均分子量(Mn)は、ゲルパーミエーションクロマトグラフィ(GPC)により測定したポリスチレン換算値として定義される。
本発明の感光性着色組成物は、
メタノール中での波長365nmの光の吸光係数が1.0×102mL/gcmを超える光重合開始剤aと、
メタノール中での波長365nmの光の吸光係数が1.0×102mL/gcm以下であり、波長254nmの光の吸光係数が1.0×103mL/gcm以上である光重合開始剤bと、
アルカリ可溶性樹脂と、
重合性基を有する色材と、を含有する感光性着色組成物であって、
感光性着色組成物の全固形分中における光重合開始剤aの含有量が1.5質量%以上であり、光重合開始剤bの含有量が1.5質量%以上であることを特徴とする。
また、本発明の感光性着色組成物によれば、最初の露光(現像前の露光)では、感光性着色組成物を適度に硬化させることができる。このため、矩形性の良いパターンを形成することができる。そして、次の露光(現像後の露光)で感光性着色組成物全体をほぼ硬化させることができる。このため、優れたパターン形成性を有しつつ、現像液に対する耐色抜け性に優れたパターンを形成することもできる。
また、本発明の感光性着色組成物は、重合性基を有する色材として、重合性基を有する染料を用いた場合において特に顕著な効果が得られる。色材として染料を用いた場合、現像液に対する親和性が高い傾向にあり、現像液に対する色抜けが生じやすい傾向にあった。このため、従来の感光性着色組成物では高温での加熱処理を行い、膜を十分に硬化させる必要があった。しかしながら、本発明の感光性着色組成物によれば、重合性基を有する染料を用いることで、低温で硬化しても現像液に対する耐色抜け性に優れた硬化膜を形成することができるので特に本発明の効果が顕著である。また、染料を用いることでより鮮明で色価の高い硬化膜を形成することもできる。
本発明の感光性着色組成物は、光重合開始剤を含有する。光重合開始剤としては、例えば、ハロゲン化炭化水素誘導体(例えば、トリアジン骨格を有する化合物、オキサジアゾール骨格を有する化合物など)、アシルホスフィンオキサイド等のアシルホスフィン化合物、ヘキサアリールビイミダゾール化合物、オキシム誘導体等のオキシム化合物、有機過酸化物、チオ化合物、ケトン化合物、芳香族オニウム塩、ケトオキシムエーテル化合物、アミノアセトフェノン化合物、ヒドロキシアセトフェノン化合物、フェニルグリオキシレート化合物などが挙げられる。光重合開始剤の具体例としては、例えば、特開2013-29760号公報の段落番号0265~0268の記載を参酌することができ、この内容は本明細書に組み込まれる。
式(V)
式中Rv1は、置換基を表し、Rv2およびRv3は、それぞれ独立して水素原子または置換基を表し、Rv2とRv3とが互いに結合して環を形成していてもよく、mは0~4の整数を表す。
メタノール中での波長365nmの光の吸光係数が1.0×102mL/gcm以下であり、波長254nmの光の吸光係数が1.0×103mL/gcm以上である光重合開始剤b(以下、光重合開始剤bともいう)と、を併用する。光重合開始剤aおよび光重合開始剤bとしては、上述した化合物のなかから上記の吸光係数を有する化合物を選択して用いることができる。
上記式においてεは吸光係数(mL/gcm)、Aは吸光度、cは光重合開始剤の濃度(g/mL)、lは光路長(cm)を表す。
また、光重合開始剤aのメタノール中での波長254nmの光の吸光係数は、1.0×104~1.0×105mL/gcmであることが好ましく、1.5×104~9.5×104mL/gcmであることがより好ましく、3.0×104~8.0×104mL/gcmであることが更に好ましい。
本発明の感光性着色組成物は、重合性基を有する色材を含有する。重合性基を有する色材は、顔料であってもよく、染料であってもよいが、染料であることが好ましい。すなわち、重合性基を有する色材は、重合性基を有する染料であることが好ましい。色材として染料を含む感光性着色組成物を用いて得られる硬化膜は、現像液によって色抜けが生じやすい傾向にあったが、染料として重合性基を有するものを用いることにより、低温で硬化しても現像液に対する耐色抜け性に優れた硬化膜を形成できる。このため、本発明の効果がより顕著である。
なお、本明細書において、染料とは、水または有機溶剤に溶解する色素化合物を指す。たとえば、25℃のシクロヘキサノンまたはプロピレングリコールモノメチルエーテルアセテート(PGMEA)に対して0.1質量%以上溶解する色素化合物が好ましい。
トリアリールメタン色素構造を有する化合物としては、下記式(TP)で表される化合物が挙げられる。
式(P)
式(P)中、Lは単結合または2価の連結基を表し、X1は、アニオンを表す。
-NR10-において、R10は、水素原子または炭素数1~5のアルキル基を表し、水素原子が好ましい。
フッ素原子を含むアルキレン基の炭素数は、1~10が好ましく、1~6がより好ましく、1~3がさらに好ましい。これらのアルキレン基は、パーフルオロアルキレン基がより好ましい。フッ素置換アルキレン基の具体例としては、ジフルオロメチレン基、テトラフルオロエチレン基、ヘキサフルオロプロピレン基などが挙げられる。
フッ素原子を含むアリーレン基の炭素数は、6~20が好ましく、6~14がより好ましく、6~10がさらに好ましい。フッ素原子を含むアリーレン基の具体例としては、テトラフルオロフェニレン基、ヘキサフルオロ-1-ナフチレン基、ヘキサフルオロ-2-ナフチレン基などが挙げられる。
式(P-1)
式(P-1)中、L1は、単結合または2価の連結基を表し、単結合であることが好ましい。L1が表す2価の連結基としては、炭素数1~6のアルキレン基、炭素数6~12のアリーレン基、-O-、-S-、またはこれらの組み合わせからなる基等が挙げられる。L2は、-SO2-または-CO-を表す。Gは、炭素原子または窒素原子を表す。n1は、Gが炭素原子の場合2を表し、Gが窒素原子の場合1を表す。R6は、フッ素原子を含むアルキル基またはフッ素原子を含むアリール基を表す。n1が2の場合、2つのR6はそれぞれ同一でも異なっていても良い。R6が表すフッ素原子を含むアルキル基の炭素数は、1~10が好ましく、1~6がより好ましく、1~3がさらに好ましい。R6が表すフッ素原子を含むアリール基の炭素数は、6~20が好ましく、6~14がより好ましく、6~10がさらに好ましい。
キサンテン色素構造を有する化合物としては、下記式(J)で表される化合物が挙げられる。
形成される環が、さらに置換可能な基である場合には、R81~R85で説明した置換基で置換されていてもよく、2個以上の置換基で置換されている場合には、それらの置換基は同一であっても異なっていてもよい。
ジピロメテン色素構造を有する化合物としては、ジピロメテン化合物、および、ジピロメテン化合物と金属または金属化合物とから得られるジピロメテン金属錯体化合物が好ましい。たとえば、式(PM)で表されるジピロメテン色素が好ましい。
式(PM)
式中、R1、R2、R3、R4、R5、及びR6は、各々独立に、水素原子、又は置換基を表し、R7は水素原子、ハロゲン原子、アルキル基、アリール基、又はヘテロ環基を表す。これらの置換基としては、後述する置換基T群が挙げられる。R1~R7の少なくとも1つが重合性基を含む。
置換基T群として、次の基が挙げられる。アルキル基(好ましくは炭素数1~30のアルキル基)、アルケニル基(好ましくは炭素数2~30のアルケニル基)、アルキニル基(好ましくは炭素数2~30のアルキニル基)、アリール基(好ましくは炭素数6~30のアリール基)、アミノ基(好ましくは炭素数0~30のアミノ基)、アルコキシ基(好ましくは炭素数1~30のアルコキシ基)、アリールオキシ基(好ましくは炭素数6~30のアリールオキシ基)、ヘテロアリールオキシ基、アシル基(好ましくは炭素数1~30のアシル基)、アルコキシカルボニル基(好ましくは炭素数2~30のアルコキシカルボニル基)、アリールオキシカルボニル基(好ましくは炭素数7~30のアリールオキシカルボニル基)、アシルオキシ基(好ましくは炭素数2~30のアシルオキシ基)、アシルアミノ基(好ましくは炭素数2~30のアシルアミノ基)、アルコキシカルボニルアミノ基(好ましくは炭素数2~30のアルコキシカルボニルアミノ基)、アリールオキシカルボニルアミノ基(好ましくは炭素数7~30のアリールオキシカルボニルアミノ基)、スルファモイル基(好ましくは炭素数0~30のスルファモイル基)、カルバモイル基(好ましくは炭素数1~30のカルバモイル基)、アルキルチオ基(好ましくは炭素数1~30のアルキルチオ基)、アリールチオ基(好ましくは炭素数6~30のアリールチオ基)、ヘテロアリールチオ基(好ましくは炭素数1~30)、アルキルスルホニル基(好ましくは炭素数1~30)、アリールスルホニル基(好ましくは炭素数6~30)、ヘテロアリールスルホニル基(好ましくは炭素数1~30)、アルキルスルフィニル基(好ましくは炭素数1~30)、アリールスルフィニル基(好ましくは炭素数6~30)、ヘテロアリールスルフィニル基(好ましくは炭素数1~30)、ウレイド基(好ましくは炭素数1~30)、ヒドロキシル基、カルボキシル基、スルホ基、リン酸基、カルボン酸アミド基、スルホン酸アミド基、イミド酸基、メルカプト基、ハロゲン原子、シアノ基、アルキルスルフィノ基、アリールスルフィノ基、ヒドラジノ基、イミノ基、ヘテロアリール基(好ましくは炭素数1~30)。これらの基は、さらに置換可能な基である場合、さらに置換基を有してもよい。置換基としては、上述した置換基Tで説明した基が挙げられる。
色素多量体(A)は、式(A)で表される繰り返し単位を含むことが好ましい。式(A)で表される繰り返し単位の割合は、色素多量体(A)を構成する全繰り返し単位の10質量%以上が好ましく、20質量%以上がより好ましく、30質量%以上が更に好ましく、50質量%以上が特に好ましい。上限は、100質量%以下とすることもでき、95質量%以下とすることもできる。
式(A)中、X1は繰り返し単位の主鎖を表し、L1は単結合または2価の連結基を表し、D1は色素構造を表す。
アリーレン基の炭素数は、6~20が好ましく、6~12がより好ましい。アリーレン基は置換基を有していてもよく、無置換であってもよい。置換基としては、置換基T群で説明した基が挙げられる。
ヘテロ環連結基は、5員環または6員環が好ましい。ヘテロ環連結基が有するヘテロ原子は、酸素原子、窒素原子および硫黄原子が好ましい。ヘテロ環連結基が有するヘテロ原子の数は、1~3個が好ましい。ヘテロ環連結基は、置換基を有していてもよく、無置換であってもよい。置換基としては、置換基T群で説明した基が挙げられる。
色素多量体(B)は、式(B)で表される繰り返し単位を含む。式(B)で表される繰り返し単位の割合は、色素多量体(B)を構成する全繰り返し単位の10質量%以上が好ましく、20質量%以上がより好ましく、30質量%以上が更に好ましく、50質量%以上が特に好ましい。上限は、100質量%以下とすることもでき、95質量%以下とすることもできる。
式(B)中、X2は繰り返し単位の主鎖を表し、L2は単結合または2価の連結基を表し、D2はY2とイオン結合もしくは配位結合可能な基を有する色素構造を表し、Y2はD2とイオン結合または配位結合可能な基を表す;
L2は、単結合または2価の連結基を表す。2価の連結基としては、炭素数1~30のアルキレン基、炭素数6~30のアリーレン基、ヘテロ環連結基、-CH=CH-、-O-、-S-、-C(=O)-、-COO-、-NR-、-CONR-、-OCO-、-SO-、-SO2-およびこれらを2個以上連結して形成される連結基が挙げられる。ここで、Rは、それぞれ独立に、水素原子、アルキル基、アリール基、またはヘテロアリール基を表す。2価の連結基の詳細については、式(A)のL1と同じである。L2は、単結合、または、アルキレン基、アリーレン基、-NH-、-CO-、-O-、-COO-、-OCO-およびこれらを2以上組み合わせた2価の連結基が好ましい。
色素多量体(C)は、式(C)で表される繰り返し単位を含むことが好ましい。式(C)で表される繰り返し単位の割合は、色素多量体(C)を構成する全繰り返し単位の10質量%以上が好ましく、20質量%以上がより好ましく、30質量%以上が更に好ましく、50質量%以上が特に好ましい。上限は、100質量%以下とすることもでき、95質量%以下とすることもできる。
式(C)中、L3は単結合または2価の連結基を表し、D3は色素構造を表し、mは0または1を表す。
アリール基およびアリーレン基の炭素数は、6~20が好ましく、6~12がより好ましい。
ヘテロ環連結基およびヘテロ環基は、5員環または6員環が好ましい。ヘテロ環連結基およびヘテロ環基が有するヘテロ原子は、酸素原子、窒素原子および硫黄原子が好ましい。ヘテロ環連結基およびヘテロ環基が有するヘテロ原子の数は、1~3個が好ましい。
アルキレン基、アリーレン基、ヘテロ環連結基、アルキル基、アリール基、およびヘテロ環基は、無置換であってもよく、置換基を有してもよい。置換基としては、重合性基、酸基が挙げられる。また、2~20個の無置換のアルキレンオキシ鎖の繰り返しからなる基、ラクトン、酸無水物、アミド、シアノ基等の現像促進基、長鎖および環状アルキル基、アラルキル基、アリール基、ポリアルキレンオキシド基、ヒドロキシル基、マレイミド基、アミノ基等の親疎水性調整基等を置換基として有してもよい。
D3は色素構造を表す。色素構造の種類としては、特に限定は無くD1で説明した種類の色素構造が挙げられる。D3が表す色素構造は、重合性基を有してもよい。
mは0または1を表し、1が好ましい。
色素多量体(D)は、式(D)で表されることが好ましい。
式(D)中、L4は(n+k)価の連結基を表し、L41およびL42は、それぞれ独立に、単結合または2価の連結基を表し、D4は色素構造を表し、P4は置換基を表す;nは2~15を表し、kは0~13を表し、n+kは2~15である。n個のD4は互いに異なっていても良く、同一であってもよい。kが2以上の場合、複数のP4は互いに異なっていても良く、同一であってもよい。
式(D-1)のB41およびB42は、単結合、-O-、-CO-、-O2C-、-CO2-、-NROC-、または、-CONR-が好ましく、単結合、-O-、-CO-、-O2C-または-CO2-がより好ましい。Rは、水素原子、アルキル基またはアリール基を表す。
また、重合性基を有する色材の含有量は、光重合開始剤aと光重合開始剤bとの合計100質量部に対して、25~500質量部であることが好ましい。下限は、30質量部以上がより好ましく、50質量部以上が更に好ましく、100質量部以上が特に好ましい。上限は、450質量部以下がより好ましく、400質量部以下が更に好ましく、350質量部以下が特に好ましい。この範囲であれば、より現像液に対する耐色抜け性に優れた硬化膜が得られやすい。
本発明の感光性着色組成物は、更に、重合性基を有さない色材(以下、他の色材ともいう)を含有することができる。他の色材は、顔料、染料のいずれでよい。顔料としては、無機顔料、有機顔料が挙げられ、有機顔料であることが好ましい。顔料の平均粒径としては、20~300nmが好ましく、25~250nmがより好ましく、30~200nmが更に好ましい。ここでいう「平均粒径」とは、顔料の一次粒子が集合した二次粒子についての平均粒径を意味する。また、顔料の二次粒子の粒径分布(以下、単に「粒径分布」ともいう。)は、(平均粒径±100)nmに入る二次粒子が全体の70質量%以上、好ましくは80質量%以上であることが好ましい。なお、二次粒子の粒径分布は、散乱強度分布を用いて測定することができる。また、一次粒子の平均粒径は、走査型電子顕微鏡(SEM)あるいは透過型電子顕微鏡(TEM)で観察し、粒子が凝集していない部分で粒子サイズを100個計測し、平均値を算出することによって求めることができる。
カラーインデックス(C.I.)Pigment Yellow 1,2,3,4,5,6,10,11,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,36,36:1,37,37:1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,86,93,94,95,97,98,100,101,104,106,108,109,110,113,114,115,116,117,118,119,120,123,125,126,127,128,129,137,138,139,147,148,150,151,152,153,154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188,193,194,199,213,214等(以上、黄色顔料)、
C.I.Pigment Orange 2,5,13,16,17:1,31,34,36,38,43,46,48,49,51,52,55,59,60,61,62,64,71,73等(以上、オレンジ色顔料)、
C.I.Pigment Red 1,2,3,4,5,6,7,9,10,14,17,22,23,31,38,41,48:1,48:2,48:3,48:4,49,49:1,49:2,52:1,52:2,53:1,57:1,60:1,63:1,66,67,81:1,81:2,81:3,83,88,90,105,112,119,122,123,144,146,149,150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279等(以上、赤色顔料)、
C.I.Pigment Green 7,10,36,37,58,59等(以上、緑色顔料)、
C.I.Pigment Violet 1,19,23,27,32,37,42等(以上、紫色顔料)、
C.I.Pigment Blue 1,2,15,15:1,15:2,15:3,15:4,15:6,16,22,60,64,66,79,80等(以上、青色顔料)。
また、青色顔料として、リン原子を有するアルミニウムフタロシアニン化合物を用いることもできる。具体例としては、特開2012-247591号公報の段落0022~0030、特開2011-157478号公報の段落0047に記載の化合物などが挙げられる。
また、他の色材は顔料の含有量が50質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることが更に好ましい。
また、重合性基を有する色材と他の色材との合計量は、感光性着色組成物中の全固形分中20~70質量%が好ましい。下限は、25質量%以上がより好ましく、30質量%以上が更に好ましい。上限は、70質量%以下がより好ましく、55質量%以下が更に好ましい。
また、本発明の感光性着色組成物に含まれる色材(重合性基を有する色材と他の色材との合計)中における染料の含有量は、10質量%以上であることが好ましく、20質量%以上であることがより好ましく、30質量%以上であることが更に好ましい。
本発明の感光性着色組成物は、樹脂を含む。樹脂としてはアルカリ可溶性樹脂などが挙げられる。樹脂は、例えば、顔料などの粒子を組成物中で分散させる用途、バインダーの用途で配合される。なお、主に顔料などの粒子を分散させるために用いられる樹脂を分散剤ともいう。ただし、樹脂のこのような用途は一例であって、このような用途以外の目的で樹脂を使用することもできる。
本発明の感光性着色組成物は、アルカリ可溶性樹脂を含む。アルカリ可溶性樹脂としては、アルカリ溶解を促進する基を有する樹脂の中から適宜選択することができる。アルカリ溶解を促進する基(以下、酸基ともいう)としては、例えば、カルボキシル基、リン酸基、スルホ基、フェノール性水酸基などが挙げられ、カルボキシル基が好ましい。アルカリ可溶性樹脂が有する酸基の種類は、1種のみであってもよいし、2種以上であってもよい。
式(X)において、R1は、水素原子またはメチル基を表し、R2は炭素数2~10のアルキレン基を表し、R3は、水素原子またはベンゼン環を含んでもよい炭素数1~20のアルキル基を表す。nは1~15の整数を表す。
本発明の感光性着色組成物は、分散剤としての樹脂を含有することができる。分散剤としては、酸性分散剤(酸性樹脂)、塩基性分散剤(塩基性樹脂)が挙げられる。
また、塩基性分散剤(塩基性樹脂)とは、塩基性基の量が酸基の量よりも多い樹脂を表す。塩基性分散剤(塩基性樹脂)としては、酸基の量と塩基性基の量の合計量を100モル%としたときに、塩基性基の量が50モル%を超える樹脂が好ましい。塩基性分散剤が有する塩基性基は、アミノ基が好ましい。
本発明の感光性着色組成物は、樹脂として上述した分散剤やアルカリ可溶性樹脂以外の樹脂(その他の樹脂ともいう)を含有することができる。その他の樹脂としては、例えば、(メタ)アクリル樹脂、(メタ)アクリルアミド樹脂、エン・チオール樹脂、ポリカーボネート樹脂、ポリエーテル樹脂、ポリアリレート樹脂、ポリスルホン樹脂、ポリエーテルスルホン樹脂、ポリフェニレン樹脂、ポリアリーレンエーテルホスフィンオキシド樹脂、ポリイミド樹脂、ポリアミドイミド樹脂、ポリオレフィン樹脂、環状オレフィン樹脂、ポリエステル樹脂、スチレン樹脂、シロキサン樹脂などが挙げられる。他の樹脂は、これらの樹脂から1種を単独で使用してもよく、2種以上を混合して使用してもよい。
本発明の感光性着色組成物は、重合性基を有する色材の他に、更に、重合性化合物を含有することが好ましい。重合性化合物としては、例えば、エチレン性不飽和基を有する化合物などが挙げられる。エチレン性不飽和基としては、ビニル基、(メタ)アリル基、(メタ)アクリロイル基などが挙げられる。重合性化合物はラジカルにより重合可能な化合物(ラジカル重合性化合物)であることが好ましい。なお、本明細書において、重合性化合物は、重合性基を有する色材とは異なる化合物である。重合性化合物は、色素構造を有さない化合物であることが好ましい。
また、重合性化合物としては、8UH-1006、8UH-1012(以上、大成ファインケミカル(株)製)、ライトアクリレートPOB-A0(共栄社化学(株)製)などを用いることも好ましい。
また、重合性化合物としては、特開2017-48367号公報、特許第6057891号公報、特許第6031807号公報に記載されている化合物を用いることもできる。
また、重合性化合物の含有量は、重合性基を有する色材の100質量部に対して25~500質量部であることが好ましい。下限は、30質量部以上がより好ましく、50質量部以上が更に好ましい。上限は、450質量部以下がより好ましく、300質量部以下が更に好ましい。重合性化合物の含有量が上記範囲であれば、現像パターンのより微細化が期待できる。
また、重合性化合物と重合性基を有する色材の合計量は、感光性着色組成物の全固形分中、20~80質量%が好ましい。下限は、25質量%以上がより好ましく、40質量%以上が更に好ましい。上限は、75質量%以下がより好ましく、60質量%以下が更に好ましい。上述の合計量が上記範囲であれば、支持体とのより密着性に優れた硬化膜が得られやすい。
また、重合性化合物と重合性基を有する色材の合計量は、光重合開始剤aと光重合開始剤bとの合計100質量部に対して、25~500質量部であることが好ましい。下限は、30質量部以上がより好ましく、50質量部以上が更に好ましい。上限は、450質量部以下がより好ましく、300質量部以下が更に好ましい。この範囲であれば、より現像液に対する耐色抜け性や支持体との密着性などに優れた硬化膜が得られやすい。
本発明の感光性着色組成物は、更にエポキシ基を有する化合物を含有することが好ましい。この態様によれば、得られる硬化膜の機械強度などを向上できる。エポキシ基を有する化合物としては、1分子内にエポキシ基を2つ以上有する化合物が好ましい。エポキシ基は、1分子内に2~100個有することが好ましい。上限は、例えば、10個以下とすることもでき、5個以下とすることもできる。
本発明の感光性着色組成物は、溶剤を含有することが好ましい。溶剤は有機溶剤が好ましい。溶剤は、各成分の溶解性や感光性着色組成物の塗布性を満足すれば特に制限はない。
本発明の感光性着色組成物は、重合性化合物の反応を促進させたり、硬化温度を下げる目的で、硬化促進剤を添加してもよい。硬化促進剤としては、分子内に2個以上のメルカプト基を有する多官能チオール化合物などが挙げられる。多官能チオール化合物は安定性、臭気、解像性、現像性、密着性等の改良を目的として添加してもよい。多官能チオール化合物は、2級のアルカンチオール類であることが好ましく、式(T1)で表される化合物であることがより好ましい。
式(T1)
(式(T1)中、nは2~4の整数を表し、Lは2~4価の連結基を表す。)
本発明の感光性着色組成物は、塗布性をより向上させる観点から、各種の界面活性剤を含有させてもよい。界面活性剤としては、フッ素系界面活性剤、ノニオン系界面活性剤、カチオン系界面活性剤、アニオン系界面活性剤、シリコーン系界面活性剤などの各種界面活性剤を使用できる。
上記の化合物の重量平均分子量は、好ましくは3,000~50,000であり、例えば、14,000である。
本発明の感光性着色組成物は、シランカップリング剤を含有することができる。シランカップリング剤としては、一分子中に少なくとも2種の反応性の異なる官能基を有するシラン化合物が好ましい。シランカップリング剤は、ビニル基、エポキシ基、スチレン基、メタクリル基、アミノ基、イソシアヌレート基、ウレイド基、メルカプト基、スルフィド基、および、イソシアネート基から選ばれる少なくとも1種の基と、アルコキシ基とを有するシラン化合物が好ましい。シランカップリング剤の具体例としては、例えば、N-β-アミノエチル-γ-アミノプロピルメチルジメトキシシラン(信越化学工業社製、KBM-602)、N-β-アミノエチル-γ-アミノプロピルトリメトキシシラン(信越化学工業社製、KBM-603)、N-β-アミノエチル-γ-アミノプロピルトリエトキシシラン(信越化学工業社製、KBE-602)、γ-アミノプロピルトリメトキシシラン(信越化学工業社製、KBM-903)、γ-アミノプロピルトリエトキシシラン(信越化学工業社製、KBE-903)、3-メタクリロキシプロピルトリメトキシシラン(信越化学工業社製、KBM-503)、3-グリシドキシプロピルトリメトキシシラン(信越化学工業社製、KBM-403)等が挙げられる。シランカップリング剤の詳細については、特開2013-254047号公報の段落番号0155~0158の記載を参酌でき、この内容は本明細書に組み込まれる。
本発明の感光性着色組成物は、重合禁止剤を含有することも好ましい。重合禁止剤としては、ハイドロキノン、p-メトキシフェノール、ジ-t-ブチル-p-クレゾール、ピロガロール、t-ブチルカテコール、ベンゾキノン、4,4’-チオビス(3-メチル-6-t-ブチルフェノール)、2,2’-メチレンビス(4-メチル-6-t-ブチルフェノール)、N-ニトロソフェニルヒドロキシアミン塩(アンモニウム塩、第一セリウム塩等)等が挙げられる。
本発明の感光性着色組成物が重合禁止剤を含有する場合、重合禁止剤の含有量は、感光性着色組成物の全固形分中0.01~5質量%が好ましい。本発明の感光性着色組成物は、重合禁止剤を、1種類のみを含んでいてもよいし、2種類以上含んでいてもよい。2種類以上含む場合は、その合計量が上記範囲となることが好ましい。
本発明の感光性着色組成物は、紫外線吸収剤を含有することができる。紫外線吸収剤としては、共役ジエン化合物、アミノブタジエン化合物、メチルジベンゾイル化合物、クマリン化合物、サリシレート化合物、ベンゾフェノン化合物、ベンゾトリアゾール化合物、アクリロニトリル化合物、ヒドロキシフェニルトリアジン化合物などを用いることができる。これらの詳細については、特開2012-208374号公報の段落番号0052~0072、特開2013-68814号公報の段落番号0317~0334の記載を参酌でき、これらの内容は本明細書に組み込まれる。紫外線吸収剤の市販品としては、例えば、UV-503(大東化学(株)製)などが挙げられる。また、ベンゾトリアゾール化合物としてはミヨシ油脂製のMYUAシリーズ(化学工業日報、2016年2月1日)を用いてもよい。
本発明の感光性着色組成物には、必要に応じて、各種添加剤、例えば、充填剤、密着促進剤、酸化防止剤、凝集防止剤等を配合することができる。これらの添加剤としては、特開2004-295116号公報の段落番号0155~0156に記載の添加剤を挙げることができ、この内容は本明細書に組み込まれる。また、酸化防止剤としては、例えばフェノール化合物、リン系化合物(例えば特開2011-90147号公報の段落番号0042に記載の化合物)、チオエーテル化合物などを用いることができる。市販品としては、例えば(株)ADEKA製のアデカスタブシリーズ(AO-20、AO-30、AO-40、AO-50、AO-50F、AO-60、AO-60G、AO-80、AO-330など)が挙げられる。酸化防止剤は1種のみを用いてもよく、2種以上を用いてもよい。本発明の着色組成物は、特開2004-295116号公報の段落番号0078に記載の増感剤や光安定剤、同公報の段落番号0081に記載の熱重合防止剤を含有することができる。
本発明の感光性着色組成物は、前述の成分を混合して調製できる。感光性着色組成物の調製に際しては、全成分を同時に溶剤に溶解および/または分散して感光性着色組成物を調製してもよいし、必要に応じて、各成分を適宜2つ以上の溶液または分散液としておいて、使用時(塗布時)にこれらを混合して感光性着色組成物を調製してもよい。
例えば、上述した範囲内で異なる孔径のフィルタを組み合わせてもよい。ここでの孔径は、フィルタメーカーの公称値を参照することができる。市販のフィルタとしては、例えば、日本ポール株式会社(DFA4201NIEYなど)、アドバンテック東洋株式会社、日本インテグリス株式会社(旧日本マイクロリス株式会社)または株式会社キッツマイクロフィルタ等が提供する各種フィルタの中から選択することができる。
また、第1のフィルタでのろ過は、分散液のみで行い、他の成分を混合した後で、第2のフィルタでろ過を行ってもよい。第2のフィルタとしては、第1のフィルタと同様の材料等で形成されたものを使用することができる。
本発明の硬化膜は、上述した本発明の感光性着色組成物から得られる硬化膜である。本発明の硬化膜は、カラーフィルタの着色画素として好ましく用いることができる。着色画素としては、赤色画素、緑色画素、青色画素、マゼンタ色画素、シアン色画素、イエロー色画素などが挙げられる。硬化膜の膜厚は、目的に応じて適宜調整できる。例えば、膜厚は、20μm以下が好ましく、10μm以下がより好ましく、5μm以下がさらに好ましい。膜厚の下限は、0.1μm以上が好ましく、0.2μm以上がより好ましく、0.3μm以上がさらに好ましい。
本発明のパターン形成方法は、上述した本発明の感光性着色組成物を用いて支持体上に感光性着色組成物層を形成する工程と、
感光性着色組成物層に対して、波長350nmを超え380nm以下の光を照射してパターン状に露光する工程と、
露光後の感光性着色組成物層をアルカリ現像する工程と、
アルカリ現像後の感光性着色組成物層に対して、波長254~350nmの光を照射して露光する工程と、を有する。さらに、必要に応じて、感光性着色組成物層を支持体上に形成した後であって露光する前にベークする工程(プリベーク工程)、および、アルカリ現像されたパターンをベークする工程(ポストベーク工程)を設けてもよい。以下、各工程について説明する。
また、画素上の水の接触角は適宜好ましい値に設定することができるが、典型的には、50~110°の範囲である。接触角は、例えば接触角計CV-DT・A型(協和界面科学(株)製)を用いて測定できる。
次に、本発明のカラーフィルタについて説明する。本発明のカラーフィルタは、上述した本発明の硬化膜を有する。本発明のカラーフィルタにおいて、硬化膜の膜厚は、目的に応じて適宜調整できる。膜厚は、20μm以下が好ましく、10μm以下がより好ましく、5μm以下がさらに好ましい。膜厚の下限は、0.1μm以上が好ましく、0.2μm以上がより好ましく、0.3μm以上が更に好ましい。本発明のカラーフィルタは、CCD(電荷結合素子)やCMOS(相補型金属酸化膜半導体)などの固体撮像素子や画像表示装置などに用いることができる。
本発明の固体撮像素子は、上述した本発明の硬化膜を有する。本発明の固体撮像素子の構成としては、本発明の硬化膜を備え、固体撮像素子として機能する構成であれば特に限定はないが、例えば、以下のような構成が挙げられる。
本発明の硬化膜は、液晶表示装置や有機エレクトロルミネッセンス表示装置などの、画像表示装置に用いることができる。画像表示装置の定義や各画像表示装置の詳細については、例えば「電子ディスプレイデバイス(佐々木昭夫著、(株)工業調査会、1990年発行)」、「ディスプレイデバイス(伊吹順章著、産業図書(株)平成元年発行)」などに記載されている。また、液晶表示装置については、例えば「次世代液晶ディスプレイ技術(内田龍男編集、(株)工業調査会、1994年発行)」に記載されている。本発明が適用できる液晶表示装置に特に制限はなく、例えば、上記の「次世代液晶ディスプレイ技術」に記載されている色々な方式の液晶表示装置に適用できる。
(顔料分散液P1)
C.I.Pigment Blue15:6の20.0質量部(平均一次粒子径55nm)と、顔料分散剤(DISPERBYK-161、BYKChemie社製)の2.40質量部と、分散剤1の2.40質量部と、プロピレングリコールモノメチルエーテルアセテート(PGMEA)の175.2質量部との混合液を、ビーズミル(直径0.3mmのジルコニアビーズ)を用いて3時間混合および分散した。その後、さらに、減圧機構付き高圧分散機NANO-3000-10(日本ビーイーイー(株)製)を用いて、2000kg/cm3の圧力下で流量500g/minとして分散処理を行なった。この分散処理を10回繰り返し、顔料分散液P1を得た。得られた顔料分散液P1について、顔料の平均一次粒子径を動的光散乱法(Microtrac Nanotrac UPA-EX150(日機装社製))により測定したところ、24nmであった。
(顔料分散液P2)
分散剤1のかわりに特開2013-195854号公報の段落番号0577に記載の分散樹脂Aを用いた以外は、顔料分散液P1と同様にして顔料分散液P2を得た。
(実施例1)
以下に示す原料を混合し、撹拌した後、孔径0.45μmのナイロン製フィルタ(日本ポール(株)製)でろ過して、感光性着色組成物を調製した。
・顔料分散液P1・・・60.0質量部
・光重合開始剤(開始剤1)・・・1.68質量部
・光重合開始剤(開始剤4)・・・0.63質量部
・アルカリ可溶性樹脂(樹脂A)・・・0.60質量部
・重合性化合物(M1)・・・6.00質量部
・染料(V1)・・・20.0質量部
・エポキシ化合物(EHPE 3150、(株)ダイセル製)・・・0.66質量部
・重合禁止剤(p-メトキシフェノール)・・・0.0007質量部
・界面活性剤(下記構造の化合物(Mw=14000、繰り返し単位の割合を示す%の数値はモル%である)の1質量%シクロヘキサノン溶液)・・・2.50質量部
・シクロヘキサノン・・・7.74質量部
顔料分散液の種類、光重合開始剤の種類および含有量、アルカリ可溶性樹脂の種類、染料の種類および重合性化合物の種類をそれぞれ下記表に記載の通り変更した以外は実施例1と同様にして感光性着色組成物を調製した。なお、下記表の光重合開始剤の欄に記載の含有量の数値は、感光性着色組成物の全固形分中における含有量である。
染料(V1)の含有量を下記表に記載の通り変更した以外は、実施例1と同様にして感光性着色組成物を調製した。下記表に重合性基を有する色材と光重合開始剤(開始剤1と開始剤4の合計量)の質量比をあわせて記す。
開始剤1:IRGACURE-OXE01(BASF社製、メタノール中での波長365nmの光の吸光係数が6969mL/gcmである)
開始剤2:IRGACURE-OXE02(BASF社製、メタノール中での波長365nmの光の吸光係数が7749mL/gcmである)
開始剤3:下記構造の化合物(メタノール中での波長365nmの光の吸光係数が18900mL/gcmである)
開始剤4:IRGACURE 2959(BASF社製、メタノール中での波長365nmの光の吸光係数が48.93mL/gcmであり、波長254nmの光の吸光係数が3.0×104mL/gcmである。)
開始剤5:IRGACURE 184(BASF社製、メタノール中での波長365nmの光の吸光係数が88.64mL/gcmであり、波長254nmの光の吸光係数が3.3×104mL/gcmである。)
樹脂A:下記構造の樹脂(Mw=11000、酸価=31.5mgKOH/g、主鎖に付記した数値はモル比である。)
樹脂B:下記構造の樹脂(Mw=30000、酸価=112.8mgKOH/g、主鎖に付記した数値はモル比である。)
樹脂C:特開2013-225112号公報の段落番号0573に記載のアルカリ可溶性樹脂J5
樹脂D:特開2010-049161号公報の段落番号0150に記載の樹脂B-1
染料V1:下記構造の色素多量体(重合性基を有する染料)の20質量%のシクロヘキサノン溶液
染料V2:下記構造の色素多量体(重合性基を有する染料、主鎖に付記した数値はモル比である、Mw=13000)の20質量%のシクロヘキサノン溶液
染料V3:下記構造の色素多量体(重合性基を有さない染料、主鎖に付記した数値はモル比である、Mw=12000)の20質量%のシクロヘキサノン溶液
染料V4:下記構造の色素化合物(重合性基を有する染料)の20質量%のシクロヘキサノン溶液
(耐色抜け性)
ガラス基板上に、各感光性着色組成物をプリベーク後の膜厚が1.6μmになるようにスピンコーターを用いて塗布し、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行った。
次いで、紫外線フォトレジスト硬化装置(UMA-802-HC-552;ウシオ電気株式会社製)を用いて、3000mJ/cm2の露光量で露光を行い、硬化膜を作製した。
得られた硬化膜について、紫外可視近赤外分光光度計UV3600(島津製作所製)の分光光度計(レファレンス:ガラス基板)を用いて波長300~800nmの範囲の光の透過率を測定した。また、OLYMPUS製光学顕微鏡 BX60を用いて、反射観測(倍率50倍)にて微分干渉像を観察した。
次いで、硬化膜を、25℃のアルカリ現像液(FHD-5、富士フイルムエレクトロニクスマテリアルズ(株)製)の中に5分間浸漬し、乾燥させた後に再度分光測定を実施し、アルカリ現像液浸漬前後の透過率変動を算出して以下の基準で耐色抜け性を評価した。
透過率変動=|T0-T1|
T0は、アルカリ現像液浸漬前の硬化膜の透過率であり、T1は、アルカリ現像液浸漬後の硬化膜の透過率である。
AA:波長300~800nmの全範囲での透過率変動が2%未満である。
A:波長300~800nmの全範囲での透過率変動が5%未満であり、かつ、一部の範囲において透過率変動が2%以上5%未満である。
B:波長300~800nmの全範囲での透過率変動が7.5%未満であり、かつ、一部の範囲において透過率変動が5%以上7.5%未満である。
C:波長300~800nmの全範囲での透過率変動が10%未満であり、かつ、一部の範囲において透過率変動が7.5%以上10%未満である。
D:波長300~800nmの少なくも一部の範囲において透過率変動が10%以上である。
ヘキサメチルジシラザンを噴霧した8インチ(20.32cm)のガラス基板の上に、各感光性着色組成物をプリベーク後の膜厚が1.6μmになるようにスピンコーターを用いて塗布し、100℃のホットプレートを用いて120秒間加熱処理(プリベーク)を行った。
次いで、i線ステッパー露光装置FPA-3000i5+(Canon(株)製)を使用して、365nmの波長で3.0μm四方のアイランドパターンマスクを通して300mJ/cm2にて照射した(3.0μmの線幅を得るのに必要な露光量である)。
次いで、露光後の塗布膜が形成されているガラス基板をスピン・シャワー現像機(DW-30型;(株)ケミトロニクス製)の水平回転テーブル上に載置し、現像液(CD-2000(富士フイルムエレクトロニクスマテリアルズ(株)製)の40%希釈液)を用いて23℃で180秒間パドル現像を行ない、ガラス基板上に着色パターン(画素)を形成した。この着色パターン(画素)が形成されたガラス基板を真空チャック方式で水平回転テーブルに固定し、回転装置によってガラス基板を回転数50rpmで回転させつつ、その回転中心の上方より純水を噴出ノズルからシャワー状に供給してリンス処理を行ない、その後スピン乾燥して着色パターン(画素)を形成した。
残膜率(%)=(現像前の厚み/現像後の厚み)×100
AA:残膜率が87.5%以上
A:残膜率が82.5%以上、87.5%未満
B:残膜率が80%以上、82.5%未満
C:残膜率が80%未満
AA:着色パターンの剥がれがない。
A:着色パターンの剥がれが100画素中1~5画素存在する
B:着色パターンの剥がれが100画素中6~15画素存在する
C:着色パターンの剥がれが100画素中16画素以上存在する
Claims (12)
- メタノール中での波長365nmの光の吸光係数が1.0×102mL/gcmを超える光重合開始剤aと、
メタノール中での波長365nmの光の吸光係数が1.0×102mL/gcm以下であり、波長254nmの光の吸光係数が1.0×103mL/gcm以上である光重合開始剤bと、
アルカリ可溶性樹脂と、
重合性基を有する色材と、を含有する感光性着色組成物であって、
前記感光性着色組成物の全固形分中における前記光重合開始剤aの含有量が1.5質量%以上であり、前記光重合開始剤bの含有量が1.5質量%以上である、感光性着色組成物。 - 前記光重合開始剤aのメタノール中での波長365nmの光の吸光係数が1.0×103mL/gcm以上である、請求項1に記載の感光性着色組成物。
- 前記光重合開始剤aがオキシム化合物である、請求項1または2に記載の感光性着色組成物。
- 前記光重合開始剤bがヒドロキシアセトフェノン化合物である、請求項1~3のいずれか1項に記載の感光性着色組成物。
- 前記光重合開始剤bの100質量部に対して、前記光重合開始剤aを50~500質量部含有する、請求項1~4のいずれか1項に記載の感光性着色組成物。
- 前記感光性着色組成物の全固形分中における前記光重合開始剤aと前記光重合開始剤bとの合計の含有量が3~17質量%である、請求項1~5のいずれか1項に記載の感光性着色組成物。
- 前記色材は色素多量体である、請求項1~6のいずれか1項に記載の感光性着色組成物。
- 請求項1~7のいずれか1項に記載の感光性着色組成物を硬化して得られる硬化膜。
- 請求項1~7のいずれか1項に記載の感光性着色組成物を用いて支持体上に感光性着色組成物層を形成する工程と、
前記感光性着色組成物層に対して、波長350nmを超え380nm以下の光を照射してパターン状に露光する工程と、
前記露光後の感光性着色組成物層をアルカリ現像する工程と、
前記現像後の感光性着色組成物層に対して、波長254~350nmの光を照射して露光する工程と、を有するパターンの形成方法。 - 請求項8に記載の硬化膜を有するカラーフィルタ。
- 請求項8に記載の硬化膜を有する固体撮像素子。
- 請求項8に記載の硬化膜を有する画像表示装置。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020207004279A KR102382227B1 (ko) | 2017-09-28 | 2018-08-21 | 감광성 착색 조성물, 경화막, 패턴의 형성 방법, 컬러 필터, 고체 촬상 소자 및 화상 표시 장치 |
JP2019544421A JP6997202B2 (ja) | 2017-09-28 | 2018-08-21 | 感光性着色組成物、硬化膜、パターンの形成方法、カラーフィルタ、固体撮像素子および画像表示装置 |
CN201880055966.1A CN111095103B (zh) | 2017-09-28 | 2018-08-21 | 感光性着色组合物、固化膜、图案的形成方法、滤色器、固体摄像元件及图像显示装置 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2017-188006 | 2017-09-28 | ||
JP2017188006 | 2017-09-28 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019065001A1 true WO2019065001A1 (ja) | 2019-04-04 |
Family
ID=65901703
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/030863 WO2019065001A1 (ja) | 2017-09-28 | 2018-08-21 | 感光性着色組成物、硬化膜、パターンの形成方法、カラーフィルタ、固体撮像素子および画像表示装置 |
Country Status (4)
Country | Link |
---|---|
JP (1) | JP6997202B2 (ja) |
KR (1) | KR102382227B1 (ja) |
CN (1) | CN111095103B (ja) |
WO (1) | WO2019065001A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020066919A1 (ja) * | 2018-09-26 | 2020-04-02 | 富士フイルム株式会社 | 着色組成物、硬化膜の形成方法、カラーフィルタの製造方法および表示装置の製造方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013041097A (ja) * | 2011-08-15 | 2013-02-28 | Fujifilm Corp | 着色組成物、着色感放射線性組成物、重合体の製造方法、パターンの形成方法、カラーフィルタ、及びその製造方法、並びに固体撮像素子 |
JP2015041058A (ja) * | 2013-08-23 | 2015-03-02 | 富士フイルム株式会社 | 感光性着色組成物、カラーフィルタ、カラーフィルタの製造方法、有機el液晶表示装置 |
WO2016190162A1 (ja) * | 2015-05-22 | 2016-12-01 | 富士フイルム株式会社 | 着色組成物、膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および赤外線センサ |
JP2018146630A (ja) * | 2017-03-01 | 2018-09-20 | 富士フイルム株式会社 | カラーフィルタの下地膜用組成物、積層体、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH519553A (de) * | 1967-04-19 | 1972-02-29 | Ici Ltd | Verfahren zur Herstellung von neuen Azofarbstoffen |
JPH0728911B2 (ja) * | 1988-05-06 | 1995-04-05 | 株式会社メニコン | 眼用レンズを着色するための重合性色素並びにそれを用いた着色眼用レンズ材料の製造法及び着色眼用レンズ材料 |
CN103205139B (zh) * | 2012-01-16 | 2014-10-22 | 清华大学 | 可聚合染料单体、彩色聚合物乳液及其制备方法 |
JP6166711B2 (ja) | 2013-12-25 | 2017-07-19 | 富士フイルム株式会社 | 着色組成物、およびこれを用いた硬化膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および画像表示装置 |
-
2018
- 2018-08-21 WO PCT/JP2018/030863 patent/WO2019065001A1/ja active Application Filing
- 2018-08-21 CN CN201880055966.1A patent/CN111095103B/zh active Active
- 2018-08-21 JP JP2019544421A patent/JP6997202B2/ja active Active
- 2018-08-21 KR KR1020207004279A patent/KR102382227B1/ko active IP Right Grant
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2013041097A (ja) * | 2011-08-15 | 2013-02-28 | Fujifilm Corp | 着色組成物、着色感放射線性組成物、重合体の製造方法、パターンの形成方法、カラーフィルタ、及びその製造方法、並びに固体撮像素子 |
JP2015041058A (ja) * | 2013-08-23 | 2015-03-02 | 富士フイルム株式会社 | 感光性着色組成物、カラーフィルタ、カラーフィルタの製造方法、有機el液晶表示装置 |
WO2016190162A1 (ja) * | 2015-05-22 | 2016-12-01 | 富士フイルム株式会社 | 着色組成物、膜、カラーフィルタ、パターン形成方法、カラーフィルタの製造方法、固体撮像素子および赤外線センサ |
JP2018146630A (ja) * | 2017-03-01 | 2018-09-20 | 富士フイルム株式会社 | カラーフィルタの下地膜用組成物、積層体、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置 |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2020066919A1 (ja) * | 2018-09-26 | 2020-04-02 | 富士フイルム株式会社 | 着色組成物、硬化膜の形成方法、カラーフィルタの製造方法および表示装置の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
JPWO2019065001A1 (ja) | 2020-11-05 |
JP6997202B2 (ja) | 2022-01-17 |
CN111095103B (zh) | 2023-06-27 |
CN111095103A (zh) | 2020-05-01 |
KR20200030567A (ko) | 2020-03-20 |
KR102382227B1 (ko) | 2022-04-04 |
TW201918794A (zh) | 2019-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6546652B2 (ja) | 着色感光性組成物、硬化膜、パターン形成方法、遮光膜付き赤外光カットフィルタ、固体撮像素子、画像表示装置および赤外線センサ | |
JP7090628B2 (ja) | 着色組成物、硬化膜、パターン形成方法、カラーフィルタ、固体撮像素子及び画像表示装置 | |
US11287739B2 (en) | Photosensitive coloring composition, cured film, color filter, solid-state imaging element, and image display device | |
WO2019039172A1 (ja) | 構造体、構造体の製造方法、吸収層形成用組成物、固体撮像素子および画像表示装置 | |
TWI742233B (zh) | 濾色器的著色像素形成用的著色組成物、硬化膜、結構體、濾色器、固體攝像元件及圖像顯示裝置 | |
WO2018155104A1 (ja) | 感光性組成物、硬化膜、カラーフィルタ、固体撮像素子および画像表示装置 | |
WO2019059075A1 (ja) | 着色組成物、硬化膜、パターン形成方法、カラーフィルタ、固体撮像素子及び画像表示装置 | |
JP7057412B2 (ja) | 着色組成物、顔料分散液、顔料分散液の製造方法、硬化膜、カラーフィルタ、固体撮像素子および画像表示装置 | |
JP7462807B2 (ja) | 感光性着色組成物、硬化膜、パターンの形成方法、カラーフィルタ、固体撮像素子および画像表示装置 | |
WO2020110873A1 (ja) | 着色感光性組成物、膜、カラーフィルタ、固体撮像素子および画像表示装置 | |
WO2020022248A1 (ja) | 硬化性組成物、膜、カラーフィルタ、カラーフィルタの製造方法、固体撮像素子および画像表示装置 | |
US11518827B2 (en) | Curable composition, method for producing curable composition, film, color filter, method for manufacturing color filter, solid-state imaging element, and image display device | |
JP6997202B2 (ja) | 感光性着色組成物、硬化膜、パターンの形成方法、カラーフィルタ、固体撮像素子および画像表示装置 | |
WO2019049635A1 (ja) | 近赤外線吸収有機顔料、樹脂組成物、近赤外線吸収有機顔料の製造方法、近赤外線吸収有機顔料の分光調整方法、膜、積層体、近赤外線カットフィルタ、近赤外線透過フィルタ、固体撮像素子、画像表示装置および赤外線センサ | |
JP7016879B2 (ja) | 着色組成物、膜の製造方法、カラーフィルタの製造方法、固体撮像素子の製造方法および画像表示装置の製造方法 | |
TWI840333B (zh) | 感光性著色組成物、硬化膜、圖案的形成方法、濾色器、固體攝像元件及圖像顯示裝置 | |
WO2019077913A1 (ja) | 着色組成物、膜、カラーフィルタ、固体撮像素子および画像表示装置 | |
JP7162397B2 (ja) | 着色組成物、硬化膜、パターン形成方法、カラーフィルタ、固体撮像素子および画像表示装置 | |
WO2020045209A1 (ja) | 着色組成物、画素の形成方法、カラーフィルタの製造方法および表示装置の製造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18862321 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20207004279 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2019544421 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 18862321 Country of ref document: EP Kind code of ref document: A1 |