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WO2025044765A1 - Composé ester d'oxime, résine photosensible et son utilisation - Google Patents

Composé ester d'oxime, résine photosensible et son utilisation Download PDF

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Publication number
WO2025044765A1
WO2025044765A1 PCT/CN2024/111978 CN2024111978W WO2025044765A1 WO 2025044765 A1 WO2025044765 A1 WO 2025044765A1 CN 2024111978 W CN2024111978 W CN 2024111978W WO 2025044765 A1 WO2025044765 A1 WO 2025044765A1
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alkyl
group
formula
substituted
cycloalkyl
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Chinese (zh)
Inventor
麻忠利
杭德余
毕新鉴
王东方
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Beijing Yunji Technology Co Ltd
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Beijing Yunji Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/62—Oximes having oxygen atoms of oxyimino groups esterified
    • C07C251/64—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids
    • C07C251/66—Oximes having oxygen atoms of oxyimino groups esterified by carboxylic acids with the esterifying carboxyl groups bound to hydrogen atoms, to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/60—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
    • 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
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used

Definitions

  • the invention belongs to the technical field of organic chemistry and photocuring, and in particular relates to a new oxime ester compound, a photoresist containing the oxime ester compound and application thereof.
  • Patent WO2002/100903 discloses oxime ester compounds with more complex substituents on the diphenyl sulfide parent structure and oxime ester compounds based on carbazole.
  • Patent CN101528694A discloses oxime ester compounds with nitrocarbazole as the parent
  • patent CN103153952A discloses oxime ester compounds with benzocarbazole as the parent.
  • the present invention provides a novel oxime ester compound.
  • the present invention unexpectedly found that this type of compound has very high sensitivity and can meet the process requirements for the use of photoresists.
  • the novel oxime ester compound provided by the present invention has both a dicarbonyl amide group and an oxime ester group, and can be used as a photoinitiator in photocuring technology, especially showing high sensitivity and low yellowing characteristics in photoresists, and can be used in the manufacture of color displays.
  • R 1 is selected from NR 4 R 5 ;
  • R2 is selected from a hydrogen atom, a deuterium atom, a substituted or unsubstituted C1-C10 alkyl group, a C3-C10 alkyl group inserted by one or more O atoms, a substituted or unsubstituted C3-C7 cycloalkyl group, a substituted or unsubstituted C3-C7 heterocyclic group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C4-C20 heteroaryl group,
  • the substituent in the C1-C10 alkyl group is selected from one or more of phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, and C1-C4 alkyl acyloxy.
  • the substituents in the C6-C20 aryl and C4-C20 heteroaryl are selected from one or more of C1-C4 alkyl, C3-C7 cycloalkyl, F, Cl, C1-C4 alkoxy, C1-C4 alkylthio, -COCOOR 4 ;
  • R3 is selected from C1-C3 alkyl, C3-C7 cycloalkyl substituted C1-C3 alkyl, C3-C6 alkenyl, C1-C4 alkoxy, phenyl, phenoxy;
  • R 4 , R 5 , R 4 ′ and R 5 ′ are each independently selected from H, substituted or unsubstituted C1-C8 alkyl, C3-C8 alkyl interrupted by one or more oxygen atoms and/or sulfur atoms, C3-C7 cycloalkyl, C3-C7 heterocyclyl, C6-C20 aryl, C4-C20 heteroaryl,
  • the substituent in the C1-C8 alkyl group is selected from one or more of F atom, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, R 3 COO-, -R 6 CONR 6 ';
  • NR 4 R constitutes a three-membered, four-membered, five-membered, six-membered or seven-membered nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring further having an additional heteroatom, the additional heteroatom selected from one or two nitrogen atoms, an oxygen atom, a sulfur atom and a silicon atom; optionally, the nitrogen-containing heterocyclic ring has the following side chain substituents: C1-C4 alkyl, C1-C4 alkyl substituted with one or more substituents selected from F atom, phenyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C1-C4 alkoxy, R 3 COO-, -R 6 CONR 6 ', C3-C7 cycloalkyl, substituted or unsubstituted phenyl, R 6 CO-, R 6 COCO-, R 6 SO 2 -; optionally, the nitrogen-containing heterocyclic
  • R6 is selected from C1-C12 alkyl, C1-C4 alkyl substituted by one or more substituents selected from F, Cl, Phenyl, thienyl, phenyl substituted by one or more substituents selected from methyl, F, Cl, nitro, thienyl substituted by one or more substituents selected from methyl, F, Cl, nitro;
  • R 6 ' is selected from hydrogen, C1-C4 alkyl
  • n 0 or 1
  • Ar 1 is selected from the structures shown in Formula A-1 to Formula A-5:
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from a hydrogen atom, a deuterium atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, and optionally, two adjacent groups of R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 together with the carbon atoms on the connected benzene ring form a five-membered, six-membered or seven-membered ring;
  • the substituents on the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR 4 ,
  • the substituents in the C6-C20 aryl group and the C4-C20 heteroaryl group are selected from one or more of halogen, NO 2 , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR 4 ', and -COR 5 ';
  • R7 and R8 together with the carbon atom to which they are directly attached form a five-membered, six-membered or seven-membered ring;
  • R 9 is selected from substituted or unsubstituted C1-C8 alkyl, substituted or unsubstituted C3-C7 cycloalkyl, substituted or unsubstituted C3-C7 heterocyclic group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C4-C20 heteroaryl group,
  • the substituents on the C3-C7 cycloalkyl and C3-C7 heterocyclic groups are selected from one or more of F, Cl, C1-C4 alkyl, C1-C4 alkoxy, -COCOOR 4 ,
  • the substituents in the C6-C20 aryl group and the C4-C20 heteroaryl group are selected from one or more of halogen, NO 2 , C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkylthio, -COOR 4 ', and -COR 5 ';
  • X 2 is selected from O, S, NR 7 , CR 7 R 8 , R 7 and R 8 are defined the same as in formula A-2,
  • Ar 2 and Ar 3 are each independently selected from substituted or unsubstituted C6-C20 arylene groups, and the substituents in Ar 2 and Ar 3 are selected from the group consisting of: deuterium atoms, C1-C4 alkyl groups, C1-C4 alkoxy groups, and optionally, two adjacent substituents and the atoms of the aromatic ring to which they are connected form a five-membered, six-membered or seven-membered ring.
  • examples of C6-C20 aryl and substituted C6-C20 aryl include phenyl, naphthyl, 4-fluorophenyl, and 4-methoxynaphthalen-1-yl.
  • R1 is selected from the group consisting of:
  • R6 is selected from C1-C8 alkyl, C1-C4 alkyl substituted by one or more F, phenyl, phenyl substituted by one or more substituents selected from methyl, F.
  • R 1 is selected from N(CH 3 ) 2 ,
  • R 4 and R 5 are each independently selected from C1-C4 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclyl, benzyl, 4-methylbenzyl, C1-C3 alkyl substituted with one or more substituents selected from C3-C7 cycloalkyl and C3-C7 heterocyclyl, C2-C4 alkyl substituted with one or more substituents selected from C1-C4 alkoxy and R 3 COO-, and C3-C8 alkyl interrupted by one or more oxygen atoms and/or sulfur atoms.
  • R 1 is selected from NR 4 R 5 , R 4 and R 5 are each independently selected from hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, phenyl, CH 3 COO-substituted methyl, CH 3 COO-substituted ethyl.
  • R2 is selected from C1-C6 alkyl, benzyl, cyclohexyl, cyclopentyl, cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl, cyclohexylethyl, tetrahydrofuranmethyl,
  • R 3 is selected from C1-C4 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, C6-C10 aryl, -COOCH 3 .
  • R 3 is selected from methyl, ethyl, cyclohexylmethyl, 2-cyclohexylethyl, phenyl, -COOCH 3 .
  • R6 is selected from C1-C8 alkyl, C1-C4 alkyl substituted with one or more F, phenyl, phenyl substituted with one or more substituents selected from methyl, F, nitro.
  • the structure is selected from the structure shown in Formula A-1, A-2, A-3 or Formula A-5, wherein,
  • R 7 and R 8 are each independently selected from a hydrogen atom or a C1-C4 alkyl group, preferably hydrogen, methyl, ethyl, n-propyl and n-butyl; optionally, R 7 and R 8 together with the carbon atom to which they are directly connected form a cyclopentyl ring or a cyclohexyl ring;
  • R 4 'and R 5 ' are each independently selected from C1-C8 alkyl, C3-C7 cycloalkyl, C3-C7 heterocyclic group, C6-C12 Aryl; preferably, R 9 is selected from methyl, ethyl, n-propyl, n-butyl, 2-ethylhexyl, phenyl, or the following groups:
  • X 2 is selected from O or S;
  • Ar 2 and Ar 3 are each independently selected from a substituted or unsubstituted C6-C12 arylene group, a substituted or unsubstituted C5-C12 heteroarylene group, preferably, Ar 2 and Ar 3 are each independently selected from a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, and the substituents in Ar 2 and Ar 3 are each independently selected from one or more of a C1-C4 alkyl group and a C1-C4 alkoxy group;
  • R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 and R 18 are each independently selected from hydrogen or C1-C4 alkyl, preferably hydrogen, methyl or ethyl.
  • the oxime ester compound has a structure shown in formula (I-1), formula (I-2) or formula (I-3):
  • R 1 , R 2 , R 3 , R 7 , R 8 and R 9 are as defined in formula (I).
  • R 1 is selected from NR 4 R 5 , wherein NR 4 R 5 constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring containing at least one nitrogen atom, an optional oxygen atom, an optional a sulfur atom, optionally a silicon atom; preferably, the nitrogen-containing heterocyclic ring has a parallel ring structure, a bicyclic structure and a spirocyclic structure;
  • R 2 is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or cyclohexylethyl;
  • R 3 is selected from C1-C4 alkyl.
  • R 1 is selected from
  • R 1 is selected from NR 4 R 5 , wherein NR 4 R 5 constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring, wherein the nitrogen-containing heterocyclic ring contains at least one nitrogen atom, optionally one oxygen atom, optionally one sulfur atom, and optionally one silicon atom;
  • R 2 is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or cyclohexylethyl;
  • R 3 is selected from C1-C4 alkyl;
  • R 7 and R 8 are each independently selected from hydrogen or C1-C4 alkyl.
  • R 1 is selected from
  • R 1 is selected from NR 4 R 5 , wherein NR 4 R 5 constitutes a three-membered to seven-membered nitrogen-containing heterocyclic ring, wherein the nitrogen-containing heterocyclic ring contains at least one nitrogen atom, optionally one oxygen atom, optionally one sulfur atom, and optionally one silicon atom;
  • R 2 is selected from C1-C4 alkyl, C5-C8 alkyl, C1-C4 alkyl substituted by C5-C7 cycloalkyl, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl or cyclohexylethyl;
  • R 3 is selected from C1-C4 alkyl;
  • R 9 is each independently selected from the following groups of C1-C4 alkyl:
  • R 1 is selected from
  • the oxime ester compound is selected from the group consisting of the following compounds:
  • the method for preparing the oxime ester compound comprises the following steps:
  • Step (1) reacting the raw material HAr 1 H with an acyl chloride compound R 2 CH 2 COCl, R 2 COCl or an acid anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate M 1 or M 1 ′;
  • Step (2) reacting the intermediate M 1 or M 1 ′ in step (1) with R 1 ′COCOCl under Friedel-Crafts acylation conditions to obtain the intermediate M 2 or M 2 ′;
  • R 1 ′ is selected from methoxy, ethoxy or H 3 N;
  • Step (3) reacting the intermediate M 2 or M 2 ′ in step (2) with an HR 1 organic amine compound HNR 4 R 5 to obtain an intermediate M 3 or M 3 ′;
  • Step (4) reacting the intermediate M3 in step (3) with a nitrite or nitrous acid under corresponding acid conditions to obtain an intermediate M4 , or reacting the intermediate M3 ' in step (3) with hydroxylamine hydrochloride under neutral or alkaline conditions to obtain Intermediate M 4 ', which is in trans or cis configuration or a mixture of both;
  • Step (5) reacting the intermediate M 4 or M 4 ' in step (4) with R 3 COCl or (R 3 CO) 2 O to obtain a compound of formula II or III;
  • the preparation method of the compound of formula (I) comprises the following steps:
  • Step (1) using the compound of formula IV as a raw material, reacting with an acylating agent, an acyl chloride compound R 2 CH 2 COCl or an acid anhydride compound under Friedel-Crafts acylation conditions to obtain an intermediate compound of formula V; the compound of formula V undergoes a thioetherification reaction with a phenol or thiophenol compound of formula VII to obtain an intermediate compound of formula VI; wherein Z is selected from F, Cl, Br or I;
  • Step (2) reacting the intermediate compound represented by formula VI in step (1) with R 1 'COCOCl under Friedel-Crafts acylation conditions to obtain intermediate M 2 ;
  • R 1 ' is selected from methoxy or ethoxy;
  • Ar 1 is -Ar 2 -X 2 -Ar 3 -;
  • Step (3) reacting the intermediate M 2 of step (2) with an HR 1 organic amine compound HNR 4 R 5 to obtain an intermediate M 3 ;
  • Step (4) the intermediate M 3 of step (3) is subjected to an oximation reaction with a nitrite or nitrous acid under acid catalysis to obtain an intermediate M 4 , which is a trans or cis configuration or a mixture of the two;
  • Step (5) The intermediate M 4 in step (4) is subjected to an esterification reaction with R 3 COCl or (R 3 CO) 2 O to obtain an oxime ester product of formula (II),
  • Ar 2 , Ar 3 , R 1 , R 2 , R 3 , R 4 and R 5 are as defined in formula (I).
  • the present invention further provides a photocurable composition comprising a photoinitiator and at least one free radical polymerizable compound, wherein the photoinitiator comprises the oxime ester compound described in the first aspect of the present invention.
  • the free radical polymerizable compound is selected from acrylate compounds, methacrylate compounds, and combinations thereof.
  • the photocurable composition of the present invention may further include other photoinitiators or co-initiators.
  • the present invention does not specifically limit the specific types of the other initiators or co-initiators. It is sufficient to select photoinitiators or co-initiators that are helpful for photocuring performance in the art.
  • the free radical polymerizable compounds of the present invention include low molecular weight double bond compounds, compounds containing two or more double bonds, and double bond compounds with relatively high molecular weight (eg, 500-3000).
  • Examples of the low molecular weight double bond compound include: alkyl acrylates, cycloalkyl acrylates, hydroxyalkyl acrylates, dialkylaminoalkyl acrylates, alkyl methacrylates, cycloalkyl methacrylates, hydroxyalkyl methacrylates, dialkylaminoalkyl methacrylates, such as methyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-hydroxyethyl acrylate, isobornyl acrylate, ethyl methacrylate, silicone acrylate, acrylonitrile, vinyl acetate, vinyl ether, styrene, N-vinyl pyrrolidone, etc.
  • Examples of the compound containing two or more double bonds include: diacrylates of ethylene glycol, polyethylene glycol, propylene glycol, neopentyl glycol, 1,6-hexanediol, trihydroxymethane triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, vinyl acrylate, triallyl isocyanurate, and the like.
  • Examples of the relatively high molecular weight double bond compounds include a large class of substances generally referred to as oligomers, such as acrylated epoxy resins, acrylated polyester resins, unsaturated polyester resins, acrylated polyether resins, and acrylated polyurethane resins.
  • oligomers such as acrylated epoxy resins, acrylated polyester resins, unsaturated polyester resins, acrylated polyether resins, and acrylated polyurethane resins.
  • the mass proportion of the oxime oxalate compound in the photocurable composition is 0.1%-8.0%, for example, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or any value therebetween.
  • the present invention further provides an ink or coating, which, in addition to containing the photocurable composition of the second aspect of the present invention, may also contain other necessary ingredients according to the ink color, printing application and other performance requirements.
  • the present invention further provides an adhesive which, in addition to containing the photocurable composition of the second aspect of the present invention, may also add other necessary components such as a polymer with a molecular weight of 5000-100000 to improve the adhesive properties according to the performance requirements of the adhesive, and is used for bonding glass, plastic, metal components, etc.
  • an adhesive which, in addition to containing the photocurable composition of the second aspect of the present invention, may also add other necessary components such as a polymer with a molecular weight of 5000-100000 to improve the adhesive properties according to the performance requirements of the adhesive, and is used for bonding glass, plastic, metal components, etc.
  • the present invention further provides a photoresist, the raw materials of which include a photoinitiator, a multifunctional acrylate monomer, an alkali-soluble resin and a solvent, wherein the photoinitiator includes the oxime ester compound described in the first aspect of the present invention.
  • the multifunctional acrylate monomer in the photoresist raw material of the present invention refers to a trifunctional or higher functionality acrylate monomer.
  • the present invention does not specifically limit the specific type of the multifunctional acrylate monomer, and those skilled in the art can select and use from conventional multifunctional acrylate monomers in the art.
  • Examples of the multifunctional acrylate include, but are not limited to: dipentaerythritol hexaacrylate, pentaerythritol acrylate.
  • the alkali-soluble resin in the photoresist raw material of the present invention refers to a polymer with an acidic group, which can be dissolved or dispersed when encountering an alkaline solution.
  • the present invention does not specifically limit the specific type of the alkali-soluble resin, and those skilled in the art can select and use it from the conventional alkali-soluble resins in the art.
  • the alkali-soluble resin include, but are not limited to, polyacrylates or methacrylates with carboxylic acid groups, such as copolymers obtained by copolymerizing methacrylic acid, itaconic acid, maleic acid, etc.
  • common monomers examples include, but are not limited to, methyl acrylate, butyl methacrylate, benzyl acrylate, hydroxyethyl acrylate, styrene, butadiene, maleic anhydride, etc.
  • alkali-soluble resins include, but are not limited to, copolymers of methyl methacrylate and methacrylic acid, copolymers of benzyl methacrylate and methacrylic acid, copolymers of methyl methacrylate and butyl methacrylate, and copolymers of methacrylic acid and styrene.
  • the photoresist is a transparent photoresist without pigment.
  • the transparent photoresist can be used to manufacture optical films, polarizers, insulating films, passivation films, sealing protective layers, etc.
  • the photoresist is a colored photoresist containing a pigment.
  • the colored photoresist includes a colored photoresist and a black photoresist, wherein the colored photoresist includes a red photoresist, a green photoresist, and a blue photoresist.
  • the pigment in the raw material of the red photoresist includes a red pigment such as C.I. Pigment Red 177.
  • the pigment in the raw material of the green photoresist includes a green pigment, such as C.I. Pigment Green 7.
  • the pigment in the raw material of the blue pigment photoresist includes a blue pigment, such as C.I. Pigment Blue 15:6, Solvent Blue 25.
  • the pigment in the raw material of the black photoresist includes a black pigment, such as carbon black, titanium black, C.I. Pigment Black 1, etc. Black photoresist can be used to manufacture black matrix and cell gap spacers.
  • the present invention does not specifically limit the solvent of the photoresist raw material, and those skilled in the art can select it according to needs, such as propylene glycol monomethyl ether acetate.
  • the photoinitiator may also include other photoinitiators or co-initiators known in the art, such as 2,2-dimethoxy-2-phenylacetophenone, 2-dimethylamino-2-benzyl-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)-1-butanone, 2-dimethylamino-2-benzyl-1-(4-piperidinylphenyl)-1-butanone, 2,4,6-trimethylbenzoylbenzene-diphenylphosphine oxide, di(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2-isopropylthioxanthone, 2,4-diethylthioxanthone, and bis(2,6-difluoro-3-pyrrolophenyl)titanocene.
  • those skilled in the art may also add a heat stabilizer or a light stabilizer, such as p-methoxyphenol, to the raw materials as needed.
  • a heat stabilizer or a light stabilizer such as p-methoxyphenol
  • Other resins may also be added, such as polyalkyl methacrylate, ethyl cellulose, carboxymethyl cellulose, phenolic resin, polyvinyl butyral, polyvinyl acetate, polyester, polyimide, etc.
  • the photoresist of the present invention as a raw material, through the color filter processing process such as multiple coating, exposure, development and other existing technical processes of different color photoresists, a color filter device with excellent optical properties can be obtained, which is an important component of a color display screen, wherein the color unit has pure color and high transmittance, and the colorless part has low yellowing and high transmittance.
  • the photoresist coating is usually evenly distributed on the substrate by spin coating, and then dried at 80-90°C to separate the volatile components such as solvents, leaving the solids as films, and placing a mask on the top of the film.
  • the film is exposed to a radiation light source such as a 365nm mercury lamp or LED lamp for a suitable exposure amount.
  • the exposed material is developed in a solution of alkaline substances such as sodium carbonate or sodium hydroxide to remove the unexposed film and leave the exposed image. After that, it is washed and baked at 200-230°C to make the image better adhere to the substrate. According to the designed procedure, different colors and patterns are produced, or combined with the necessary protective film processing procedures to obtain the filter device.
  • the present invention provides a black matrix or photo spacer, which is prepared from a raw material including the photoresist described in the fifth aspect of the present invention, wherein the pigment in the photoresist is a black pigment, preferably carbon black and titanium black.
  • the present invention provides a color filter device, which comprises the color filter device described in the fifth aspect of the present invention.
  • the raw materials of the photoresist are prepared, wherein the pigment in the photoresist is a red pigment, a green pigment or a blue pigment.
  • any article such as a color filter, an LCD color display, an OLED color display, a PCB, or a printed matter obtained by using the compound of formula (I) of the present invention or the photoinitiator composition containing the compound of formula (I) as a raw material and processing through necessary steps.
  • C3-C10 alkyl group interrupted by one or more O atoms or S atoms or “C3-C10 alkyl group interrupted by one or more oxygen atoms or sulfur atoms” have equivalent meanings, and refer to a C3-C10 alkyl group interrupted by O or S once or more times, for example 1-9 times, 1-5 times, 1-3 times, or 2 times or 1 time. If there is more than one spacer group, they are of the same type or different.
  • Two O atoms are separated by at least one methylene group, preferably at least two methylene groups (i.e., ethylene groups). These alkyl groups are linear or branched.
  • alkylthio refers to an alkyl group interrupted by a S atom, for example, a C1-C4 alkylthio group is an alkyl group interrupted by a S atom. Atoms are spaced apart from alkyl groups having 1 to 4 carbon atoms.
  • cycloalkyl refers to an alkyl group containing at least one ring
  • C3-C7 cycloalkyl refers to a cyclic alkyl group having 3 to 7 carbon atoms, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclooctyl, especially cyclopentyl and cyclohexyl.
  • heterocyclic group as used herein is used interchangeably with “heterocycle”, “carbocyclic ring”, and “carboheterocyclic group”, and includes aromatic cyclic groups and non-aromatic cyclic groups.
  • Aromatic cyclic groups include heteroaromatic cyclic groups having 3-10 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms.
  • Non-aromatic heterocyclic groups include saturated heterocyclic groups having 3-10 ring atoms and unsaturated non-aromatic heterocyclic groups having 3-10 ring atoms, wherein at least one ring atom is selected from the group consisting of nitrogen atoms, oxygen atoms, sulfur atoms, selenium atoms, silicon atoms, phosphorus atoms, germanium atoms, and boron atoms.
  • Preferred non-aromatic heterocyclic groups are those having 3 to 7 ring atoms, including at least one heteroatom such as nitrogen, oxygen, silicon, or sulfur.
  • non-aromatic heterocyclic groups include oxirane, oxetanyl, tetrahydrofuranyl, tetrahydropyranyl, dioxolane, dioxanyl, aziridinyl, dihydropyrrolyl, tetrahydropyrrolyl, piperidinyl, oxazolidinyl, morpholinyl, piperazinyl, oxepinyl, thiepineyl, azepineyl and tetrahydrothiazolyl.
  • the heterocyclic group may be optionally substituted.
  • aryl or aromatic group as used herein includes both non-fused and fused systems.
  • the aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms.
  • Examples of aryl groups include phenyl, biphenyl, terphenyl, triphenylene, tetraphenylene, naphthalene, anthracene, phenanthrene, fluorene, pyrene, , perylene and azulene, preferably phenyl, biphenyl, biphenyl, triphenylene, fluorene and naphthalene.
  • Genomer 4212 aliphatic polyurethane acrylate, a product of RAHN;
  • DPHA dipentaerythritol hexaacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.;
  • HDDA 1,6-hexanediol diacrylate, a product of Tianjin Tianjiao Chemical Co., Ltd.
  • Step 1a Add 22g (0.118mol) of diphenyl sulfide and 100g of o-dichlorobenzene (hereinafter referred to as DCB) into a 250mL three-necked flask, cool to -10°C, add 17.28g (0.13mol) of anhydrous aluminum chloride, stir, add 21.65g (0.124mol) of 3-cyclohexylpropionyl chloride dropwise within 30min, and then stir and react at 10°C overnight. The reaction solution was acidified and washed with water until neutral, and DCB was removed by vacuum rotary evaporation to obtain 37.98g of light yellow oil, with a yield of 99.1% and a HPLC purity of 98.56%. After cooling, Solidified, DSC melting point 38.1°C; intermediate 4-(3-cyclohexylpropionyl) diphenyl sulfide;
  • Step 1c 4 g (9.7 mmol) of the product obtained in step 1b and 2 g (22.96 mmol) of morpholine were added to a 50 mL single-mouth bottle, stirred and reacted at 50 ° C for 2 h, 15 mL of hot ethanol was added, the temperature was lowered to precipitate white crystals, filtered, and dried under reduced pressure to obtain 4.1 g, a yield of 90.8%, HPLC content of 98.60%, DSC melting point: 110.1 ° C; intermediate 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(3-cyclohexylpropionyl) diphenyl sulfide;
  • Step 1d Add 3.8 g (8.2 mmol) of the product obtained in step 1c, 15 g DMSO and 1.0 g (9.8 mmol) of butyl nitrite into a 50 mL three-necked flask, stir and keep warm at 30 °C. Continuously introduce HCl gas in small amounts and react for 4 h.
  • reaction solution to 20 mL of dichloromethane (hereinafter referred to as DCM) and 50 ml of water, stir for 30 min, separate the lower organic layer, extract the upper aqueous phase with 20 ml of DCM again, combine the DCM, dry with 1 g of Na2SO4 for 4 h, filter the desiccant, and evaporate the filtrate to dryness.
  • DCM dichloromethane
  • the obtained light yellow solid was added with 20g of ethyl acetate and heated to dissolve, 5g of heptane was added, the temperature was lowered to crystallize, the temperature was lowered to -10°C overnight, the precipitated crystals were filtered, and the white crystalline powder weighed 3.24g after reduced pressure drying, the yield was 80%, the HPLC purity was 99.73%, and the DSC melting point was 152.9°C; the intermediate 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(3-cyclohexyl-2-hydroxyiminopropionyl) diphenyl sulfide was obtained;
  • the target compound is 4-(2-morpholin-4-yl-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide.
  • Steps 2a-2e The steps 1a-1e of Preparation Example 1 were followed, wherein piperidine was used instead of morpholine in step 1c to obtain the corresponding intermediate and target product from step 2c: 4-(2-piperidinyl-2-oxoacetyl)-4'-(3-cyclohexyl-2-acetoxyiminopropionyl) diphenyl sulfide; the appearance was light yellow glass, and the HPLC purity was 97.65%.
  • Steps 3a-3e The steps 1a-1e of Preparation Example 1 were followed, wherein 4,5-benzopiperidine was used instead of morpholine in step 1c in step 3c, and the corresponding intermediate and target product were obtained from step 3c: 4-[2-(3,4-benzopiperidinyl)-2-oxoacetyl]-4'-(3-cyclohexyl-2-acetoxyiminopropanoyl)diphenyl sulfide; the appearance was light yellow glass, and the HPLC purity was 99.52% (of which the main isomer content was 96.3%, and the minor isomer content was 3.22%).
  • Steps 4a-4e The process was carried out in accordance with steps 1a-1e of Preparation Example 1, wherein fluorene was used instead of diphenyl sulfide in step 1a in step 4a, and the corresponding intermediate and target product were obtained starting from step 4a: 6-(2-morpholin-4-yl-2-oxoacetyl)-2-(3-cyclohexyl-2-acetoxyiminopropanoyl)fluorene; the product was a light yellow powder, with a DSC melting point of 108.1°C and a HPLC purity of 98.05%.
  • Step 5a Add 4g (13.8mmol) of N-(4-nitrophenyl) carbazole and 20g of o-dichlorobenzene (hereinafter referred to as DCB) into a 100mL three-necked flask, cool to -10°C, add 3.14g (23.6mmol) of anhydrous aluminum chloride, stir, add 2.36g (14.6mmol) of octanoyl chloride dropwise within 30min, and then stir and react at 0°C overnight.
  • DCB o-dichlorobenzene
  • reaction solution was acid-lyzed and washed with water until neutral, and DCB was removed by vacuum rotary evaporation to obtain 6.0g of yellow solid, which was recrystallized from 30ml of ethanol to obtain 5.33g of dried yellow crystalline powder, with a yield of 93.2%, HPLC purity of 99.4%, and DSC melting point of 130.6°C; the intermediate 3-octanoyl-N-(4-nitrophenyl) carbazole;
  • Step 5b Add 5.13g (38.6mmol) of anhydrous aluminum chloride and 30g of 1,2-dichloroethane (DCE) into a 100mL three-necked flask, stir and cool to 0°C. Add 5.0g (12.1mmol) of the product of step 5a, control the temperature not to exceed 10°C; then drop 1.63g (13.3mmol) of monomethyl oxalyl chloride, and react at 5-10°C for 3h. Add the reaction solution dropwise to a solution of 6g of hydrochloric acid and 20mL of water at 0°C, stir for 1h, and stand to separate. Add 20mL of water to the organic phase, stir for 30min, and stand to separate.
  • DCE 1,2-dichloroethane
  • Step 5c Add 2 g (4 mmol) of the product obtained in step 5b and 10 g (0.1 mol) of 3-methylpiperidine into a 50 mL single-mouth bottle, stir and react at 65 ° C for 8 h, cool the reaction solution, add 30 ml of DCM and 30 ml of water, separate the lower organic phase and wash it with water once, evaporate the DCM to obtain a yellow solid, and beat it with a mixture of tetrahydrofuran and n-heptane, filter, and dry the filter cake under reduced pressure to obtain 1.76 g, yield 77.5%, HPLC content 97.7%, DSC melting point: 202.3°C; intermediate 3-octanoyl-6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-N-(4-nitrophenyl)carbazole;
  • Step 5d Add 0.8 g (1.4 mmol) of the product obtained in step 5c, 5 g of ethanol, 0.1 g (1.6 mmol) of hydroxylamine hydrochloride and 0.14 g (1.6 mmol) of pyridine into a 50 mL three-necked flask, stir and keep warm at 50°C; react for 14 h. Evaporate the reaction solution to dryness under reduced pressure, add 5 ml of DCM to dissolve, add 10 mL of water to wash, dry with 1 g of anhydrous Na 2 SO 4 for 4 h, filter the desiccant, and evaporate the filtrate to dryness. The residue weighs 1.0 g of light yellow solid.
  • the obtained light yellow solid was added with 4g toluene and dissolved by heating, and 3g heptane was added, and the temperature was lowered to crystallize, and the temperature was lowered to -10°C overnight, and the precipitated crystals were filtered out, and the yellow crystalline powder weighed 0.65g after reduced pressure drying, with a yield of 79.3%, a HPLC purity of 97.3%, and a DSC melting point of 178.7°C; the intermediate 3-(1-hydroxyiminooctyl)-6-[2-(3-methylpiperidinyl)-2-oxoacetyl]-N-(4-nitrophenyl)carbazole was obtained;
  • Step 5e In a 50mL single-mouth bottle, add 0.52g (0.8mmol) of the product obtained in step 5d, add 5.0mL DCM, and then add 0.1g (1mmol) of acetic anhydride, heat to 40°C, and react with magnetic stirring for 5h.

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Abstract

La présente invention concerne un composé ester d'oxime, une résine photosensible et son utilisation. Le composé ester d'oxime de la présente invention a une structure représentée par la formule (I), et la résine photosensible préparée en utilisant le composé ester d'oxime en tant que photo-initiateur présente des caractéristiques de sensibilité élevée.
PCT/CN2024/111978 2023-08-29 2024-08-14 Composé ester d'oxime, résine photosensible et son utilisation Pending WO2025044765A1 (fr)

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CN102640055A (zh) * 2009-12-07 2012-08-15 爱克发-格法特公司 Uv-led可固化组合物和墨水
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