WO2013172469A1 - Radiation-sensitive compositions, color filters, and processes for preparing color filters - Google Patents

Radiation-sensitive compositions, color filters, and processes for preparing color filters Download PDF

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Publication number
WO2013172469A1
WO2013172469A1 PCT/JP2013/063869 JP2013063869W WO2013172469A1 WO 2013172469 A1 WO2013172469 A1 WO 2013172469A1 JP 2013063869 W JP2013063869 W JP 2013063869W WO 2013172469 A1 WO2013172469 A1 WO 2013172469A1
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radiation
formula
group
compounds
acid
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PCT/JP2013/063869
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English (en)
French (fr)
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Kazuya Oota
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Fujifilm Corporation
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    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • 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

Definitions

  • the present invention relates to radiation-sensitive compositions, color filters formed by using them and processes for preparing color filters. It also relates to solid-state image sensors, liquid crystal display devices or organic EL display devices comprising such color filters.
  • Patent document 1 JP-A2011-127096.
  • Radiation-sensitive compositions are not always exposed/developed immediately after they have been prepared, but sometimes they are exposed/developed later. In the latter case, our studies revealed that patternability may decrease or impurity defects may increase. Especially, radiation-sensitive compositions are often cold-stored, but it was found that these performances tend to be worse when they are cold-stored.
  • the present invention aims to solve the problems described above and to provide radiation-sensitive compositions capable of retaining excellent patternability and reducing the increase in impurity defects even after a lapse of time.
  • a radiation-sensitive composition comprising a compound represented by formula (1) , inorganic particles, a dispersant, a polymerization initiator and a solvent.
  • L each represents a group consisting of a combination of an alkylene group and -0-
  • Ac each represents a
  • ⁇ 4> The radiation-sensitive composition according to any one of ⁇ 1> to ⁇ 3>, wherein the inorganic particles comprise titanium dioxide.
  • ⁇ 5> The radiation-sensitive composition according to any one of ⁇ 1> to ⁇ 4>, wherein the dispersant is an oligoimine dispersant.
  • ⁇ 6> The radiation-sensitive composition according to any one of ⁇ 1> to ⁇ 5>, comprising an ether and a ketone as the solvent.
  • ⁇ 7> The radiation-sensitive composition according to any one of ⁇ 1> to ⁇ 5>, comprising propylene glycol monomethyl ether acetate and cyclohexanone as the solvent.
  • ⁇ 8> A cured film obtained by curing the radiation-sensitive composition according to any one of ⁇ 1> to ⁇ 7>.
  • a color filter comprising a colored layer obtained by curing the radiation-sensitive composition according to any one of ⁇ 1> to ⁇ 7>.
  • a process for preparing a cured film comprising the steps of:
  • a process for preparing a color filter comprising the steps of:
  • a solid-state image sensor, liquid crystal display device or organic EL display device comprising the color filter according to ⁇ 9> or a color filter prepared by the process according to ⁇ 11>.
  • the radiation-sensitive composition according to any one of ⁇ 1> to ⁇ 7> and ⁇ 13>, comprising the content of the composition of the formula (1) is 10 to 95 % by mass based on the total components excluding the solvent, the content of the disparsant is 5 to 50 % by mass based on the total components excluding the solvent, and the solvent (however the total components excluding the solvent does not exceed. ) .
  • the present invention made it possible to provide radiation-sensitive compositions capable of retaining excellent patternability and reducing the increase in impurity defects even after a lapse of time.
  • (meth) acrylate refers to acrylate and methacrylate
  • (meth) acrylic refers to acrylic and methacrylic
  • (meth) acryloyl refers to acryloyl and methacryloyl .
  • monomers as used herein are distinguished from oligomers and polymers, and refer to compounds having a weight average molecular weight of 2,000 or less.
  • polymerizable compound refers to a compound having a polymerizable functional group, and may be a monomer or polymer. The polymerizable functional group refers to a group involved in polymerization reaction.
  • alkyl means to include not only alkyls having no substituent (unsubstituted alkyls) but also alkyls having a substituent (substituted alkyls) .
  • the viscosity denotes the value at 25 °C.
  • radiation means to include visible rays, ultraviolet rays, far-ultraviolet rays, electron beams, X rays and the like.
  • compositions of the present invention (hereinafter sometimes simply referred to as “the compositions of the present invention") , cured films,
  • the radiation-sensitive compositions of the present invention are characterized by comprising a compound represented by formula (1) , inorganic particles, a dispersant, a
  • compositions of the present invention comprise a compound represented by formula (1) .
  • L each represents a group consisting of a combination of an alkylene group and -0-
  • Ac each represents a (meth) acryloyloxy group.
  • L preferably each represents a group consisting of a combination of -CH 2 - and -0-, more preferably a group consisting of a combination of -C2H4- and -0-, even more preferably a group consisting of alternately repeating -C 2 H 4 - and -0-.
  • both of the group bonded to L and the group bondedto Ac are preferably -C 2 H 4 -.
  • the number of -C2H4- groups in L is preferably 1 to 4, more preferably 2 or 3.
  • the number of atoms constituting the main chain of L (the number of atoms of the chain between Ac and the 0 atom) is preferably each 3 to 12, more preferably 4 to 10.
  • the number of atoms constituting the main chain of L is five when the L moiety is -C 2 H 4 -0-C 2 H 4 - .
  • Ac is more preferably an acryloyloxy group.
  • the compound represented by formula (1) preferably has a molecular weight of 400 to 1100, more preferably 600 to 1000.
  • the compound represented by formula (1) preferably has a viscosity of 100 to 900 mPa-s, more preferably 200 to 500 mPa-s.
  • the compound represented by formula (1) is preferably contained in the compositions of the present invention in a proportion of 1 to 30 % by mass, more preferably 5 to 15 % by mass based on the total components excluding the solvent. Only one compound represented by formula (1) may be used or two or more such compounds may be used. When two or more compounds are used, the total amount preferably falls within the above ranges.
  • compositions of the present invention may comprise polymerizable compounds other than the compounds represented by formula (1) .
  • polymerizable compounds are specifically selected from compounds having at least one, preferably two or more
  • ethylenically unsaturated terminal bonds Such compounds are commonly known in the field of industry, and can be used in the present invention without specific limitation. These may be in any chemical forms such as, e.g., monomers, prepolymers, i.e., dimers, trimers and oligomers, or mixtures thereof and polymers thereof.
  • the polymerizable compounds in the present invention may be used alone or as a combination of two or more of them.
  • examples of monomers and prepolymers thereof include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like) and their esters, amides, and polymers thereof, preferably esters of unsaturated carboxylic acids and aliphatic polyalcohol compounds; amides of unsaturated carboxylic acids and aliphatic polyamine compounds; and polymers thereof.
  • unsaturated carboxylic acids e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid and the like
  • esters, amides, and polymers thereof preferably esters of unsaturated carboxylic acids and aliphatic polyalcohol compounds
  • amides of unsaturated carboxylic acids and aliphatic polyamine compounds e.g., amides, and polymers thereof.
  • reaction products of unsaturated carboxylic acid esters or amides having a nucleophilic substituent such as a hydroxyl, amino or mercapto group by addition reaction with monofunctional or polyfunctional isocyanates or epoxies or by dehydrative condensation reaction with monofunctional or polyfunctional carboxylic acid and the like can also be conveniently used.
  • the addition reaction products of unsaturated carboxylic acid esters or amides having an electrophilic substituent such as isocyanate or epoxy with monofunctional or polyfunctional alcohols, amines or thiols, as well as the substitution reaction products of unsaturated carboxylic acid esters or amides having an eliminatable substituent such as halogen or tosyloxy with monofunctional or polyfunctional alcohols, amines or thiols are also preferred.
  • compounds obtained by replacing the unsaturated carboxylic acids by unsaturated phosphonic acids, vinyl benzene derivatives such as styrene, vinyl ethers, allyl ethers or the like can also be used.
  • the polymerizable compounds also preferably include compounds having a boiling point of 100 °C or more under atmospheric pressure and containing at least one addition polymerizable ethylenically unsaturated group.
  • examples of such compounds include monofunctional acrylates and
  • methacrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, and phenoxyethyl
  • (meth) acrylate polyfunctional acrylates and methacrylate such as polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol
  • (meth) acrylate trimethylolpropane tri (acryloyloxypropyl ) ether, tri (acryloyloxyethyl) isocyanurate, compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as glycerin or trimethylolethane and then
  • polyfunctional (meth) acrylates obtained by reacting a polyfunctional carboxylic acid with a compound having a cyclic ether group and an ethylenically unsaturated group such as glycidyl (meth) acrylate and the like.
  • Other preferred polymerizable compounds that can be used include the cardo resins described in JP-A2010-160418 , JP-A2010-129825, Japanese Patent No. 4364216 and the like, i.e., the compounds having a fluorene ring and two or more ethylenically
  • radically polymerizable monomers represented by the formulae (MO-1) to (MO-5) below can also be conveniently used. It should be noted that when T is an oxyalkylene group in the formulae, it is bonded to R at the carbon atom end.
  • n 0 to 14, and m is 1 to 8.
  • R and T occurring more than one time in one molecule may each be the same or different.
  • Specific examples of the radically polymerizable monomers represented by the formulae (MO-1) to (MO-5) above include the compounds described in paragraphs 0248 to 0251 of JP-A2007-269779, which can also be conveniently used in the present invention.
  • preferred polymerizable compounds include dipentaerythritol triacrylate (commercially available under the brand name KAYARAD D-330 from Nippon Kayaku Co., Ltd.), dipentaerythritol tetraacrylate (commercially available under the brand name KAYARAD D-320 from Nippon Kayaku Co., Ltd.), dipentaerythritol penta (meth) acrylate (commercially available under the brand name KAYARAD D-310 from Nippon Kayaku Co. , Ltd. ) , dipentaerythritol hexa (meth) acrylate (commercially available under the brand name KAYARAD DPHA from Nippon Kayaku Co. , Ltd. ) , and those structures in which the (meth) acryloyl has been introduced via an ethylene glycol or propylene glycol group. Oligomers of these compounds can also be used.
  • the polymerizable compounds may be polyfunctional monomers having an acid group such as a carboxyl group, sulfonic acid group, or phosphoric acid group.
  • an acid group such as a carboxyl group, sulfonic acid group, or phosphoric acid group.
  • ethylenic compounds having an unreacted carboxyl group as in the case of mixtures as described above can be directly used, or if desired, a non-aromatic carboxylic anhydride may be reacted with the hydroxyl group of the ethylenic compounds to introduce an acid group.
  • the monomers having an acid value are preferably polyfunctional monomers consisting of esters of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid in which an unreacted hydroxyl group of the aliphatic polyhydroxy compound has been reacted with a non-aromatic carboxylic anhydride to introduce an acid group, especially preferably those esters in which the aliphatic polyhydroxy compound is pentaerythritol and/or
  • dipentaerythritol dipentaerythritol .
  • They include polybasic acid-modified acrylic oligomers commercially available from, for example, Toagosei Co., Ltd. under the brand names M-510, M-520 and the like.
  • a polyfunctional monomer having a caprolactone structure is preferably contained as a polymerizable monomer.
  • the polyfunctional monomer having a caprolactone structure is not specifically limited so far as it has a caprolactone structure in the molecule, but exemplified by ⁇ -caprolactone-modified polyfunctional (meth) acrylates obtained by esterifying a polyhydric alcohol such as trimethylolethane,
  • ditrimethylolethane trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol or trimethylol melamine with (meth) acrylic acid and ⁇ -caprolactone .
  • polyfunctional monomers having a caprolactone structure represented by formula (1) below are preferred.
  • R represents a hydrogen atom or a methyl group
  • m represents an integer of 1 or 2
  • the asterisk (*) represents the bonding point, while the remainder are a group represented by formula (3) below:
  • R represents a hydrogen atom or a methyl group
  • the asterisk (*) represents the bonding point
  • the polyfunctional monomers having a caprolactone structure can be used alone or as a mixture of two or more of them.
  • specific monomers in the present invention also preferably include at least one selected from compounds .
  • the total number of acryloyl and methacryloyl groups is three or four, m each independently represents an integer of 0 to 10, and the sum of m is an integer of 0 to 40 provided that when the sum of m is zero, any one of X is a carboxyl group.
  • the total number of acryloyl and methacryloyl groups is five or six, n each independently represents an integer of 0 to 10, and the sum of n is an integer of 0 to 60 provided that when the sum of n is zero, any one of X is a carboxyl group.
  • m is preferably an integer of 0 to 6, more preferably an integer of 0 to 4.
  • m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, especially preferably an integer of 4 to 8.
  • n is preferably an integer of 0 to 6, more preferably an integer of 0 to .
  • n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24 , especially preferably an integer of 6 to 12.
  • the total content of the compounds represented by formula (i) or (ii) in a specific monomer is preferably 20 % by mass or more, more preferably 50 % by mass or more.
  • dipentaerythritol by a ring-opening addition reaction of ethylene oxide or propylene oxide; and reacting e.g.,
  • examples include the compounds represented by formula (a) to (f) below (hereinafter also referred to as "exemplary compounds (a) to (f)”), among which exemplary compounds (a) , (b) , (e) and (f) are preferred.
  • compositions having a very high exposure speed can be obtained by using the addition
  • polymerizable compounds include the urethane oligomers UAS-10 and UAB-140 (from Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 (from Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (from Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (from Kyoeisha Chemical Co. , Ltd.) and the like.
  • UAS-10 and UAB-140 from Sanyo Kokusaku Pulp Co., Ltd.
  • UA-7200 from Shin-Nakamura Chemical Co., Ltd.
  • DPHA-40H from Nippon Kayaku Co., Ltd.
  • UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 from Kyoeisha Chemical Co. , Ltd.
  • polyfunctional thiol compounds having two or more mercapto (SH) groups in the same molecule are preferred.
  • those represented by formula (I) below are preferred.
  • R 1 represents an alkyl group
  • R 2 represents an n-valent aliphatic group, which may contain atom(s) other than carbon atom
  • R° represents an alkyl group but not H
  • n represents 2 to 4.
  • the polyfunctional thiols are desirably incorporated into the compositions in the range of 0.3 to 8.9 % by weight, more preferably 0.8 to 6.4 % by weight of the total solids excluding the solvent.
  • the compositions can be improved in stability, odor, sensitivity, resolution, developability, adhesion and the like by adding the polyfunctional thiols.
  • polymerizable compounds having a functionality of three or more and different ethylene oxide chain lengths are preferably used in combination because the developability of the compositions can be optimized and excellent patternability can be achieved.
  • the method for selecting / using polymerizable compounds is also an important factor for compatibility and dispersibility with other components contained in the compositions (e.g., photoinitiators, colorants (pigments), binder polymers and the like) , and for example, compatibility can be sometimes improved by using low-purity compounds or combining two or more compounds. It is also possible to select a specific structure to improve adhesion to hard surfaces such as substrates.
  • These other polymerizable compounds in the compositions of the present invention are preferably contained at 30 % by mass or less, more preferably 10 % by mass or less of the amount of the all polymerizable compounds.
  • the radiation-sensitive compositions of the present invention comprise inorganic particles.
  • the inorganic particles are preferably a metal oxide including, for example, Ti0 2 , Zr0 2 , Si0 2 , BeO, gO, CaO, SrO, BaO, Sc 2 0 3 , Y2O3, La 2 0 3 , Ce 2 0 3 , Gd 2 0 3 , Tb 2 0 3 , Dy 2 0 3 , Yb 2 0 3 , Lu 2 0 3 , Hf0 2 , Nb 2 0 5 , Mo0 3 , W0 3 , ZnO, B 2 0 3 , A1 2 0 3 , Ge0 2 , Sn0 2 , PbO, Bi 2 0 3 , Te0 2 , and composite oxides containing them and the like.
  • titanium dioxide is more preferred.
  • the inorganic particles used in the present invention preferably have an average primary particle size (hereinafter sometimes simply referred to as "primary particle size") of 1 nm to 100 nm, more preferably 1 nm to 80 nm, especially preferably 1 nm to 50 nm.
  • primary particle size 1 nm to 100 nm, more preferably 1 nm to 80 nm, especially preferably 1 nm to 50 nm.
  • the refractive index and transmittance of pixels formed by the radiation-sensitive compositions of the present invention can be further improved.
  • the average primary particle size of the inorganic particles can be determined from photographs of dispersed inorganic particles observed by transmission electron microscopy. Specifically, the projected areas of inorganic particles are determined, and the average of their corresponding circle equivalent diameters is reported as the average primary particle size of the inorganic particles. As used herein, the average primary particle size refers to the arithmetic average of the circle equivalent diameters determined for 300 inorganic particles .
  • the average particle size can also be used as an indicator of primary particle size.
  • a mixed solution or dispersion containing inorganic particles is diluted 1:80 with propylene glycol monomethyl ether acetate and the resulting dilution is observed by dynamic light scattering to determine the particle size, which can be used as the average primary particle size of the inorganic particles in the present invention.
  • This measurement represents the number average particle size obtained by using Microtrac (brand name) UPA-EX150 from NIKKISO CO., LTD.
  • the refractive index of the inorganic particles in the present invention are not specifically limited, but preferably 1.70 to 2.70, more preferably 1.90 to 2.70 to provide a high refractive index.
  • the inorganic particle preferably has a specific surface area of 10 m 2 /g to 400 m 2 /g, more preferably 20 m 2 /g to 200 m 2 /g, especially preferably 30 m 2 /g to 150 m/g.
  • the shape of the inorganic particle is not specifically limited, and can be, for example, rice grain-like, spherical, cubic, spindle-like or irregular.
  • the inorganic particle in the present invention may have been surface-treated with an organic compound.
  • organic compounds used for surface treatment of the inorganic particle include polyol, alkanolamine, stearic acid, silane coupling agents and titanate coupling agents. Among others, silane coupling agents are preferred.
  • the surface treatment may be performed with a single
  • Titanium dioxide used in the present invention may be commercially available. These commercially available products specifically include, for example, TTO series (TTO-51 (A) , TTO-5KC), TTO-55(C), etc.), TTO-S, V series (TTO-S-1, TTO-S-2, TTO-V-3, etc.) (all brand names from ISHIHARA SANGYO KAISHA, LTD.), MT series (MT-01, T-05, etc.) (brand name from Tayca Corporation) and the like.
  • TTO series TTO-51 (A) , TTO-5KC), TTO-55(C), etc.
  • TTO-S V series
  • TTO-S-1, TTO-S-2, TTO-V-3, etc. all brand names from ISHIHARA SANGYO KAISHA, LTD.
  • MT series MT-01, T-05, etc.
  • inorganic particles may be used alone or as a combination of two or more of them in the present invention.
  • the inorganic particle may be prepared as an inorganic particle dispersion containing the inorganic particles and a dispersant (see the description herein below as for details of dispersants) , and the inorganic particle dispersion may be added to the radiation-sensitive compositions.
  • the inorganic particles are preferably contained in the inorganic particle dispersion at 10 % by mass to 50 % by mass, more preferably 15 % by mass to 40 % by mass, even more preferably 15 % by mass to 35 % by mass.
  • the content of the inorganic particles based on the total solids of the radiation-sensitive compositions i.e., the content of the inorganic particles (the total content if two or more types are used) based on the all components excluding the solvent is preferably 10 % by mass to 95 % by mass, more preferably 15 % by mass to 90 % by mass, even more preferably 15 % by mass to 70 % by mass, still more preferably 18 % by mass to 50 % by mass, especially preferably 20 % by mass to 40 % by mass.
  • compositions of the present invention comprise a dispersant.
  • Dispersants that can be used in the present invention include polymeric dispersants [for example, polyamidoamines and their salts, polycarboxylic acids and their salts, high-molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates,
  • polymeric dispersants for example, polyamidoamines and their salts, polycarboxylic acids and their salts, high-molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, modified poly (meth) acrylates,
  • polyoxyethylene alkylphosphoric acid esters polyoxyethylene alkylamines, alkanolamines and the like.
  • Polymeric dispersants can be further classified by their structure into straight chain polymers, terminally modified polymers, graft polymers, and block polymers.
  • Terminally modified polymers having a surface-anchoring moiety include, for example, the polymers having a terminal phosphoric acid group described in JP-A-H3-112992 ,
  • JP-A2003-533455 and the like the polymers having a terminal sulfonic acid group described in JP-A2002-273191 and the like; the polymers having a partial skeleton or heterocycle of an organic dye described in JP-A-H9-77994 and the like; the polymers prepared by modification with an oligomer or polymer having a hydroxyl or amino group at one end and with an acid anhydride described in JP-A2008-29901 and the like; etc.
  • polymers containing two or more terminal anchoring moieties for surfaces of infrared blocking material are also preferred because of excellent dispersion stability.
  • Graft polymers having a surface-anchoring moiety include, for example, the reaction products of a poly (lower alkyleneimine) and a polyester described in JP-A-S54-37082 , JP-A-H8-507960, JP-A2009-258668 and the like; the reaction products of a polyallylamine and a polyester described in JP-A-H9-169821 and the like; the amphoteric dispersant resins having a basic group and an acidic group described in JP-A2009-203462; the copolymers of a macromonomer and a nitrogen-containing monomer described in JP-A-H10-339949, JP-A2004-37986 and the like; the graft polymers having a partial skeleton or heterocycle of an organic dye described in JP-A2003-238837, JP-A2008-9426, JP-A2008-81732 and the like; the copolymers of a macromonomer and an acid
  • Macromonomers that can be used for preparing graft polymers having a surface-anchoring moiety by radical
  • polymerization include known macromonomers such as
  • AA-6 methyl polymethacrylate having a terminal methacryloyl group
  • AS-6 polystyrene having a terminal methacryloyl group
  • AN-6S a styrehe-acrylonitrile copolymer having a terminal methacryloyl group
  • AB-6 butyl polyacrylate
  • PLACCELs FM5 an adduct of 2-hydroxyethyl methacrylate with 5 molar equivalents of ⁇ -caprolactone
  • FA10L an adduct of
  • macromonomers having high flexibility and affinity for solvents are especially preferred to improve the dispersibility and dispersion stability of infrared-blocking materials in the compositions and the developability shown by the compositions using the infrared-blocking materials, among which those represented by the polyester macromonomers described in
  • JP-A-H2-272009 are especially preferred.
  • Preferred block polymers having a surface-anchoring moiety include the block polymers described in JP-A2003-49110, JP-A2009-52010 and the like.
  • polycarboxylic acids available from BYK Chemie; "EFKA 4047, 4050 to 4010 to 4165 (polyurethane polymers), EFKA 4330 to 4340 (block copolymers) , 4400 to 4402 (modified polyacrylates) , 5010 (polyester amide) , 5765 (high-molecular weight polycarboxylic acid salt) , 6220 (fatty acid polyester) , 6745 (phthalocyanine derivative) " available from EFKA; "AJISPER PB821, PB822, PB880, PB881” available from Aj inomoto Fine-Techno Co., Inc.; "FLOWLEN TG-710 (urethane oligomer)", and "POLYFLOW No. 50E, No. 300 (acrylic copolymers)” available from Kyoeisha Chemical Co., Ltd.; "DISPARLON KS-860, 873SN, 874, #2150 (aliphatic
  • polycarboxylic acids #7004 (polyether ester) , DA-703-50,
  • DA-705, DA-725" available from Kusumoto Chemicals, Ltd.; "DEMOL RN, N (naphthalenesulfonic acid / formaldehyde polycondensates ) , MS, C, SN-B (aromatic sulfonic acid / formaldehyde polycondensates) ", “H0M0GEN0L L-18 (polycarboxylate polymer) "EMULGEN 920, 930, 935, 985 (polyoxyethylene nonylphenyl ethers)", and “ACETAMIN 86 ( stearylamine acetate)” available from Kao Corporation; "Solsperse 5000 (phthalocyanine derivative), 13240 (polyester amine), 3000, 17000, 27000 (terminally functionalized polymers) , 24000, 28000, 32000, 38500 (graft polymers)” available from Lubrizol Japan Limited; "Nikkol T106 (polyoxyethylene sorbitan monooleate)
  • dispersants may be used alone or as a combination of two or more of them. Further, the dispersants of the present invention may be used as a combination of the terminally modified polymers having an anchoring moiety for surfaces of infrared blocking materials, the graft polymers or the block polymers with alkali-soluble resins.
  • Such alkali-soluble resins include (meth) acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers and the like, as well as acidic cellulose derivatives having a carboxylic acid in the side chain and resins obtained by modifying a hydroxyl-containing polymer with an acid anhydride, among which (meth) acrylic acid copolymers are especially preferred.
  • JP-A-H7-319161 are also preferred.
  • the resins described in JP-A2010-106268 shown.below are preferred to improve dispersibility, developability and precipitation, among which polymeric dispersants having a polyester chain in the side chain are especially preferred to improve dispersibility while resins having an acid group and a polyester chain are preferred to improve dispersibility and resolution of patterns formed by photolithography.
  • Preferred acid groups in the dispersants are acid groups having a pKa of 6 or less because of adsorptivity, among which carboxylic acids, sulfonic acids and phosphoric acid are especially preferred.
  • a preferred dispersant is a graft copolymer having a grafted chain containing 40 to 10000 atoms excluding hydrogen atoms selected from a polyester structure, a polyether structure, and a polyacrylate structure in the molecule, and preferably containing at least a structural unit represented by any one of formula (1) to formula (4) below, more preferably at least a structural unit represented by any one of formula (1A) , formula (2A) , formula (3), and formula (4) below.
  • W 1 , W 2 , W 3 and W 4 each independently represent an oxygen atom or NH, especially preferably an oxygen atom.
  • X 1 , X 2 , X 3 , X 4 and X 5 each independently represent a hydrogen atom or a monovalent organic group.
  • X 1 , X 2 , X 3 , X 4 and X 5 preferably represent a hydrogen atom, or a Cl-12 alkyl group, more preferably a hydrogen atom or a methyl group, especially preferably a methyl group because of synthetic limitations .
  • Y 1 , Y 2 , Y 3 and Y 4 are each independently a divalent linking group without any specific structural limitation.
  • the divalent linking group represented by Y 1 , Y 2 , Y 3 and Y 4 is exemplified by the linking groups (Y-l) to (Y-21) shown below and the like .
  • a and B represent bonds to the left terminal group and the right terminal group respectively in formula (1) to formula (4) .
  • (Y-2) and (Y-13) are more preferred because of ease of synthesis.
  • Z 1 , Z 2 , Z 3 and Z 4 are each independently a monovalent organic group without any specific structural limitation, but specifically include alkyl group, hydroxyl group, alkoxy group, aryloxy group or heteroaryloxy group, alkylthioether group, arylthioether group or
  • the monovalent organic groups represented by Z 1 , Z 2 , Z 3 and Z 4 preferably have a steric repulsion effect especially to improve dispersibility, wherein the organic groups represented by Z 1 to Z 3 are preferably each independently a C5-24 alkyl group or a C5-24 alkoxy group, especially preferably each independently an alkoxy group containing a C5-24 branched chain alkyl group or an alkoxy group containing a C5-24 cyclic alkyl group.
  • the organic group represented by Z 4 is each independently a C5-24 alkyl group, especially preferably each independently a C5-24 branched chain alkyl group or a C5-24 cyclic alkyl group.
  • n, m, p and q are each an integer of 1 to 500.
  • j and k each independently represent an integer of 2 to 8.
  • j and k are preferably an integer of 4 to 6, especially preferably 5 to improve dispersion stability and developability.
  • R 3 represents a branched or straight chain alkylene group.
  • R 3 is preferably a Cl-10 alkylene group, more preferably a C2 or C3 alkylene group.
  • R 4 represents a hydrogen atom or a monovalent organic group, and the monovalent organic group is not specifically limited in structure.
  • R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, more preferably a hydrogen atom or an alkyl group.
  • the alkyl group is preferably a Cl-20 straight chain alkyl group, a C3-20 branched chain alkyl group, or a C5-20 cyclic alkyl group, more preferably a Cl-20 straight chain alkyl group, especially preferably a Cl-6 straight chain alkyl group.
  • two or more R 4 groups having different structures may be used in combination in the graft copolymer.
  • the graft copolymer preferably contains a structural units represented by formula (1) to formula (4) in the range of 10 % to 90 %, more preferably in the range of 30 % to 70 % by mass based on the total mass of the graft copolymer.
  • a structural unit represented by formula (1) to formula (4) is contained in such ranges, pigments are dispersed well and light-shielding films are formed with good developability.
  • the graft copolymer may contain two or more graft copolymers of different structures.
  • the structural unit represented by formula (1) above is more preferably a structural unit represented by formula (1A) below to improve dispersion stability and developability.
  • the structural unit represented by formula (2) above is more preferably a structural unit represented by formula (2A) below to improve dispersion stability and developability.
  • X 1 , Y 1 , Z 1 and n have the same meanings as defined for X 1 , Y 1 , Z 1 and n in formula (1) , and also cover similar preferred ranges.
  • X 2 , Y 2 , Z 2 and m have the same meanings as defined forX 2 , Y 2 , Z 2 and m in formula (2), and also cover similar preferred ranges.
  • the structural unit represented by formula (3) below is more preferably a structural unit represented by formula (3A) or formula (3B) below to improve dispersion stability and developability.
  • X 3 , Y 3 , Z 3 and p have the same meanings as defined for X 3 , Y 3 , Z 3 and p in formula (3) above, and also cover similar preferred ranges.
  • the dispersant used in the present invention is especially preferably an oligoimine dispersant containing a nitrogen atom in at least one of the main chain and side chain.
  • the oligoimine dispersant in the present invention is preferably a dispersant resin comprising: a repeat unit containing a partial structure X ional group having a pKa of 14 or less; and a side chain having an oligomer chain or polymer chain Y containing 40 to 10,000 atoms; wherein at least one of the main chain and side chain bears a basic nitrogen atom (hereinafter referred to as "oligoimine dispersant" as appropriate) .
  • the basic nitrogen atom here is not specifically limited so far as it is a nitrogen atom showing basicity.
  • the oligoimine dispersant preferably contains a structure having a nitrogen atom having a pK b of 14 or less, more preferably contains a structure having a nitrogen atom having a pK of 10 or less.
  • the basicity strength pK b refers to a pK b at a water temperature of 25 °C, which is one of indicators quantitatively expressing the strength of a base and synonymous with basicity constant.
  • the partial structure X having a functional group having a pKa of 14 or less in the oligoimine dispersant is the same as the partial structure X described herein below in the explanation of specific resins as preferred embodiments of the oligoimine dispersant .
  • the oligomer chain or polymer chain Y containing 40 to 10,000 atoms borne by the side chain of the oligoimine dispersant is also the same as the oligomer chain or polymer chain Y containing 40 to 10,000 atoms described herein below in the explanation of specific resins.
  • An example of the oligoimine dispersant is a resin containing the repeat unit containing a group X having a functional group having a pKa of 14 or less represented by the formula below; the repeat unit having a basic nitrogen atom represented by the formula below; and the repeat unit having an oligomer chain or polymer chain Y containing 40 to 10,000 atoms represented by the formula below (corresponding to the structures of the repeat units shown below in order from the left) or the like .
  • x, y and z each represent the polymerization molar ratio of the repeat unit, and preferably x is 5 to 50, y is 5 to 60, and z is 10 to 90.
  • 1 represents the number of linked polyester chains corresponding to an integer capable of forming an oligomer chain or polymer chain containing 40 to 10,000 atoms, preferably 70 to 2000 atoms.
  • the oligoimine dispersant is more preferably a dispersant resin comprising: a repeat unit having a basic nitrogen atom to which a partial structure X having a functional group having a pKa of 14 or less is bonded; and a side chain having an oligomer chain or polymer chain Y containing 40 to 10,000 atoms .
  • the oligoimine dispersant is especially preferably a dispersant resin comprising: (i) at least one repeat unit having a basic nitrogen atom selected from a poly (lower alkyleneimine) repeat unit, a polyallylamine repeat unit, a polydiallylamine repeat unit, an m-xylylenediamine-epichlorohydrin
  • oligoimine dispersant (1) oligoimine dispersant
  • the oligoimine dispersant (1) comprises (i) at least one repeat unit having a basic nitrogen atom selected from a poly (lower alkyleneimine) repeat unit, a polyallylamine repeat unit, a polydiallylamine repeat unit, an
  • the poly may have a linear or network structure.
  • the lower alkyleneimine refers to an alkyleneimine containing a Cl-5 alkylene chain.
  • the at least one repeat unit having a basic nitrogen atom selected from a poly (lower alkyleneimine) repeat unit, a polyallylamine repeat unit, a polydiallylamine repeat unit, an m-xylylenediamine-epichlorohydrin polycondensate repeat unit, and a polyvinylamine repeat unit (i) preferably forms the main chain moiety in a specific dispersant resin.
  • the number average molecular weight of the main chain moiety i.e., the number average molecular weight of the moiety of the oligoimine dispersant (1) excluding the side chain having an oligomer chain or polymer chain Y moiety is preferably 100 to 10,000, more preferably 200 to 5, 000, especially preferably 300 to 2, 000.
  • the number average molecular weight of the main chain moiety can be determined from the proportion of the integral of the hydrogen atoms in the terminal groups and the main chain moiety measured by nuclear magnetic resonance spectroscopy or by measuring the molecular weight of a starting amino-containing oligomer or polymer.
  • the repeat unit having a basic nitrogen atom (i) is especially preferably a poly (lower alkyleneimine) repeat unit or a polyallylamine repeat unit.
  • the oligoimine dispersant (1) comprising the repeat unit (i) is preferably a dispersant resin comprising the repeat unit represented by formula (1-1) and the repeat unit represented by formula (1-2), or the repeat unit represented by formula (II-l) and the repeat unit represented by formula (II-2).
  • R 1 and R 2 each independently represent a hydrogen atom, a halogen atom or an alkyl group, a each independently represents an integer of 1 to 5.
  • the asterisk (*) represents the junction between the repeat units.
  • X represents a group having a functional group having a pKa of 14 or less.
  • Y represents an oligomer chain or polymer chain containing 40 to 10,000 atoms.
  • the oligoimine dispersant (1) preferably comprises the repeat unit represented by formula (1-3) as a component to be copolymer!zed.
  • the oligoimine dispersant (1) comprises such a repeat unit, the dispersibility in the radiation-sensitive compositions of the present invention can be further improved.
  • R 1 , R 2 and a have the same meanings as defined for R 1 , R 2 and an in formula (1-1) .
  • Y' represents an oligomer chain or polymer chain containing 40 to 10,000 atoms and having an anion group.
  • the repeat unit represented by formula (1-3) can be formed by adding an oligomer or polymer having a group reacting with an amine to form a salt to a resin having a primary or secondary amino group in the main chain moiety to react them.
  • R 1 and R 2 are especially preferably a hydrogen atom, a is preferably 2 because of the availability of starting materials.
  • the oligoimine dispersant (1) may comprise a lower alkyleneimine containing a primary or tertiary amino group as a repeat unit. Further, the group represented by X, Y or Y' may be bonded to the nitrogen atom in such a lower alkyleneimine repeat unit. A resin containing both of a repeat unit having the group represented by X bonded thereto and a repeat unit having the group represented by Y bonded thereto in such a main chain structure is also included in the oligoimine dispersant (1) .
  • the repeat unit represented by formula (1-1) is a repeat unit having a basic nitrogen atom to which is bonded a partial structure X having a functional group having a pKa of 14 or less, and such a repeat unit having a basic nitrogen atom is preferably contained at 1 to 80 mol %, especially preferably 3 to 50 mol % of the all repeat units contained in the oligoimine dispersant (1) because of shelf stability and developability.
  • the repeat unit represented by formula (1-2) is a repeat unit having an oligomer chain or polymer chain containing 40 to 10,000 atoms, and such a repeat unit is preferably contained at 10 to 90 mol %, especially preferably 30 to 70 mol % of the all repeat units contained in the oligoimine dispersant (1) because of shelf stability.
  • the ratio of the contents of the repeat unit (1-1) and the repeat unit (1-2) [(1-1) : (1-2)] is preferably in the range of 10:1 to 1:100, more preferably in the range of 1:1 to 1:10 expressed in molar ratio to achieve dispersion stability and
  • the optional repeat unit represented by formula (1-3) wherein the partial structure having an oligomer chain or polymer chain Y' containing 40 to 10,000 atoms is ionically bonded to the nitrogen atom of the main chain is preferably contained at 0.5 to 20 mol %, especially preferably 1 to 10 mol % of the all repeat units contained in the oligoimine dispersant (1) because of effectiveness.
  • the ionic bond of the polymer chain Y' can be ascertained by infrared spectroscopy or base titration.
  • R 3 , R 4 , R 5 and R 6 each independently represent a hydrogen atom, a halogen atom or an alkyl group.
  • the asterisk (*) , X and Y have the same meanings as defined for the asterisk (*) , X and Y in formulae (1-1) and (1-2).
  • the oligoimine dispersant (1) preferably further comprises the repeat unit represented by formula (II-3) as a component to be copolymer!zed.
  • the combination use with such a repeat unit allows further improvements in dispersion performance in the radiation-sensitive compositions of the present invention.
  • R 3 , R 4 , R 5 and R 6 have the same meanings as defined for R 3 , R 4 , R 5 and R 6 in formula (II-l) .
  • Y' has the same meaning as defined for Y' in formula (1-3).
  • R 3 , R 4 , R 5 and R 6 are preferably a hydrogen atom because of the availability of starting materials.
  • Formula (II-l) represents a repeat unit having a basic nitrogen atom to which is bonded a partial structure X having a functional group having a pKa of 14 or less, and such a repeat unit having a basic nitrogen atom is preferably contained at 1 to 80 mol %, especially preferably 3 to 50 mol % of the all repeat units contained in the oligoimine dispersant (1) because of shelf stability and developability.
  • Formula (II-2) represents a repeat unit having an oligomer chain or polymer chain Y containing 40 to 10, 000 atoms, and such a repeat unit is preferably contained at 10 to 90 mol %, especially preferably 30 to 70 mol % of the all repeat units in the oligoimine dispersant (1) because of shelf stability.
  • the ratio of the contents of the repeat unit (II-l) and the repeat unit (II-2) [(II-l): (II-2) ] is preferably in the range of 10:1 to 1:100, more preferably in the range of 1:1 to 1:10 expressed in molar ratio to achieve dispersion stability and hydrophilic/hydrophobic balance.
  • the optional repeat unit represented by formula (II-3) is preferably contained at 0.5 to 20 mol %, especially preferably 1 to 10 mol % of the all repeat units contained in the oligoimine dispersant (1) .
  • the oligoimine dispersant (1) is especially preferably an embodiment specifically containing both of the repeat unit represented by formula (I-l) and the repeat unit represented by formula (1-2) because of dispersibility.
  • the partial structure X having a functional group having a pKa of 14 or less is explained below.
  • X bears a functional group having a pKa of 14 or less at a water temperature of 25 °C.
  • pKa is as defined in Handbook of Chemistry (II) (Revised 4th Edition, 1993, Edited by The Chemical Society of Japan, published by Maruzen Company, Limited) .
  • the "functional group having a pKa of 14 or less” is not specifically limited in its structure or the like so far as its properties satisfy this criterion, and any known functional groups having a pKa satisfying the above range are included, specifically preferably a functional group having a pKa of 12 or less, especially preferably a functional group having a pKa of 11 or less.
  • the partial structure X is specifically, for example, a carboxylic acid group (pKa: about 3 to 5) , a sulfonic acid group (pKa: about -3 to -2) , -COCH 2 CO- (pKa: about 8 to 10) , -COCH 2 CN (about pKa: 8 to 11) , -CONHCO-, a phenolic hydroxyl group, -R F CH20H or -(R F ) 2CHOH wherein R F represents a perfluoroalkyl group (pKa: about 9 to 11), a sulfonamide group (pKa: about 9 to 11) or the like, especially preferably a carboxylic acid group (pKa: about 3 to 5) , a sulfonic acid group (pKa: about -3 to -2) , or -COCH2CO- (pKa: about 8 to 10).
  • R F represents a perfluoroalkyl group (
  • partial structure X bears a functional group having a pKa of 14 or less, interaction with titanium dioxide particles can be achieved.
  • This partial structure X having a functional group having a pKa of 14 or less is preferably directly bonded to the basic nitrogen atom in the basic nitrogen atom-having repeat unit.
  • the nitrogen atom in the basic nitrogen atom-having repeat unit and the partial structure X may be linked not only via a covalent bond but also via an embodiment in which they are ionically bonded to each other to form a salt.
  • the partial structure X having a functional group having a pKa of 14 or less especially preferably has a structure represented by formula (V-l) , formula (V-2) or formula (V-3) below.
  • U represents a single bond or a divalent linking group.
  • d and e each independently represent 0 or 1.
  • Q represents an acyl group or an alkoxycarbonyl group.
  • the divalent linking group represented by U is, for example, an alkylene (more specifically, e.g., -CH 2 -, -CH2CH2- , -CH 2 CHMe-, -(CH 2 ) 5 -/ ⁇ CH 2 CH (n-Ci 0 H 2 i) - and the like), an oxygen-containing alkylene (more specifically, e.g., -CH2OCH2- , -CH2CH2OCH2CH2- and the like), an arylene (e.g., phenylene, tolylene, biphenylene, naphthylene, furanylene, pyrrolylene and the like), an alkyleneoxy (e.g., ethyleneoxy, propyleneoxy, phenyleneoxy and the like) or the like, among which a Cl-30 alkylene groups or a C6-20 arylene group is preferred, especially preferably a Cl-20 alkylene group or a C6-15 arylene group.
  • d d
  • Q represents an acyl group or an alkoxycarbonyl group.
  • the acyl group represented by Q is preferably a Cl-30 acyl group (e.g., formyl, acetyl, n-propanoyl, benzoyl and the like), especially preferably acetyl.
  • the alkoxycarbonyl group represented by Q is especially preferably an acyl group, preferably an acetyl group because of the ease of preparation and the availability of starting materials (precursor X' for X) .
  • the partial structure X in the present invention is preferably bonded to the basic nitrogen atom in the basic nitrogen atom-having repeat unit. Thereby, the dispersibility and dispersion stability of titanium dioxide particles dramatically improve. The reason for this is unknown, but may be explained as follows. It is thought that the partial structure X acts as an acid group and therefore can interact with metal atoms (Ti) contained in titanium dioxide particles, whereby adsorptivity increases and dispersibility and shelf stability dramatically improve .
  • Ti metal atoms
  • partial structure X confers solubility in solvents to inhibit deposition of resins over time, thereby contributing to dispersion stability.
  • the partial structure X bears a functional group having a pKa of 14 or less, and therefore also acts as an alkali-soluble group. This may lead to the result that when a coating layer formed from a radiation-sensitive composition of the present invention is partially cured by exposure to an energy and unexposed regions are removed by dissolution to form a pattern, the developability of the uncured regions with alkaline developing solutions improves, thereby achieving dispersibility, dispersion stability and developability simultaneously.
  • the content of the functional group having a pKa of 14 or less in the partial structure X is not specifically limited, but preferably 0.01 to 5 mmol, especially preferably 0.05 to 1 mmol per gram of the oligoimine dispersant (1) .
  • the dispersibility and dispersion stability of titanium dioxide particles improve and the developability of uncured regions improve when a cured film is formed from a radiation-sensitive composition of the present invention.
  • the content is preferably selected in such a manner that the acid value of the oligoimine dispersant (1) falls within about 5 to 50 mg KOH/g to improve developability when a cured film is formed from a radiation-sensitive composition of the present invention.
  • the oligomer chain or polymer chain Y containing 40 to 10,000 atoms is explained below.
  • Y may be a known polymer chain that can be linked to the main chain moiety of the oligoimine dispersant (1), such as polyester, polyamide, polyimide or poly (meth) acrylic acid ester.
  • the point of attachment of Y to the oligoimine dispersant (1) is preferably an end of the oligomer chain or polymer chain Y.
  • Y is preferably attracted to the nitrogen atom of at least one nitrogen atom-having repeat unit selected from a poly (lower alkyleneimine) repeat unit, a polyallylamine repeat unit, a polydiallylamine repeat unit, an
  • Y m-xylylenediamine-epichlorohydrin polycondensate repeat unit, and a polyvinylamine repeat unit.
  • polycondensate repeat unit, and a polyvinylamine repeat unit or the like is a covalent bond, an ionic bond or a mixture of covalent and ionic bonds.
  • Y is preferably bonded to the nitrogen atom of the basic nitrogen atom-having repeat unit via an amide bond or as a carboxylic acid salt via an ionic bond.
  • the oligomer chain or polymer chain Y preferably contains 50 to 5,000 atoms, more preferably 60 to 3,000 atoms to improve dispersibility, dispersion stability and developability.
  • the oligomer chain or polymer chain Y contains less than 40 atoms per chain, the grafted chain is short so that steric repulsion effect decreases and dispersibility may decrease. If the oligomer chain or polymer chain contains more than 10000 atoms per chain, however, the oligomer chain or polymer chain Y is too long so that the adsorptivity to titanium dioxide particles decreases and dispersibility may decrease.
  • the number average molecular weight of Y can be determined as a polystyrene equivalent molecular weight by GPC.
  • the number average molecular weight of Y is specifically preferably 1,000 to 50,000, especially preferably 1,000 to 30,000 because of dispersibility, dispersion stability and developability.
  • the side chain structure represented by Y is preferably linked to the main chain sequence at a ratio of two or more moieties, especially preferably five or more moieties in one resin molecule .
  • Y preferably has a structure represented by formula (III-l) .
  • Z represents a polymer or oligomer ing a polyester chain as a partial structure derived by removing the carboxyl group from a polyester having a free carboxylic acid represented by formula (IV) below.
  • Z has the same meaning as defined for Z in formula (III-l) .
  • Y' preferably represents formula (III-2) .
  • the polyester having a carboxyl group at one end can be obtained by (IV-1) polycondensation of a carboxylic acid with a lactone, (IV-2) polycondensation of a hydroxy-containing carboxylic acid, (IV-3) polycondensation of a dihydric alcohol with a dicarboxylic acid (or a cyclic anhydride) or the like.
  • the carboxylic acid used in (IV-1) polycondensation reaction of a carboxylic acid with a lactone is an aliphatic carboxylic acid (preferably a Cl-30 straight or branched chain carboxylic acid, e.g., formic acid, acetic acid, propionic acid, butyric acid, valeric acid, n-hexanoic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, palmitic acid,
  • hydroxy-containing carboxylic acid preferably a Cl-30 straight or branched chain hydroxy-containing carboxylic acid, e.g., glycolic acid, lactic acid, 3-hydroxypropionic acid,
  • 4-hydroxydodecanoic acid 5-hydroxydodecanoic acid, ricinoleic acid, 12-hydroxydodecanoic acid, 12-hydroxystearic acid,
  • Lactones that can be used include known lactones such as, e.g., ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -butyrolactone, ⁇ -hexalactone, ⁇ -octalactone, ⁇ -valerolactone, ⁇ -hexalactone, ⁇ -octalactone, ⁇ -caprolactone, ⁇ -dodecalactone, -methyl-y-butyrolactone and the like, especially preferably ⁇ -caprolactone because of reactivity and availability.
  • lactones can be used as a mixture of different types.
  • the dihydric alcohol includes a straight or branched chain aliphatic diol (preferably a C2-30 diol, e.g., ethylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, 1, 2-propanediol,
  • the dicarboxylic acid includes a straight or branched chain aliphatic dicarboxylic acid (preferably a Cl-30 aliphatic dicarboxylic acid, e.g., succinic acid, maleic acid, adipic acid, sebacic acid, dodecanoic diacid, glutaric acid, suberic acid, tartaric acid, oxalic acid, malonic acid and the like) , especially preferably a C3-20 dicarboxylic acid.
  • Acid anhydrides corresponding to these dicarboxylic acids e.g., succinic anhydride, glutaric anhydride and the like
  • the dicarboxylic acids and dihydric alcohols are preferably introduced in a molar ratio of 1:1. Thereby, a carboxylic acid can be terminally introduced.
  • the polycondensation during the preparation of the polyester preferably takes place by adding a catalyst.
  • the catalyst preferably acts as a Lewis acid, and specifically includes, for examples, Ti compounds (e.g., Ti(OBu) 4 , Ti(0-Pr) 4 and the like), Sn compounds (e.g., tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyloxide, stannic chloride and the like), protonic acids (e.g., sulfuric acid, p-toluenesulfonic acid and the like) , etc.
  • Ti compounds e.g., Ti(OBu) 4 , Ti(0-Pr) 4 and the like
  • Sn compounds e.g., tin octylate, dibutyltin oxide, dibutyltin laurate, monobutyltin hydroxybutyloxide, stannic chloride and the like
  • the amount of the catalyst is preferably 0.01 mol % to 10 mol %, especially preferably 0.1 mol % to 5 mol % based on the number of moles of the all monomers.
  • the reaction temperature is preferably 80 °C to 250 °C, especially preferably 100 °C to 180 °C.
  • the reaction period depends on the reaction conditions, but generally ranges from 1 hour to 24 hours.
  • the number average molecular weight of the polyester can be determined as a polystyrene equivalent molecular weight by GPC.
  • the number average molecular weight of the polyester is 1,000 to 1,000,000, preferably 2,000 to 100,000, especially preferably 3, 000 to 50, 000. When the molecular weight is in the above ranges, both dispersibility and developability improve.
  • oligoimine dispersants including the oligoimine dispersant (1) are shown below by listing specific structures of repeat units contained in the resins and combinations thereof, but the present invention is not limited to these embodiments.
  • p and q represent the number of polyester chains linked, and each independently represent 5 to 100,000.
  • R' represents a hydrogen atom or an alkoxycarbonyl group.
  • the oligoimine dispersant (1) can be synthesized by (1) reacting a resin having a primary or secondary amino group with a precursor x for the partial structure X and a precursor y for Y; (2) polymerizing a monomer containing a structure
  • the partial structure X and a macromonomer containing Y, or the like is prepared by initially synthesizing a resin having a primary or secondary amino group in the main chain and then reacting a precursor x for X and a precursor y for Y with the resin to introduce them into the nitrogen atom present in the main chain by polymer reaction.
  • the resin having a primary or secondary amino group may be an oligomer or polymer containing a primary or secondary amino group constituting the main chain moiety having a nitrogen atom, examples of which include poly (lower alkyleneimine) ,
  • oligomer or polymer consisting of a poly (lower alkyleneimine) or a polyallylamine is preferred.
  • the precursor x for the partial structure X having a functional group having a pKa of 14 or less refers to a compound capable of reacting with the resin having a primary or secondary amino group to introduce X into the main chain.
  • Examples of x include cyclic carboxylic anhydrides (preferably C4-30 cyclic carboxylic anhydrides, e.g., succinic anhydride, glutaric anhydride, itaconic anhydride, maleic anhydride, allylsuccinic anhydride, butylsuccinic anhydride,
  • cyclic carboxylic anhydrides preferably C4-30 cyclic carboxylic anhydrides, e.g., succinic anhydride, glutaric anhydride, itaconic anhydride, maleic anhydride, allylsuccinic anhydride, butylsuccinic anhydride,
  • halogen-containing carboxylic acids e.g., bicyclo [2.2.2] oct-7-ene-2, 3, 5, 6-tetracarboxylic dianhydride, pyromellitic dianhydride, meso-butane-1, 2, 3, 4-tetracarboxylic dianhydride, 1, 2, 3, 4-cyclopentanecarboxylic dianhydride and the like); halogen-containing carboxylic acids (e.g.,
  • 4-chloro-n-butyric acid and the like 4-chloro-n-butyric acid and the like); sultones (e.g., propanesultone, 1, -butanesultone and the like); diketenes; cyclic sulfocarboxylic anhydrides (e.g., 2-sulfobenzoic anhydride and the like) ; -COCH 2 COCl-containing compounds (e.g., ethyl malonyl chloride and the like) ; or cyanoacetic acid chloride and the like; especially preferably cyclic carboxylic anhydrides, sultones and diketenes because of productivity.
  • sultones e.g., propanesultone, 1, -butanesultone and the like
  • diketenes cyclic sulfocarboxylic anhydrides (e.g., 2-sulfobenzoic anhydride and the like) ;
  • the precursor y for the oligomer chain or polymer chain Y containing 40 to 10,000 atoms refers to a compound capable of reacting with the resin having a primary or secondary amino group to introduce the oligomer chain or polymer chain Y.
  • y is preferably an oligomer or polymer containing 40 to 10,000 atoms having a terminal group that can be covalently or ionically bonded to the nitrogen atom of the oligoimine dispersant (1), especially preferably an oligomer or polymer containing 40 to 10,000 atoms having a free carboxyl group at one end.
  • Examples of y include a polyester having a free carboxylic acid at one end represented by formula (IV) , a polyamide having a free carboxylic acid at one end, a poly (meth) acrylic acid resin having a free carboxylic acid at one end and the like, among which a polyester having a free carboxylic acid at one end represented by formula (IV) is especially preferred.
  • y can be synthesized by a known method.
  • a polyester having a free carboxylic acid at one end represented by formula (IV) can be prepared by (IV-1) polycondensation of a carboxylic acid with a lactone, (IV-2) polycondensation of a hydroxy-containing carboxylic acid, or (IV-3) polycondensation of a dihydric alcohol with a dicarboxylic acid (or a cyclic anhydride) as described above.
  • a polyamide having a free carboxylic acid at one end can be prepared by self-condensation of an amino-containing carboxylic acid (e.g., glycine, alanine, ⁇ -alanine, 2-aminobutyric acid or the like) or the like.
  • a poly (meth) acrylic acid ester having a free carboxylic acid at one end can be prepared by radical polymerization of a
  • carboxyl-containing chain transfer agent e.g., N-(2-aminoethyl)-2-aminoethyl-containing chain transfer agent
  • the oligoimine dispersant (1) can be prepared by (a) reacting the resin having a primary or secondary amino group with x and y simultaneously; or (b) reacting the resin having a primary or secondary amino group with x, and then with y; or (c) reacting the resin having a primary or secondary amino group with y, and then with x. Especially preferred is the method of (c) reacting the resin having a primary or secondary amino group with y, and then with x.
  • reaction temperature can be appropriately selected depending on the conditions, but preferably ranges from 20 to
  • reaction period is preferably 1 to 48 hours, more preferably 1 to 24 hours to improve productivity.
  • the reaction may be performed in the presence of a solvent .
  • the solvent includes water, sulfoxide compounds (e.g., dimethyl sulfoxide and the like) , ketone compounds (e.g. , acetone, methyl ethyl ketone, cyclohexanone and the like) , ester compounds (e.g., ethyl acetate, butyl acetate, ethyl propionate, propylene glycol 1-monomethyl ether 2-acetate and the like) , ether compounds (e.g., diethyl ether, dibutyl ether, tetrahydrofuran and the like) , aliphatic hydrocarbon compounds (e.g., pentane, hexane and the like), aromatic hydrocarbon compounds (e.g., toluene, xylene, mesitylene and the like) , nitrile compounds (e.g., acetonitrile, pro
  • N-methylpyrrolidone and the like N-methylpyrrolidone and the like
  • carboxylic acid compounds e.g., acetic acid, propionic acid and the like
  • alcohol compounds e.g., methanol, ethanol, isopropanol, n-butanol, 3-methylbutanol, l-methoxy-2-propanol and the like
  • halogenated solvents e.g., chloroform, 1 , 2-dichloroethane and the like
  • a solvent when used, it should preferably be used 0.1 to 100-fold by mass, especially preferably 0.5 to 10-fold by mass based on the substrate.
  • the oligoimine dispersant (1) of the present invention may be purified by reprecipitation .
  • the oligoimine dispersant (1) obtained by removing low-molecular weight components by reprecipitation is used as a dispersant, dispersion performance improves.
  • Reprecipitation is preferably performed by using a hydrocarbon solvent such as hexane or an alcoholic solvent such as methanol.
  • the oligoimine dispersant (1) in the present invention obtained in this manner preferably has a weight average molecular weight of 3,000 to 100,000, more preferably 5,000 to 55,000 as determined by GPC.
  • a weight average molecular weight of 3,000 to 100,000, more preferably 5,000 to 55,000 as determined by GPC.
  • the presence of a nitrogen atom in the nitrogen atom-having repeat unit (i) in the oligoimine dispersant (1) can be ascertained by acid titration or the like technique, while the presence of a functional group having a pKa of 14 or less and the attachment of the functional group to the nitrogen atom of the repeat unit can be ascertained by acid titration, nuclear magnetic resonance spectroscopy, infrared spectroscopy or the like technique. Further, the presence of (ii) an oligomer chain or polymer chain Y containing 40 to 10,000 atoms in the side chain can be ascertained by nuclear magnetic resonance spectroscopy, GPC or the like technique.
  • oligoimine dispersants (1) are described along with their molecular weights below.
  • the dispersants can be used alone or as a combination of two or more of them.
  • the content of the dispersants (the total content if two or more dispersants are used) based on the total solids of the radiation-sensitive compositions of the present invention is preferably in the range of 5 to 50 % by mass, more preferably in the range of 5 to 40 % by mass, even more preferably in the range of 5 to 30 % by mass, still more preferably 5 to .20 % by mass to improve dispersibility and dispersion stability.
  • compositions of the present invention preferably further comprise a polymerization initiator to further improve sensitivity.
  • Polymerization initiators that can be used in the present invention are those known as polymerization initiators described below.
  • the polymerization initiator is not specifically limited so far as it has the ability to initiate polymerization of the polymerizable compound, and it can be appropriately selected from known polymerization initiators. For example, it is preferably sensitive to radiations from UV to visible regions. Further, it may be an activator producing some reaction with a photoexcited sensitizer to generate active radicals or an initiator functioning to initiate cationic polymerization depending on the types of monomers .
  • the polymerization initiator preferably contains at least one compound having a molecular absorption coefficient of at least about 50 in the range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm) .
  • the polymerization initiators include, for example, halogenated hydrocarbon derivatives (e.g., those having a triazine skeleton, those having an oxadiazole skeleton, and the like) , acyl phosphine compounds such as acyl phosphine oxide, hexaaryl biimidazole, oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, hydroxyacetophenone and the like.
  • halogenated hydrocarbon derivatives e.g., those having a triazine skeleton, those having an oxadiazole skeleton, and the like
  • acyl phosphine compounds such as acyl phosphine oxide, hexaaryl biimidazole
  • oxime compounds such as oxime derivatives, organic peroxides, thio compounds, ketone compounds
  • the halogenated hydrocarbon compounds having a triazine skeleton include, for example, the compounds described in Bull. Chem. Soc. Japan, 42, 2924 (1969) by akabayashi et al. ; the compounds described in British Patent No. 1388492; the compounds described in JP-A-S53-133428 ; the compounds described in German Patent No. 3337024; the compounds described in J. Org. Chem.: 29, 1527 (1964) by F.C. Schaefer et al.; the compounds described in JP-A-S62-58241; the compounds described in JP-A-H5-281728 ; the compounds described in JP-A-H5-34920; the compounds described in US Patent No. 4212976 and the like.
  • the compounds described in US Patent No.4212976 include, for example, compounds having an oxadiazole skeleton (e.g., 2-trichloromethyl-5-phenyl-l , 3, 4-oxadiazole,
  • Polymerization initiators other than those described above include acridine derivatives (e.g., 9-phenylacridine, 1, 7-bis (9, 9' -acridinyl) heptane and the like), N-phenylglycine and the like, polyhalogen compounds (e.g., carbon tetrabromide, phenyl tribromomethyl sulfone, phenyl trichloromethyl ketone and the like), coumarins (e.g.,
  • the ketone compounds include, for example, benzophenone,
  • Hydroxyacetophenone compounds, aminoacetophenone compounds, and acyl phosphine compounds can also be conveniently used as polymerization initiators. More specifically, for example, the aminoacetophenone initiators described in
  • JP-A-H10-291969 and the acyl phosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
  • Hydroxyacetophenone initiators that can be used include
  • IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959 and IRGACURE-127 all brand names from BASF.
  • Aminoacetophenone initiators that can be used include commercially available products IRGACURE-907 , IRGACURE-369, and IRGACURE-379 (all brand names from BASF) .
  • Other aminoacetophenone initiators that can be used include the compounds having an absorption wavelength matched to a source of long wave radiation such as 365 nm or 405 nm described in JP-A2009-191179.
  • Acyl phosphine initiators that can be used include commercially available products IRGACURE-819 and DAROCUR-TPO (both brand names from BASF) .
  • Polymerization initiators more preferably include oxime compounds.
  • oxime initiators that can be used include the compounds described in JP-A2001-233842, the compounds described in JP-A2000-80068 , and the compounds described in JP-A2006-342166.
  • Oxime compounds such as oxime derivatives conveniently used as polymerization initiators in the present invention include, for example, 3-benzoyloxyiminobutan-2-one,
  • Oxime ester compounds include the compounds described inJ.C.S. Perkin II (1979) pp. 1653-1660, J.C.S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp.202-232 and JP-A2000-66385; the compounds described in JP-A2000-80068, JP-A2004-534797, and JP-A2006-342166 and the like.
  • IRGACURE-OXE01 from BASF
  • IRGACURE-OXE02 from BASF
  • Oxime ester compounds other than those described above that may be used include the compounds having an oxime bonded to the nitrogen atom of a carbazole described in JP-A2009-519904; the compounds containing a heterosubstituent in the benzophenone moiety described in US Patent No. 7626957; the compounds containing a nitro group in a dye moiety described in
  • the cyclic oxime compounds described in JP-A2007-231000 and JP-A2007-322744 can also be conveniently used.
  • the cyclic oxime compounds annulated with a carbazole dye described in JP-A2010-32985 and JP-A2010-185072 are especially preferred because they have high light absorption and high sensitivity.
  • oxime compounds having an unsaturated bond at a specific site described in JP-A2009-242469 can also be conveniently used because they can achieve high sensitivity by regenerating active radicals from polymerization-inactive radicals .
  • oxime compounds having a specific substituent shown in JP-A2007-269779 and the oxime compounds having a thioaryl group shown in JP-A2009-191061.
  • a preferred oxime polymerization initiator is a compound represented by formula (OX-1) below. It should be noted that the oxime compound may be the (E) -isomer or the (Z) -isomer or a mixture of the (E) -isomer and the (Z) -isomer depending on the geometry of the N-0 bond of the oxime.
  • R and B each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group.
  • the monovalent non-metal group may be alkyl, aryl, acyl, alkoxycarbonyl, aryloxycarbonyl, heterocycle,
  • alkylthiocarbonyl arylthiocarbonyl or the like. These groups may have one or more substituents .
  • the substituents listed above may be further substituted by another substituent.
  • the substituents include a halogen atom, aryloxy, alkoxycarbonyl or aryloxycarbonyl, acyloxy, acyl, alkyl, aryl and the like.
  • the optionally substituted alkyl is preferably Cl-30 alkyl, example of which specifically include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, octadecyl, isopropyl, isobutyl, sec-butyl, t-butyl, 1-ethylpentyl, cyclopentyl, cyclohexyl, trifluoromethyl , 2-ethylhexyl, phenacyl, 1-naphthoylmethyl , 2-naphthoylmethyl, 4-methylsulfanylphenacyl, 4-phenylsulfanylphenacyl,
  • the optionally substituted aryl is preferably C6-30 aryl, example of which specifically include phenyl, biphenyl,
  • hexaphenyl hexacenyl, rubicenyl, coronenyl, trinaphthylenyl, heptaphenyl, heptacenyl, pyranthrenyl, and ovalenyl.
  • the optionally substituted acyl is preferably C2-20 acyl, example of which specifically include acetyl, propanoyl, butanoyl, trifluoroacetyl, pentanoyl, benzoyl, 1-naphthoyl,
  • the optionally substituted alkoxycarbonyl is preferably C2-20 alkoxycarbonyl, example of which specifically include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl,
  • optionally substituted aryloxycarbonyls specifically include phenoxycarbonyl, 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl, 4-methylsulfanylphenyloxycarbonyl , 4-phenylsulfanylphenyloxycarbonyl,
  • the optionally substituted heterocycle is preferably an aromatic or aliphatic heterocycle containing a nitrogen atom, oxygen atom, sulfur atom or phosphorus atom.
  • optionally substituted alkylthiocarbonyls specifically include methylthiocarbonyl, propylthiocarbonyl, butylthiocarbonyl, hexylthiocarbonyl, octylthiocarbonyl, decylthiocarbonyl, octadecylthiocarbonyl, and
  • Optionally substituted arylthiocarbonyls specifically include 1-naphthylthiocarbonyl, 2-naphthylthiocarbonyl,
  • the monovalent substituent represented by B is aryl, heterocycle, arylcarbonyl or heterocyclic carbonyl. These groups may have one or more substituents. Examples of substituents include those listed above. Moreover, the substituents listed above may be further substituted by another substituent.
  • Y, X and n have the same meanings as defined herein below for Y, X and n respectively in formula (OX-2) , and also include similar preferred examples.
  • the divalent organic group represented by A includes Cl-12 alkylene, cycloalkylene, and alkynylene. These groups may have one or more substituent. Examples of substituents include those listed above. Moreover, the substituents listed above may be further substituted by another substituent.
  • a in formula (OX-1) is preferably an unsubstituted alkylene, an alkylene substituted by alkyl (e.g., methyl, ethyl, tert-butyl, dodecyl) , an alkylene substituted by alkenyl (e.g., vinyl, allyl) , or an alkylene substituted by aryl (e.g., phenyl, p-tolyl, xylyl, cumenyl, naphthyl, anthryl, phenanthryl, styryl) to increase sensitivity and inhibit discoloration by heat over time.
  • alkyl e.g., methyl, ethyl, tert-butyl, dodecyl
  • alkenyl e.g., vinyl, allyl
  • aryl e.g., phenyl, p-tolyl, xylyl, cumenyl, naphthyl,
  • the aryl represented by Ar is preferably C6-30 aryl, which may have a substituent.
  • substituents include those similar to the substituents on the substituted aryls listed as specific examples of optionally substituted aryls.
  • a substituted or unsubstituted phenyl is preferred to increase sensitivity and inhibit discoloration by heat over time .
  • the structure of the "SAr" formed by Ar in formula (OX-1) above together with adjacent S is preferably any one of the structures shown below to improve sensitivity, wherein Me represents methyl, and Et represents ethyl.
  • the oxime compound is preferably a compound represented by formula (OX-2) below.
  • R and X each independently represent a monovalent substituent
  • a and Y each independently represent a divalent organic group
  • Ar represents an aryl group
  • n is an integer of 0 to 5.
  • the monovalent substituent represented by X may be alkyl, aryl, alkoxy, aryloxy, acyloxy, acyl, alkoxycarbonyl, amino, heterocycle, or a halogen atom. Further, these groups may have one or more substituents .
  • substituents include those listed above. Moreover, the substituents listed above may be further substituted by another substituent.
  • X in formula (OX-2) is preferably alkyl to improve solubility in solvents and absorption in long wavelength regions .
  • n in formula (OX-2) represents an integer of 0 to 5, preferably an integer of 0 to 2.
  • the divalent organic group represented by Y may be any one of the structures shown below wherein the asterisk (*) represents the bonding point of Y to an adjacent carbon atom in formula (OX-2) above.
  • the oxime compound is preferably a compound represented by formula (OX-3) below.
  • R and X each independently represent a monovalent substituent
  • A represents a divalent organic group
  • Ar represents an aryl group
  • n is an integer of 0 to 5.
  • R, X, A, Ar and n have the same meanings as defined for R, X, A, Ar and n respectively in formula (OX-2) above, and also include similar preferred examples.
  • the oxime compound has a maximum absorption wavelength in the wavelength region of 350 nm to 500 nm, preferably has an absorption wavelength in the wavelength region of 360 nm to 480 nm, especially preferably has a high absorbance at 365 nm and 455 nm.
  • the oxime compound preferably has a molar absorption coefficient of 1, 000 to 300, 000, more preferably 2 , 000 to 300, 000, especially preferably 5,000 to 200,000 at 365 nm or 405 nm to improve sensitivity.
  • the molar absorption coefficient of the compound can be determined by known methods, and specifically, it is preferably determined at a concentration of 0.01 g/L in ethyl acetate as a solvent by using an ultraviolet-visible spectrophotometer (Carry-5 spectrophotometer from Varian) , for example.
  • an ultraviolet-visible spectrophotometer Carry-5 spectrophotometer from Varian
  • Two or more of the polymerization initiators may be used in combination in the present invention, if desired.
  • the polymerization initiator used in the compositions of the present invention is preferably a compound selected from the group consisting of trihalomethyl triazine compounds, benzil dimethyl ketal compounds, a-hydroxyketone compounds,
  • ⁇ -aminoketone compounds acyl phosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triaryl imidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxadiazole compounds, and
  • it is at least one compound selected from the group consisting of trihalomethyl triazine compounds, a-aminoketone compounds, acyl phosphine compounds, phosphine oxide compounds, oxime compounds, triaryl imidazole dimers, onium compounds, benzophenone compounds, and acetophenone compounds; most preferably trihalomethyl triazine compounds, a-aminoketone compounds, oxime compounds, triaryl imidazole dimers, and benzophenone compounds.
  • compositions of the present invention are used to prepare color filters for solid-state image sensors, it is important that they should be not only readily curable but also developable without leaving residue in unexposed regions because well-defined micropatterns must be formed.
  • oxime compounds are especially preferred for use as polymerization initiators.
  • stepper exposure systems are used for curing but such exposure systems may be damaged by halogens and the amount of polymerization initiators added must be reduced, which leads to the conclusion that oxime compounds are most preferred for use as polymerization initiators for forming such micropatterns as in solid-state image sensors.
  • the content of the polymerization initiators in the compositions of the present invention is preferably 0.1 % by mass or more and 50 % by mass or less, more preferably 0.5 % by mass or more and 30 % by mass or less, even more preferably 1 % by mass or more and 20 % by mass or less based on the total solids of the compositions. When it is in such ranges, good sensitivity and patternability can be achieved.
  • compositions of the present invention typically can be prepared by using a solvent.
  • the solvent is not specifically limited so far as the solubility of various components and the coatability of the compositions are satisfied.
  • two or more solvents may be used.
  • Solvents preferably include esters such as, e.g., ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, alkyl oxyacetate (such as methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl
  • 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate, ethyl 3-oxypropionate and the like (e.g., methyl
  • 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate and the like (e.g. , methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl
  • 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; ketones such as, e.g., methyl ethyl ketone, cyclohexanone,
  • solvents are also preferably used as a mixture of two or more of them to improve the solubility of UV absorbers and alkali-soluble resins, the state of coated surfaces or the like.
  • mixed solutions composed of two or more members selected from methyl
  • mixed solvents of ethers and ketones are preferred because the radiation-sensitive compositions can be prevented from precipitation over time during cold storage.
  • a mixed solution composed of propylene glycol monomethyl ether acetate and cyclohexanone among the above list.
  • the proportion of the mixed solution preferably consists of 5 to 90 % by mass, more preferably 10 to 85 % by mass, even more preferably 15 to 80 % by mass of cyclohexanone in the organic solvents in the radiation-sensitive compositions.
  • the increase of impurity defects during cold storage of resists can be effectively reduced by adding cyclohexane as a solvent. This may be attributed to the improvements in compatibility between various components in the compositions, which prevented impurities from being deposited over time.
  • radiation-sensitive compositions is selected in such a manner that the total solids content of the compositions preferably account for 5 to 80 % by mass, more preferably 5 to 75 % by mass, especially preferably 10 to 65 % by mass to improve coatability.
  • compositions of the present invention preferably contain an alkali-soluble resin as a binder polymer.
  • alkali-soluble resin is contained, developability and patternability are improved.
  • the alkali-soluble resin can be appropriately selected from alkali-soluble resins consisting of a high-molecular weight organic linear polymer containing at least one group promoting alkali solubility in the molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as the main chain) .
  • alkali-soluble resins consisting of a high-molecular weight organic linear polymer containing at least one group promoting alkali solubility in the molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as the main chain) .
  • Polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred to improve heat resistance, while acrylic resins, acrylamide resins, and acrylic/acrylamide copolymer resins are preferred for optimizing developability.
  • Groups promoting alkali solubility include, for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, a phenolic hydroxyl group and the like, preferably those soluble in solvents and developable with aqueous solutions of weak bases, especially preferably (meth) acrylic acid.
  • acid groups may be contained alone or as a combination of two or more of them.
  • polymerization include, for example, hydroxyl-containing monomers such as 2-hydroxyethyl (meth) acrylate;
  • epoxy-containing monomers such as glycidyl (meth) acrylate; isocyanate-containing monomers such as 2-isocyanatoethyl (meth) acrylate; and the like.
  • These monomers for introducing an acid group may be used alone or as a combination of two or more of them.
  • monomer for introducing an acid group may be used as a monomer component and polymerized, for example. It should be noted that when a monomer capable of donating an acid group after polymerization is used as a monomer component to introduce the acid group, a treatment for donating the acid group as described herein below, for example, is required after polymerization.
  • High-molecular weight organic linear polymers used as alkali-soluble resins are preferably polymers having a carboxylic acid in the side chain, e.g., methacrylic acid copolymers, acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenol resins such as Novolac resins and the like; and acidic cellulose derivatives having a carboxylic acid in the side chain, and the adducts of hydroxyl-containing polymers with acid anhydrides.
  • methacrylic acid copolymers e.g., acrylic acid copolymers, itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, alkali-soluble phenol resins such as Novolac resins and the like
  • copolymers of (meth) acrylic acid and other monomers polymerizable therewith are preferred as alkali-soluble resins.
  • Other monomers polymerizable with (meth) acrylic acid include alkyl, (meth) acrylates, aryl (meth) acrylates, vinyl compounds and the like.
  • Alkyl (meth) acrylates and aryl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl
  • vinyl compounds include styrene, a-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone,
  • N-substituted maleimide monomers described in JP-A-H10-300922 include N-phenylmaleimide, N-cyclohexylmaleimide and the like. These other monomers polymerizable with (meth) acrylic acid may be used alone or as a combination of two or more of them.
  • the alkali-soluble resin also preferably comprises a polymer obtained by polymerizing a monomer component essentially based on a compound (hereinafter sometimes referred to as "ether dimer”) represented by formula (ED) below:
  • R 1 and R 2 each independently represent a hydrogen atom or an optionally substituted Cl-25 hydrocarbon group.
  • the optionally substituted Cl-25 hydrocarbon group represented by R 1 and R 2 is not specifically limited, but includes, for example, a straight or branched chain alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, t-amyl, stearyl, lauryl, or 2-ethylhexyl; an aryl group such as phenyl; an alicyclic group such as cyclohexyl, t-butylcyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl, or 2-methyl
  • ether dimer examples include, for example, dimethyl-2, 2' - [oxybis (methylene) ] bis-2-propenoate,
  • dicyclohexyl-2 , 2 '- [oxybis (methylene) ] bis-2-propenoate, and dibenzyl-2, 2' - [oxybis (methylene) ] bis-2-propenoate are examples of dicyclohexyl-2 , 2 '- [oxybis (methylene) ] bis-2-propenoate, and dibenzyl-2, 2' - [oxybis (methylene) ] bis-2-propenoate.
  • ether dimers may be used alone or as a combination of two or more of them. Structures derived from the compound represented by formula (ED) above may be
  • the alkali-soluble phenol resins can be conveniently used when the compositions of the present invention are used as positive resist compositions.
  • the alkali-soluble phenol resins include, for example, Novolac resins, or vinyl polymers and the like .
  • the Novolac resins include, for example, those obtained by condensing a phenol with an aldehyde in the presence of an acid catalyst.
  • the phenol includes, for example, phenol, cresol, ethylphenol, butylphenol, xylenol, phenylphenol, catechol, resorcinol, pyrogallol, naphthol, or bisphenol A or the like.
  • the aldehyde includes, for example, formaldehyde,
  • the phenols and aldehydes can be used alone or as a combination of two or more of them.
  • Novolac resins include, for example, the condensation products of m-cresol, p-cresol or a mixture thereof with formaldehyde.
  • the molecular weight distribution of the Novolac resins may be modified by fractionation or other means. Further, the Novolac resins may be mixed with low-molecular weight components having a phenolic hydroxyl group such as bisphenol C and bisphenol A.
  • an alkali-soluble resin having a polymerizable group may be used.
  • Useful alkali-soluble resins having a polymerizable group are alkali-soluble resins containing an allyl, (meth) acryl or allyloxyalkyl group or the like in the side chain and the like.
  • Examples of the polymers having a polymerizable group include Dianal NR series (from Mitsubishi Rayon Co., Ltd.); Photomer 6173 (a COOH-containing polyurethane acrylic oligomer from Diamond Shamrock Co. , Ltd.
  • VISCOAT R-264 and KS RESIST 106 both available from Osaka Organic Chemical Industry Ltd.
  • CYCLOMER P Series and PLACCEL CF200 Series both available from Daicel Chemical Industries, Ltd. (now Daicel Corporation)
  • Ebecryl 3800 from Daicel-UCB Co., Ltd.
  • alkali-soluble resins containing a polymerizable group preferably include urethane-modified polymerizable double bond-containing acrylic resins obtained by preliminarily reacting isocyanate groups and OH groups except that one isocyanate group remains unreacted and reacting a (meth) acryloyl-containing compound and a carboxyl-containing acrylic resin; unsaturated group-containing acrylic resins obtained by reacting a carboxyl-containing acrylic resin and a compound containing both of an epoxy group and a polymerizable double bond in the molecule; acid pendant epoxy acrylate resins; polymerizable double bond-containing acrylic resins obtained by reacting an OH-containing acrylic resin and a dibasic acid anhydride containing a polymerizable double bond; the resins obtained by reacting an OH-containing acrylic resin and a compound containing an isocyanate and a polymerizable group; the resins obtained by basic treatment of a resin containing an ester group having a leaving group such as a
  • alkali-soluble resins are benzyl (meth) acrylate/ (meth) acrylic acid copolymers and
  • (meth) acrylate/ (meth) acrylic acid/other monomers examples include 2-hydroxyethyl methacrylate copolymers; the 2-hydroxypropyl (meth) acrylate/polystyrene
  • the alkali-soluble resin preferably has an acid value of 30 mg KOH/g to 200 mg KOH/g, more preferably 50 mg KOH/g to 150 mg KOH/g, most preferably 70 to 120 mg KOH/g.
  • the alkali-soluble resin preferably has a weight average molecular weight (Mw) of 2,000 to 50,000, more preferably 5,000 to 30,000, most preferably 7,000 to 20,000.
  • the alkali-soluble resin When the alkali-soluble resin is contained, its content in the compositions is preferably 1 to 40 % by mass, more preferably 10 to 35 % by mass, especially preferably 15 to 30 % by mass based on the total solids of the compositions. Only one or two or more alkali-soluble resins may be contained, and when two or more are contained, the total amount should be within the above ranges.
  • compositions of the present invention may contain a UV absorber.
  • UV absorbers that can be used include salicylate, benzophenone, benzotriazole, substituted acrylonitrile, and triazine UV absorbers.
  • salicylate UV absorbers examples include phenyl salicylate, p-octylphenyl salicylate,/ p-t-butylphenyl salicylate and the like; and examples of benzophenone UV absorbers include
  • benzotriazole UV absorbers examples include
  • Examples of substituted acrylonitrile UV absorbers include ethyl 2-cyano-3, 3-diphenylacrylate, 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate and the like.
  • examples of triazine UV absorbers include mono (hydroxyphenyl ) triazine compounds such as
  • compositions of the present invention a conjugated diene compound represented by formula (I) below is also preferably used as a UV absorber.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group containing 1 to 20 carbon atoms, or an aryl group containing 6 to 20 carbon atoms, and R 1 and R 2 may be the same or different provided that both cannot simultaneously be a hydrogen atom.
  • the alkyl group containing 1 to 20 carbon atoms represented by R 1 and R 2 includes, for example, methyl, ethyl, propyl, n-butyl, n-hexyl, cyclohexyl, n-decyl, n-dodecyl, n-octadecyl, eicosyl, methoxyethyl, ethoxypropyl, 2-ethylhexyl, hydroxyethyl, chloropropyl, ⁇ , ⁇ -diethylaminopropyl, cyanoethyl, phenethyl, benzyl, p-t-butylphenethyl, p-t-octylphenoxyethyl, 3- (2, 4-di-t-amylphenoxy) propyl, ethoxycarbonylmethyl,
  • the alkyl group represented by R 1 and R 2 may have a substituent, and the substituent on the substituted alkyl group includes alkyl, aryl, alkoxy, aryloxy, acyloxy, halogen atom, acylamino, acyl, alkylthio, arylthio, hydroxy, cyano, alkyloxycarbonyl, aryloxycarbonyl, substituted carbamoyl, substituted sulfamoyl, nitro, substituted amino, alkylsulfonyl, arylsulfonyl and the like .
  • the aryl group containing 6 to 20 carbon atoms represented by R 1 and R 2 may be a monocyclic or fused ring, and may be substituted or unsubstituted. Examples include phenyl,
  • the substituent on the substituted aryl includes, for example, alkyl, aryl, alkoxy, aryloxy, acyloxy, halogen atom, acylamino, acyl, alkylthio, arylthio, hydroxy, cyano, alkyloxycarbonyl, aryloxycarbonyl, substituted carbamoyl, substituted sulfamoyl, nitro,
  • substituted amino, alkylsulfonyl, arylsulfonyl and the like substituted or unsubstituted phenyl, 1-naphthyl, and 2-naphthyl are preferred.
  • R 1 and R 2 together with a nitrogen atom may form a cyclic amino group.
  • the cyclic amino group includes, for example, piperidino, morpholino, pyrrolidino,
  • R 1 and R 2 are preferably a Cl-8 lower alkyl group (e.g., methyl, ethyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, octyl, 2-ethylhexyl, tert-octyl and the like) ; or a substituted or unsubstituted phenyl (e.g., tolyl, phenyl, anisyl, mesityl, chlorophenyl, 2 , 4-di-t-amylphenyl and the like) .
  • R 1 and R 2 are also preferably joined together with the nitrogen atom represented by N in the formula to form a ring (e.g., piperidine ring, pyrrolidine ring, morpholino ring or the like) .
  • R 3 and R 4 represent an electron withdrawing group.
  • the electron withdrawing group refers to an electron withdrawing group having a Hammett substituent constant ⁇ ⁇ value (hereinafter simply referred to as "Op value”) of 0.20 or more and 1.0 or less. Preferably, it refers to an electron withdrawing group having a o p value of 0.30 or more and 0.8 or less.
  • the Hammett rule is an experimental rule proposed by L. P. Hammett in 1935 to quantitatively explain the influence of substituents on the reaction or equilibrium of benzene derivatives and currently widely recognized as valid.
  • the substituent constants determined by the Hammett rule include o p value and o m value, which are described in many standard textbooks such as, e.g., "Lange's Handbook of Chemistry” edited by J.A. Dean, 12th Edition, 1979 (Mc Graw-Hill); “Fields of Chemistry, Extra Issue", 122, pp. 96-103, 1979 (NankodoCo., Ltd.); and Chemical Reviews, vol. 91, pp. 165-195, 1991.
  • electron withdrawing groups having a ⁇ ⁇ .of 0.20 or more and 1.0 or less include, acyl, acyloxy, carbamoyl, alkyloxycarbonyl, aryloxycarbonyl, cyano, nitro, dialkylphosphono, diarylphosphono, diarylphosphinyl,
  • the groups that may be further substituted may further have such substituents as listed above.
  • R 3 is preferably a group selected from cyano, -COOR 5 , -CONHR 5 , -COR 5 and -S0 2 R 5
  • R 4 is preferably a group selected from cyano, -COOR 6 , -CONHR 6 , -COR 6 and -S0 2 R 6 in the present invention.
  • R 5 and R 6 each independently represent an alkyl group containing 1 to 20 carbon atoms, or an aryl group containing 6 to 20 carbon atoms.
  • the alkyl group containing 1 to 20 carbon atoms and the aryl group containing 6 to 20 carbon atoms represented by R 5 and R 6 are as defined for R 1 and R 2 above and also include similar preferred embodiments.
  • R 3 and R 4 are preferably acyl, carbamoyl,
  • R 3 and R 4 may be joined together to form a ring.
  • R 1 , R 2 , R 3 and R 4 may be in the form of a polymer derived from a monomer bonded to vinyl via a linking group. It may also be a copolymer with another monomer.
  • the other monomers include esters, preferably lower alkyl esters and amides derived from acrylic acids such as acrylic acid, a—chloroacrylic acid and a—acrylic acid (e.g., methacrylic acid) (e.g., acrylamide, methacrylamide, t-butyl acrylamide, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, n-hexyl acrylate, octyl methacrylate and lauryl methacrylate, methylene bisacrylamide and the like), vinyl esters (e.g., vinyl acetate, vinyl propionate and vinyl laurate and the like) , acrylonitrile, methacrylonitrile, aromatic vinyl compounds (e.g., styrene and
  • acrylic acid esters methacrylic acid esters and aromatic vinyl compounds are especially preferred.
  • Two or more of the comonomer compounds can also be used in combination.
  • combinations of n-butyl acrylate with divinyl benzene, styrene with methyl methacrylate, methyl acrylate with methacrylic acid and the like can be used.
  • the compound represented by formula (I) in the present invention can be synthesized by the methods described in JP-B-S44-29620, JP-A-S53-128333, JP-A-S61-169831 ,
  • JP-A-S63-53543 JP-A-S63-53544
  • JP-A-S63-56651 JP-A-S63-56651
  • a diethylamino-phenylsulfonyl-pentadienoate UV absorber from FUJIFILM Finechemicals Co., Ltd. under the brand name DPO
  • DPO diethylamino-phenylsulfonyl-pentadienoate UV absorber
  • compositions of the present invention desirably contain a small amount of a polymerization inhibitor to inhibit the polymerizable compound from undesired heat polymerization during the preparation or storage of the compositions.
  • Polymerization inhibitors that can be used in the present invention include hydroquinone, p-methoxyphenol,
  • the amount of the polymerization inhibitors to be added is preferably about 0.01 % by mass to about 5 % by mass based on the mass of all the components excluding the solvent.
  • compositions of the present invention man contain various surfactants to further improve coatability.
  • Surfactants that can be used include various surfactants such as fluorosurfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants.
  • compositions of the present invention contain a fluorosurfactant
  • the liquid properties (especially flowability) of coating solutions prepared therefrom are further improved so that the uniformity of the coating thickness and the reduction of coating consumption can be further improved.
  • the fluorine content of the fluorosurfactant is preferably 3 % by mass to 40 % by mass, more preferably 5 % by mass to 30 % by mass, especially preferably 7 % by mass to 25 % by mass.
  • Fluorosurfactants having a fluorine content in the above ranges are effective for the uniformity of the thickness of coated films and the reduction of coating consumption, and also highly soluble in the compositions.
  • Fluorosurfactants include, for example, Megafac F171, F172, F173, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F781 (all from DIC Corporation) ; Fluorad FC430, FC431, FC171 (all from Sumitomo 3 Limited) ; SURFLON S-382, SC-101, SC-103, SC-104, SC-105, SC1068, SC-381, SC-383, S393, KH-40 (all from ASAHI GLASS CO., LTD.); PF636, PF656, PF6320, PF6520, PF7002 (from OMNOVA) and the like.
  • Nonionic surfactants specifically include glycerol, trimethylolpropane, trimethylolethane and ethoxylates and propoxylates thereof (e.g., glycerol propoxylate, glycerin ethoxylate and the like) ; polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid esters (Pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 from BASF) , Tetronic 304, 701, 704, 901, 904, 150R1, Solsperse 20000 (from Lubrizol Japan Limited) and the like.
  • glycerol trimethylolpropane, trimethylolethane and ethoxylates and prop
  • Cationic surfactants specifically include
  • phthalocyanine derivatives available from Morishita Sangyo K.K. under the brand name EFKA-745) ; the organosiloxane polymer KP341 (from Shin-Etsu Chemical Co., Ltd.); the (meth) acrylic
  • Anionic surfactants specifically include 004, 005, W017 (from Yusho Co., Ltd.) and the like.
  • Silicone surfactants include, for example, “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Toray Silicone DCllPA”, “Toray Silicone SH21PA”, “Toray Silicone SH28PA”, “Toray
  • the surfactants may be used alone or as a combination of two or more of them.
  • the amount of the surfactants to be added is preferably 0.001 % by mass to 2.0 % by mass, more preferably 0.005 % by mass to 1.0 % by mass based on the total mass of the compositions.
  • the radiation-sensitive compositions of the present invention may contain additives such as accelerators,
  • radiation-sensitive compositions of the present invention have a refractive index of 1.55 to 1.90 for the radiation at a wavelength of 500 nm.
  • the radiation-sensitive compositions of the present invention are transparent compositions, and more specifically, cured films of 0.6 pm in thickness formed from the compositions preferably have a light transmittance of 85 % or more in the direction of the thickness of the cured films over the entire wavelength region of 400 nm to 700 nm.
  • the radiation-sensitive compositions of the present invention preferably have a light transmittance of 85 % or more over the entire wavelength region of 400 nm to 700 nm is because white filter pixels contained in color filters play a sufficient role as white filter pixels (i.e., images are captured by image sensors with high sensitivity) .
  • the light transmittance is preferably 90 % or more, more preferably 95% or more, especially preferably 100 % over the entire wavelength regio of 400 nm to 700 nm.
  • the radiation-sensitive compositions of the present invention are substantially free from colorant (the content of colorants is preferably 0 % by mass based on the total solids of the compositions ) . It should be noted that the titanium dioxide particles and the optional inorganic particles and UV absorbers described above are not included in the colorants here.
  • the radiation-sensitive compositions of the present invention are radiation-sensitive compositions for solid-state image sensors, and they are preferably used for forming pixels of color filters incorporated in solid-state image sensors, more specifically, they are preferably used for white filter pixels in color filters of solid-state image sensors.
  • the radiation-sensitive compositions of the present invention preferably contain sufficiently low levels of impurity metals.
  • the metal levels in the compositions can be determined by ICP-MS or the like with high sensitivity, and the metal levels excluding transition metals as determined by such analysis are preferably 300 ppm or less, more preferably 100 ppm or less.
  • the process for preparing the radiation-sensitive compositions is not specifically limited, but they are obtained by, for example, adding various components to be contained in the compositions to an organic solvent and stirring them.
  • the radiation-sensitive compositions are preferably filtered through a filter for the purpose of removing impurities or reducing defects or for other purposes. Any filters conventionally used for filtration purposes and the like can be used without any specific limitation.
  • materials for the filter include fluororesins such as PTFE (polytetrafluoroethylene) ; polyamide resins such as nylon-6, and nylon-6, 6; polyolefin resins (including high density and ultrahigh molecular weight polyolefins) such as polyethylene, and polypropylene (PP) ; etc.
  • fluororesins such as PTFE (polytetrafluoroethylene)
  • polyamide resins such as nylon-6, and nylon-6, 6
  • polyolefin resins including high density and ultrahigh molecular weight polyolefins
  • polyethylene polyethylene
  • polypropylene polypropylene
  • the pore size of the filter is not specifically limited, but for example about 0.01 to 20.0 ⁇ , preferably about 0.01 to 5 ⁇ , more preferably about 0.01 to 2.0 ⁇ .
  • the pore size of the filter herein can be selected by referring to nominal values specified by filter manufacturers.
  • filters can be selected from various filters supplied by, for example, Nihon Pall Ltd. , Advantec Toyo Kaisha, Ltd., Entegris Japan Co., Ltd. (former Nihon ykrolis K.K.), KITZ MICRO FILTER CORPORATION and the like.
  • the filtration may be performed by using two or more filters in combination.
  • the filtration can be performed by using a first filter initially and then a second filter having a different pore size from that of the first filter.
  • a filter formed from a material similar to those described for the first filter above or the like can be used as the second filter.
  • the radiation-sensitive compositions of the present invention can be cured and preferably used as cured films for various devices or the like. Specifically, they can be used as colored layers of color filters.
  • Examples of devices comprising the color filters of the present invention include solid-state image sensors, liquid crystal display devices and organic EL display devices.
  • a process for preparing a cured film of the present invention comprising the steps of:
  • the process preferably comprises (4) a postbaking step by heat-curing the developed radiation-sensitive composition.
  • a process for preparing a color filter of the present invention is characterized by comprising the steps of: (1) applying a radiation-sensitive composition of the present invention on a substrate (hereinafter also referred to as “the step of forming a radiation-sensitive composition layer”) ; (2) exposing the applied radiation-sensitive composition (hereinafter also referred to as “exposing step”) ; and (3) developing the exposed radiation-sensitive composition. Further, the process preferably comprises (4) a postbaking step by heat-curing the developed radiation-sensitive composition.
  • the substrate on which a pattern is formed by the patterning processes of the present invention is not specifically limited so far as it can be applied for patterning.
  • the color filters of the present invention should comprise at least a transparent (white) pattern consisting of a pixel formed by using a radiation-sensitive composition of the present invention (white filter pixel) .
  • a specific preferred embodiment of a color filter of the present invention is, for example, a multicolor filter comprising a transparent pattern (white filter pixel) in combination with other colored patterns (e.g., a color filter of four or more colors comprising at least a transparent pattern, a red pattern, a blue pattern, and a green pattern) .
  • color filters of the present invention are hereinafter sometimes simply referred to as "color filters”.
  • a radiation-sensitive composition of the present invention is preferably applied on a substrate to form a radiation-sensitive composition layer.
  • the substrate that can be used in this step is, for example, a substrate (e.g., silicon substrate) for solid-state image sensors on which image sensors (photodetectors ) such as CCDs (Charge Coupled Devices) or CMOSs (Complementary Metal-Oxide Semiconductors) are mounted.
  • a substrate e.g., silicon substrate
  • image sensors photodetectors
  • CCDs Charge Coupled Devices
  • CMOSs Complementary Metal-Oxide Semiconductors
  • the transparent pattern in the present invention may be formed on the side of the substrate for solid-state image sensors comprising the image sensors (front side) or the side not comprising the image sensors (backside) .
  • a light-shielding film may be provided between the image sensors on the substrate for solid-state image sensors or on the backside of the substrate for solid-state image sensors.
  • a primer layer may be provided on the substrate to improve adhesion to the overlying layers or to prevent diffusion of substances or to smoothen the surface of the substrate, if desired.
  • the radiation-sensitive composition layer of the present invention can be applied on the substrate by various coating techniques such as slit coating, inkjet coating, spin coating, flow coating, roll coating, and screen printing.
  • the thickness of the radiation-sensitive composition layer is preferably 0.1 ⁇ to 10 ⁇ , more preferably 0.2 um to 5 ⁇ , even more preferably 0.2 ⁇ to 3 ym.
  • the radiation-sensitive composition layer applied on the substrate can be dried (prebaked) by using a hot plate, oven or the like at a temperature of 50 °C to 140 °C for 10 seconds to 300 seconds.
  • the radiation-sensitive composition layer formed during the step of forming a radiation-sensitive composition layer is exposed in a pattern through a mask having a predetermined mask pattern using an exposure system such as a stepper, for example.
  • Radiations (light) that can be used for exposure include visible rays, ultraviolet rays, far-ultraviolet rays, electron beams, X rays and the like, especially preferably ultraviolet rays such as g-line and i-line (especially preferably i-line) .
  • the radiation dose (exposure does) is preferably 30 to 1500 mJ/cm 2 , more preferably 50 to 1000 mJ/cm 2 , especially preferably 80 to 500 mJ/cm 2 .
  • unirradiated during the exposing step dissolve in an aqueous alkaline solution while only photocured regions remain.
  • the developing solution is desirably an organic alkaline developing solution that is harmless to the underlying image sensors or circuits or the like.
  • the developing temperature is typically 20 °C to 30 °C, and the developing period was conventionally 20 seconds to 90 seconds. To further remove residues, development may recently continue for 120 seconds to 180 seconds. Alternatively, the steps of removing the developing solution by spinning every 60 seconds and freshly supplying the developing solution may be repeated several times to further improve removal of residues.
  • Alkaline agents used for developing solutions include, for example, organic alkaline compounds such as aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine,
  • alkaline agents are preferably diluted with pure water to prepare an aqueous alkaline solution at a concentration of 0.001 to 10 % by mass, preferably 0.01 to 1 % by mass and used as a developing solution.
  • Inorganic alkalis may also be used for developing solutions, preferably including, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, sodium silicate, sodium metasilicate and the like.
  • a cured film can be prepared by sequentially repeating the steps described above for each color. Thereby, a color filter is obtained.
  • Postbaking is a heat treatment after development to complete curing, typically a heat curing treatment at 100 °C to 240 °C, preferably 200 °C to 240 °C.
  • This postbaking treatment can be performed on the developed coated layer by continuous or batch operation using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater under the conditions described above.
  • a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater under the conditions described above.
  • the preparation process of the present invention may optionally comprise other steps known for preparation processes of color filters for solid-state image sensors.
  • the process may optionally comprise the step of curing the formed transparent pattern by heating and/or exposure after the step of forming a radiation-sensitive composition layer, exposing step, and developing step.
  • the radiation-sensitive compositions of the present invention When the radiation-sensitive compositions of the present invention are used, ejector nozzles of coaters or pipes may be clogged or the radiation-sensitive compositions or inorganic particles may be deposited / precipitated / dried in coaters to cause contamination or the like, for example.
  • the solvents listed above for the compositions are preferably used as cleaning solutions. Further, the cleaning solutions described in JP-A-H7-128867 , JP-A-H7-146562, JP-A-H8-278637 , JP-A2000-273370 ,
  • JP-A2006-85140, JP-A2006-291191, JP-A2007-2101, JP-A2007-2102 , JP-A2007-281523 and the like can also be conveniently used as cleaning solutions for washing out the radiation-sensitive compositions of the present invention.
  • alkylene glycol monoalkyl ether carboxylate and alkylene glycol monoalkyl ether are preferred.
  • solvents may be used alone or as a mixture of two or more of them.
  • a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group are preferably mixed.
  • the mass ratio of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 80/20.
  • a mixed solvent of propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) at a ratio of 60/40 is especially preferred.
  • the cleaning solution may contain the surfactants listed above for the compositions.
  • the color filters of the present invention can be used in liquid crystal display devices, solid-state image sensors and organic EL devices, especially preferably for applications of solid-state image sensing.
  • the alignment of liquid crystal molecules is less affected by resistivity loss and high-quality images with good hue can be displayed while they contain a metal complex dye having excellent spectroscopic properties and heat resistance as colorants.
  • the color filters of the present invention comprise a colored pixel excellent in hue and light resistance so that they are especially suitable as color filters for liquid crystal display devices. Liquid crystal display devices incorporating such color filters allow high-quality images to be displayed with good hue .
  • the color filters of the present invention are especially effective for color TFT liquid crystal display devices.
  • Color TFT liquid crystal display devices are described in, for example, "Color TFT Liquid Crystal Displays (KYORITSU SHUPPAN CO., LTD., 1996)".
  • the present invention can also be applied to wide viewing angle liquid crystal display devices such as In-Plane Switching (IPS) or Halftone-Grayscale Method such as MVA as well as STN, TN, VA, OCS, FFS, and R-OCB and the like.
  • IPS In-Plane Switching
  • MVA Halftone-Grayscale Method
  • the color filters of the present invention are obtained by combining (A) the metal complex dye with (B) the complex-forming compound of the present invention in the proportions described above and curing them, which may dramatically prevent liquid crystal materials from resistivity loss, thereby eliminating the alignment loss of liquid crystal molecules, i.e., display quality loss. This contributes to improvements in hue such as high color purity, whereby COA mode liquid crystal display devices with high resolution and excellent long-term durability can be provided.
  • a resin coating may be applied on the color filter layer.
  • a conducting path of even 5 pm or less can be formed by using the present invention, consistent with the requirements for COA mode colored layers which must comprise conducting paths for connecting ITO electrodes on the colored layers to the terminals of a driver board under the colored layers such as a square through-hole having a side length of about 1 to 15 ⁇ or a U-shaped groove, especially preferably conducting paths having a size (i.e., side length) of 5 ⁇ or less.
  • image display modes are described in, for example, "EL, PDP, and LCD Displays - The Latest Trends in Technologies and Markets- p. 43
  • the liquid crystal display devices of the present invention comprise various elements such as an electrode substrate, polarizing films, retardation films, a backlight, a spacer, and viewing angle compensation films.
  • the color filters of the present invention can be applied to liquid crystal display devices composed of these known elements. These elements are described in, for example, “'94 The Market of Liquid Crystal Display-Related Materials and Chemicals (Kentaro Shima CMC Publishing Co., Ltd. 1994)"; and "LCD Market 2003 Vol. II - Present Aspect & Future Outlook (Ryokichi Omote Fuji Chimera Research Institute, Inc., 2003)".
  • Liquid crystal display devices using the color filters of the present invention can achieve high contrast when they are combined with a three-wavelength tube of a conventionally known cold cathode tube, and they can further provide liquid crystal display devices with high luminance, high color purity and good color reproducibility when red, green and blue LED light sources (RGB-LEDs) are used as a backlight.
  • RGB-LEDs red, green and blue LED light sources
  • Image sensors incorporating the color filters of the present invention can capture images with high sensitivity and high quality.
  • the color filters for solid-state image sensors of the present invention can be conveniently used in solid-state image sensors such as CCDs and CMOSs, especially suitably for high resolution CCDs and CMOSs containing more than a million pixels and the like.
  • the color filters of the present invention can be used as, for example, a color filter placed between the light-capturing part of each pixel constituting a CCD or CMOS and a microlens for focusing light.
  • the film thickness of a colored pattern (colored pixel) in the color filters for solid-state image sensors of the present invention is preferably 2.0 ⁇ or less, more preferably 1.0 ⁇ or less.
  • the term "colored" in a colored pattern (colored pixel) means to include transparent (white) .
  • the size (pattern width) of a colored pattern (colored pixel) is preferably 2.5 ⁇ or less, more preferably 2.0 ⁇ or less, especially preferably 1.7 ⁇ or less.
  • the architecture of the solid-state image sensors of the present invention is not specifically limited so far as it comprises a color filter of the present invention and functions as a solid-state image sensor, but specifically designed as follows, for example.
  • An architecture is designed to comprise a plurality of photodiodes each constituting a light-capturing area of a solid-state image sensor (CCD image sensor, CMOS image sensor or the like) and transfer electrodes made from polysilicon or the like on a substrate; a light-shielding film made from tungsten or the like provided on the photodiodes and the transfer electrodes to open only at the light-capturing part of each photodiode; a device-protecting film made from silicon nitride or the like formed on the light-shielding film to cover the entire surface of the light-shielding film and the light-capturing part of each photodiode; and a color filter for solid-state image sensors of the present invention on the device-protecting film.
  • the architecture may be designed to comprise a light-focusing means (e.g., a microlens or the like; same as below) on the device-protecting layer and under the color filter (on the side near the substrate) or a light-focusing means on the color filter and the like.
  • a light-focusing means e.g., a microlens or the like; same as below
  • a mixed solution of the following composition was dispersd by using a circulation disperser (bead mill) available fromKOTOBUKI INDUSTRIES CO., LTD. under the brand name ULTRA APEX MILL as follows to give a titanium dioxide dispersion as a dispersion composition .
  • Titanium dioxide available from ISHIHARA SANGYO KAISHA, LTD. under the brand name TTO-51 (C) ) : 25.00 parts
  • the disperser was operated under the following conditions .
  • the projected areas of 300 titanium dioxide particles contained in the resulting dispersion were determined by transmission electron microscopy and the arithmetic average of their corresponding circle equivalent diameters was determined to be 40 nm.
  • Each of the radiation-sensitive compositions obtained in the Examples and Comparative examples was applied in a thickness after coating of 0.6 pm by spin coating on a primed silicon wafer, and then heated on a hot plate at 100 °C for 2 minutes to give a radiation-sensitive composition layer. Then, the resulting radiation-sensitive composition layer was exposed in a Bayer pattern of 1.2 ⁇ through a mask by using the i-line stepper exposure system FPA-3000i5+ (from Canon, Inc.). Then, the exposed radiation-sensitive composition layer was puddle developed with a 0.3 % aqueous solution of tetramethylammonium hydroxide (TMAH) at 23 °C for 60 seconds. This was followed by spin shower rinsing and further washing with pure water to give a transparent pattern.
  • TMAH tetramethylammonium hydroxide
  • the shape of the resulting transparent pattern was observed with length measurement SEM (available from Hitachi, Ltd. under the brand name S-7800H) at a magnification of 20000x on the silicon wafer .
  • the patternability evaluation was performed after cold storage for 1 month to evaluate the pattern shape. Ratings of 3 or higher are desirable for practical uses.

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9864121B2 (en) 2011-11-22 2018-01-09 Samsung Electronics Co., Ltd. Stress-resistant component for use with quantum dots

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6388776B2 (ja) * 2014-03-12 2018-09-12 新日鉄住金化学株式会社 白色感光性樹脂組成物、それを用いた硬化物、及びその硬化物を構成成分として含むタッチパネル
KR20170008581A (ko) * 2015-07-14 2017-01-24 삼성에스디아이 주식회사 감광성 수지 조성물 및 이를 이용한 컬러필터
JP2017116787A (ja) * 2015-12-25 2017-06-29 三洋化成工業株式会社 感光性樹脂組成物
KR101895310B1 (ko) * 2016-01-25 2018-09-05 삼성에스디아이 주식회사 감광성 수지 조성물, 감광성 수지막 및 이를 이용한 컬러필터
TWI765170B (zh) * 2018-08-21 2022-05-21 神盾股份有限公司 光學感測器、光學感測系統及其製造方法
WO2022045113A1 (ja) 2020-08-28 2022-03-03 富士フイルム株式会社 下層膜形成用組成物、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

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10321040A (ja) * 1997-05-23 1998-12-04 Dai Ichi Kogyo Seiyaku Co Ltd 固体電解質
JP2008083508A (ja) * 2006-09-28 2008-04-10 Nippon Kayaku Co Ltd ネガ型着色感光性組成物
JP2010006932A (ja) * 2008-06-26 2010-01-14 Fujifilm Corp 分散液、黒色硬化性組成物、製造方法、固体撮像素子用の遮光膜または反射防止膜の製造方法、および固体撮像素子

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5189392B2 (ja) * 2008-03-28 2013-04-24 富士フイルム株式会社 感光性樹脂組成物、遮光性カラーフィルター及びその製造方法、並びに、固体撮像素子
JP5701576B2 (ja) * 2009-11-20 2015-04-15 富士フイルム株式会社 分散組成物及び感光性樹脂組成物、並びに固体撮像素子
JP5849011B2 (ja) * 2012-04-24 2016-01-27 富士フイルム株式会社 ソルダーレジスト組成物、硬化膜、および硬化膜の製造方法
JP5833969B2 (ja) * 2012-04-27 2015-12-16 富士フイルム株式会社 感放射線性組成物、遮光膜および固体撮像素子

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH10321040A (ja) * 1997-05-23 1998-12-04 Dai Ichi Kogyo Seiyaku Co Ltd 固体電解質
JP2008083508A (ja) * 2006-09-28 2008-04-10 Nippon Kayaku Co Ltd ネガ型着色感光性組成物
JP2010006932A (ja) * 2008-06-26 2010-01-14 Fujifilm Corp 分散液、黒色硬化性組成物、製造方法、固体撮像素子用の遮光膜または反射防止膜の製造方法、および固体撮像素子

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9864121B2 (en) 2011-11-22 2018-01-09 Samsung Electronics Co., Ltd. Stress-resistant component for use with quantum dots
US10012778B2 (en) 2011-11-22 2018-07-03 Samsung Electronics Co., Ltd. Stress-resistant component for use with quantum dots

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