WO2018196619A1 - Photoinitiateur à base d'ester d'oxime fluorène contenant un groupe polymérisable, son procédé de préparation et son utilisation - Google Patents

Photoinitiateur à base d'ester d'oxime fluorène contenant un groupe polymérisable, son procédé de préparation et son utilisation Download PDF

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WO2018196619A1
WO2018196619A1 PCT/CN2018/082761 CN2018082761W WO2018196619A1 WO 2018196619 A1 WO2018196619 A1 WO 2018196619A1 CN 2018082761 W CN2018082761 W CN 2018082761W WO 2018196619 A1 WO2018196619 A1 WO 2018196619A1
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group
meth
acrylate
oxime ester
alkyl group
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PCT/CN2018/082761
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English (en)
Chinese (zh)
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钱晓春
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常州强力先端电子材料有限公司
常州强力电子新材料股份有限公司
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Priority claimed from CN201710274018.4A external-priority patent/CN108727517B/zh
Priority claimed from CN201710796351.1A external-priority patent/CN109459914B/zh
Application filed by 常州强力先端电子材料有限公司, 常州强力电子新材料股份有限公司 filed Critical 常州强力先端电子材料有限公司
Priority to KR1020197032437A priority Critical patent/KR102362859B1/ko
Priority to JP2019558470A priority patent/JP7034175B2/ja
Publication of WO2018196619A1 publication Critical patent/WO2018196619A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
    • C07C13/28—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
    • C07C13/32—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings
    • C07C13/54—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings
    • C07C13/547—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered
    • C07C13/567—Polycyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with condensed rings with three condensed rings at least one ring not being six-membered, the other rings being at the most six-membered with a fluorene or hydrogenated fluorene ring system
    • 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
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

  • the present invention relates to the field of photocuring, and in particular to an oxime ester photoinitiator containing a polymerizable group, a preparation method and application thereof.
  • UV curable materials have the advantages of rapid curing, low solvent evaporation, energy saving, etc., and are widely used in the field of photocuring, especially inks, coatings, adhesives, printed wiring boards, and liquid crystal display manufacturing.
  • Photoinitiators are a key component in the formulation. At present, oxime ester photoinitiators have been gradually developed, and oxime ester photoinitiators with carbazole and diphenyl sulfide as main structures have been proven to have excellent sensitizing properties and have been promoted and applied, especially in liquid crystal display manufacturing. Excellent development performance, but it also reflects the disadvantages of high cost and unsatisfactory solubility.
  • the oxime ester photoinitiator with ruthenium as the main structure is low in cost, but the problems of mobility and solubility have not been effectively solved.
  • high mobility photoinitiators are not only limited in application areas (such as food, toys, sanitary packaging materials, etc.), but also have an adverse impact on the environment.
  • the liquid crystal panel is provided with a black matrix for accentuating the contrast of an image, and a color filter formed with a colored layer of RGB (which is usually formed of red (R), green (G), and blue (B) colors).
  • RGB red
  • G green
  • B blue
  • These black matrixes and color filters are formed by repeatedly applying a photosensitive resin composition (also referred to as a photocurable resin composition) in which black or various coloring agents are dispersed, onto a substrate, and drying. Thereafter, the obtained coating film is exposed and developed to form a desired pattern.
  • the publications of CN104395824A, CN101923287A, CN103309154A, CN104345559A and the like disclose the use of different oxime ester compounds in the production of color filters, black matrices, and color resists, such as patent publications CN105838149A, CN106483764A, CN106537254A.
  • the use of different oxime ester initiators in color resists, color filters, optical spacers, and insulating films has high photosensitivity, but it has been found that there is a risk of migration after prolonged use.
  • an oxime ester photoinitiator containing a polymerizable group is provided.
  • the oxime ester photoinitiator formed has good solubility, high photoinitiation efficiency, and is combined with the matrix resin after curing, and hardly migrates, and has a strong application prospect. .
  • the present invention provides an oxime ester photoinitiator containing a polymerizable group, having the structure represented by the general formula (I):
  • n an integer of 1 to 4.
  • the -CH 2 - in these groups may be substituted by -O-, -S-, -NH-, -CO-, -COO- or -OCO-.
  • R 2 represents a polymerizable group
  • X represents an empty or carbonyl group (ie -CO-);
  • R 3 represents a C 1 -C 20 linear or branched alkyl group, a C 3 -C 20 cycloalkyl group, a C 4 -C 20 cycloalkylalkyl group, a C 4 -C 20 alkylcycloalkyl group.
  • R 4 represents a C 1 - C 20 linear or branched alkyl group, a C 3 - C 20 cycloalkyl group, a C 4 - C 20 cycloalkylalkyl group, a C 4 - C 20 alkyl cycloalkyl group.
  • R 1 is preferably H, a nitro group, a halogen, a C 1 - C 10 linear or branched alkyl group, a C 6 - C 12 aryl group, or a C 7 - C 16 group.
  • Aralkyl, thienyl, pyrrolyl, C 1 -C 4 alkyl terminated with thienyl or pyrrolyl, or -XC(R 3 ) NO-CO-R 4 , optionally, among these groups -CH 2 - may be substituted by -O-, -S-, -NH-, -CO-, -COO- or -OCO-.
  • R 2 is a polymerizable group containing a double bond, an epoxy group or a combination thereof.
  • R 2 is selected from the group consisting of
  • alkenyl group of C 2 -C 12 optionally wherein one or more of -CH 2 - may each independently be -O-, -CO-, -COO-, -OCO- or Replaced
  • Ethylene oxide alkyl or propylene oxide alkyl, optionally one or more -CH 2 - in the alkyl group between the epoxy group and the fluorene structure may be independently -O -, -CO-, -COO-, -OCO- or -O-CH 2 -CH(OH)-CH 2 -O-.
  • R 2 is selected from the group consisting of
  • An alkenyl group of C 3 -C 8 optionally wherein one or more —CH 2 — may be independently independently —O—, —CO—, —COO—, —OCO— or Replaced
  • R 3 is preferably a C 1 - C 10 linear or branched alkyl group, a C 3 - C 10 cycloalkyl group or a C 4 - C 10 cycloalkylalkyl group.
  • R 3 is selected from a C 2 -C 6 straight or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, a C 4 -C 10 group
  • An alkylcycloalkyl group a phenyl group (one or more of which H may be optionally substituted by a C 1 -C 4 alkyl group), a C 7 -C 10 phenylalkyl group (one of the phenyl groups or more H may be optionally substituted with C 1 -C 4 alkyl), thienyl, thienyl terminated in thiazol C 1 -C 4 alkyl.
  • R 4 is preferably a C 1 -C 6 linear or branched alkyl group, a C 3 -C 10 cycloalkyl group or a C 4 -C 14 cycloalkylalkyl group. a C 4 -C 14 alkylcycloalkyl group or a C 6 -C 12 aryl group.
  • R 4 is a C 1 -C 4 linear or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, or a phenyl group.
  • oxime ester-based photoinitiator containing a polymerizable group may be selected from the following structures:
  • the present invention also provides a process for preparing a fluorenyl ester-based photoinitiator containing a polymerizable group represented by the above formula (I), comprising the steps of:
  • the raw material a and the raw material b, that is, R 2 -Y, are reacted in the presence of a catalyst to form an intermediate a; wherein Y represents a halogen, preferably F, Cl or Br;
  • the intermediate a and the starting material c, R 3 '-CO-Cl undergo a Friedel acylation reaction in an organic solvent under the catalytic action of aluminum trichloride or zinc chloride to obtain an intermediate b; wherein R 3 ' represents R 3 or R 3 -CH 2 -, specifically, when X is empty, R 3 ' represents R 3 , when X is a carbonyl group, R 3 ' represents R 3 -CH 2 -;
  • the starting materials used in the above synthesis are all known compounds, which are commercially available or conveniently prepared by known synthetic methods.
  • the synthesis process in turn comprises a nucleophilic reaction, a Friedel acylation reaction, a deuteration reaction, and an esterification reaction, all of which are conventional reaction types in the field of organic chemical synthesis.
  • the specific reaction conditions will be readily ascertainable to those skilled in the art after clarifying the reaction scheme.
  • the starting material a and R 2 -Y undergo a nucleophilic reaction in the presence of a catalyst to obtain an intermediate a.
  • the catalyst may be selected from the group consisting of sodium methoxide, sodium t-butoxide, potassium t-butoxide, potassium methoxide, and the like.
  • the reaction is carried out in a solvent system, and the type of the solvent to be used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, and DMSO, THF, and DMF are preferable.
  • the reaction temperature is usually room temperature; the reaction time varies slightly depending on the kind of the raw material, and is usually 2 to 10 hours.
  • the reaction temperature in the step (2) is usually from -10 to 30 °C.
  • the type of the organic solvent to be used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene, and the like.
  • the preparation of the intermediate c is carried out in a solvent system, and the type of the solvent to be used is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected.
  • the solvent used may be a mixed solvent of an alcohol and water, preferably a mixed solvent of ethanol and water; the reaction is carried out under heating under reflux.
  • the solvent used may be dichloromethane, benzene, toluene, tetrahydrofuran or the like, and the nitrite may be selected from the group consisting of ethyl nitrite, isoamyl nitrite, isooctyl nitrite, and the like.
  • the nitrite described may be selected from sodium nitrite, potassium nitrite, and the like.
  • the esterification reaction is carried out in an organic solvent
  • the type of the solvent is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, such as dichloromethane, dichloroethane, benzene, toluene, Xylene and the like.
  • the present invention provides the use of the polymerizable group-containing oxime ester photoinitiator represented by the above formula (I) in the field of photocuring, and the light containing the oxime ester A photocurable resin composition of an initiator.
  • the photocurable resin composition of the present invention may further contain a polymerizable compound, an alkali-soluble resin, and optionally a polymerizable group-containing oxime ester photoinitiator represented by the formula (I). Other components.
  • the polymerizable compound is a photopolymer monomer compound having an ethylenically unsaturated double bond, for example, (meth)acrylamide, hydroxymethyl (meth)acrylamide, methoxymethyl (Meth)acrylamide, ethoxymethyl (meth)acrylamide, propoxymethyl (meth)acrylamide, butoxymethoxymethyl (meth)acrylamide, N-hydroxyl (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, (meth)acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, Citraconic anhydride, crotonic acid, 2-acrylamido-2-methylpropanesulfonic acid, t-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, (me
  • the alkali-soluble resin can be appropriately selected from resins which have been conventionally used in various photocurable compositions.
  • the alkali developability can be further improved by using an alkali-soluble resin in the photocurable composition.
  • the alkali-soluble resin is preferably a (meth) acrylate-based copolymer.
  • the content of the alkali-soluble resin may be from 0 to 90% by weight, preferably from 10 to 80% by weight, based on the solid content of the photocurable resin composition.
  • the photocurable resin composition may further contain various conventional auxiliaries in the art as needed.
  • Non-limiting examples thereof include a solvent, a surface conditioner, a sensitizer, a curing accelerator, a photocrosslinking agent, a photosensitizer, a dispersing aid, a filler, an adhesion promoter, an antioxidant, and an ultraviolet absorber.
  • anti-flocculant thermal polymerization inhibitor, defoamer, surfactant, chain transfer agent, etc. All additives can be used with existing known materials.
  • the surfactant may, for example, be an anionic compound, a cationic compound or a nonionic compound.
  • the adhesion improving agent may, for example, be a silane coupling agent.
  • the thermal polymerization inhibitor may, for example, be hydroquinone or hydroquinone monoethyl ether.
  • the antifoaming agent may, for example, be a polysiloxane compound or a fluorine compound.
  • the practical application shows that the above-mentioned oxime ester photoinitiator of the invention has the characteristics of high photo-initiation efficiency, good solubility and no migration, and has a good market prospect.
  • FIG. 1 shows a schematic view of a development pattern formed using the photocurable composition provided herein;
  • Fig. 2 is a view showing a undercut phenomenon occurring in a developing pattern formed using an existing photocurable composition.
  • the present application provides an oxime ester-based photoinitiator containing a polymerizable group, and the oxime ester-based photoinitiator containing a polymerizable group has a structure represented by the general formula (I):
  • n an integer of 1 to 4.
  • R 1 is selected from the group consisting of H, a nitro group, a halogen atom, a C 1 - C 20 linear alkyl group or a branched alkyl group, a C 6 - C 20 aryl group, and a C 6 - C 14 aryl group substituted by C 1 - C 10 alkyl group, C 3 ⁇ C 5 containing heterocyclic double bond containing heterocyclic C 3 ⁇ C 5 double bond-terminated C 1 ⁇ C 12 alkyl group, or And -CH 2 - in R 1 may be substituted by -O-, -S-, -NH-, -CO-, -COO- or -OCO-;
  • Two R 2 are each selected from a substituent containing an ethylenic double bond, a substituent containing a three-membered epoxy group, or a substituent containing a four-membered epoxy group, and two R 2 are the same or different;
  • R 3 is selected from a C 1 - C 20 linear alkyl group or a branched alkyl group, a C 3 - C 20 cycloalkyl group, a C 3 - C 8 cycloalkyl group substituted C 1 - C 10 alkyl group, C 1 - a C 20 alkyl group-substituted C 3 -C 8 cycloalkyl group, a group in which at least one hydrogen atom of a phenyl group or a phenyl group is substituted by a C 1 -C 4 alkyl group, a C 1 -C 4 alkoxy group, C a group obtained by substituting at least one hydrogen atom of 1 to C 4 alkoxy groups with a fluorine atom, a thienyl group, or a C 1 -C 4 alkyl group terminated with a thienyl group;
  • R 4 is selected from C 1 -C 20 straight or branched alkyl, C 3 -C 20 cycloalkyl, C 3 -C 8 cycloalkyl substituted C 1 -C 10 alkyl, C 6 -C 20 Aryl, C 1 -C 5 alkyl-substituted C 6 -C 20 aryl, C 4 -C 20 heteroaryl, C 2 -C 20 alkenyl or C 1 -C 5 alkyl substituted C 6 to C 20 heteroaryl.
  • the photoinitiator having the structure represented by formula (I) itself has a relatively large molecular weight, and it also has a polymerizable group capable of reacting with the olefinic double in the polymer monomer during photocuring.
  • the bond undergoes polymerization to form a polymer having a relatively large molecular weight.
  • this allows the photocuring process to be carried out at a relatively uniform rate while increasing the priming activity of the photoinitiator.
  • the molecular weight of the polymer obtained after curing is relatively large, it is difficult to produce a sublimate in a heated state, and thus the photoinitiator has low mobility after curing.
  • the photoinitiator having the above structure has high photoinitiation activity and low and mobility.
  • the photoinitiator having the above structure has high photoinitiation activity and low and mobility. Further, in order to further improve the overall performance of the photoinitiator, each group in the photoinitiator may be further preferred.
  • n 1
  • R 2 is a polymerizable group containing a double bond, an epoxy group, or a combination thereof.
  • R 2 is selected from C 2 -C 12 alkenyl, oxiranylalkyl or propylene oxide alkyl;
  • R 2 is a C 2 -C 12 alkenyl group
  • one or more of -CH 2 - in R 2 may each independently be -O-, -CO-, -COO-, -OCO -or Replaced
  • R 2 is oxiranylalkyl or propylene oxide alkyl
  • one or more -CH 2 - in the alkyl group between the epoxy group in R 2 and the fluorene structure may each be independently substituted by -O-, -CO-, -COO-, -OCO- or -O-CH 2 -CH(OH)-CH 2 -O-.
  • R 2 is selected from a C 3 -C 8 alkenyl group or a C 1 -C 8 alkyl group terminated with an oxiranyl or propylene oxide group;
  • R 2 is an alkenyl group of C 3 ⁇ C 8
  • a plurality of R 2 or -CH 2 - may be each independently substituted with -O -, - CO -, - COO -, - OCO -or Replaced
  • R 2 is a C 1 -C 8 alkyl group terminated with an oxiranyl group or an propylene oxide group
  • one or more of the C 1 -C 8 alkyl groups -CH 2 - may be independently substituted by -O-, -CO-, -COO-, -OCO- or -O-CH 2 -CH(OH)-CH 2 -O-, and oxiranyl or propylene oxide
  • the H in the group may be substituted by a C 1 -C 4 alkyl group.
  • R 3 represents a C 1 -C 10 linear or branched alkyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, C 4 a C 10 alkylcycloalkyl group, a C 6 -C 10 aryl group, a C 3 -C 5 heterocyclic group containing an O, N or S hetero atom and a double bond or a C 3 -C 5 heterocyclic group Blocked C 1 -C 6 alkyl.
  • R 3 is selected from a C 2 -C 6 straight or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group, C alkylcycloalkyl of 4 ⁇ C 10, phenyl, phenyl-C 7 ⁇ C 10 alkyl group, and a thienyl group or thienyl group-terminated C 1 ⁇ C 4 alkyl, phenyl and phenylalkyl on One or more H's may be substituted by a C 1 -C 4 alkyl group; alternatively, when R 3 is a phenyl group, one or more H's in the phenyl group may be C 1 -C 4 alkyl Substituting; optionally, when R 3 is a C 7 -C 10 phenylalkyl group, one or more of the phenyl groups in the C 7 -C 10 phen
  • R 4 is a C 1 -C 6 linear or branched alkyl group, a C 3 -C 10 cycloalkyl group, a C 4 -C 14 cycloalkylalkyl group, C 4 An alkylcycloalkyl group of -C 14 or an aryl group of C 6 -C 12 .
  • R 4 is a C 1 -C 4 linear or branched alkyl group, a C 3 -C 8 cycloalkyl group, a C 4 -C 10 cycloalkylalkyl group or a phenyl group. .
  • the oxime ester-containing photoinitiator is selected from the group consisting of
  • One aspect of the present invention provides a process for producing a polymerizable group-containing oxime ester photoinitiator represented by the above formula (I), comprising the steps of:
  • the raw material a and the raw material b, that is, R 2 -Y, are reacted in the presence of a catalyst to form an intermediate a; wherein Y represents a halogen, preferably F, Cl or Br;
  • the intermediate a and the starting material c, R 3 '-CO-Cl undergo a Friedel acylation reaction in an organic solvent under the catalytic action of aluminum trichloride or zinc chloride to obtain an intermediate b; wherein R 3 ' represents R 3 or R 3 -CH 2 -, specifically, when X is empty, R 3 ' represents R 3 , when X is a carbonyl group, R 3 ' represents R 3 -CH 2 -;
  • the starting materials used in the above synthesis are all known compounds, which are commercially available or conveniently prepared by known synthetic methods.
  • the synthesis process in turn comprises a nucleophilic reaction, a Friedel acylation reaction, a deuteration reaction, and an esterification reaction, all of which are conventional reaction types in the field of organic chemical synthesis.
  • the specific reaction conditions will be readily ascertainable to those skilled in the art after clarifying the reaction scheme.
  • the starting material a and R 2 -Y undergo a nucleophilic reaction in the presence of a catalyst to obtain an intermediate a.
  • the catalyst may be selected from the group consisting of sodium methoxide, sodium t-butoxide, potassium t-butoxide, potassium methoxide, and the like.
  • the reaction is carried out in a solvent system, and the type of the solvent to be used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, and DMSO, THF, and DMF are preferable.
  • the reaction temperature is usually room temperature; the reaction time varies slightly depending on the kind of the raw material, and is usually 2 to 10 hours.
  • the reaction temperature in the step (2) is usually from -10 to 30 °C.
  • the type of the organic solvent to be used is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, such as dichloromethane, dichloroethane, benzene, toluene, xylene, and the like.
  • the preparation of the intermediate c is carried out in a solvent system, and the type of the solvent to be used is not particularly limited as long as the raw material can be dissolved and the reaction is not adversely affected.
  • the solvent used may be a mixed solvent of an alcohol and water, preferably a mixed solvent of ethanol and water; the reaction is carried out under heating under reflux.
  • the solvent used may be dichloromethane, benzene, toluene, tetrahydrofuran or the like, and the nitrite may be selected from the group consisting of ethyl nitrite, isoamyl nitrite, isooctyl nitrite, and the like.
  • the nitrite described may be selected from sodium nitrite, potassium nitrite, and the like.
  • the esterification reaction is carried out in an organic solvent
  • the type of the solvent is not particularly limited as long as it can dissolve the raw material and has no adverse effect on the reaction, such as dichloromethane, dichloroethane, benzene, toluene, Xylene and the like.
  • still another aspect of the present invention provides a photocurable resin composition
  • a photoinitiator comprises the above oxime ester-containing photoinitiator.
  • the photoinitiator having the structure represented by the formula (I) itself has a large molecular weight, and also has a polymerizable group capable of being polymerized with the photoinitiator during photocuring.
  • the olefinic double bond in the monomer undergoes polymerization to form a polymer having a relatively large molecular weight.
  • this facilitates the curing of the above-mentioned photocurable composition at a relatively uniform rate, so that the occurrence of undercut of the pattern during photocuring can be effectively suppressed.
  • the photocurable composition since the molecular weight of the polymer obtained after curing is relatively large, it is difficult to produce a sublimate in a heated state, and thus the cured product formed by the above photocurable composition also has high thermal stability. As described above, even in the case where the photosensitive resin composition contains an opacifier or the amount of exposure is insufficient, the photocurable composition provided by the present application can suppress the occurrence of undercut in the pattern after development, and has a comparative effect after development. High thermal stability.
  • the photocurable composition provided by the present application can suppress the occurrence of undercut in the developed pattern even when the photosensitive resin composition contains an opacifier or insufficient exposure amount, and has high thermal stability after development.
  • the photocurable resin composition further includes an alkali-soluble resin and an auxiliary.
  • the above alkali-soluble resin can be selected from resins commonly used in the art.
  • the addition of an alkali-soluble resin to the photocurable composition is advantageous for further improving the alkali developability.
  • the alkali-soluble resin is a (meth) acrylate-based copolymer. More preferably, it is an alkali-soluble resin disclosed in the published patent (CN106397752A).
  • the photocurable composition comprises 0.5 to 10 parts by weight of a phthalate-containing photoinitiator, 10 to 100 parts of the above polymer monomer, 0 to 80 parts of an alkali-soluble resin, and 0 to 500 parts by weight. Auxiliary.
  • the photocurable composition comprises 0.5 to 5 parts by weight of a phthalate-containing photoinitiator, 10 to 80 parts of the above polymer monomer, 0 to 60 parts of an alkali-soluble resin, and 0 to parts by weight. 200 parts of auxiliaries.
  • the above polymer monomers include, but are not limited to, (meth)acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxylate Methyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxy methoxy methyl (meth) acrylamide, N-methylol (meth) acrylamide, N- Hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2-propene Amido-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-(meth)acrylate Ethylhexyl ester,
  • the above photocurable resin composition may further comprise various additives in the art including, but not limited to, solvents, dyes, pigments, fillers, surface conditioners, antifoaming agents, leveling agents, wetting agents, dispersing agents, matting agents.
  • additives include, but not limited to, solvents, dyes, pigments, fillers, surface conditioners, antifoaming agents, leveling agents, wetting agents, dispersing agents, matting agents.
  • solvents e.g., solvents, dyes, pigments, fillers, surface conditioners, antifoaming agents, leveling agents, wetting agents, dispersing agents, matting agents.
  • a curing accelerator e.g., a chain transfer agent, an antioxidant, a UV absorber, a deflocculant, a thermal polymerization inhibitor, and an adhesion promoter.
  • the surfactant includes, but is not limited to, one or more of the group consisting of an anionic compound, a cationic compound, and a nonionic compound.
  • the adhesion improving agent includes, but is not limited to, a silane coupling agent.
  • the thermal polymerization inhibitor includes, but is not limited to, hydroquinone and/or hydroquinone monoethyl ether.
  • the antifoaming agent includes, but is not limited to, a polysiloxane compound and/or a fluorine compound.
  • the above photocurable resin composition can also be used in combination with a photoinitiator or a sensitizer which is conventional in the art.
  • the photoinitiators currently available in the art include, but are not limited to, benzophenones, thioxanthones, acetophenones, alpha-hydroxyketones, alpha-aminoketones, benzoylformates. And one or more of the group consisting of triazines.
  • the sensitizer includes, but is not limited to, one or more of the group consisting of a coumarin compound, an anthraquinone compound, an oxime ester compound, and an acridine compound.
  • Another aspect of the present application also provides a method of producing a photosensitive resin composition.
  • the preparation method comprises batching according to a desired composition; and mixing the above ingredients in a mixer to obtain.
  • each component of the above photocurable composition is filtered using a filter to make the formulated photosensitive resin composition uniform.
  • Another aspect of the present application also provides a color filter comprising a development pattern formed by the photocurable composition provided herein.
  • the method for preparing the above-mentioned imaging pattern comprises the following steps:
  • a photocurable resin composition is applied onto a substrate using a roll coater or a coater.
  • the coating film is irradiated with an active energy ray such as an ultraviolet ray or an excimer laser through a negative image mask to partially expose it.
  • an active energy ray such as an ultraviolet ray or an excimer laser
  • the exposed coating film is developed with a developing solution to form a pattern of a desired shape.
  • Another aspect of the present application also provides a display device including the above color filter.
  • the photocurable resin composition of the present invention As described above, by using the photocurable resin composition of the present invention, undercut in the pattern formed after development can be suppressed.
  • the development pattern on the color filter is produced by using the photocurable resin composition of the present invention, it is possible to suppress the bubble from entering the vicinity of the boundary portion of each pixel, which is advantageous in improving the picture quality of the liquid crystal display device including the above filter.
  • the structure of the intermediate 1a was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • Compound 1 was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • n-hexane product was dried over anhydrous magnesium sulfate, and then evaporated to remove n-hexane, and then recrystallized from methanol to give a white solid product 134.8 g, intermediate 2a, yield 88 wt%, purity 98 wt%.
  • the structure of the intermediate 2a was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • Compound 2 was confirmed by nuclear magnetic resonance spectroscopy and mass spectrometry.
  • a photocurable resin composition having the following composition is prepared:
  • the photoinitiator is a compound of formula (I) of the invention or a photoinitiator known in the prior art (for comparison).
  • the above composition was stirred under a yellow light, and the film was taken up on a PET template by roll coating, and dried at 90 ° C for 2 minutes to obtain a coating film having a dry film thickness of 2 ⁇ m, and then cooled to room temperature, using a high-pressure mercury lamp (exposure machine).
  • Exposure machine Model: RW-UV70201, single exposure amount 50 mJ/cm 2 )
  • the coating film was exposed to light to form a film.
  • the number of passes of the viscous exposure tape after the film was cured to form a cured film was evaluated. The more the number of passes, the less the curing speed was.
  • the cured film was cut, and 0.5 g of the cured film sample was weighed into a 50 mL beaker, 4.5 mL of methanol was added, and ultrasonic sonication was performed for 30 min, and the obtained methanol solution was transferred to a 10 mL volumetric flask, and the sample was further washed twice with methanol ( 2mL*2), pour into the volumetric flask, pipette 0.1mL of toluene as the internal standard, add methanol to dissolve, shake evenly, and let stand.
  • the solubility of photoinitiators in reactive diluents and oligomers is an important indicator of the performance of the initiator.
  • the solubility of the photoinitiator in PGMEA is one of the index parameters representing its solubility properties and the performance of the photoinitiator.
  • the polymerizable group-containing oxime ester photoinitiator represented by the general formula (I) of the present invention is excellent in solubility, high in initiator efficiency and curing in photocuring applications.
  • the speed is fast and no migration occurs, and the overall performance is significantly better than the existing oxime ester photoinitiator products.
  • the photoinitiator prepared in the present application and the photoinitiator conventional in the art were separately prepared as photocurable compositions, and the compositions of the respective photocurable compositions are shown in Tables 3 and 4.
  • the alkali-soluble resin A1 has the following structure:
  • the sensitivity of the photosensitive resin compositions of Examples 11 to 29 and Comparative Examples 4 to 9 was evaluated in the following steps. First, the film was taken up on a PET template, and the film was coated with a wire bar and dried at 90 ° C for 5 minutes to remove the solvent. A coating film having a film thickness of about 2 ⁇ m was formed. The substrate on which the coating film was formed was cooled to room temperature, a mask was attached, and a long-wavelength radiation was realized by a FWHM filter using a high-pressure mercury lamp 1 PCS light source.
  • the coating film was exposed to ultraviolet light having a wavelength of 370 to 420 nm through a slit of a mask, and then immersed in a 2.5 wt% sodium carbonate solution for 20 s at 25 ° C, washed with ultrapure water, air-dried, and hard at 220 ° C.
  • the pattern was fixed by baking for 30 minutes, and the obtained pattern was evaluated.
  • the minimum exposure amount at which the residual film ratio is 90% or more after development in the light irradiation region in the exposure step is evaluated as the exposure demand amount.
  • the shapes of the patterns of the photosensitive resin compositions of Examples 11 to 29 and Comparative Examples 4 to 9 were evaluated in the following steps. First, the film was taken on a PET template, and coated with a wire bar, and dried at 90 ° C for 5 minutes. The solvent was removed to form a coating film having a film thickness of about 2 ⁇ m. The substrate on which the coating film was formed was cooled to room temperature, a mask was attached, and a long-wavelength radiation was realized by a FWHM filter using a high-pressure mercury lamp 1 PCS light source.
  • the coating film is fully exposed (exposure amount 100 mJ/cm 2 ) by ultraviolet rays having a wavelength of 370 to 420 nm through the slit of the mask, and then immersed in a 2.5 wt% sodium carbonate solution for 20 s at 25 ° C, and then ultrapure. Washed, air-dried, hard baked at 220 ° C for 30 min to fix the pattern, and the angle of joint (cone angle) between the pattern and the substrate was measured by a scanning electron microscope, which corresponds to the corresponding angle ⁇ in FIGS. 1 and 2 . . If the cone angle is an acute angle, it means that there is no undercut in the pattern, and if the cone angle is an obtuse angle, it means that there is a undercut in the pattern. The specific results are shown in Table 5.
  • the photocurable composition prepared in Examples 11 to 29 of the present application forms a pattern having an angle of engagement with the substrate at an acute angle as shown in FIG. 1 and in Comparative Examples 4 to 9.
  • the angle at which the photocurable composition forms a pattern and the bonding angle of the substrate is an obtuse angle. Therefore, the polymerizable quinone photoinitiator of the present invention has excellent photographic performance, and can be effectively solved for the undercut problem whether used alone or in combination with other photoinitiators.
  • the sublimation product of the initiator in the exposed composition was tested, and 80 films were prepared for exposure to the formulations of the above Examples 11, 19, 20, 24 and Comparative Examples 4 and 9 under the conditions of 100 mJ/cm 2 .
  • the mask was cleaned with an equal amount of tetrahydrofuran, and the mask deposit was quantitatively analyzed by Shimadzu liquid chromatography (LC-200), and the peak area and peak height were recorded at the peak position of the initiator. The higher the peak area and peak height, the more significant the sublimation. The results are shown in Table 6.
  • the photosensitive composition of the present invention exhibits the characteristic of suppressing the generation of sublimate.

Abstract

L'invention concerne un photoinitiateur à base d'ester d'oxime fluorène contenant un groupe polymérisable, un procédé de préparation et son utilisation, le photoinitiateur d'ester d'oxime fluorène ayant la structure telle que représentée par la formule générale (I), R2 représentant un groupe polymérisable. L'invention concerne également une composition photodurcissable et son utilisation, la composition photodurcissable comprenant le photoinitiateur contenant un ester d'oxime fluorène et un monomère de polymère.
PCT/CN2018/082761 2017-04-25 2018-04-12 Photoinitiateur à base d'ester d'oxime fluorène contenant un groupe polymérisable, son procédé de préparation et son utilisation WO2018196619A1 (fr)

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JP2019558470A JP7034175B2 (ja) 2017-04-25 2018-04-12 重合可能基含有フルオレンオキシムエステル系光開始剤、製造方法およびその応用

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KR102361560B1 (ko) * 2017-12-22 2022-02-14 창저우 트론리 어드벤스드 일렉트로닉 머티어리얼스 컴퍼니, 리미티드 불소-함유 플루오렌 옥심 에스테르 광개시제, 이를 포함하는 광경화성 조성물, 및 이의 용도
CN111320714B (zh) * 2018-12-13 2022-04-19 常州强力先端电子材料有限公司 肟酯类光引发剂、其制备方法及应用
CN115368341B (zh) * 2021-05-20 2024-01-26 常州强力先端电子材料有限公司 肟磺酸酯化合物、含其的抗蚀剂组合物、电子器件及应用
WO2023085056A1 (fr) * 2021-11-09 2023-05-19 富士フイルム株式会社 Composition durcissable, procédé de production d'une composition durcissable, film, dispositif optique, capteur d'image, dispositif d'imagerie à semi-conducteurs, dispositif d'affichage d'image et initiateur de polymérisation radicalaire
CN115650886A (zh) * 2022-10-15 2023-01-31 瑞红(苏州)电子化学品股份有限公司 肟磺酸酯类光产酸剂及其抗蚀剂组合物应用
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JP2020106755A (ja) * 2018-12-28 2020-07-09 日鉄ケミカル＆マテリアル株式会社 遮光膜用感光性樹脂組成物及びその硬化物、並びに当該硬化物を用いたカラーフィルター及びタッチパネルの製造方法
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