WO2019074262A1 - Résine liante et composition de résine photosensible ou solution de revêtement la contenant - Google Patents

Résine liante et composition de résine photosensible ou solution de revêtement la contenant Download PDF

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Publication number
WO2019074262A1
WO2019074262A1 PCT/KR2018/011861 KR2018011861W WO2019074262A1 WO 2019074262 A1 WO2019074262 A1 WO 2019074262A1 KR 2018011861 W KR2018011861 W KR 2018011861W WO 2019074262 A1 WO2019074262 A1 WO 2019074262A1
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Prior art keywords
independently
group
formula
carbon atoms
binder
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PCT/KR2018/011861
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English (en)
Korean (ko)
Inventor
류미선
김근수
정통일
임철규
임홍규
Original Assignee
타코마테크놀러지 주식회사
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Application filed by 타코마테크놀러지 주식회사 filed Critical 타코마테크놀러지 주식회사
Priority to CN201880079581.9A priority Critical patent/CN111448517B/zh
Priority to JP2020520644A priority patent/JP7017270B2/ja
Publication of WO2019074262A1 publication Critical patent/WO2019074262A1/fr

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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—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
    • 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
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable

Definitions

  • the present invention relates to a binder resin having high performance and high performance properties such as heat resistance, chemical resistance, permeability, high refractive index, mechanical properties, flexibility, developability and pattern straightness, and a photosensitive resin composition or coating solution containing the same.
  • a photosensitive resin composition for a display applied to a thin film transistor type liquid crystal display (TFT-LCD), an organic light emitting element (OLED), a touch screen panel (TSP) or the like causes a curing reaction and a photolysis reaction by UV and ultraviolet irradiation to form a pattern
  • a negative photosensitive material and a negative photosensitive material according to a method in which a negative photosensitive material is used The positive photosensitive material is dissolved in the developing solution in a region irradiated with UV and ultraviolet rays to form a pattern.
  • the negative photosensitive material is photocured at the portion irradiated with UV and ultraviolet rays, and the unexposed portion dissolves in the developing solution This is how the pattern is formed.
  • a high transmittance and a high refractive index are important in the photosensitive resin composition in recent years.
  • the structure and properties of the binder among the compositions constituting the photosensitive material are very important. For this reason, studies for imparting photosensitivity to a binder resin such as novolak resin system, polyimide and the like, including acrylic photosensitive resin used as a typical binder resin of a photosensitive resin composition, have been actively studied.
  • U.S. Patent No. 4,139,391 discloses a photosensitive resin composition prepared by using a copolymer of an acrylate compound and an acrylate compound as a binder resin and an acrylate compound as a polyfunctional monomer.
  • the difference in solubility between the exposed portion and the unexposed portion is not sufficiently large, and the developing property is not good, and the binder resin to be left in the developing process is partially dissolved in the developing solution, making it difficult to obtain a fine pattern of 10 ⁇ or less.
  • Japanese Patent Application Laid-Open Nos. 52-13315 and 62-135824 disclose photosensitive photoresist compositions containing polyamic acid as a polyimide precursor and a naphthotquinonediazide compound as a dissolution inhibitor to increase thermal stability
  • a problem that the difference in dissolution rate between the exposed portion and the non-exposed portion is large enough to form a high-resolution pattern.
  • the photosensitive resin composition has good adhesion with the lower layer and the upper layer and has a large process margin capable of forming a fine pattern of high resolution under various process conditions in accordance with the purpose of use, and high sensitivity characteristics are required as the photosensitive material, Research to improve the characteristics is also being actively pursued.
  • Patent Document 1 Japanese Unexamined Patent Publication No. 52-13315
  • Patent Document 2 Japanese Patent Application Laid-Open No. 62-135824
  • Patent Document 3 United States Patent No. 4,139,391
  • the present invention relates to a binder resin having high performance and high performance properties such as heat resistance, chemical resistance, permeability, high refractive index, mechanical properties, flexibility, developability and pattern straightness, and the like. It is an object of the present invention to provide a photosensitive resin composition or coating solution using a resin.
  • the present invention provides a binder resin comprising a unit represented by the following general formula (I) or a polymer comprising both a unit represented by the following general formula (I) and a unit represented by the following general formula to provide.
  • R 3 is independently a (meth) acryloyloxy or R a ZR b (R c), g (R d) h
  • R '3 is independently a (meth) acryloyloxy or R a ZR b (R c), g (R d) h and, R 3 and R '3 at least one of which is a (meth) and one oxy-acryloyl, wherein R a is a bond (bonding), an alkylene group or carbon number of 1 to 10 carbon atoms 6 is an arylene group to 20, wherein Z is O, S, N, Si or Se, and wherein R b, R c and R d are independently 1 to 10 carbon atoms which contain a hetero element, or that is an alkyl group or a carbon number of not contain
  • g 0 and h is 0 when Z is O, S or Se
  • R is an ary
  • R 2 and R ' 2 are each independently selected from the group consisting of hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH 2 ), a nitro group (-NO 2 )
  • X represents O, S, Se, NR 6 or SiR 7 (R 8 ), and R 6 , R 7 or R 8 represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms or 6 to 15 carbon atoms.
  • the binder resin is, for example, used as a binder in a photosensitive material for a display.
  • the binder resin is, for example, a resin terminated with an organic acid, an organic acid anhydride or an amic acid.
  • the weight average molecular weight of the binder resin is, for example, 1,000 to 100,000 g / mol.
  • the binder resin has, for example, a dispersion degree of 1.0 to 5.0.
  • the present invention also provides a negative photosensitive resin composition
  • a negative photosensitive resin composition comprising the binder resin, the photoinitiator, the organic solvent, and the surfactant.
  • the negative photosensitive resin composition may include, for example, 100 parts by weight of a binder resin, 1 to 20 parts by weight of a photoinitiator, 0.01 to 5 parts by weight of a surfactant, and 0 to 10 parts by weight of a bonding agent in an amount of 5 to 80% .
  • the present invention also provides a positive photosensitive resin composition
  • a positive photosensitive resin composition comprising the binder resin, a photoactive compound, an organic solvent, and a surfactant.
  • the positive photosensitive resin composition includes, for example, 100 parts by weight of a binder resin, 0.1 to 30 parts by weight of a photoactive compound, 0.01 to 5 parts by weight of a surfactant, and 0 to 10 parts by weight of an adhesion promoter in an organic solvent in an amount of 5 to 80% .
  • the present invention also provides a substrate comprising a resin curing pattern formed from the photosensitive resin composition.
  • the present invention also relates to a monomer represented by the formula (13), or a monomer represented by the formula (13) and a monomer represented by the formula (14); A carboxylic acid dianhydride represented by the formula (9); And a step of subjecting the resulting mixture to polymerization reaction.
  • R 5 and R '5 are both independently selected from (meth) are acryloyloxy or both independently an R a ZR b (R c), g (R d) h, wherein A' is independently selected from the general formula (I-1) To I-4, Wherein D is O, S, CH 2 , Se, and m is an integer of 1 to 6.
  • R 2 and R ' 2 are each independently selected from the group consisting of hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH 2 ), a nitro group (-NO 2 )
  • X represents O, S, Se, NR 6 or SiR 7 (R 8 ), and R 6 , R 7 or R 8 represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 15 carbon atoms.
  • R 4 is a tetravalent cycloaliphatic hydrocarbon radical having 4 to 20 carbon atoms and containing or not containing a heteroatom or a tetravalent aromatic hydrocarbon radical having 6 to 20 carbon atoms and containing or not containing a heteroatom .
  • a photosensitive resin composition comprising a binder resin having excellent heat resistance and transmittance characteristics and high optical refractive index exhibits excellent heat resistance, transmittance and refractive index characteristics. Since the binder resin of the present invention is excellent in heat resistance and can minimize the taper angle and outgassing and has excellent adhesion to the substrate and excellent chemical resistance against strong acids and strong bases, It exhibits excellent properties as a high-performance, high-performance coating material as well as a photosensitive material for a TSP display.
  • the binder resin of the present invention is excellent in developability with respect to an aqueous solution of an inorganic alkali and an aqueous solution of an organic alkali, excellent developability can be secured for the positive and negative photosensitive material compositions, and excellent resolution And it is easy to control the taper angle of the pattern.
  • excellent pattern stability can be secured.
  • the present invention relates to a binder resin and a photosensitive resin composition containing the binder resin.
  • the photosensitive resin composition may contain a photoinitiator, a photoactive compound, a solvent, etc. in addition to the binder, and may further include additives such as a heat stabilizer, a thermal crosslinking agent, a photo-curing accelerator, or a surfactant.
  • the present invention provides a binder resin comprising a unit represented by the following general formula (I) or a polymer comprising both a unit represented by the following general formula (I) and a unit represented by the following general formula (II).
  • R 3 is independently a (meth) acryloyloxy or R a ZR b (R c), g (R d) h
  • R '3 is independently a (meth) acryloyloxy or R a ZR b (R c), g (R d) h and, R 3 and R '3 at least one of which is a (meth) and one oxy-acryloyl, wherein R a is a bond (bonding), an alkylene group or carbon number of 1 to 10 carbon atoms 6 is an arylene group to 20, wherein Z is O, S, N, Si or Se, and wherein R b, R c and R d are independently 1 to 10 carbon atoms which contain a hetero element, or that is an alkyl group or a carbon number of not contain
  • g 0 and h is 0 when Z is O, S or Se
  • R is an ary
  • R 5 and R '5 are both independently a (meth) acryloyloxy, or in both a ZR b independently R (R c), g (R d) h,
  • Formula II is comprising R 5 and R '5 is a (meth) admitted acryloyloxy monomers and R 5 and R' 5 is R a ZR b (R c), g (R d) a mixture between h monomer monomer
  • R a is an alkylene group having 1 to 10 carbon atoms or an arylene group having 6 to 15 carbon atoms
  • Z is O, S, N, Si, or Se
  • R 2 and R ' 2 are each independently selected from the group consisting of hydrogen, a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH 2 ), a nitro group (-NO 2 )
  • X represents O, S, Se, NR 6 or SiR 7 (R 8 ), and R 6 , R 7 or R 8 represents hydrogen, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms or 6 to 15 carbon atoms.
  • the p and q may be an integer of 3 to 20, 4 to 10, or 4 to 7, for example. Within this range, there is an excellent effect of heat resistance, chemical resistance, permeability, high refractive index and optical characteristics.
  • a polymer comprising a unit represented by the formula (I), a polymer containing both a unit represented by the formula (I) and a unit represented by the formula (II) or a terminal group derived from a polymerization inhibitor May mean a polymer or a polymer comprising a unit represented by the formula (I) and a unit represented by the formula (II).
  • the binder resin of the present invention can be synthesized by synthesizing a monomer containing a hydroxy group of the formulas (5) to (8) from the compounds represented by the formulas (1) to (4) and then reacting the monomer with the carboxylic acid dianhydride have.
  • a polymer represented by the general formula (I) a polymer containing the unit represented by the general formula (I) and a unit represented by the general formula (II) in the main chain, or a terminal group derived from the terminator for stopping the polymerization reaction, May denote a polymer composed of a unit, a polymer represented by the formula (I) and a polymer represented by the formula (II).
  • the binder resin of the present invention can be prepared, for example, by synthesizing a monomer containing a hydroxy group of the formula (13) or (14) from the compound represented by the formulas (1) to (4) and then reacting the monomer with a carboxylic acid dianhydride.
  • R 1 and R 1 each represent a C 1 to C 8 hydrocarbon group containing a heteroatom such as a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH 2 ), a nitro group (-NO 2 ) to 20 aliphatic or alicyclic group, or a hetero element represents a carbon number of 6 to 20 or 6 to 15, an aryl group containing a, R 2, R '2 are independently a hydrogen or a hydroxyl group (-OH), thiol (-SH) , An amino group (-NH 2 ), a nitro group (-NO 2 ), or a halogenated group.
  • X represents O, S, N, Si or Se.
  • &quot means " independently " and includes both cases where the two components are the same or different.
  • R 1 and R ' 1 each represent an aliphatic or alicyclic alkyl group having 1 to 10 carbon atoms, 3 to 8 carbon atoms, or 3 to 5 carbon atoms, An aryl group having 6 to 15, 6 to 10, or 7 to 10 carbon atoms.
  • R 3 are independently a (meth) acryloyloxy or R a ZR b (R c), g (R d) h
  • R 5 and R '5 are both independently represent a (meth) acryloyloxy or both independently ZR b a R (R c), g (R d) and h, wherein A' is independently selected from formula I- 1 to I-4, D is O, S, CH 2 , Se, and m is an integer of 1 to 6.
  • R 2 and R ' 2 each represent hydrogen or a hydroxyl group (-OH), a thiol group (-SH), an amino group (-NH 2 ), a nitro group (-NO 2 ), or a halogenated group.
  • X represents O, S, N, Si or Se.
  • n is an integer of 1 to 6.
  • Each of R b , R c and R d may be an alkyl group having 1 to 5 carbon atoms or 1 to 3 carbon atoms, or an aryl group having 6 to 10 carbon atoms or 6 to 8 carbon atoms.
  • the R may be, for example, a bond, an alkylene group having 1 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms.
  • the R ' may be, for example, an alkyl group or an alkenyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 15 carbon atoms.
  • N and m may be, for example, 1 to 3, or 1 to 2, respectively.
  • the hetero element means a monovalent or divalent radical of an element other than carbon and hydrogen, and examples thereof include at least one selected from the group consisting of oxygen, nitrogen, sulfur, halogen, selenium (Se) , R a ZR b (R c ) g (R d ) h can be, for example, R a SR b and is excellent in heat resistance, transparency and high refractive index, and excellent in developability for KOH aqueous solution and aqueous TMAH solution And the formation of the undercut is prevented.
  • the present invention is characterized by being a polymer comprising a unit represented by the following formula (Ia), or a polymer represented by the following formula (Ia).
  • R 3 are independently a (meth) acryloyloxy or R a ZR b (R c), g (R d) h
  • R '3 is independently a (meth) acryloyloxy or R a ZR b (R c), g (R d) h and, R 3 and R '3 at least one of which is a (meth) and one oxy-acryloyl, wherein R a is a bond (bonding), an alkylene group or carbon number of 1 to 10 carbon atoms 6 is an arylene group to 20, wherein Z is O, S, N, Si or Se, and wherein R b, R c and R d are independently 1 to 10 carbon atoms which contain a hetero element, or that is an alkyl group or a carbon number of not contain
  • g 0 and h is 0 when Z is O, S or Se
  • R is an ary
  • n may be, for example, 1 to 3, or 1 to 2, and in this case, heat resistance, transmittance and high refractive index are excellent.
  • the binder resin represented by the above formula (Ia) is an example in which p is an integer of 1 to 30, or an integer of 1 to 10, and has an excellent heat resistance, transmittance and high refractive index in this range.
  • the method for producing the binder resin of the present invention includes, for example, a monomer represented by the formula (13) or a monomer represented by the formula (13) and a monomer represented by the formula (14); A carboxylic acid dianhydride represented by the formula (9); And then conducting a polymerization reaction.
  • the monomer represented by the formula (13) and the monomer represented by the formula (14) may be added in a molar ratio of 1:99 to 99: 1, for example.
  • the method for producing a binder resin according to the present invention may include a step of polymerizing a carboxylic acid dianhydride represented by the formula (9) with one or more of the monomers represented by the formulas (5) to (8).
  • the process for producing the binder resin of the base is "over ilrok admitted monomer 1 species trivalent acrylic and, R 3, and R, R 3 and R from a monomer represented by the following Formula 5 to 83 the R a SR b with at least one carboxylic acid dihydrate represented by the formula (9).
  • R 4 is a tetravalent cycloaliphatic hydrocarbon radical having 4 to 20 carbon atoms and containing or not containing a heteroatom or a tetravalent aromatic hydrocarbon radical having 6 to 20 carbon atoms and containing or not containing a heteroatom .
  • R 4 in the general formula (9) is a cycloaliphatic hydrocarbon radical having 4 to 10 carbon atoms, or 4 to 6 carbon atoms, with or without a heteroatom, or a heteroatom having 6 to 15 carbon atoms or 6 to 12 carbon atoms, Is a tetravalent aromatic hydrocarbon radical containing or not containing an element, and has an excellent heat resistance, high transmittance and high refractive index in this range.
  • carboxylic acid dianhydride examples include pyromellitic dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride , 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 2,2 ', 3,3'-benzo Phenanetetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 1,1-bis Bis (2,3-dicarboxyphenyl) ethane dianhydride, bis (3,4-dicarboxyphenyl) methane dianhydride, bis (2,3- Bis (3,4-dicarboxyl)
  • the polymerization may be carried out, for example, at from 100 to 130 ° C, or from 110 to 120 ° C for from 2 hours to 24 hours, or from 4 hours to 12 hours.
  • the carboxylic acid dianhydride may be added in an amount of 5 to 40 parts by weight, 10 to 30 parts by weight, or 10 to 20 parts by weight based on 100 parts by weight of the total amount of the monomers.
  • the binder resin of the present invention can be prepared by, for example, introducing an end-capping agent after the initiation of the polymerization reaction.
  • the end capping reaction may be carried out at from 100 to 130 ° C, or from 110 to 120 ° C for 30 minutes to 4 hours, or 1 hour to 3 hours, for example.
  • the end capping agent may be added in an amount of 2 to 10 parts by weight, 2 to 5 parts by weight, or 3 to 5 parts by weight based on 100 parts by weight of the total amount of the monomers.
  • the weight average molecular weight of the binder resin may be, for example, 1,000 to 100,000 g / mol, preferably 2,000 to 50,000 g / mol, more preferably 2,000 to 12,000 g / mol, and most preferably 3,000 to 5,000 g / mol In this range, the heat resistance is excellent, and the development speed of the photosensitive material and the development due to the developing solution are favorable, and pattern formation is good and the residual film ratio is high.
  • the weight average molecular weight of the present invention can be measured by a gel permeation chromatography (GPC) method.
  • the degree of dispersion (PDI) of the binder resin may be in the range of 1.0 to 5.0, preferably in the range of 1.5 to 4.0, and is excellent in heat resistance within this range, and the developing rate of the photosensitive material and development by the developer are appropriate, It is good and has a high residual film ratio.
  • the dispersion degree of the present invention can be measured by a GPC measurement method.
  • the refractive index of the binder resin is, for example, from 1.50 to 1.70, or from 1.60 to 1.69, preferably from 1.61 to 1.68, or from 1.63 to 1.67, and the refractive index and transmittance after curing of the thin film produced within this range are excellent.
  • the transmittance of the binder resin is, for example, 90% or more, 95% or more, or 96% or more, and preferably 96 to 99%, and the refractive index and transmittance after curing of the thin film produced within this range are excellent.
  • the method of measuring the refractive index and the transmittance of the binder resin is not particularly limited as long as it is a conventional method for measuring the refractive index and transmittance of the binder resin, and may be, for example, a method of measuring the refractive index and transmittance of the photosensitive resin composition of the present invention.
  • the acid value of the binder resin is, for example, 30 to 180 mgKOH / g. Within this range, the heat resistance is excellent, and the developing rate of the photosensitive material and the development by the developer are appropriate.
  • the acid value is a value obtained by an acid value measurement method commonly used in this technical field. For example, 0.5 g of a binder polymer is sampled and 100 mL of a mixed solvent (25% by weight of H 2 O, 75% ) And titrated with 0.1 N-KOH ethanol.
  • the binder resin of the present invention can be used, for example, as a photosensitive resin composition for a black mattress containing a binder resin, a pigment and a photopolymerization initiator, or a touch panel comprising a black matrix or a black matrix material,
  • the present invention is applicable to a column spacer that supports between two thin film transistors (TFTs) and a C / F substrate that are present in the substrate.
  • TFTs thin film transistors
  • the binder resin of the present invention can be used for a color filter, and when applied to an image display device, a color filter made of the binder resin of the present invention is self-emitting by the light of the light source, Since the optical path is increased, a higher optical efficiency can be realized.
  • the binder resin of the present invention can be used as a material for forming a PDL (Pixel Defined Layer) layer that isolates the boundaries between pixels in an OLED display device and isolates them.
  • PDL Pixel Defined Layer
  • the negative photosensitive resin composition of the present invention is characterized by comprising the binder resin, photoinitiator, organic solvent and additives of the present invention.
  • the negative-working photosensitive resin composition of the present invention is characterized in that the binder resin of the present invention contains a photoinitiator, a crosslinkable compound having an ethylenically unsaturated bond, an additive, and an organic solvent.
  • the photoinitiator refers to a component that generates active species capable of initiating polymerization of the above-mentioned binder resin by visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-
  • photoinitiator examples include oxime ester compounds, imidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, alpha-diketone compounds, polynuclear quinone compounds, phosphine compounds, Compounds and the like. Of these, acetophenone compounds or oxime ester compounds are preferable.
  • the oxime ester compound has excellent exposure sensitivity, is excellent in pattern stability after the development process, forms a stable development pattern even at a low exposure dose, is excellent in adhesiveness to a substrate, light diffusing property and insulation property, Has the advantage of forming an excellent resin.
  • oxime ester compound examples include 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (0-acetyloxime), 1,3- 1 [(4-phenylthio) phenyl] 2-benzoyl-oxime and the like.
  • acetophenone-based compound examples include an alpha-hydroxy ketone compound, an alpha-amino ketone compound, and other compounds.
  • alpha-hydroxyketone compound examples include 1-phenyl-2-hydroxy-2-methylpropan-1-one, 1- (4-i-propylphenyl) -2- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, and the like, and the above-mentioned alpha-amino ketone compound 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- -Butanone-1, and specific examples of the other compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone and the like . These acetophenone compounds may be used singly or in combination of two or more. By using these acetophenone compounds, the strength of the thin film can be further improved.
  • nonimidazole-based compound examples include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2 -Imidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'- -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl
  • 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis , 4,4'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are particularly preferable, and 2,2'-bis (2,4-dichlorophenyl) -4,4' , 5'-tetraphenyl-1,2'-biimidazole.
  • the content of the photoinitiator is, for example, 1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight based on 100 parts by weight of the binder resin.
  • the crosslinkable compound having an ethylenically unsaturated bond is generally a crosslinkable unit having at least two ethylenic double bonds, and examples thereof include ethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, tri Ethylene glycol diacrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, butylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, Trimethylolpropane triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, tetramethylolpropane tetraacrylate, tetramethylolpropane tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pent
  • the crosslinkable compound having an ethylenically unsaturated bond is preferably contained in an amount of 10 to 200 parts by weight, more preferably 30 to 150 parts by weight, based on 100 parts by weight of the binder resin. Within this range, The pattern is well-formed and the hardness and resolution of the formed pattern are excellent.
  • the polymer may be dissolved in an organic solvent such as acetate, ether, glycol, ketone, alcohol, or carbonate used in a general photopolymerizable composition It is not particularly limited.
  • solvent examples include ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, ethyl carbitol acetate, butyl carbitol acetate, ethylene glycol, cyclohexanone, cyclopentanone, 3-ethoxypropionic acid, N , N-dimethylacetamide, N-methylpyrrolidone, N-methylcaprolactam, and the like.
  • the content of the solvent may be, for example, 20 to 95 parts by weight, preferably 30 to 90 parts by weight, and more preferably 50 to 80 parts by weight based on 100 parts by weight of the entire photosensitive resin composition. Within this range, It is easy to form a thin film by a coating method and a thin film having a desired thickness after coating can be easily obtained.
  • additives may be used if necessary.
  • additives include heat stabilizers, heat crosslinking agents, photocuring accelerators, surfactants, base quenchers, antioxidants, adhesion promoters, light stabilizers and antifoaming agents, and may be used alone or in combination as required.
  • the adhesion aid is a component having an action to improve adhesion with the substrate, and includes, for example, reactive functional groups such as carboxyl group, methacryloyl group, vinyl group, isocyanate group, epoxy group, Is preferred.
  • reactive functional groups such as carboxyl group, methacryloyl group, vinyl group, isocyanate group, epoxy group, Is preferred.
  • Specific examples include trimethoxysilylbenzoic acid,? -Methacryloyloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane,? -Glycidoxypropyl Trimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane.
  • the content of the adhesive aid is preferably 0 to 10 parts by weight, 0.01 to 10 parts by weight, 0.02 to 1 part by weight, or 0.05 to 0.1 part by weight based on 100 parts by weight of the binder resin,
  • the adhesive strength of the adhesive layer is excellent.
  • the surfactant is a component having an effect of improving coatability, coatability, uniformity and stain removal on a substrate, and may contain one or more selected from the group consisting of a fluorinated surfactant, a silicone surfactant and a nonionic surfactant And may be used in combination.
  • the surfactant is a silicone surfactant.
  • the surfactant include polysiloxane modified with polyisocyanate. More specific examples thereof include polyether-modified polydimethylsiloxane.
  • the amount of the surfactant is, for example, 0.01 to 5 parts by weight, 0.02 to 1 part by weight, or 0.05 to 0.1 parts by weight based on 100 parts by weight of the binder resin.
  • the adhesion aid is not particularly limited in the case of an adhesion aid which can be generally used in a photosensitive resin composition, but it is preferable that at least one member selected from the group consisting of an isocyanate compound, an epoxy compound, an acrylate compound, a vinyl compound and a mercapto- More preferably an epoxy-based compound, for example, an organosilane compound having an epoxy group, and more specifically, a methoxysilane having an epoxy group.
  • the stabilizer may be, for example, a heat stabilizer, a light stabilizer, or a mixture thereof.
  • the heat stabilizer is not particularly limited in the case of a heat stabilizer that can be generally used in a photosensitive resin composition.
  • the heat stabilizer is a heat stabilizer capable of suppressing lowering of the transmittance during the post-heat treatment process of the organic film formed to increase the permeability of the residual organic film, May be at least one member selected from the group consisting of a phenolic heat stabilizer, a phosphite-based heat stabilizer and a lactone-based heat stabilizer, more preferably at least one member selected from the group consisting of heat It is a stabilizer.
  • the light stabilizer is not particularly limited when it is a light stabilizer that can be generally used in a photosensitive resin composition.
  • the light stabilizer may be a light stabilizer capable of maximizing the light resistance of the organic insulating film composition.
  • the light stabilizer is a benzotriazole light stabilizer, Based light stabilizer, a benzophenone light stabilizer, a hindered aminoether light stabilizer, and a hindered amine light stabilizer.
  • the present invention also provides an element comprising a photosensitive curing pattern formed from the photosensitive resin composition.
  • the photosensitive binder composition may be applied to a semiconductor device, an LCD device, an OLED device, a solar cell device, a flexible display device, a touch screen device, or a nanoimprint lithography device.
  • the negative-working photosensitive resin composition of the present invention can be used for producing a color conversion medium layer, and can be used for a color conversion panel including an insulating substrate, a color conversion medium layer, and a light- It is applicable to production.
  • the photosensitive resin composition of the present invention may have a sensitivity of 140 mJ / cm 2 or less, 100 to 20 mJ / cm 2 , or 60 to 30 mJ / cm 2 , and the effect of excellent photosensitivity have.
  • the photosensitive resin composition of the present invention may have a residual film ratio of 91% or more, 95% or more, or 96 to 98% after development, and the optical characteristics of the photosensitive material are excellent within this range.
  • the photosensitive resin composition of the present invention may have a residual film ratio after curing of 89% or more, 93% or 94-97%, and the optical characteristics of the photosensitive material are excellent within this range.
  • the photosensitive resin composition of the present invention may have a teepahr angle of 45 degrees or more, 50 degrees or 55 to 75 degrees, for example, and has an excellent heat resistance within this range.
  • the photosensitive resin composition of the present invention may have a refractive index of 1.51 or more, 1.60 or 1.62 to 1.66 as an example, and the optical property of the photosensitive material is excellent within this range.
  • the photosensitive resin composition of the present invention may have a transmittance of 94% or more, 95% or more, or 96 to 99% after curing, and the optical characteristics of the photosensitive material are excellent within this range.
  • the present invention provides a positive photosensitive resin composition comprising the binder resin.
  • the photosensitive resin composition of the present invention is characterized in that the binder resin contains a photoactive compound, an additive and an organic solvent.
  • the photoactive compound is not particularly limited as long as it is a photoactive compound (PAC) that can be used in a photoresist, but may be a photo-acid generator, for example.
  • PAC photoactive compound
  • the positive photosensitive resin composition of the present invention may include (A) the binder resin of the present invention, (F) the photoactive compound, (G) the base resin, (D) the solvent and (E) the additive.
  • the photoacid generator is a compound that generates an acid when irradiated with an actinic ray or radiation. Any material can be used as long as it does not adversely affect film formation, as the photoacid generator has a suitable light absorption at a wavelength of 250 nm to 450 nm.
  • Examples of the photoacid generator include a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imidosulfonate, an oxime sulfonate, a diazodisulfone, a disulfone, ortho-nitrobenzylsulfonate Based compounds and triazine-based compounds.
  • the content of the photoacid generator which is a photoactive compound, is 0.1 to 15 parts by weight, more preferably 1 to 10 parts by weight, per 100 parts by weight of the binder resin. In this range, The solubility of the composition in the solvent is not lowered, and the solubility of the composition in the composition is not compromised and the solid particles are not likely to be precipitated.
  • the base quencer may be at least one selected from the group consisting of primary amines, secondary amines, tertiary amines and amide compounds, although it is not particularly limited.
  • an organic solvent and an additive may be included.
  • the kind and content of the organic solvent and the additive are the same as those for producing a negative photosensitive resin composition.
  • the photosensitive resin composition of the present invention may have a sensitivity of 200 mJ / cm 2 or less, 100 to 20 mJ / cm 2 , or 70 to 30 mJ / cm 2 , and an effect of excellent optical characteristics of the photosensitive material within this range .
  • the photosensitive resin composition of the present invention may have a residual film ratio after development of 90% or more, 91% or 92% to 97%, and the optical property of the photosensitive material is excellent within this range.
  • the photosensitive resin composition of the present invention may have a residual film ratio after curing of 85% or more, 87% or 88% or 92%, and the optical characteristics of the photosensitive material are excellent within this range.
  • the photosensitive resin composition of the present invention may have a tephar angle of at least 41 degrees, at least 45 degrees, or at least 49 degrees and at most 65 degrees, and has an excellent heat resistance within this range.
  • the photosensitive resin composition of the present invention may have a refractive index of 1.51 or more, 1.60 or more, 1.60 to 1.70, 1.63 to 1.68, or 1.64 to 1.66 as an example, and the optical property of the photosensitive material is excellent within this range.
  • the photosensitive resin composition of the present invention may have a transmittance of 94% or more, 95% or more, 96% or 96% or 98% or more after curing, and the optical characteristics of the photosensitive material are excellent within this range.
  • the method of applying the photosensitive resin composition containing the binder resin of the present invention as a thin film to a display device such as a TFT-LCD, an OLED and a touch screen panel is not particularly limited, and a method known in the art can be used .
  • the coating solution may be applied by spin coating, dip coating, roll coating, screen coating, spray coating, flow coating, screen printing, printing, ink jet, drop casting, and the like can be applied.
  • the applied film thickness may vary depending on the application method, the solid content concentration of the composition, the viscosity, and the like, and is usually applied so that the film thickness after drying is 0.5 to 100 m, but is not limited thereto.
  • the solvent is volatilized by applying vacuum, infrared rays or heat.
  • the selective exposure process may be performed using an excimer laser, a deep ultraviolet ray, an ultraviolet ray, a visible ray, an electron ray, an X ray or a g-ray (wavelength 436 nm), an i- ray (wavelength 365 nm) And irradiated using a mixed light of these.
  • the exposure may be performed by a contact method, a proximity method, or a projection method.
  • the photosensitive resin composition of the present invention can use an aqueous alkali solution as a developer, which is eco-friendly and economical than an organic solvent.
  • the alkali developing solution include aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide and tetraethylammonium hydroxide or amine-based aqueous solutions such as ammonia, ethylamine, diethylamine and triethylamine, or aqueous solutions of KOH, NaOH , NaHCO 3 and the like.
  • a KOH aqueous solution and an aqueous solution of tetramethylammonium hydroxide (TMAH) are preferable for achieving the specific purpose.
  • the present invention also provides an element comprising a photosensitive curing pattern formed from the binder.
  • the photosensitive binder resin composition can be applied to a semiconductor device, an LCD device, an OLED device, a solar cell device, a flexible display device, a touch screen manufacturing device, or a nanoimprint lithography device.
  • Step 1 Preparation of 2,2 '- ((((9H- ⁇ -9,9- diyl bis (4,1-phenylene)) bis (oxy)) bis (methylene)) bis (oxirane)
  • Step A After setting the reflux condenser and thermometer in a 3-neck flask, 42.5 g of 9,9-bisphenolfluorene was added and 220 mL of 2- (chloromethyl) oxirane was injected. After 100 mg of tetrabutylammonium bromide was added, the temperature was raised to 90 ° C while stirring was started, and the mixture was distilled under reduced pressure.
  • Step B After cooling, dichloromethane was injected and NaOH was slowly added. After confirming the product by high performance liquid chromatography (HPLC) method, HCl aqueous solution was added dropwise to terminate the reaction. The organic layer was dried over MgSO 4 and concentrated by distillation under reduced pressure using a rotary evaporator. Dichloromethane and methanol were added to the concentrated product, and the resulting solid was filtered and vacuum dried to obtain 52.7 g (yield 94%) of a white solid. The structure was confirmed by 1H NMR as follows.
  • the monomers having the structures of formulas (2) to (4) can be conventionally prepared by the method disclosed in the one-step synthesis method.
  • Step 2 Synthesis of 3,3 '- ((9H-fluorene-9,9-diyl) bis (4,1-phenylene)
  • Monomers having the structures of formulas (6) to (8) can be conventionally prepared by the method disclosed in the two-step synthesis method.
  • Step 1 The same synthesis method as in Step 1 of Synthesis Example 1 was carried out.
  • Step 2 (((9H- ⁇ -9,9- diyl ) bis (4,1- henylene )) bis (oxy)) bis (2-hydroxypropane-3,1-diyl) diacrylate
  • the monomers having the structures of formulas (6) to (8) can be conventionally prepared by the method disclosed in the two-step synthesis method of Synthesis Example 2.
  • Step 1 The same synthesis method as in Step 1 of Synthesis Example 1 was carried out.
  • Step 2 1. Synthesis of 1- (4- (9- (4- (oxiran-2-ylmethoxy) phenyl) -9H-fluoren-9-yl) phenoxy) -3- (phenylthio) propan-
  • the monomers having the structures of Formulas (2) to (4) can be conventionally prepared by the method shown in the two-step synthesis method of Synthesis Example 3.
  • the other monomers having the structures of formulas (6) to (8) can be conventionally prepared by the method disclosed in the three-step synthesis method of Synthesis Example 3.
  • the polymerization reaction shown in Production Example 1 can produce a BTCP / PMDA binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol according to the amount of PMDA used.
  • the binder can be prepared by the synthesis method of Preparation Example 1 by applying the monomers having the structures of Formulas 6 to 8 and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 2 can produce a BTCP / BPDA binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol according to the amount of BPDA used.
  • the binder can be prepared by the synthesis method of Preparation Example 2 by applying the monomers having the structures of Formulas 6 to 8 and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 3 can produce a BTCP / BTDA binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol according to the amount of BTDA to be used.
  • the binder can be produced by the synthesis method of Preparation Example 3 by applying the monomers having the structures of Formulas 6 to 8 and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 4 is applicable to monomer I and monomer II at a ratio of 99: 1 to 1:99, and using a monomer CBDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be produced by the synthesis method of Production Example 4 by applying the monomer I, the monomer II and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 5 is applicable to monomer I and monomer II in a ratio of 99: 1 to 1:99, and using a monomer CHDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be produced by the synthesis method of Production Example 5 by applying the monomer I, the monomer II and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 6 is applicable to monomer I and monomer II in a ratio of 99: 1 to 1:99, and using monomer PMDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be produced by the synthesis method of Preparation Example 6 by applying the monomer I, the monomer II and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 7 is applicable to monomer I and monomer II in a ratio of 99: 1 to 1:99, and using monomer BPDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be produced by the synthesis method of Preparation Example 7 by applying the monomer I, the monomer II and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 8 is applicable to monomer I and monomer II at a ratio of 99: 1 to 1:99, and using monomer BTDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be produced by the synthesis method of Production Example 8 by applying the monomer I, the monomer II and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 9 is applicable to monomer III and monomer CBDA in a ratio of 99: 1 to 1:99, and using a monomer CBDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be produced by the synthesis method of Preparation Example 9 by applying the monomer III and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 10 is applicable to monomer III and monomer CHDA in a ratio of 99: 1 to 1:99, and using monomer CHDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be prepared by the synthesis method of Preparation Example 10 by applying the monomer III and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 11 is applicable to monomer III and monomer PMDA in a ratio of 99: 1 to 1:99, and using monomer PMDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be produced by the synthesis method of Production Example 11 by applying the monomer III and the carboxylic acid dianhydride.
  • the polymerization reaction shown in Production Example 12 can be carried out in a ratio of from 99: 1 to 1:99 of the monomer III and the monomer BPDA, and a binder having a molecular weight of from 2,000 g / mol to 20,000 g / mol using the monomer BPDA Can be produced.
  • the binder can be produced by the synthesis method of Production Example 12 by applying the monomer III and the carboxylic acid dianhydride.
  • a reflux condenser and a thermometer were set in a 3-neck flask, and 100 g of the compound of Synthesis Example 3 dissolved in 50% PGMEA solvent was added and the temperature was raised to 110 ° C. At 110 ° C, 16.9 g of BTDA was added dropwise and stirred for 4 hours. After adding 3.0 g of tetrahydrophthalic anhydride (THPA), the reaction was terminated after stirring for another 2 hours. After cooling, a binder solution having a weight average molecular weight of 4,000 g / mol was obtained.
  • THPA tetrahydrophthalic anhydride
  • the polymerization reaction shown in Production Example 13 is applicable to monomer III and monomer BTDA in a ratio of 99: 1 to 1:99, and using a monomer BTDA, a binder having a weight average molecular weight of 2,000 g / mol to 20,000 g / mol Can be produced.
  • the binder can be produced by the synthesis method of Preparation Example 13 by applying the monomer III and the carboxylic acid dianhydride.
  • a positive type organic insulating film composition was prepared in the same manner as in Reference Example 1, except that 35 g of the binder resin prepared in the above-mentioned binder preparation example 2 was used.
  • a positive type organic insulating film composition was prepared in the same manner as in Reference Example 1, except that 35 g of the binder resin produced by the binder production example 3 was used.
  • a positive type organic insulating film composition was prepared in the same manner as in Reference Example 1, except that 35 g of the binder resin prepared in the binder preparation example 4 was used.
  • a positive type organic insulating film composition was prepared in the same manner as in Reference Example 1, except that 35 g of the binder resin produced by the binder production example 5 was used.
  • a negative photosensitive resin composition was prepared in the same manner as in Example 3, except that 35 g of the binder resin prepared in the binder production example 7 was used.
  • a negative photosensitive resin composition was prepared in the same manner as in Example 3 except that 35 g of the binder resin prepared in the above-mentioned binder preparation example 8 was used.
  • a negative photosensitive resin composition was prepared in the same manner as in Example 3 except that 35 g of the binder resin prepared in the above-mentioned binder production example 9 was used.
  • a negative photosensitive resin composition was prepared in the same manner as in Example 3 except that 35 g of the binder resin prepared in the binder preparation example 10 was used.
  • a negative-type photosensitive resin composition was prepared in the same manner as in Example 3 except that 35 g of the binder resin prepared in the above-mentioned binder production example 11 was used.
  • a negative-type photosensitive resin composition was prepared in the same manner as in Example 3 except that 35 g of the binder resin prepared in the above-mentioned binder production example 12 was used.
  • a negative photosensitive resin composition was prepared in the same manner as in Example 3 except that 35 g of the binder resin prepared in the above binder preparation example 13 was used.
  • BPDA tetrahydrophthalic anhydride
  • the binder 35 g to put the Tris-P PAC ® 3 g The solids content of 35 was dissolved in organic solvent PGMEA such that the weight% of the binder solution of a silicone surfactant to 60 g (BYK333, BYK) 0.03 g, an epoxy-based adhesive And 0.02 g of a dispersant (KBM403, Shin-Etsu) were added and mixed to prepare a positive-type organic insulating film composition.
  • the solids content of this was dissolved in organic solvent PGMEA such that 35% by weight, surfactant (BYK333) 0.03 g, adhesive preparation (KBM403) to the solution g were added and mixed to prepare a negative photosensitive resin composition.
  • Each of the photosensitive resin compositions obtained through Reference Examples 1 to 3, Examples 1 to 10 and Comparative Examples 1 to 4 was applied to a spin coater at 800 to 900 rpm for 15 seconds, Lt; 0 > C for 100 seconds. After exposure using an ultrahigh pressure mercury lamp as a light source using a predetermined mask, it was spin-developed at 25 DEG C for 60 seconds in a water-soluble alkali developing solution and then washed with water. After washing with water, post-baking was carried out in an oven at 230 ° C for 40 minutes to obtain a pattern, and the physical properties corresponding to the following items were evaluated.
  • Each of the thus-formed photosensitive resin compositions was applied to a glass substrate (Eagle 2000, manufactured by Samsung Corning Incorporated) with a spin coater and dried at 90 ⁇ for 1 minute with a hot plate. After drying, the film was measured with a contact-type film thickness meter (KLA-Tencor, a-step 500) to obtain a photosensitive thin film. After exposure with an ultra-high pressure mercury lamp using a photomask having a pattern, the resist was spray-developed with a water-soluble alkali developer to obtain a photoresist pattern. (MJ / cm < 2 >) capable of forming the same dimensions as the mask pattern of 20 microns. That is, a resist having a small exposure dose shows high sensitivity because a pattern can be formed even with a small light energy.
  • the residual film ratio after development was measured by measuring the pattern thickness after development, and then post-baked in a 230 ° C oven for 40 minutes to measure the residual film ratio after curing.
  • the composition was spin-coated on a glass substrate to form the same thickness of 3 microns and then subjected to a 400 mJ / cm 2 front exposure and post-baking at 240 ° C for 40 minutes. Using a UV-spectrometer, The average transmittance up to 800 nm was measured.
  • the pattern substrate on which sensitivity of the same dimension as the 20-micron mask pattern was formed was subjected to post-baking at 240 ° C for 40 minutes, and then the patter angle of the pattern was measured using SEM.
  • a crosscut was formed in a lattice pattern on a coated film heated at 240 ⁇ for 40 minutes after exposure and development, and then subjected to a peeling test with a cellophane tape to observe and evaluate the lattice peeling state .
  • a peeling test with a cellophane tape to observe and evaluate the lattice peeling state .
  • the composition was spin-coated on a glass substrate to form the same thickness of 3 microns, and the refractive index was measured through a prism coupler.
  • Table 1 shows the results of sensitivity, residual film ratio and adhesion of the photosensitive resin composition obtained through Examples 1 to 13 and Comparative Examples 1 to 4.
  • Example bookbinder TaePeugak Refractive index Transparency after curing (%) Reference Example 1 Production Example 1 53 1.65 96 Reference Example 2 Production Example 2 56 1.66 97 Reference Example 3 Production Example 3 51 1.65 97 Example 1 Production Example 4 49 1.65 98 Example 2 Production Example 5 52 1.64 98 Example 3 Production Example 6 68 1.64 98 Example 4 Production Example 7 73 1.64 98 Example 5 Production Example 8 71 1.65 98 Example 6 Production Example 9 69 1.65 99 Example 7 Production Example 10 68 1.64 99 Example 8 Production Example 11 72 1.65 98 Example 9 Production Example 12 70 1.65 98 Example 10 Production Example 13 74 1.65 98 Comparative Example 1 Acrylic binder 32 1.46 91 Comparative Example 2 Acrylic binder 33 1.45 93 Comparative Example 3 BACP / BPDA binder 35 1.59 88 Comparative Example 4 BACP / BPDA binder 38 1.59 90
  • Tables 1 and 2 show the characteristics of the organic high-sensitivity organic film composition and the negative-type organic film composition according to the present invention and the organic film composition using the acrylic binder not according to the present invention.
  • the characteristics of the organic film photosensitive material are very important for the characteristics of the display.
  • optical properties such as sensitivity, heat resistance, transmittance and refractive index are very important characteristics of the organic photoresist.
  • the sensitivity characteristic is a very important characteristic for shortening the TACT time. The high sensitivity characteristics can improve the productivity by shortening the processing time.
  • the organic film compositions according to Examples 1 to 10 exhibit excellent high sensitivity characteristics as compared with the organic film compositions of Comparative Examples 1 to 4. These characteristics indicate that the binder structure according to the present invention is excellent in the interaction property with the photoactive material (PAC) or the photoinitiator that affects the sensitivity characteristics, thereby maximizing the dissolution rate difference between the exposed region and the non- .
  • PAC photoactive material
  • the binder produced by the present invention has excellent heat resistance and can control taper angle and outgassing characteristics.
  • the heat resistance of the binder is an important property for securing the heat resistance of the organic photosensitive film.
  • the organic photoresist using an acrylic binder having a low heat resistance characteristic has been decomposed in a high temperature heat treatment process and found to be impurities or foreign substances in the process, causing degradation of display characteristics. Since it is difficult to control the pattern shape and taper angle, it is difficult to realize the high resolution characteristic of the photosensitive material.
  • the binder structure of the present invention is capable of securing a heat resistance property of 300 ⁇ ⁇ or more, thereby solving the problem of deterioration due to impurities due to a high-temperature heat treatment step and realizing a pattern having high-resolution characteristics.
  • the binder structure according to the present invention exhibits high refractive index and transmittance characteristics. Since the binder structure of the present invention contains a specific monomer structure and a specific element, it can exhibit a high refractive index characteristic compared to a binder having a general acrylic structure.
  • the high refractive index characteristic of the light-sensitive material can minimize the optical property degradation of the display caused by light, thereby improving the transmittance characteristic of light and the sharpness characteristic of the display.
  • the thin film produced from the photosensitive resin composition using the binder according to the present invention exhibited a very high transmittance of 97% or more even after heat curing at a temperature of 200 ° C or higher. Since the transparency characteristic of the photosensitive material can realize a clear display characteristic and can realize a wide aperture ratio of the TFT layer, a display having an excellent contrast ratio can be realized and the power consumption for driving can be reduced.
  • the organic film composition (Example 1-10) according to the present invention was excellent in optical characteristics and the like compared to Reference Example 1-3 in which monomers were different, .
  • the use of the binder resin according to the present invention makes it possible to produce photosensitive resin compositions having excellent properties such as sensitivity, heat resistance, transmittance and refractive index.

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Abstract

La présente invention concerne une résine liante ou un produit similaire qui, en tant que matériau organique utilisé dans des dispositifs d'affichage tels que des écrans TFT-LCD, OLED et TSP, est appliqué à des compositions de résine photosensible et à des matériaux de revêtement, et qui se caractérise par un haut degré de fonctionnalité et par des performances élevées en ce qui concerne la résistance à la chaleur, la résistance chimique, la transmissivité, la réfringence, les propriétés mécaniques, la flexibilité, le potentiel de développement ou la rectitude de motif et autre propriétés analogues.
PCT/KR2018/011861 2017-10-11 2018-10-10 Résine liante et composition de résine photosensible ou solution de revêtement la contenant WO2019074262A1 (fr)

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JP2020537184A (ja) 2020-12-17
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