Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
  • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
  • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/54—Three nitrogen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
  • C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
  • C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
  • C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
  • C07D251/40—Nitrogen atoms
  • C07D251/54—Three nitrogen atoms
  • C07D251/70—Other substituted melamines
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D309/10—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
• • G—PHYSICS
  • G02—OPTICS
  • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
  • G02B5/00—Optical elements other than lenses
  • G02B5/20—Filters
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups

Definitions

• the present invention relates to a novel thiol compound. Moreover, it is related with the manufacturing method of a thiol compound, a polymer, a composition, a curable composition, and a coloring composition. Furthermore, it is related with the cured film using a curable composition or a coloring composition, and the color filter using a coloring composition.
• Patent Document 1 discloses the following compound.
• R is a hydrogen atom or an alkyl group
• a is an integer of 1 to 4
• b is an integer of 1 to 4.
• Patent Documents 2 and 3 describe using a polyfunctional thiol compound as a raw material for the synthesis of a dispersant.
• the object of the present invention is to provide a thiol compound having excellent heat resistance. Moreover, it aims at providing the manufacturing method of a thiol compound, a composition, a curable composition, a coloring composition, a cured film, and a color filter.
• a predetermined linking group and a thiol are separated by separating the predetermined linking group and the thiol group (SH) by 5 atoms or more by a group such as an alkylene group. It has been found that thermal decomposition between groups is suppressed and heat resistance can be improved, and the present invention has been completed. Specifically, the above problem has been solved by the following means ⁇ 1>, preferably ⁇ 2> to ⁇ 17>.
• a thiol compound represented by the following formula (1) (HS-R 1 -M 1- ) n L 1 (1)
• L 1 represents an n-valent organic linking group
• n represents an integer of 3 to 15
• M 1 represents —O—, —S—, —N (R 2 ) —, —C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —C ( ⁇ O) —NH—, —O—C ( ⁇ O) —NH—, —S ( ⁇ O) —, —S ( ⁇ O) —O—, —S ( ⁇ O) 2 —, — S ( ⁇ O) 2 —O— or —CH ⁇ N—
• R 1 represents an alkylene group or a group consisting of a combination of an alkylene group and an etheric oxygen atom
• R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may contain an
• R 1 is a linear alkylene group having 5 to 30 carbon atoms, a branched alkylene group having 6 to 30 carbon atoms, a group consisting of a combination of a linear alkylene group having 3 to 27 carbon atoms and an etheric oxygen atom, or
• the thiol compound according to ⁇ 1> which represents a group consisting of a combination of a branched alkylene group having 4 to 28 carbon atoms and an etheric oxygen atom.
• R 1 is a linear alkylene group having 5 to 20 carbon atoms, an alkylene group having 5 to 20 carbon atoms including an ethyleneoxy chain, or an alkylene group having 5 to 20 carbon atoms including an isopropyleneoxy chain.
• the thiol compound according to ⁇ 1>, which represents ⁇ 4> The thiol compound according to any one of ⁇ 1> to ⁇ 3>, wherein L 1 is a linking group derived from a polyhydric alcohol.
• L 1 is 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 to The thiol compound according to any one of ⁇ 1> to ⁇ 4>, comprising a group consisting of up to 20 sulfur atoms.
• L 1 is a thiol compound according to any one of ⁇ 1> to ⁇ 4>, selected from the structures represented by any of (L-1) to (L-21) below;
• r is an integer of 0 to 10
• R 31 to R 41 each independently represents an alkyl group
• R 42 represents a hydrogen atom, an alkyl group or an alkoxy group
• R 43 and R 44 each represent Independently, it is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms
• s is an integer of 0 to 9
• L 4 represents —O— or —C ( ⁇ O) —.
• L 1 is selected from the structures represented by any of the following, the thiol compound according to any one of ⁇ 1> to ⁇ 4>;
• r is an integer of 0 to 10
• R 42 , R 43 and R 44 are ethyl groups.
• a compound represented by the following formula (3) and a compound represented by the following formula (4) are reacted, and the resulting product is reacted with a sulfur-containing compound having a protecting group Z, followed by protection.
• L 1 represents an n-valent organic linking group
• R H represents at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and represents a group that includes a hydrogen atom linked to any one of an oxygen atom, a nitrogen atom, and a sulfur atom
• n represents an integer of 3 to 15
• Y represents a group capable of leaving by reaction with a sulfur-containing compound having a protecting group Z
• R 1 is an alkylene group, or a group composed of a combination of an alkylene group and an etheric oxygen atom, the R 1 and the atoms connecting the M a R 1 a bond to atoms Y, 5 or more of R 1 Separated by M a represents a single bond
• a method for producing a thiol compound comprising generating a thiol group by removing the group Z;
• Y represents a group capable of leaving by reaction with a sulfur-containing compound having a protecting group Z;
• R 1 represents an alkylene group or a group composed of a combination of an alkylene group and an etheric oxygen atom, and the atom bonded to R 1 of Y and the atom bonded to R 1 of M a1 are 5 or more of R 1 Separated by M a1 represents —C ( ⁇ O) —,
• X represents a group containing at least one of a halogen atom and a sulfonate.
• a method for producing a thiol compound comprising generating a thiol group by removing the group Z;
• Y represents a group capable of leaving by reaction with a sulfur-containing compound having a protecting group Z;
• R 1 represents an alkylene group or a group consisting of a combination of an alkylene group and an etheric oxygen atom, and the atom bonded to R 1 of Y and the atom bonded to R 1 of X are 5 or more of R 1 Separated by atoms,
• X represents a group containing at least one of a halogen atom and a sulfonate.
• the protecting group Z is a group represented by the following formula (5), a group represented by the following formula (6), or a salt of a group represented by the following formula (6), ⁇ 8> A process for producing a thiol compound according to any one of ⁇ 10>;
• R 4 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms.
• L 1 represents an (n1 + n2) -valent organic linking group
• n1 represents 1 to
• n2 represents 0 to 14
• M 1 represents —O—, —S—, —N (R 2 ) —, — C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —C ( ⁇ O) —NH—, —O—C ( ⁇ O) —NH— , —S ( ⁇ O) —, —S ( ⁇ O) —O—, —S ( ⁇ O) 2 —, —S ( ⁇ O) 2 —O—, or —CH ⁇ N—
• R 1 represents an alkylene group or a group consisting of a combination of an alkylene group and an etheric oxygen atom
• R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may contain an ether
• a composition comprising the thiol compound produced by the method for producing a thiol compound according to any one of ⁇ 8> to ⁇ 11>, wherein 50% by mass or more of the composition is represented by formula (1):
• a composition which is a specific one of the thiol compounds to be produced.
• a composition comprising the thiol compound according to any one of ⁇ 1> to ⁇ 7>, wherein 50% by mass or more of the composition is a specific thiol compound represented by formula (1).
• One type of composition is ⁇ 15> A composition comprising the polymer according to ⁇ 12>.
• ⁇ 16> The thiol compound according to any one of ⁇ 1> to ⁇ 7>, the thiol compound obtained by the method for producing a thiol compound according to any one of ⁇ 8> to ⁇ 11>, A curable composition comprising a polymer and at least one of the compositions according to any one of ⁇ 13> to ⁇ 15>, and a polymerizable compound.
• ⁇ 17> The thiol compound according to any one of ⁇ 1> to ⁇ 7>, the thiol compound obtained by the method for producing a thiol compound according to any one of ⁇ 8> to ⁇ 11>, A colored composition comprising a polymer, at least one of the compositions according to any one of ⁇ 13> to ⁇ 15>, a polymerizable compound, and a colorant.
• ⁇ 19> A color filter obtained using the colored composition according to ⁇ 17>.
• a thiol compound having excellent heat resistance can be provided.
• a cured film and a color filter having excellent heat resistance can be provided.
• the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
• the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
• active light or “radiation” means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light), X-rays, electron beams, and the like.
• light means actinic rays or radiation.
• exposure in this specification is not limited to exposure with an emission line spectrum of a mercury lamp, far ultraviolet rays typified by excimer laser, X-rays, EUV light, etc., but also particles such as electron beams and ion beams. Line drawing is also included in the exposure.
• a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
• the total solid content refers to the total mass of components excluding the solvent from the total composition of the colored composition.
• (meth) acrylate represents both and / or acrylate and methacrylate
• (meth) acryl represents both and / or acryl
• (meth) acryloyl "Represents both acryloyl and / or methacryloyl.
• the monomer in this specification is distinguished from an oligomer and a polymer, and refers to a compound having a weight average molecular weight of 2,000 or less.
• the polymerizable compound means a compound having a polymerizable functional group, and may be a monomer or a polymer.
• the polymerizable functional group refers to a group that participates in a polymerization reaction.
• Me in the chemical formula represents a methyl group
• Et represents an ethyl group
• Pr represents a propyl group
• Bu represents a butyl group
• Ph and PH represent a phenyl group.
• NMR nuclear magnetic resonance resonance
• DMSO means dimethyl sulfoxide
• MALDI Matrix Assisted Laser Desorption / Ionization
• MS means mass spectrum
• HPLC High performance liquid chromatography
• PGMEA means propylene glycol-1-methyl ether acetate.
• process is not limited to an independent process, and is included in the term if the intended action of the process is achieved even when it cannot be clearly distinguished from other processes. .
• the weight average molecular weight and the number average molecular weight are defined as polystyrene conversion values by GPC (gel permeation chromatography) measurement.
• the weight average molecular weight (Mw) and the number average molecular weight (Mn) are, for example, HLC-8220 (manufactured by Tosoh), and TSKgel Super Super AWM-H (manufactured by Tosoh, 6.0 mm (inner diameter) ⁇ 15.0 cm) can be obtained by using a 10 mmol / L lithium bromide NMP (N-methylpyrrolidinone) solution as an eluent.
• the thiol compound of the present invention is represented by the following formula (1).
• L 1 represents an n-valent organic linking group
• n represents an integer of 3 to 15
• M 1 represents —O—, —S—, —N (R 2 ) —, —C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —C ( ⁇ O) —NH—, —O—C ( ⁇ O) —NH—, —S ( ⁇ O) —, —S ( ⁇ O) —O—, —S ( ⁇ O) 2 —, —S ( ⁇ O) 2 —O—, or —CH ⁇ N—, wherein R 1 is , An alkylene group, or a group composed of a combination of an alkylene group and an etheric oxygen atom, SH represents a thiol group, and R 2
• the polyfunctional thiol compound having a plurality of SH groups acts as a chain transfer agent in the presence of a polymerizable compound, for example.
• the polyfunctional thiol compound in the cured product is sterically crowded because of its polyfunctionality, and as the curing proceeds, nearby polymerization occurs.
• heat resistance is improved by providing an alkylene group or a group consisting of a combination of an alkylene group and an etheric oxygen atom between the predetermined linking group represented by M 1 and the SH group. I am letting. This is because the presence of an alkylene group having 5 or more carbon atoms between the predetermined linking group and the SH group makes it difficult for the reaction between them to proceed even when heated.
• L 1 represents an n-valent organic linking group, 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to It is a group consisting of up to 200 hydrogen atoms and 0 to 20 sulfur atoms, which may be unsubstituted or substituted.
• L 1 include a group (which may form a cyclic structure) formed by combining two or more of the following structural units or the following structural units.
• L 1 is 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, 1 to 120 hydrogen atoms, and 0 to 10 atoms.
• Groups consisting of up to sulfur atoms are preferred. More preferably, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 hydrogen atoms, and 0 to 7 atoms. It is a group consisting of the sulfur atom. More preferably, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms, 1 to 80 hydrogen atoms, and 0 to 5 atoms. It is a group consisting of the sulfur atom.
• L 1 may have a substituent.
• substituents include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, an aryl group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, and a sulfonamide group.
• C1-C6 acyloxy groups such as N-sulfonylamido and acetoxy groups, C1-C6 alkoxy groups such as methoxy and ethoxy groups, halogen atoms such as chlorine and bromine, methoxycarbonyl groups and ethoxycarbonyl Group, a C2-C7 alkoxycarbonyl group such as cyclohexyloxycarbonyl group, a cyano group, a carbonic acid ester group such as t-butyl carbonate, and the like. However, it is preferable not to have a substituent.
• L 1 as described above is derived from, for example, a polyhydric alcohol.
• the valence of the polyhydric alcohol is preferably 3 to 15.
• L 1 is preferably represented by any of (L-1) to (L-21) below. * Indicates a binding site with M 1 .
• r is an integer of 0 to 10, preferably an integer of 1 to 10, and more preferably an integer of 1 to 5.
• R 31 to R 41 each independently represents an alkyl group, preferably a branched alkyl group having 3 to 10 carbon atoms, and more preferably a t-butyl group. R 31 to R 41 may be different from each other but are preferably the same group.
• R42 represents a hydrogen atom, an alkyl group or an alkoxy group, preferably a hydrogen atom, a methyl group, an ethyl group or a methoxy group, more preferably an ethyl group.
• R 43 and R 44 are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, and even more preferably an ethyl group.
• s is an integer of 0 to 9, preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
• L 4 represents —O— or —C ( ⁇ O) —.
• n represents an integer of 3 to 15.
• the lower limit of n is preferably 4 or more, and more preferably 5 or more.
• the upper limit of n is preferably 10 or less, and more preferably 8 or less.
• M 1 represents —O—, —S—, —N (R 2 ) —, —C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —C ( ⁇ O) —NH—, —O—C ( ⁇ O) —NH—, —S ( ⁇ O) —, —S ( ⁇ O) —O—, —S ( ⁇ O) 2 —, — Represents S ( ⁇ O) 2 —O— or —CH ⁇ N— and represents —O—, —S—, —C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —C ( ⁇ O)
• the n M 1 s may be the same or different.
• the n M 1 are preferably the same.
• the linking group represented by M 1 has one end bonded to R 1 and the other end bonded to L 1 , but either end may be bonded to which group.
• -C ( O)
• carbon atoms may be bonded to R 1
• the oxygen atom may be bonded with R 1.
• R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may contain an etheric oxygen atom, or an aromatic hydrocarbon group which may contain an etheric oxygen atom, A methyl group is preferred, and a hydrogen atom is more preferred.
• R 1 represents an alkylene group or a group comprising a combination of an alkylene group and an etheric oxygen atom
• SH represents a thiol group
• the atom bonded to the sulfur atom of SH and R 1 of M 1 is R 1.
• An etheric oxygen atom refers to an oxygen atom contained between an alkylene group and an alkylene group, and an etheric oxygen atom means that the two oxygen atoms are not continuous.
• the n R 1 s may be the same or different. The n R 1 s are preferably the same.
• the alkylene group as R 1 is a linear, branched or cyclic alkylene group, preferably a linear or branched alkylene group, and more preferably a linear alkylene group or a branched alkylene group having a methyl chain as a branched chain.
• the group comprising a combination of an alkylene group and an etheric oxygen atom is also preferably a group comprising a combination of a linear or branched alkylene group and an etheric oxygen atom, and a branched alkylene having a linear alkylene group or a methyl chain as a branched chain.
• a group composed of a combination of a group and an etheric oxygen atom is more preferable.
• the alkylene group may have a substituent, but preferably has no substituent.
• examples of the substituent that L 1 may have are exemplified.
• R 1 is a linear alkylene group
• the lower limit of the carbon number can be 5 or more, 6 or more, or 7 or more.
• the upper limit is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and particularly preferably 20 or less.
• the upper limit may be 12 or less, 10 or less, or 8 or less.
• R 1 is a branched alkylene group
• the lower limit of the carbon number can be 6 or more, 7 or more, or 8 or more.
• the upper limit is preferably 50 or less, more preferably 40 or less, still more preferably 30 or less, and particularly preferably 20 or less.
• the upper limit may be 12 or less, and may be 10 or less.
• R 1 is a cyclic alkylene group, it is usually a group comprising a combination of the linear or branched alkylene group and the cyclic alkylene group.
• the number of carbon atoms constituting the ring of the cyclic alkylene group is preferably 3 to 8, and more preferably 6.
• R 1 is a group consisting of a combination of a linear alkylene group and an etheric oxygen atom
• the lower limit of the carbon number can be 3 or more, preferably 4 or more, and more preferably 5 or more.
• the upper limit is preferably 50 or less, more preferably 40 or less, further preferably 27 or less, and particularly preferably 20 or less.
• the upper limit can be 10 or less, 8 or less, or 6 or less.
• R 1 is a group composed of a combination of a linear alkylene group and an etheric oxygen atom
• the number of atoms including an ethyleneoxy chain and separating the sulfur atom of SH and the atom bonded to R 1 of M 1 Examples are 5 to 20 groups, and it is preferable that 2 to 5 ethyleneoxy chains are repeated.
• R 1 is a group composed of a combination of a branched alkylene group and an etheric oxygen atom
• the lower limit of the carbon number can be 4 or more, 5 or more, or 6 or more.
• the upper limit is preferably 50 or less, more preferably 40 or less, still more preferably 28 or less, particularly preferably 20 or less, and may be 10 or less, or may be 8 or less.
• R 1 is a group consisting of a combination of a branched alkylene group and an etheric oxygen atom
• the number of atoms that contains an isopropyleneoxy chain and separates the sulfur atom of SH and the atom bonded to R 1 of M 1 5 to 20 groups are exemplified, and an embodiment including a structure in which 2 to 5 isopropyleneoxy chains are repeated is exemplified.
• R 1 is a group comprising a combination of a cyclic alkylene group and an etheric oxygen atom, it is usually a group comprising a combination of the above linear or branched alkylene group and a etheric oxygen atom and a cyclic alkylene group.
• R 1 is particularly a linear alkylene group having 5 to 20 carbon atoms, an alkylene group having 5 to 20 carbon atoms including an ethyleneoxy chain, or an alkylene group having 5 to 20 carbon atoms including an isopropyleneoxy chain. It preferably represents an alkylene group, more preferably a linear alkylene group having 5 to 20 carbon atoms or an alkylene group containing 5 to 20 carbon atoms including an ethyleneoxy chain, and further preferably a linear alkylene group having 5 to 20 carbon atoms. .
• the number of atoms connecting the R 1 of M 1 and the atom to be bonded at the shortest is 5 or more.
• This atom consists of a carbon atom or a carbon atom and an oxygen atom, and the total number is 5 atoms or more.
• the number of atoms from which SH and M 1 are separated is 6 atoms
• the number of atoms from which SH and M 1 are separated Becomes 6 atoms.
• the molecular weight of the thiol compound of the present invention is preferably 300 to 3000, more preferably 500 to 2500.
• the thiol compound of the present invention preferably has no following group. By not having the following groups, the heat resistance tends to be further improved.
• Acid anhydride group (—C ( ⁇ O) —O—C ( ⁇ O) —, —S ( ⁇ O) 2 —O—S ( ⁇ O) 2 —, —P ( ⁇ O) (OH) —O —P ( ⁇ O) (OH) —, —S ( ⁇ O) 2 —O—C ( ⁇ O) —), phosphate ester group (—P ( ⁇ O) (OH) —O—), dioxy group (—O—O—), disulfide group (—S—S—), methylenedioxy group (—OCH 2 O—), oxalyl group (—C ( ⁇ O) C ( ⁇ O) —), malonyl group ( —C ( ⁇ O) CH 2 C ( ⁇ O) —), ureylene group (—NH—C ( ⁇ O) —NH—), hydrazinylene group (—NHNH—), —C ( ⁇ O) —S—, —O—C ( ⁇ O) —S—, —C
• n is an integer of 1 to 13.
• n is an integer of 1 to 13.
• n is an integer of 1 to 13. In the above (S-32), n is an integer of 1 to 13.
• (S-1) to (S-48) and (S-51) are preferable, and (S-1) to (S-3), (S-4) to (S-16), ( (S-22) to (S-38), (S-41) to (S-48), and (S-51) are more preferable, (S-2) to (S-3), (S-5) (S-8), (S-13), (S-22) to (S-24), (S-26) to (S-28), (S-31), (S-37) to (S More preferred are S-38), (S-41), and (S-44).
• the thiol compound of the present invention reacts a compound represented by the following formula (3) with a compound represented by the following formula (4), and reacts the resulting product with a sulfur-containing compound having a protecting group Z. And then producing a thiol group by removing the protecting group Z.
• L 1 represents an n-valent organic linking group
• R H represents at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and represents a group that includes a hydrogen atom linked to any one of an oxygen atom, a nitrogen atom, and a sulfur atom
• n represents an integer of 3 to 15
• Y represents a group capable of leaving by reaction with a sulfur-containing compound having a protecting group Z
• R 1 is an alkylene group, or a group composed of a combination of an alkylene group and an etheric oxygen atom, the R 1 and the atoms connecting the M a R 1 a bond to atoms Y, 5 or more of R 1 Separated by M a represents a single bond or a divalent linking group
• X represents a group containing at least one of a halogen atom and a sulfonate.
• R H is a group containing at least one of an oxygen atom, a nitrogen atom, and a sulfur atom, and a hydrogen atom linked to any one of the oxygen atom, the nitrogen atom, and the sulfur atom, preferably a hydroxyl group, a thiol group, a substituted or non-substituted group. Substituted amino groups and carboxyl groups are included.
• X represents a group containing at least one of a halogen atom or a sulfonate, and is preferably a halogen atom.
• a halogen atom a fluorine atom, a chlorine atom, and a bromine atom are preferable, a chlorine atom or a bromine atom is more preferable, and a chlorine atom is further more preferable.
• X is specifically trifluoromethanesulfonate, p-toluenesulfonate, benzenesulfonate, methanesulfonate, Cl—C ( ⁇ O) —, Br—C ( ⁇ O) —, p-toluenesulfonyloxycarbonyl, methanesulfonyl Examples are oxycarbonyl.
• M a is preferably a single bond, —C ( ⁇ O) —, —O—, —C ( ⁇ O) —O—, —NH— or —S ( ⁇ O) —, and is preferably a single bond or —C ( ⁇ O)-is more preferable.
• Y represents a group capable of leaving by reaction with a sulfur-containing compound having a protecting group Z, and more preferably a group leaving by reaction with an acyl group or an amidino group.
• Specific examples include halogen atoms, trifluoromethane sulfonate, p-toluene sulfonate, benzene sulfonate, methane sulfonate, and the like.
• a halogen atom a chlorine atom, a bromine atom, and an iodine atom are preferable, and a bromine atom is more preferable.
• the sulfur-containing compound containing a protecting group Z is not particularly defined as long as it contains a sulfur atom and a protecting group Z, but is preferably composed of a sulfur atom and a protecting group Z.
• the protecting group include an acyl group, an amidino group, and a salt of an amidino group, a group represented by the following formula (5), a group represented by the following formula (6), or a group represented by the following formula (6).
• R 4 represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms.
• R 4 is preferably an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, and more preferably an alkyl group having 1 to 5 carbon atoms or a phenyl group.
• amidino group salts include sodium salts, potassium salts, calcium salts, and magnesium salts.
• a trivalent to 15-valent polyhydric alcohol is reacted with a compound represented by the following formula (4-1), and the resulting product is protected.
• An example is a method of producing a thiol group by reacting a sulfur-containing compound having a group Z and then removing the protecting group Z.
• R 1 represents an alkylene group or a group composed of a combination of an alkylene group and an etheric oxygen atom
• the atom bonded to R 1 of Y and the atom bonded to R 1 of M a1 are 5 or more of R 1 Separated by M a1 represents —C ( ⁇ O) —
• X represents a group containing at least one of a halogen atom and a sulfonate.
• a trivalent to 15-valent polyhydric alcohol is reacted with a compound represented by the following formula (4-2), and the resulting product is protected.
• An example is a method in which a sulfur-containing compound having a group Z is reacted and then a protecting group Z is eliminated to generate a thiol group.
• Y represents a group capable of leaving by reaction with a sulfur-containing compound having a protecting group Z
• R 1 represents an alkylene group or a group consisting of a combination of an alkylene group and an etheric oxygen atom, and the atom bonded to R 1 of Y and the atom bonded to R 1 of X are 5 or more of R 1 Separated by atoms
• X represents a group containing at least one of a halogen atom and a sulfonate.
• the polyhydric alcohol is exemplified by the polyhydric alcohol having an OH group bonded to the portion * in the structure represented by the above (L-1) to (L-21). Is done.
• the preferred range is the same as the description of the structures represented by the above (L-1) to (L-21).
• the valence of the polyhydric alcohol is synonymous with n in the formula (1), and the preferred range is also the same.
• X and Y in the above formulas (4-1) and (4-2) have the same meanings as X and Y in the formula (4), and the preferred ranges are also the same.
• R 1 in formula (4-1) and formula (4-2) has the same meaning as R 1 in formula (1), and the preferred range is also the same.
• the sulfur-containing compound having a protecting group Z is synonymous with the above-described sulfur-containing compound having a protecting group Z, and the preferred range is also the same.
• a polyhydric alcohol and a compound represented by HS—R 1 —COOH are directly condensed.
• the polyhydric alcohol in the present embodiment include polyhydric alcohols in which OH is bonded to the portion * in the structures represented by the above (L-1) to (L-21).
• the preferred range is the same as the description of the structures represented by the above (L-1) to (L-21).
• the valence of the polyhydric alcohol is synonymous with n in the formula (1), and the preferred range is also the same.
• the valence of the polyhydric alcohol is synonymous with n in the formula (1), and the preferred range is also the same.
• R 1 in this embodiment has the same meaning as R 1 in the formula (1), and preferred ranges are also the same. In the present embodiment, since it is obtained by dehydration condensation, there is an advantage that the production process may be reduced. The method is more preferred.
• Applications Applications of the thiol compound of the present invention include pigment raw materials, resin (polymer) raw materials such as dispersants, curing agents and crosslinking agents, resin stabilizers, rubber vulcanizers, adhesive raw materials, mercury and lead. Materials for heavy metal elements and ion removing agents such as, and materials for functionalizing metal surfaces such as sensors can be considered.
• the polyfunctional thiol compound in Patent Document 1 International Publication WO2009 / 129221 pamphlet
• Patent Document 2 JP 2007-277514 A
• Patent Document 3 JP 2013-79380 A
• the thiol compound of the present invention can be used.
• Examples of the use of the curing agent or the crosslinking agent include curing agents of a compound having an epoxy group or a compound having an isocyanate group.
• a compound having an epoxy group also referred to as an epoxy compound
• a compound having two or more epoxy groups in one molecule is preferable.
• Specific examples of the epoxy compound include compounds having an epoxy group described in the curable composition described later.
• the thiol compound of the present invention is used as a curing agent for an epoxy compound, it is preferably blended so that the SH group is 70 to 120 mol with respect to 100 mol of the epoxy group of the epoxy compound. More preferably, the SH group is blended in an amount of 80 to 110 moles per 100 moles.
• the epoxy group consumed by the other curing agent is subtracted, and with respect to 100 mol of the remaining epoxy group, It is preferable to blend so that the SH group is 70 to 120 mol (preferably 80 to 110 mol).
• the isocyanate compound may be either an aromatic compound or an aliphatic compound.
• Specific examples of the isocyanate compound include, for example, 2,4-tolylene diisocyanate, dimer of 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, p-xylylene diisocyanate, m-xylylene diisocyanate, Aromatic diisocyanate compounds such as 4,4'-diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate; hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate Aliphatic diisocyanate compounds such as dimer acid di
• the thiol compound of the present invention is used as a curing agent for a compound having an isocyanate group, it is preferably blended so that the SH group is 50 to 300 mol with respect to 100 mol of the isocyanate group, More preferably, the SH group is blended in an amount of 50 to 150 mol.
• the SH group is 50 to 300 mol (preferably 50 to 150 mol).
• the thiol compound of the present invention can be preferably used as a raw material for a resin (polymer). In particular, it can be preferably used as a raw material for alkali-soluble resins.
• the polymer obtained using the thiol compound of the present invention is excellent in heat resistance. Moreover, this polymer has a low viscosity compared with a linear polymer, and is excellent in leveling property. For this reason, when a color filter is formed using a colored composition containing this polymer, a difference in height can hardly be generated in one pixel (suppression of dishing). Further, the thiol compound of the present invention can be used as a raw material for a dye.
• the polymer of the present invention is represented by the following formula (7).
• L 1 represents an (n1 + n2) -valent organic linking group
• n1 represents 1 to
• n2 represents 0 to 14
• M 1 represents —O—, —S—, —N (R 2 ) —, — C ( ⁇ O) —, —C ( ⁇ O) —O—, —O—C ( ⁇ O) —O—, —C ( ⁇ O) —NH—, —O—C ( ⁇ O) —NH— , —S ( ⁇ O) —, —S ( ⁇ O) —O—, —S ( ⁇ O) 2 —, —S ( ⁇ O) 2 —O—, or —CH ⁇ N—
• R 1 represents an alkylene group or a group consisting of a combination of an alkylene group and an etheric oxygen atom
• R 2 represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms which may contain an ether
• L 1 , M 1 , R 1 and R 2 in the formula (7) are synonymous with L 1 , M 1 , R 1 and R 2 described in the formula (1), and preferred ranges are also the same.
• n1 represents 1 to 15, n2 represents 0 to 14, and the total of n1 and n2 is 3 to 15.
• N1 and n2 in one polymer are integers, respectively, but the polymer of the present invention may include a plurality of polymers in which n1 and n2 in formula (7) are different.
• n1 is preferably 2 or more, and more preferably 3 or more.
• P 1 in formula (7) represents a monovalent substituent having a repeating unit derived from a compound having an ethylenically unsaturated bond.
• P 1 s may be the same or different from each other.
• P 1 preferably has 2 or more repeating units derived from a compound having an ethylenically unsaturated bond, more preferably 2 to 10,000 repeating units, and still more preferably 2 to 1,000. .
• the compounds having an ethylenically unsaturated bond include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, and styrene. , Vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and vinyl compounds having an acidic group. These compounds can be used alone or in combination of two or more. Examples of the vinyl compound having an acid group include a vinyl compound having a carboxyl group, a vinyl compound having a sulfo group, and a vinyl compound having a phosphate group.
• the weight average molecular weight of the polymer of the present invention is preferably 3,000 to 1,000,000, more preferably 4,000 to 500,000, and further preferably 5,000 to 300,000.
• the acid value of the polymer of the present invention is not particularly limited, but when the polymer of the present invention is used as an alkali-soluble resin, 10 to 200 mgKOH / g is preferable, 20 to 160 mgKOH / g is more preferable, and 30 to 140 mgKOH / g is particularly preferable. preferable.
• the acid value is 10 mgKOH / g or more, the alkali developability is good.
• the acid value is less than 200 mgKOH / g, the dispersion stability of the composition is good.
• the polymer of the present invention can be obtained, for example, by radical polymerization of a compound having an ethylenically unsaturated bond in the presence of the thiol compound represented by the above formula (1).
• the compound having an ethylenically unsaturated bond is not particularly limited, but a compound containing one or more acid groups is preferable.
• Compounds having an ethylenically unsaturated bond include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrene , Vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, vinyl monomers having acidic groups, (meth) acrylic acid esters, (meth) acrylamides, styrenes, vinyl ethers, Maleimides and vinyl monomers having acidic groups are preferred, (meth) acrylic acid esters, styrenes, and vinyl monomers having acidic groups are more preferred.
• the monomer demonstrated with the alkali-soluble resin mentioned later can also be used as a compound which has an ethylenically unsaturated bond.
• the polymer production conditions are not particularly limited, but a thiol compound and a compound having an ethylenically unsaturated bond are dissolved in a suitable solvent, and a polymerization initiator is added thereto at about 50 ° C. to 220 ° C.
• a polymerization initiator is added thereto at about 50 ° C. to 220 ° C.
• Examples include a method of polymerizing in a solution (solution polymerization method).
• the solvent used in the solution polymerization method can be arbitrarily selected according to the solubility of the raw material compound used and the solubility of the polymer to be produced.
• solvents may be used as a mixture of two or more.
• polymerization initiator examples include 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobis ( Azo compounds such as 2-methylpropionate), peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate can be used.
• AIBN 2,2′-azobis (isobutyronitrile)
• 2,2′-azobis- (2,4′-dimethylvaleronitrile) dimethyl 2,2′-azobis ( Azo compounds such as 2-methylpropionate)
• peroxides such as benzoyl peroxide
• persulfates such as potassium persulfate and ammonium persulfate can be used.
• composition of the present invention is a composition containing the thiol compound of the present invention, and 50% by mass or more of the composition is preferably a specific one of the thiol compounds.
• the composition of the present invention is a composition containing a thiol compound produced by a method using a sulfur-containing compound having the protecting group Z, and 50% by mass or more of the composition is composed of the thiol compound. It is preferable that it is one specific type of them.
• a compound having a thioester structure is easily decomposed by a thioester structure by heating, but since the composition of the present invention has few such impurities, a molded product having higher heat resistance can be obtained.
• the specific one type means any one of the compounds represented by the formula (1).
• the upper limit of the amount of the specific one kind of thiol compound is not particularly defined and is ideally 100% by mass, but for example, 80% by mass or less is sufficient for practical use. It becomes a composition with the property.
• the composition of this invention contains the polymer represented by said (7). Since the polymer of the present invention is excellent in heat resistance, a molded product having higher heat resistance can be obtained. Furthermore, since the polymer of the present invention has low viscosity and excellent leveling properties, when a color filter is formed using a coloring composition containing the composition of the present invention, a difference in height occurs in one pixel. Can be difficult (suppression of dishing).
• the curable composition of this invention contains the thiol compound of this invention, the thiol compound obtained by the manufacturing method of this invention, at least 1 sort (s) of the composition of this invention, and a polymeric compound.
• the polyfunctional thiol compound acts as a chain transfer agent when the polymerizable compound is cured, but an unreacted thiol group remains in the obtained cured product.
• unreacted thiol groups react with other groups, causing thermal decomposition.
• the present invention is advantageous because it can hardly cause such thermal decomposition.
• the content of the thiol compound of the present invention in the curable composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the solid content. More preferably, it is 5 mass%.
• the curable composition of the present invention can be used for coloring compositions, antireflection film forming compositions, antifouling layer forming compositions, dental and bone shaping materials such as glass ionomer cements, and the like.
• at least one of the thiol compound of the present invention, the thiol compound obtained by the production method of the present invention, and the composition of the present invention, a repeating unit having a polyether structure having a fluorine atom, and four or more It can also be used as a polymerizable composition containing a compound having a polymerizable group, a photopolymerization initiator, and a solvent.
• Such a polymerizable composition can be used as a composition for forming a low refractive index layer.
• the polymerizable composition is more preferably exemplified by a composition containing a perfluoroolefin copolymer, hollow silica particles, a polymerizable compound (preferably a polymerizable monomer), a photopolymerization initiator, and a fluorine-containing monomer. Is done. Details thereof are described in paragraphs 0024 to 0060 of JP 2014-167596 A, paragraphs 0027 to 0126 of JP 2014-070165 A, paragraphs 0018 to 0167 of JP 2003-228741 A (in particular, paragraph 0043). -Description of -0048), the contents of which are incorporated herein.
• Examples of the perfluoroolefin copolymer include a structure represented by the following formula (1). In the structural formula, 50:50 represents a molar ratio.
• hollow silica particles examples include isopropyl alcohol silica sol.
• examples of commercially available products include “CS60-IPA” (manufactured by Catalyst Kasei Kogyo).
• Specific examples of the fluorine-containing monomer include the structures shown below.
• the curable composition of the present invention includes, for example, the thiol compound of the present invention and an epoxy compound, and further contains 3-aminomethyl. And a composition containing a curing accelerator such as ⁇ 3,5,5-trimethylcyclohexylamine.
• a curing accelerator such as ⁇ 3,5,5-trimethylcyclohexylamine.
• the curable composition of the present invention includes, for example, at least the thiol compound of the present invention and an isocyanate compound, and further dibutyltin dichloride.
• the composition containing hardening accelerators, such as these, is mentioned.
• the colored composition of the present invention contains the thiol compound of the present invention, the thiol compound obtained by the production method of the present invention, at least one of the compositions of the present invention, a polymerizable compound, and a colorant.
• the content of the thiol compound of the present invention in the colored composition of the present invention is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on the solid content. More preferably, it is mass%.
• the coloring composition of the present invention contains a polymerizable compound.
• a polymerizable compound a known polymerizable compound that can be crosslinked by a radical, an acid, or heat can be used.
• polymerizable compounds containing an ethylenically unsaturated bond, cyclic ether (epoxy, oxetane), methylol and the like can be mentioned.
• the polymerizable compound is suitably selected from compounds having at least one terminal ethylenically unsaturated bond, preferably two or more, from the viewpoint of sensitivity.
• a polyfunctional polymerizable compound having 4 or more functional groups is preferable, and a polyfunctional polymerizable compound having 5 or more functional groups is more preferable.
• Such a group of compounds is widely known, and these can be used without any particular limitation in the present invention. These may be in any chemical form such as, for example, monomers, prepolymers, ie dimers, trimers and oligomers or mixtures thereof and multimers thereof.
• the polymeric compound in this invention may be used individually by 1 type, and may use 2 or more types together.
• Examples of monomers and prepolymers include unsaturated carboxylic acids (eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters, amides, and multimers thereof.
• unsaturated carboxylic acids eg, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
• esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds, and multimers thereof.
• a dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
• Reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups and epoxy groups with monofunctional or polyfunctional alcohols, amines and thiols, halogen groups and tosyloxy groups A reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as monofunctional or polyfunctional alcohols, amines or thiols is also suitable.
• polymerizable compound a compound having at least one addition-polymerizable ethylene group and having an ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is also preferable.
• paragraph 0227 of JP 2013-29760 A can be referred to, the contents of which are incorporated herein.
• Examples of the compound having a boiling point of 100 ° C. or higher under normal pressure and having at least one ethylenically unsaturated group capable of addition polymerization include compounds described in paragraphs 0254 to 0257 of JP-A-2008-292970. Which is incorporated herein by reference.
• dipentaerythritol triacrylate (as a commercially available product, KAYARAD D-330; manufactured by Nippon Kayaku), dipentaerythritol tetraacrylate (as a commercially available product, KAYARAD D-320; manufactured by Nippon Kayaku), Dipentaerythritol penta (meth) acrylate (as a commercial product, KAYARAD D-310; manufactured by Nippon Kayaku), dipentaerythritol hexa (meth) acrylate (as a commercially available product, KAYARAD DPHA; manufactured by Nippon Kayaku), ethyleneoxy modified di Pentaerythritol hexaacrylate (A-DPH-12E as a commercial product; manufactured by Shin-Nakamura Chemical Co., Ltd.) and a structure in which these (meth) acryloyl groups are mediated by ethylene glycol and prop
• the polymerizable compound may have an acid group such as a carboxyl group, a sulfonic acid group, or a phosphoric acid group. If the polymerizable compound has an unreacted carboxyl group or the like, it can be used as it is. However, if necessary, a non-aromatic carboxylic acid anhydride is reacted with the hydroxyl group of the polymerizable compound. An acid group may be introduced.
• non-aromatic carboxylic acid anhydrides include tetrahydrophthalic anhydride, alkylated tetrahydrophthalic anhydride, hexahydrophthalic anhydride, alkylated hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.
• the polymerizable compound having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and is obtained by reacting a non-aromatic carboxylic acid anhydride with an unreacted hydroxyl group of the aliphatic polyhydroxy compound.
• the polymerizable compound having an acid group thus obtained is more preferred, and particularly preferably, in this ester, the aliphatic polyhydroxy compound is pentaerythritol and / or dipentaerythritol.
• Examples of commercially available products include M-510 and M-520 as polybasic acid-modified acrylic oligomers manufactured by Toagosei.
• a preferable acid value of the polymerizable compound having an acid group is 0.1 mgKOH / g to 40 mgKOH / g, and particularly preferably 5 mgKOH / g to 30 mgKOH / g.
• the acid value of the polyfunctional monomer is 0.1 mgKOH / g or more, the development and dissolution characteristics are good, and when it is 40 mgKOH / g or less, it is advantageous in production and handling. Furthermore, the photopolymerization performance is good and the curability such as the surface smoothness of the pixels is excellent.
• the acid group as the entire polymerizable compound is It is preferable to adjust so that it may enter into the said range.
• polymeric compound which has a caprolactone structure as a polymeric compound.
• the polymerizable compound having a caprolactone structure is not particularly limited as long as it has a caprolactone structure in the molecule.
• a polymerizable compound having a caprolactone structure represented by the following general formula (Z-1) is preferable.
• R 1 represents a hydrogen atom or a methyl group
• m represents a number of 1 or 2
• “*” represents a bond
• R 1 represents a hydrogen atom or a methyl group
• “*” represents a bond
• the polymeric compound which has a caprolactone structure can be used individually or in mixture of 2 or more types.
• polymerizable compound a compound represented by the following general formula (Z-4) or (Z-5) can also be used.
• each E independently represents — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O).
• — Each independently represents an integer of 0 to 10
• each X independently represents an acryloyl group, a methacryloyl group, a hydrogen atom, or a carboxyl group.
• the total number of acryloyl groups and methacryloyl groups is 3 or 4
• each m independently represents an integer of 0 to 10
• the total of each m is an integer of 0 to 40 .
• any one of X is a carboxyl group.
• the total number of acryloyl groups and methacryloyl groups is 5 or 6, each n independently represents an integer of 0 to 10, and the total of each n is an integer of 0 to 60 . However, when the total of each n is 0, any one of X is a carboxyl group.
• m is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
• the total of each m is preferably an integer of 2 to 40, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 8.
• n is preferably an integer of 0 to 6, and more preferably an integer of 0 to 4.
• the total of each n is preferably an integer of 3 to 60, more preferably an integer of 3 to 24, and particularly preferably an integer of 6 to 12.
• — ((CH 2 ) y CH 2 O) — or — ((CH 2 ) y CH (CH 3 ) O) — represents oxygen
• a form in which the end on the atom side is bonded to X is preferred.
• the compounds represented by formula (Z-4) or formula (Z-5) may be used alone or in combination of two or more.
• a form in which all six Xs are acryloyl groups is preferable.
• the total content of the compound represented by the general formula (Z-4) or (Z-5) in the polymerizable compound is preferably 20% by mass or more, and more preferably 50% by mass or more.
• the compound represented by the general formula (Z-4) or (Z-5) is a conventionally known process, which is a ring-opening addition of ethylene oxide or propylene oxide to pentaerythritol or dipentaerythritol. It can be synthesized from a step of bonding a ring-opening skeleton by a reaction and a step of introducing a (meth) acryloyl group by reacting, for example, (meth) acryloyl chloride with a terminal hydroxyl group of the ring-opening skeleton. Each step is a well-known step, and a person skilled in the art can easily synthesize a compound represented by the general formula (Z-4) or (Z-5).
• a pentaerythritol derivative and / or a dipentaerythritol derivative are more preferable.
• Specific examples include compounds represented by the following formulas (a) to (f) (hereinafter also referred to as “exemplary compounds (a) to (f)”).
• exemplary compounds (a), (f) b), (e) and (f) are preferred.
• Examples of commercially available polymerizable compounds represented by the general formulas (Z-4) and (Z-5) include SR-494, a tetrafunctional acrylate having four ethyleneoxy chains manufactured by Sartomer, manufactured by Nippon Kayaku Co., Ltd. DPCA-60, which is a hexafunctional acrylate having six pentyleneoxy chains, and TPA-330, which is a trifunctional acrylate having three isobutyleneoxy chains.
• a compound having an epoxy group can also be used as the polymerizable compound.
• the compound having an epoxy group one having two or more epoxy groups in one molecule is preferable.
• the number of epoxy groups is preferably 2 to 10, more preferably 2 to 5, and particularly preferably 3 in one molecule. Details of these are described in paragraphs 0034 to 0036 of JP2013-011869A, paragraphs 0091 to 0103 of JP2014-153554A, and paragraphs 0084 to 0095 of JP2014-089408A. Which are incorporated herein by reference.
• an oligomer or polymer having an epoxy group in the side chain can also be preferably used.
• examples of such compounds include bisphenol A type epoxy resins, bisphenol F type epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, and aliphatic epoxy resins. These compounds may be used as commercial products or can be obtained by introducing an epoxy group into the side chain of the polymer.
• jER825, jER827, jER828, jER834, jER1001, jER1002, jER1003, jER1055, jER1007, jER1009, jER1010 (above, manufactured by Japan Epoxy Resins Co., Ltd.), EPICLON860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (manufactured by DIC Corporation), etc.
• bisphenol F type epoxy resins are jER806, jER807, jER4004, jER4005, jER4007, jER4010 (above, Japan Epoxy Resin Corporation), EPICLON830 , EPICLON 835 (above, manufactured by DIC Corporation), LCE-21, RE-602S As described above, jER152, jER154, jER157S70, jER157S65 (above, Japan Epoxy Resin Co
• EPICLON N-775 (manufactured by DIC Corporation), etc.
• cresol novolac type epoxy resins include EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680 , EPICLON N-690, EPICLON N-695 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc., and ADEKA RESIN EP-4 as an aliphatic epoxy resin 80S, EP-4085S, EP-4088S (manufactured by ADEKA Corporation), Celoxide 2021P, Celoxide 2081, Celoxide 2083, Celoxide 2085, EHPE3150, EPOLEEAD PB 3600, PB 4700 (above, Daicel Chemical Industries, Ltd.) ), Denacol EX-212L, EX-214L, EX-216L, EX-321L, EX
• ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4010S, EP-4011S (above, manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD-1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), jER1031S (manufactured by Japan Epoxy Resin Co., Ltd.) and the like.
• jER1031S Mitsubishi Chemical Corporation
• jER1032H60 Mitsubishi Chemical Corporation
• EPICLON HP-4700 DIC Corporation
• EPICLON N-695 DIC Corporation
• EPICLON 840 DIC Corporation
• EPICLON N660 DIC Corporation
• EPICLON HP7200 DIC Corporation
• the like can be preferably used.
• the compounds having an epoxy group may be used singly or in combination of two or more.
• the polymerizable compound is described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765.
• Urethane acrylates and urethane compounds having an ethylene oxide skeleton described in JP-B-58-49860, JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. is there.
• addition polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238 as polymerizable compounds.
• a compound having an oxetane group can also be used as the polymerizable compound.
• the compound having an oxetane group include the compounds described in paragraphs 0134 to 0145 of JP-A-2008-224970, the contents of which are incorporated herein.
• Aron Oxetane OXT-121, OXT-221, OX-SQ, and PNOX can be used.
• polymerizable compounds include urethane oligomers UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp), UA-7200 (manufactured by Shin-Nakamura Chemical), DPHA-40H (manufactured by Nippon Kayaku), UA-306H, UA -306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
• the blending amount of the polymerizable compound in the curable composition or colored composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 30% by mass with respect to the solid content.
• the colorant used in the coloring composition of the present invention is not particularly defined, and may be a pigment, a dye, or a combination of a pigment and a dye. Only one colorant may be used, or two or more colorants may be used.
• the amount of the colorant is preferably 10 to 90% by mass, more preferably 30 to 85% by mass, and further preferably 60 to 80% by mass of the solid content of the coloring composition of the present invention.
• the dye that can be used as the colorant contained in the coloring composition is not particularly limited, and conventionally known dyes for color filters can be used.
• an acidic dye and / or its derivative may be used suitably from a viewpoint that the binder and / or dye of a light non-irradiation part are removed completely by image development.
• direct dyes, basic dyes, mordant dyes, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dyes, and / or derivatives thereof can also be used effectively.
• acid dye examples include 1, 2, 24, 48; acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40 to 45, 62, 70, 74, 80, 83, 86 , 87, 90, 92, 103, 112, 113, 120, 129, 138, 147, 158, 171, 182, 192, 243, 324: 1; acid chroma violet K; acid Fuchsin; acid green 1, 3, 5 , 9, 16, 25, 27, 50; acid orange 6, 7, 8, 10, 12, 50, 51, 52, 56, 63, 74, 95; acidred 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 8 0, 87, 88, 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 183,
• azo, xanthene and phthalocyanine acid dyes are also preferred.
• I. Acid dyes such as Solvent range 45; Rhodamine B and Rhodamine 110 and derivatives of these dyes are also preferably used.
• the colorant triarylmethane, anthraquinone, azomethine, benzylidene, oxonol, cyanine, phenothiazine, pyrrolopyrazole azomethine, xanthene, phthalocyanine, benzopyran, indigo, pyrazole azo
• the colorant is selected from a series, anilinoazo, pyrazolotriazole azo, pyridone azo, anthrapyridone, and pyromethene.
• a dipyrromethene dye in which a compound represented by the following general formula (1) is coordinated to a metal atom or a metal compound is preferably used in terms of light resistance and heat resistance.
• R 1 to R 6 each independently represents a hydrogen atom or a monovalent substituent
• R 7 represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, or a heterocyclic group. Represents.
• Known dyes other than the above-mentioned pigment (A) include, for example, JP-A 64-90403, JP-A 64-91102, JP-A-1-94301, JP-A-6-11614, No. 2592207, U.S. Pat. No. 4,808,501, U.S. Pat. No. 5,667,920, U.S. Pat.No. 505950, U.S. Pat.
• the dyes disclosed in JP-A-6-51115 and JP-A-6-194828 can be used.
• the chemical structure includes pyrazole azo, pyromethene, anilinoazo, triarylmethane, anthraquinone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, etc.
• Dyes can be used.
• a dye multimer may be used as the dye. Examples of the dye multimer include compounds described in JP2011-213925A and JP2013-041097A. Compound A-1 used in Examples described later also corresponds to an example of a preferred pyromethene dye used in the present invention.
• the pigment used in the present invention may be an organic pigment or an inorganic pigment.
• inorganic pigments include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, etc. And black pigments such as the above-described metal complex oxides, carbon black, and titanium black.
• organic pigment for example, C. I. Pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199; C. I. Pigment orange 36, 38, 43, 71; C. I. Pigment red 81,105,122,149,150,155,171,175,176,177,179,209,220,224,242,254,255,264,270; C. I. Pigment violet 19, 23, 32, 39; C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66; C. I. Pigment green 7, 36, 37, 58; C. I. Pigment brown 25, 28; C. I. Pigment black 1; and the like.
• Examples of the pigment that can be preferably used in the present invention include the following. However, the present invention is not limited to these.
• organic pigments can be used alone or in various combinations in order to adjust the spectrum and increase the color purity. Specific examples of the above combinations are shown below.
• a red pigment an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment or a perylene red pigment
• an anthraquinone pigment C.I. I. Pigment red 177
• perylene pigments include C.I. I. Pigment red 155, C.I. I.
• Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Mixing with Pigment Yellow 139 is preferred.
• the mass ratio of the red pigment to the yellow pigment is preferably from 100: 5 to 100: 50, and more preferably from 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the desired spectrum.
• a halogenated phthalocyanine pigment can be used alone, or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used.
• a disazo yellow pigment e.g., a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment
• C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83 e. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred.
• the mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150, and more preferably 100: 30 to 100: 120.
• a phthalocyanine pigment can be used alone, or a mixture of this with a dioxazine purple pigment can be used.
• C.I. I. Pigment blue 15: 6 and C.I. I. Mixing with pigment violet 23 is preferred.
• the mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100.
• the pigment for the black matrix carbon, titanium black, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium black is preferable.
• the mass ratio of carbon to titanium black is preferably in the range of 100: 0 to 100: 60.
• the primary particle diameter of the pigment is preferably 100 nm or less from the viewpoint of color unevenness and contrast, and is preferably 5 nm or more from the viewpoint of dispersion stability. preferable.
• the average primary particle diameter of the pigment is more preferably 5 to 75 nm, further preferably 5 to 55 nm, and particularly preferably 5 to 35 nm.
• the average primary particle diameter of the pigment can be measured by a known method such as an electron microscope.
• pigment dispersant When the coloring composition of the present invention has a pigment, a pigment dispersant can be used in combination as desired.
• pigment dispersants include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], and surfactants such as polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, and pigment derivatives, etc. Can do.
• the polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure. Details of the dispersant can be referred to the description in paragraphs 0098 to 0102 of JP-A-2014-130344, and the contents thereof are incorporated in the present specification.
• pigment dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a combination of a pigment derivative and a polymer dispersant.
• the pigment dispersant may be used in combination with an alkali-soluble resin together with the terminal-modified polymer, graft polymer, or block polymer having an anchor site to the pigment surface.
• Alkali-soluble resins include (meth) acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., and carboxylic acid in the side chain. Examples thereof include acidic cellulose derivatives, and (meth) acrylic acid copolymers are particularly preferable.
• An alkali-soluble resin containing is also preferred.
• an alkali-soluble resin: benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer is exemplified. Examples of commercially available products include BY-161 (manufactured by BYK).
• the total content of the pigment dispersant is preferably 1 part by weight to 80 parts by weight with respect to 100 parts by weight of the pigment, and 5 parts by weight to 70 parts by weight. More preferred is 10 parts by mass to 60 parts by mass.
• the specific dispersing resin is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more, among the dispersant components contained in the coloring composition.
• the coloring composition of the present invention may contain only one type of pigment dispersant, or two or more types of pigment dispersants. When two or more types are included, the total amount is preferably within the above range.
• the curable composition or colored composition of the present invention may further contain an alkali-soluble resin.
• the alkali-soluble resin can also be used as a pigment dispersant.
• the alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be suitably selected from alkali-soluble resins having a group. From the viewpoint of heat resistance, polyhydroxystyrene resins, polysiloxane resins, acrylic resins, acrylamide resins, and acryl / acrylamide copolymer resins are preferable. From the viewpoint of development control, acrylic resins and acrylamide resins are preferable. Resins and acrylic / acrylamide copolymer resins are preferred.
• Examples of the group that promotes alkali solubility include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group, but are soluble in a solvent and can be developed with a weak alkaline aqueous solution.
• (meth) acrylic acid is particularly preferred.
• These acid groups may be used alone or in combination of two or more.
• Examples of the monomer that can give an acid group after polymerization include, for example, a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate, a monomer having an epoxy group such as glycidyl (meth) acrylate, and 2-isocyanatoethyl (meth). And monomers having an isocyanate group such as acrylate. Only one type of monomer for introducing these acid groups may be used, or two or more types may be used. In order to introduce an acid group into the alkali-soluble resin, for example, a monomer having an acid group and / or a monomer capable of giving an acid group after polymerization may be polymerized as a monomer component.
• a known radical polymerization method can be applied.
• Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.
• a polymer having a carboxylic acid in the side chain is preferable, such as a methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, and a crotonic acid copolymer.
• a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is suitable as the alkali-soluble resin.
• examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds.
• alkyl (meth) acrylate and aryl (meth) acrylate methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl (meth) acrylate,
• vinyl compounds such as hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, styrene, ⁇ -methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfury
• a compound represented by the following general formula (ED) and / or a compound represented by the following general formula (ED2) (hereinafter, these compounds may be referred to as “ether dimers”) are essential. It is also preferable to include a polymer (a) obtained by polymerizing a monomer component as a component.
• R 1 and R 2 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms which may have a substituent.
• R represents a hydrogen atom or an organic group having 1 to 30 carbon atoms.
• ED2 general formula (ED2)
• JP 2010-168539 A the description in JP 2010-168539 A can be referred to.
• the curable composition or coloring composition of this invention can form the cured film which was extremely excellent also in heat resistance and transparency.
• the hydrocarbon group having 1 to 25 carbon atoms which may have a substituent represented by R 1 and R 2 is not particularly limited, and examples thereof include methyl, ethyl, linear or branched alkyl groups such as n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, tert-amyl, stearyl, lauryl, 2-ethylhexyl; aryl groups such as phenyl; cyclohexyl, tert-butyl An alicyclic group such as cyclohexyl, dicyclopentadienyl, tricyclodecanyl, isobornyl, adamantyl and 2-methyl-2-adamantyl; an alkyl group substituted with alkoxy such as 1-methoxyeth
• ether dimer for example, the description in paragraph 0042 of JP-A-2014-041301 can be referred to, and the contents thereof are incorporated in the present specification.
• These ether dimers may be only one kind or two or more kinds.
• the structure derived from the compound represented by the general formula (ED) may be copolymerized with other monomers.
• the alkali-soluble resin may contain a structural unit derived from an ethylenically unsaturated compound represented by the following formula (X).
• R 1 represents a hydrogen atom or a methyl group
• R 2 represents an alkylene group having 2 to 10 carbon atoms
• R 3 represents a hydrogen atom or a benzene ring which may contain a benzene ring.
• n represents an integer of 1 to 15.
• the alkylene group of R 2 preferably has 2 to 3 carbon atoms.
• the alkyl group of R 3 has 1 to 20 carbon atoms, more preferably 1 to 10, and the alkyl group of R 3 may contain a benzene ring.
• Examples of the alkyl group containing a benzene ring represented by R 3 include a benzyl group and a 2-phenyl (iso) propyl group.
• an alkali-soluble resin having a polymerizable group may be used.
• an alkali-soluble resin having a polymerizable group an alkali-soluble resin containing an allyl group, a (meth) acryl group, an allyloxyalkyl group or the like in the side chain is useful.
• the alkali-soluble resin containing a polymerizable group as described above include: Dial NR series (manufactured by Mitsubishi Rayon), Photomer 6173 (COOH-containing polyurethane acrylic oligomer.
• the resin having an ester group having a leaving group such as a halogen atom or a sulfonate group at the ⁇ -position or ⁇ -position described in JP-A-229207 and JP-A-2003-335814 is obtained by basic treatment. Resins that can be used are preferred. Further, ACRYCURE-RD-F8 (manufactured by Nippon Shokubai) is also preferable.
• alkali-soluble resin in particular, a benzyl (meth) acrylate / (meth) acrylic acid copolymer or a multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers is suitable. .
• benzyl (meth) acrylate / (meth) acrylic acid / (meth) acrylic acid-2-hydroxyethyl copolymer copolymerized with 2-hydroxyethyl methacrylate 2 described in JP-A-7-140654 -Hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl Methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc.
• alkali-soluble resin descriptions from JP2012-208494A paragraphs 0558 to 0571 (corresponding to ⁇ 0685> to ⁇ 0700> in the corresponding US Patent Application Publication No. 2012/0235099) can be referred to, and the contents thereof can be referred to. Are incorporated herein. Further, the copolymer (B) described in paragraph Nos. 0029 to 0063 described in JP 2012-32767 A and the alkali-soluble resin used in Examples, paragraph Nos. 0088 to 2020 of JP 2012-208474 A The binder resin described in 0098 and the binder resin used in Examples, the binder resin described in Paragraph Nos.
• the following polymers can be used.
• the acid value of the alkali-soluble resin is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 50 mgKOH / g to 150 mgKOH / g, and particularly preferably 70 mgKOH / g to 120 mgKOH / g.
• the weight average molecular weight (Mw) of the alkali-soluble resin is preferably 2,000 to 50,000, more preferably 5,000 to 30,000, and particularly preferably 7,000 to 20,000.
• the content of the alkali-soluble resin is preferably 1 to 15% by mass with respect to the total solid content of the colored composition, The content is preferably 2 to 12% by mass, and particularly preferably 3 to 10% by mass. Further, when the polymer of the present invention is used as the alkali-soluble resin, it is preferable to contain 5 to 100% by mass of the polymer of the present invention in the total solid content of the alkali-soluble resin.
• the lower limit is preferably 10% by mass or more, more preferably 20% by mass or more, and further preferably 50% by mass or more.
• An upper limit can be 95 mass% or less, for example, and can also be 90 mass% or less.
• the curable composition or colored composition of the present invention may contain only one type of alkali-soluble resin, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
• the curable composition or colored composition of the present invention preferably further contains a photopolymerization initiator.
• the photopolymerization initiator is not particularly limited as long as it has the ability to initiate polymerization of a polymerizable compound, and can be appropriately selected from known photopolymerization initiators. For example, those having photosensitivity to visible light from the ultraviolet region are preferable. Further, it may be an activator that generates some action with a photoexcited sensitizer and generates an active radical, or may be an initiator that initiates cationic polymerization according to the type of monomer.
• the photopolymerization initiator preferably contains at least one compound having a molecular extinction coefficient of at least about 50 within a range of about 300 nm to 800 nm (more preferably 330 nm to 500 nm).
• the photopolymerization initiator examples include halogenated hydrocarbon derivatives (for example, those having a triazine skeleton, those having an oxadiazole skeleton, etc.), acylphosphine compounds such as acylphosphine oxide, hexaarylbiimidazole, and oxime derivatives.
• Oxime compounds such as organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenone compounds, and hydroxyacetophenones.
• trihalomethyltriazine compounds trihalomethyltriazine compounds, benzyldimethylketal compounds, ⁇ -hydroxyketone compounds, ⁇ -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, oniums
• compounds selected from the group consisting of compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyloxadiazole compounds, and 3-aryl substituted coumarin compounds are preferred.
• trihalomethyltriazine compound More preferred are trihalomethyltriazine compound, ⁇ -aminoketone compound, acylphosphine compound, phosphine oxide compound, oxime compound, triallylimidazole dimer, onium compound, benzophenone compound, acetophenone compound, trihalomethyltriazine compound, ⁇ -aminoketone
• the colored composition of the present invention when used for the production of a color filter for a solid-state imaging device, it is necessary to form a fine pattern with a sharp shape. It is important that it be developed. From such a viewpoint, it is particularly preferable to use an oxime compound as the photopolymerization initiator.
• an oxime compound as the photopolymerization initiator.
• stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it is particularly preferable to use an oxime compound as a photopolymerization initiator for forming a fine pattern such as a solid-state imaging device.
• oxime compound can improve the color transfer.
• paragraphs 0265 to 0268 of JP2013-29760A can be referred to, the contents of which are incorporated herein.
• hydroxyacetophenone compounds As the photopolymerization initiator, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can also be suitably used. More specifically, for example, aminoacetophenone initiators described in JP-A-10-291969 and acylphosphine oxide initiators described in Japanese Patent No. 4225898 can also be used.
• hydroxyacetophenone initiator IRGACURE-184, DAROCUR-1173, IRGACURE-500, IRGACURE-2959, IRGACURE-127 (trade names; all manufactured by BASF) can be used.
• aminoacetophenone-based initiator commercially available products IRGACURE-907, IRGACURE-369, and IRGACURE-379 (trade names; all manufactured by BASF) can be used.
• aminoacetophenone-based initiator a compound described in JP-A-2009-191179 in which an absorption wavelength is matched with a long-wave light source such as 365 nm or 405 nm can also be used.
• acylphosphine-based initiator commercially available products such as IRGACURE-819 and DAROCUR-TPO (trade names; both manufactured by BASF) can be used.
• photopolymerization initiator examples include oxime compounds.
• oxime compounds compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-80068, and compounds described in JP-A No. 2006-342166 can be used.
• oxime compounds include J.M. C. S. Perkin II (1979) pp. 1653-1660, J.A. C. S. Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and Technology (1995) pp. Examples thereof include compounds described in 202-232, JP-A No. 2000-66385, JP-A No. 2000-80068, JP-T 2004-534797, JP-A No. 2006-342166, and the like.
• IRGACURE-OXE01 manufactured by BASF
• IRGACURE-OXE02 manufactured by BASF
• TRONLY TR-PBG-304 TRONLY TR-PBG-309, TRONLY TR-PBG-305 (manufactured by CHANGZHOU TRONLY NEW ELECTRONIC MATERIALS CO., LTD), Adeka Arcs NCI-31 Adeka Arkles NCI-930 (manufactured by ADEKA) can also be used.
• oxime compounds other than those described above compounds described in JP-A-2009-519904 in which an oxime is linked to the carbazole N-position, compounds described in US Pat. No. 7,626,957 in which a hetero substituent is introduced into the benzophenone moiety, Compounds described in Japanese Patent Application Laid-Open No. 2010-15025 and US Patent Publication No. 2009-292039, in which a nitro group is introduced into the dye moiety, ketoxime compounds described in International Patent Publication No. 2009-131189, a triazine skeleton and an oxime skeleton in the same molecule A compound described in US Pat. No.
• the oxime compound is preferably a compound represented by the following formula (OX-1).
• the oxime N—O bond may be an (E) oxime compound, a (Z) oxime compound, or a mixture of (E) and (Z) isomers. .
• R and B each independently represent a monovalent substituent
• A represents a divalent organic group
• Ar represents an aryl group.
• the monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group.
• the monovalent nonmetallic atomic group include an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic group, an alkylthiocarbonyl group, and an arylthiocarbonyl group.
• these groups may have one or more substituents.
• the substituent mentioned above may be further substituted by another substituent.
• the substituent examples include a halogen atom, an aryloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, an acyloxy group, an acyl group, an alkyl group, and an aryl group.
• the monovalent substituent represented by B is preferably an aryl group, a heterocyclic group, an arylcarbonyl group, or a heterocyclic carbonyl group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
• the divalent organic group represented by A is preferably an alkylene group having 1 to 12 carbon atoms, a cycloalkylene group, or an alkynylene group. These groups may have one or more substituents. Examples of the substituent include the above-described substituents.
• an oxime compound having a fluorine atom can also be used as a photopolymerization initiator.
• Specific examples of the oxime compound having a fluorine atom include compounds described in JP 2010-262028 A, compounds 24 and 36 to 40 described in JP-A-2014-500852, and compounds described in JP-A 2013-164471 ( C-3). This content is incorporated herein.
• the oxime compound has a maximum absorption wavelength in a wavelength region of 350 nm to 500 nm, preferably has a maximum absorption wavelength in a wavelength region of 360 nm to 480 nm, and particularly preferably has a high absorbance at 365 nm and 455 nm. .
• the molar extinction coefficient at 365 nm or 405 nm of the oxime compound is preferably from 1,000 to 300,000, more preferably from 2,000 to 300,000, more preferably from 5,000 to 200, from the viewpoint of sensitivity. Is particularly preferred.
• a known method can be used. Specifically, for example, in an ultraviolet-visible spectrophotometer (Vary Carry-5 spectrophotometer), an ethyl acetate solvent is used. It is preferable to measure at a concentration of 01 g / L. You may use the photoinitiator used for this invention in combination of 2 or more type as needed.
• the content of the photopolymerization initiator is preferably 0.1 to 50% by mass relative to the total solid content of the colored composition, and more The content is preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass. Within this range, better sensitivity and pattern formability can be obtained.
• the composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types are included, the total amount is preferably within the above range.
• the curable composition or the colored composition of the present invention includes, in addition to the above-described components, a solvent, a polymerization inhibitor, a surfactant, an organic carboxylic acid, and an organic carboxylic acid as long as the effects of the present invention are not impaired.
• Other components such as anhydrides may be included.
• the curable composition or colored composition of the present invention may contain a solvent.
• the solvent is basically not particularly limited as long as the solubility of each component and the coating property of the coloring composition are satisfied, but considering the solubility, coating property, and safety of the dye (A) and the curable compound. Are preferably selected.
• the solvent examples include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, cyclohexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, Alkyl oxyacetates (eg, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate (eg, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate)), 3-oxypropionic acid alkyl esters (Eg, methyl 3-oxypropionate, ethyl 3-oxypropionate, etc.
• esters such as ethyl acetate, n-butyl
• Oxypropionic acid alkyl esters eg, methyl 2-oxypropionate, ethyl 2-oxypropionate, propyl 2-oxypropionate, etc.
• ethers For example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether Acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate and the like and ketones such as methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone and 3-heptanone, and aromatic hydrocarbons such as , Preferable examples include toluene and xylene.
• the organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.
• the content of the solvent in the coloring composition is preferably such that the total solid concentration of the coloring composition is 5% by mass to 80% by mass, and more preferably 5% by mass to 60% by mass, from the viewpoint of applicability. 10 to 50% by mass is particularly preferable.
• the curable composition or colored composition of the present invention may contain only one type of solvent or two or more types of solvents. When two or more types are included, the total amount is preferably within the above range.
• ⁇ Polymerization inhibitor >>> In the curable composition or colored composition of the present invention, it is desirable to add a small amount of a polymerization inhibitor in order to prevent unnecessary thermal polymerization of the polymerizable compound during the production or storage of the colored composition.
• the polymerization inhibitor that can be used in the present invention include hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl-6- t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), N-nitrosophenylhydroxyamine primary cerium salt and the like.
• the content of the polymerization inhibitor is preferably about 0.01 to 5% by mass relative to the mass of the colored composition.
• the curable composition or colored composition of the present invention may contain only one type of polymerization inhibitor or two or more types of polymerization inhibitors. When two or more types are included, the total amount is preferably within the above range.
• Various surfactants may be added to the composition of the present invention from the viewpoint of further improving coatability.
• various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant can be used.
• the composition of the present invention contains a fluorosurfactant
• the liquid properties (particularly fluidity) when prepared as a coating liquid are further improved. Sex can be improved more. That is, when a film is formed using a coating liquid to which a composition containing a fluorosurfactant is applied, the wettability to the coated surface is reduced by reducing the interfacial tension between the coated surface and the coating liquid. Is improved, and the coating property to the coated surface is improved. For this reason, even when a thin film of about several ⁇ m is formed with a small amount of liquid, it is effective in that it is possible to more suitably form a film having a uniform thickness with small thickness unevenness.
• the fluorine content in the fluorosurfactant is preferably 3% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and particularly preferably 7% by mass to 25% by mass.
• a fluorine-based surfactant having a fluorine content within this range is effective in terms of uniformity of coating film thickness and liquid-saving properties, and has good solubility in the composition.
• fluorosurfactant examples include Megafac F171, F172, F173, F176, F176, F177, F141, F142, F143, F144, R30, F437, F475, F479, F482, F554, F780, F780, F781 (above DIC), Florard FC430, FC431, FC171 (above, Sumitomo 3M), Surflon S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S393, K393, KH-40 (above, manufactured by Asahi Glass), PF636, PF656, PF6320, PF6520, PF7002 (manufactured by OMNOVA), etc. Is mentioned. The following compounds are also exemplified as the fluorosurfactant used in the present invention.
• nonionic surfactant examples include glycerol, trimethylolpropane, trimethylolethane, and ethoxylates and propoxylates thereof (for example, glycerol propoxylate, glycerol ethoxylate, etc.), polyoxyethylene lauryl ether, polyoxyethylene Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester (Pluronic L10, L31, L61, L62, 10R5 manufactured by BASF) 17R2, 25R2, Tetronic 304, 701, 704, 901, 904, 150R1), Rusupasu 20000 (Lubrizol), and the like.
• glycerol trimethylolpropane
• ethoxylates and propoxylates thereof for example, glyce
• cationic surfactant examples include phthalocyanine derivatives (trade name: EFKA-745, manufactured by Morishita Sangyo), organosiloxane polymer KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), (meth) acrylic acid (co) polymer polyflow No. . 75, no. 90, no. 95 (manufactured by Kyoeisha Chemical), W001 (manufactured by Yusho) and the like.
• phthalocyanine derivatives trade name: EFKA-745, manufactured by Morishita Sangyo
• organosiloxane polymer KP341 manufactured by Shin-Etsu Chemical Co., Ltd.
• acrylic acid co
• polymer polyflow No. . 75, no. 90, no. 95 manufactured by Kyoeisha Chemical
• W001 manufactured by Yusho
• anionic surfactants include W004, W005, W017 (manufactured by Yusho) and the like.
• silicone surfactant examples include “Toray Silicone DC3PA”, “Toray Silicone SH7PA”, “Tore Silicone DC11PA”, “Tore Silicone SH21PA”, “Tore Silicone SH28PA”, and “Toray Silicone SH29PA” manufactured by Toray Dow Corning.
• Toray Silicone SH30PA examples include “Tole Silicone SH8400”, Momentive Performance Materials “TSF-4440”, “TSF-4300”, “TSF-4445”, “TSF-4460”, “TSF-4442”, Examples include “KP341”, “KF6001”, “KF6002” manufactured by Shin-Etsu Silicone, “BYK307”, “BYK323”, “BYK330” manufactured by BYK Chemie.
• the addition amount of the surfactant is preferably 0.001% by mass to 2.0% by mass, more preferably 0.001% by mass relative to the total mass of the composition. 005 mass% to 1.0 mass%.
• the composition of the present invention may contain only one type of surfactant or two or more types of surfactant. When two or more types are included, the total amount is preferably within the above range.
• the curable composition or colored composition of the present invention may contain an organic carboxylic acid having a molecular weight of 1000 or less and / or an organic carboxylic acid anhydride.
• an organic carboxylic acid and the organic carboxylic acid anhydride for example, paragraphs 0338 to 0340 of JP-A-2013-29760 can be referred to, the contents of which are incorporated herein.
• the curable composition or the colored composition of the present invention contains an organic carboxylic acid or an organic carboxylic acid anhydride, the amount of the organic carboxylic acid and / or organic carboxylic acid anhydride added is usually 0.00 in the total solid content.
• the range is from 01 to 10% by mass, preferably from 0.03 to 5% by mass, and more preferably from 0.05 to 3% by mass.
• the curable composition or colored composition of the present invention may contain only one type or two or more types of organic carboxylic acids and / or organic carboxylic anhydrides. When two or more types are included, the total amount is preferably within the above range.
• the curable composition or colored composition of the present invention may contain various additives such as fillers, adhesion promoters, antioxidants, ultraviolet absorbers, anti-aggregation agents, etc., as necessary. can do.
• additives include those described in JP-A No. 2004-295116, paragraphs 0155 to 0156, the contents of which are incorporated herein.
• the following compound can also be contained.
• the curable composition or colored composition of the present invention contains a sensitizer and a light stabilizer described in paragraph 0078 of JP-A No. 2004-295116, and a thermal polymerization inhibitor described in paragraph 0081 of the same publication. be able to. Further, a resin containing a monomer represented by the general formula (1) of JP-A-2006-215453 as a copolymer component can be contained as a binder.
• the colored composition may contain a metal element, but from the viewpoint of suppressing the occurrence of defects, the content of Group 2 elements (calcium, magnesium, etc.) in the colored composition is 50 ppm or less. It is preferable to control to 0.01 to 10 ppm.
• the total amount of the inorganic metal salt in the coloring composition is preferably 100 ppm or less, and more preferably controlled to 0.5 to 50 ppm.
• the curable composition and coloring composition of the present invention are prepared by mixing the aforementioned components.
• the components constituting the curable composition or the colored composition may be combined at once, or the components may be combined sequentially after dissolving and dispersing each component in a solvent. May be.
• the composition may be prepared by dissolving and dispersing all components in a solvent at the same time. If necessary, each component may be suitably used as two or more solutions / dispersions at the time of use (at the time of application). ) May be mixed to prepare a composition.
• the curable composition or colored composition of the present invention is preferably filtered with a filter for the purpose of removing foreign substances or reducing defects. If it is conventionally used for the filtration use etc., it can use without being specifically limited.
• fluorine resins such as PTFE (polytetrafluoroethylene), polyamide resins such as nylon-6 and nylon-6,6, polyolefin resins such as polyethylene and polypropylene (PP) (including those with high density and ultra high molecular weight) ) And the like.
• PP polypropylene
• polypropylene including high density polypropylene
• the pore size of the filter is suitably about 0.01 to 7.0 ⁇ m, preferably about 0.01 to 3.0 ⁇ m, more preferably about 0.05 to 0.5 ⁇ m. By setting it as this range, it becomes possible to remove reliably the fine foreign material which inhibits preparation of the uniform and smooth curable composition or coloring composition in a post process.
• the filtering by the first filter may be performed only once or may be performed twice or more.
• the pore diameter here can refer to the nominal value of the filter manufacturer.
• a commercially available filter for example, it can be selected from various filters provided by Nippon Pole Co., Ltd., Advantech Toyo Co., Ltd., Japan Entegris Co., Ltd. (formerly Japan Microlith Co., Ltd.) or KITZ Micro Filter Co., Ltd. .
• the second filter a filter formed of the same material as the first filter described above can be used.
• the filtering by the first filter may be performed only with the dispersion, and the second filtering may be performed after mixing other components.
• the cured film of the present invention can be obtained by curing the curable composition of the present invention or the colored composition of the present invention.
• a cured film having excellent heat resistance and color transfer can be formed, and therefore, it is preferably used for forming a colored layer of a color filter.
• the colored composition of the present invention is a color used for an image display device such as a solid-state imaging device (for example, a charge coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), etc.) or a liquid crystal display device (LCD). It can be suitably used for forming a colored pattern such as a filter. Furthermore, it can be suitably used as a production application for printing ink, inkjet ink, paint, and the like. Especially, it can use suitably for manufacture of the color filter for solid-state image sensors, such as CCD and CMOS.
• the color filter of the present invention is obtained using the colored composition of the present invention.
• a method for producing the color filter is not particularly defined, but a photolithography method and a dry etching method are preferably used.
• a photolithography method and a dry etching method are preferably used.
• the color filter of the present invention can be used for a solid-state imaging device. Details of the solid-state imaging device are described in paragraphs 0155 to 0156 of JP2014-080589A, descriptions of paragraphs 0291 to 0305 of JP2013-257543A, and paragraphs 0312 to 0314 of JP2013-257543A. The contents of which are incorporated herein by reference.
• the color filter of the present invention can be used for an image display device such as a liquid crystal display device or an organic light emitting display device, and is particularly suitable for use in a liquid crystal display device.
• image display device such as a liquid crystal display device or an organic light emitting display device
• description in paragraphs 0150 to 0154 of JP2014-080589A and the description of paragraphs 0307 to 0311 in JP2013-257543A can be referred to, and the contents thereof are incorporated in this specification. It is.
• DPE dipentaerythritol
• DMAc N, N-dimethylacetamide
• the reaction was added little by little to 350 parts of 1N aqueous hydrochloric acid to stop the reaction, and 500 parts of ethyl acetate was added to carry out a liquid separation operation. Subsequently, the organic layer was washed with 250 parts of saturated sodium bicarbonate water, 250 parts of water and 150 parts of saturated saline. Sodium sulfate was added to the obtained organic layer, followed by filtration, and the filtrate was concentrated under reduced pressure to obtain 24 parts of intermediate S-27-1 (yield 93%).
• Synthesis was performed in the same manner as in Synthesis Example 1 of (S-27), except that 5.3 parts of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dipentaerythritol in Synthesis Example 1 of (S-27). And 23.1 parts of intermediate S-3-1 were obtained (88% yield). Synthesis of (S-27) in Synthesis Example 1 except that 20 parts of intermediate S-3-1, 8.2 parts of thiourea, 200 parts of ethanol, and 18 parts of potassium iodide were used. Synthesis was performed in the same manner as in Example 1 to obtain 11.8 parts of S-3 (yield 75%).
• Synthesis Example 1 of (S-27) 5.3 parts of trimethylolpropane (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of dipentaerythritol was replaced with 10-bromodecanoic acid chloride (10-bromodecane instead of 6-bromohexanoic acid chloride). Synthesis was performed in the same manner as in Synthesis Example 1 of (S-27) except that 38.1 parts of acid (produced from Tokyo Kasei Kogyo Co., Ltd. according to a known method) was used. 29.4 parts were obtained (89% yield). Synthesis was performed in the same manner as in Synthesis Example 1 except that 25 parts of Intermediate S-8-1 was used instead of Intermediate S-27-1 in Synthesis Example 1 of (S-27).
• Synthesis was performed in the same manner as in Synthesis Example 1 of (S-27) except that 4 parts of pentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of dipentaerythritol in Synthesis Example 1 of (S-27). 22.8 parts of the product S-24-1 was obtained (yield 92%).
• Synthesis was performed in the same manner as in Synthesis Example 1 of (S-27) except that 3.6 parts of D-sorbitol (manufactured by Kanto Chemical) was used in place of dipentaerythritol in Synthesis Example 1 of (S-27). 18.8 parts of intermediate S-31-1 was obtained (76% yield). Synthesis of (S-27) in Synthesis Example 1 except that 10 parts of intermediate S-31-1, 4.4 parts of thiourea, 100 parts of ethanol, and 9 parts of potassium iodide were used. Synthesis was carried out in the same manner as in Example 1 to obtain 5.7 parts of S-31 (yield 74%).
• Synthesis Example 1 of (S-27) Synthesis Example 1 of (S-27) was used except that 3.5 parts of D (+)-glucose (manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of dipentaerythritol. In the same manner as above, 16.1 parts of intermediate S-45-1 was obtained (yield 77%).
• Synthesis Example 1 of (S-27) similar to Synthesis Example 1 of (S-27), except that 16.2 parts of Intermediate S-45-1 was used instead of Intermediate S-27-1. To obtain 10.7 parts of S-45 (yield 85%).
• Synthesis was similar to Synthesis Example 1 of (S-27) except that 7.4 parts of ditrimethylolpropane (Mitsubishi Gas Chemical) was used instead of dipentaerythritol in Synthesis Example 1 of (S-27). To obtain 22.9 parts of intermediate S-51-1 (yield 81%).
• Synthesis Example 1 of (S-27) similar to Synthesis Example 1 of (S-27), except that 21.8 parts of Intermediate S-51-1 were used instead of Intermediate S-27-1
• To obtain 14.9 parts of S-51 Yield 85%).
• MALDI-MS m / z calcd. 793 [M + Na], found 793. The purity measured by HPLC was 73%.
• Dipentaerythritol (DPE, manufactured by Tokyo Chemical Industry Co., Ltd.) 7.6 parts, thioglycolic acid (manufactured by Wako Pure Chemical Industries) 16.6 parts, toluene 75 parts, p-toluenesulfonic acid monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) ) 0.29 part was added to the flask and heated to reflux under a nitrogen atmosphere. After 8 hours, the outflow of water had stopped.
• Coloring composition 3-1 The following components were mixed and dissolved, and filtered through a nylon filter having a pore diameter of 0.45 ⁇ m to prepare a coloring composition.
• Organic solvent 1 cyclohexanone
• Dye solution 1 was prepared by mixing and dissolving the following components.
• Organic solvent 1 (cyclohexanone) 21.55 parts
• Dye (A-1) 3.02 parts
• Pigment Dispersion Liquid P1 (CI Pigment Blue 15: 6 Dispersion)
• Pigment Dispersion Liquid P1 (CI Pigment Blue 15: 6 Dispersion) was prepared as follows.
• C. I. Pigment Blue 15: 6 (blue pigment; hereinafter also referred to as “PB15: 6”) 19.4 parts by mass (average primary particle size 55 nm), and pigment dispersant BY-161 (manufactured by BYK) 2.95 parts by mass, 2.95 parts by mass (solution 9.93) of alkali-soluble resin 1 (benzyl methacrylate / methacrylic acid (47/53 [mass ratio]), 30% propylene glycol monomethyl ether solution, Mw 11,000) in terms of solid content.
• the mixed liquid obtained by mixing 165.3 parts by mass of propylene glycol monomethyl ether was dispersed by mixing for 3 hours with beads mill (zirconia beads 0.3 mm diameter). Thereafter, dispersion treatment was further performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using a high-pressure disperser NANO-3000-10 (manufactured by Nippon BEE Co., Ltd.) with a decompression mechanism. This dispersion treatment was repeated 10 times to obtain C.I. I. Pigment Blue 15: 6 dispersion was obtained. The obtained C.I. I.
• Pigment Blue 15 6 dispersion, the average primary particle diameter of the pigment was measured by a dynamic light scattering method (Microtrac Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.)) and found to be 24 nm.
• Preparation of colored cured film 4-1 Preparation of colored cured film using colored composition
• the colored composition prepared above was applied onto the undercoat layer of the silicon wafer substrate with the undercoat layer prepared above, and colored. A layer (coating film) was formed. Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 1 ⁇ m. Next, the pre-baked silicon wafer substrate was heated at 200 ° C. for 5 minutes, and the coating film was cured to produce a colored cured film.
• the above-prepared silicon wafer substrate with a colored cured film was heated on a hot plate at 280 ° C. for 30 minutes and then immersed in cyclohexanone for 10 minutes.
• the visible light transmittance difference ( ⁇ T) at 400 to 700 nm of the silicon wafer substrate with a colored cured film before and after being immersed in cyclohexanone was measured using a chromaticity meter MCPD-1000 (manufactured by Otsuka Electronics Co., Ltd.). Based on the measured ⁇ T, the heat resistance was evaluated according to the following evaluation criteria.
• ⁇ T is less than 5%
• B ⁇ T is 5% or more and less than 10%
• C ⁇ T is 10% or more and less than 20%
• D ⁇ T is 20% or more
• Example 1 A colored cured film was produced in the same manner as in Example 1 except that the colored composition was prepared by changing the thiol compound to the thiol compound shown in the following table in Example 1, and the heat resistance was evaluated.
• T-1, T-3, T-4 or commercially available product T-2 synthesized in the above synthesis example was used.
• Compound T-2 is dipentaerythritol hexakis (3-mercaptopropionate) (product name DPMP, manufactured by SC Organic Chemical Industry).
• the colored composition of the present invention was excellent in heat resistance.
• a coloring obtained by using the same amount of KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) in place of the polymerizable compound 1 in place of the NK ester A-DPH-12E Similar results were obtained for the cured film.
• the colored cured film obtained by using IRGACURE OXE-01 manufactured by BASF having the same mass in place of IRGACURE OXE-02 as photopolymerization initiator 1, Similar results were obtained.
• 50:50 represents a molar ratio
• Hollow silica particle fine particle sol isopropyl alcohol silica sol, manufactured by Catalyst Kasei Kogyo Co., Ltd., CS60-IPA, average particle diameter 60 nm, shell thickness 10 nm, silica concentration 20 mass%, silica particle refractive index 1.31
• 500 parts by mass of acryloyloxy After adding 30 parts by mass of propyltrimethoxysilane and 1.51 parts by mass of diisopropoxyaluminum ethyl acetate, 9 parts by mass of ion-exchanged water was added thereto. The mixed solution was reacted at 60 ° C.
• IPA isopropyl alcohol
• -Perfluoroolefin copolymer (1) 15 parts-Hollow silica dispersion A 50 parts-Multifunctional monomer 1 (compound (A-2) below) 20 parts-Multifunctional monomer 2 (dipentaerythritol pentaacrylate and dipenta Mixture of erythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd.
• Photopolymerization initiator BASF, Irgacure 127) 2.5 parts Thiol compound (synthesized in Synthesis Example 1 (S-27)) 0.5 part Fluorine-containing monomer (the following compound (A-3)) 5 parts
• the coating solution prepared above was applied onto a glass substrate having an area of 100 cm 2 using a gravure coater to form a coating film.
• the coating film was irradiated with ultraviolet rays.
• Ultraviolet irradiation was performed using a 240 W / cm air-cooled metal halide lamp (manufactured by Eye Graphics) while purging with nitrogen so that the atmosphere had an oxygen concentration of 0.1% by volume or less.
• the irradiated ultraviolet rays were ultraviolet rays having an illuminance of 600 mW / cm 2 and an irradiation amount of 600 mJ / cm 2 .
• the coating film was cured by irradiation with ultraviolet rays to form a cured film having a thickness of 150 nm to obtain a glass substrate with a colorless cured film.
• the film thickness was calculated using a reflection spectral film thickness meter “FE-3000” (manufactured by Otsuka Electronics).
• the mass of the fluorinated monomer (A-3) eluted in cyclohexanone (the amount of elution A-3) was calculated according to the following (formula 1).
• the heat resistance was evaluated based on the following evaluation criteria.
• a cured film was prepared in the same manner as in Example 14 except that the coating solution was prepared by changing the thiol compound to the thiol compound shown in the following table in Example 14, and the heat resistance was evaluated.
• the colored composition of the present invention was found to be excellent in heat resistance.
• Example 20> 1. 102 parts by mass of the thiol compound S-27 obtained in Synthesis Example 2, 100 parts by mass of an epoxy compound (manufactured by Mitsubishi Chemical, epoxy resin jER825, epoxy equivalent 170 [g / eq]), and a curing accelerator (Wako Pure Chemical Industries, Ltd.) A curable composition was obtained by mixing 4 parts by mass of 3-aminomethyl-3,5,5-trimethylcyclohexylamine (IPDA) manufactured by Kogyo. The mechanical strength of the cured product obtained using the obtained curable composition was evaluated by the following evaluation method.
• IPDA 3-aminomethyl-3,5,5-trimethylcyclohexylamine
• Example 9 A cured product was prepared in the same manner as in Example 20 except that the thiol compound was changed to the thiol compound shown in the following table to prepare a curable composition, and the heat resistance was evaluated.
• Example 20 the epoxy compound was replaced with 100 parts by mass of jER825, and 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate (Daicel Chemical Industries, Celoxide 2021P, epoxy equivalent 130 [g / eq]) Similar results were obtained for the curable composition obtained using 76.5 parts by mass.
• Examples 26 to 29, Comparative Example 10> A cured product was produced in the same manner as in Example 25 except that the thiol compound was changed to the thiol compound shown in the following table to prepare a curable composition, and the heat resistance was evaluated.
• ⁇ Synthesis Example 17> Synthesis of alkali-soluble resin 15.3 parts by mass of the thiol compound S-27 obtained in Synthesis Example 2, 30 parts by mass of methacrylic acid (manufactured by Wako Pure Chemical Industries), 70 masses of benzyl methacrylate (manufactured by Wako Pure Chemical Industries) And 117 parts by mass of propylene glycol monomethyl ether acetate were mixed with a polymerization initiator (manufactured by Wako Pure Chemical Industries, dimethyl 2,2′-azobis (2-methylpropionate), product name V-601). 1.5 parts by mass were mixed to obtain a monomer solution.
• a polymerization initiator manufactured by Wako Pure Chemical Industries, dimethyl 2,2′-azobis (2-methylpropionate
• Coloring composition 2-1 Blue coloring composition
• Organic solvent 1 cyclohexanone
• Alkali-soluble resin 1 alkali-soluble resin synthesized in Synthesis Example 17
• Alkali-soluble resin 2 Alkali-soluble resin 2
• Acrycure-RD-F8 manufactured by Nippon Shokubai
• NK ester A-DPH-12E 1.96 parts-polymerization inhibitor (p-methoxyphenol) 0.0007 parts-photopolymerization initiator 1 (IRGACURE)
• OXE-02 manufactured by BASF
• Fluorosurfactant manufactured by DIC, trade name: Megafac F-475
• a mixture of 2.7 parts of resin (P-1) as a solvent and 78.3 parts of propylene glycol monomethyl ether acetate as a solvent is mixed and dispersed for 15 hours using a bead mill, and the Green pigment dispersion P2 Was prepared.
• each component was mixed so as to have the following composition to obtain a solution.
• Green coloring composition ⁇ Composition> -Green pigment dispersion P2 83.3 parts-Alkali-soluble resin (resin (P-1)) 1.0 part-Photopolymerization initiator (IRGACURE OX-01, manufactured by BASF) 1.2 parts-Polymerizable compound 1 (Compound M-1 below) 1.4 parts / polymerizable compound 2 (M-305, manufactured by Toagosei Co., Ltd.) 1.4 parts / 80% solution of compound (A-8) (manufactured by Sigma-Aldrich) 1.3 Parts ⁇ p-methoxyphenol 0.001 part ⁇ polyethylene glycol methyl ether acetate 7.4 parts ⁇ surfactant (PGMEA 0.2% solution) 4.2 parts
• Polymerizable compound 1 structure shown below
• Polymerizable compound 2 the following structure
• a 1.0 ⁇ m square Bayer pattern mask is passed through a wavelength of 365 nm and an exposure amount capable of forming a 1.0 ⁇ m square Bayer pattern ( Irradiation was performed in advance (selected from 50 to 1000 mJ / cm 2 ). Thereafter, the silicon wafer on which the irradiated coating film is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type; manufactured by Chemitronics), and a developer CD-2000 (Fuji A green colored pattern was formed on the silicon wafer by paddle development at 23 ° C.
• DW-30 type manufactured by Chemitronics
• a silicon wafer on which a green coloring pattern is formed is fixed to a horizontal rotary table by a vacuum chuck method, and the silicon wafer is rotated at a rotation speed of 50 rpm by a rotating device, and pure water is ejected from above the rotation center from a jet nozzle. And then rinsed and then spray dried.
• the silicon wafer on which the green coloring pattern was formed was heated on a hot plate at 200 ° C. for 5 minutes to form a green pattern.
• a blue pattern is formed in the same manner as the formation of the green pattern except that the exposure is performed using a 1.0 ⁇ m square island pattern mask instead of the Bayer pattern mask.
• a color filter was prepared.
• ⁇ T is less than 5%
• B ⁇ T is 5% or more and less than 10%
• C ⁇ T is 10% or more and less than 20%
• D ⁇ T is 20% or more
• dishing The height of the blue pixel of the color filter produced above was measured along the diagonal line of the pixel using an atomic force microscope (AFM, manufactured by Seiko Instruments Inc., SPA-400AFM). Based on the measured values, dishing was evaluated based on the following evaluation criteria, with the difference in height between the highest point and the center as the dishing depth.
• dishing depth is 100 nm or more
• Example 31 Comparative Examples 11 to 12>
• the alkali-soluble resin 1 used in the Blue coloring composition was replaced with the alkali-soluble resin synthesized in Synthesis Example 17, except that the alkali-soluble resin synthesized in Synthesis Examples 18 to 20 was used.
• a blue colored composition was prepared in the same manner as in No. 30, and dishing was evaluated in the same manner as in Example 30.
• Examples containing an alkali-soluble resin produced using the thiol compound of the present invention were excellent in heat resistance. Furthermore, the dishing reduction performance was also excellent.
• the polymerizable compound 1 is obtained using KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., dipentaerythritol hexaacrylate) instead of the NK ester A-DPH-12E. Similar results were obtained for the colored composition. Similar results were obtained with a colored composition obtained by using IRGACURE OXE-01 (manufactured by BASF) having the same mass in place of the photopolymerization initiator instead of IRGACURE OXE-02.

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