WO2017200201A1 - Composition de résine photosensible et film durci préparé à partir de celle-ci - Google Patents

Composition de résine photosensible et film durci préparé à partir de celle-ci Download PDF

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Publication number
WO2017200201A1
WO2017200201A1 PCT/KR2017/003421 KR2017003421W WO2017200201A1 WO 2017200201 A1 WO2017200201 A1 WO 2017200201A1 KR 2017003421 W KR2017003421 W KR 2017003421W WO 2017200201 A1 WO2017200201 A1 WO 2017200201A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
siloxane polymer
siloxane
weight
Prior art date
Application number
PCT/KR2017/003421
Other languages
English (en)
Inventor
Jong Han YANG
Geun Huh
Jin Kwon
Jong-Ho Na
Original Assignee
Rohm And Haas Electronic Materials Korea Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR1020170039208A external-priority patent/KR102310794B1/ko
Application filed by Rohm And Haas Electronic Materials Korea Ltd. filed Critical Rohm And Haas Electronic Materials Korea Ltd.
Priority to JP2018556382A priority Critical patent/JP6983812B2/ja
Priority to US16/097,883 priority patent/US20190137877A1/en
Priority to CN201780025959.2A priority patent/CN109073971B/zh
Publication of WO2017200201A1 publication Critical patent/WO2017200201A1/fr
Priority to US18/065,798 priority patent/US20230109843A1/en

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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
    • G03F7/075—Silicon-containing compounds
    • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
    • 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
    • G03F7/022—Quinonediazides
    • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
    • G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
    • 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
    • G02F2201/00—Constructional arrangements not provided for in groups G02F1/00 - G02F7/00
    • G02F2201/40—Arrangements for improving the aperture ratio

Definitions

  • the present invention relates to a photosensitive resin composition and a cured film prepared therefrom. More particularly, the present invention relates to a photosensitive resin composition which has high transparency and excellent chemical resistance, and a cured film prepared therefrom that can be used in a liquid crystal display or an organic light-emitting (EL) display.
  • a photosensitive resin composition which has high transparency and excellent chemical resistance
  • a cured film prepared therefrom that can be used in a liquid crystal display or an organic light-emitting (EL) display.
  • a transparent planarization film is formed on a thin film transistor (TFT) substrate for the purpose of insulation to prevent the contact between a transparent electrode and a data line in a liquid crystal display or an organic EL display.
  • TFT thin film transistor
  • a transparent pixel electrode positioned near the data line, the aperture ratio of a panel may be increased and high luminance/resolution may be attained.
  • a positive-type photosensitive resin composition is widely employed in this process since fewer processing steps are required.
  • a positive-type photosensitive resin composition containing a siloxane polymer is well known as a material having high heat resistance, high transparency, and low dielectric constant.
  • Korean Laid-open Patent Publication No. 2006-059202 discloses a composition including a siloxane polymer containing a phenolic hydroxyl group in an amount ratio of 20 mole% or less, a quinonediazide compound that contains no methyl group in the ortho- or para-position relative to the phenolic hydroxyl group therein, and a compound containing an alcoholic hydroxyl group and/or a cyclic compound containing a carbonyl group as a solvent, wherein a cured film prepared from the composition has at least 95% transmittance and satisfies a specific chromaticity coordinate.
  • a planarization film prepared using a conventional positive-type photosensitive composition containing such a siloxane composition or a display device employing same may have limitations such as swelling or delamination of the film from a substrate when the cured film is immersed in, or comes into contact with, a solvent, an acid, a base, and the like which are used in a post-processing. Further, in line with the increasing requirement on the high sensitivity and in order to decrease a processing time, the concentration of a solvent, an acid, an alkali, and the like used in a post-processing becomes higher than before, and the requirement on a photosensitive resin composition, which may form a cured film having good chemical resistance, is increasing.
  • a photosensitive resin composition which may form a highly transparent cured film having excellent chemical resistance to chemicals (solvent, acid, alkali, and the like) which are used in a post-processing, and also provide a cured film prepared therefrom which is used in a liquid crystal display or an organic EL display.
  • the present invention provides a photosensitive resin composition, comprising:
  • the (A) mixture of siloxane polymers comprises (A-1) a first siloxane polymer which has a dissolution rate of 400 to 2,000 ⁇ /sec when pre-cured with respect to an aqueous solution of 2.38 wt% tetramethylammonium hydroxide; and (A-2) a second siloxane polymer which has a dissolution rate of 1,900 to 8,000 ⁇ /sec when pre-cured with respect to an aqueous solution of 1.5 wt% tetramethylammonium hydroxide.
  • the photosensitive resin composition of the present invention includes a mixture of two or more siloxane polymers having different dissolution rates with respect to an aqueous solution of tetramethylammonium hydroxide (TMAH), and may keep the conventional properties of high sensitivity and satisfy excellent chemical resistance when compared to a single siloxane polymer having the same degree of dissolution rate. That is, due to the use of two or more siloxane polymers having different dissolution rates, the photosensitive resin composition of the present invention may lead to good retention rate and high resolution, thereby forming a cured film having chemical resistance and high sensitivity.
  • TMAH tetramethylammonium hydroxide
  • the cured film prepared therefrom may be useful as a film constituting a liquid crystal display or an organic EL display.
  • the photosensitive resin composition according to the present invention includes (A) a mixture of two or more siloxane polymers having different dissolution rates with respect to an aqueous solution of TMAH, (B) a 1,2-quinonediazide compound, and (C) an epoxy compound, and may optionally further include (D) a solvent, and/or (E) a surfactant.
  • (meth)acryl means “acryl” and/or “methacryl”
  • (meth)acrylate means “acrylate” and/or “methacrylate”.
  • the mixture of siloxane polymers is a mixture of two or more siloxane polymers having different dissolution rates with respect to an aqueous solution of TMAH after pre-curing.
  • Such siloxane polymers may form positive-type patterns via the processes of exposure and development.
  • the solubility of the siloxane polymers may be compared on the basis of the solubility with respect to an aqueous solution of TMAH, and the siloxane polymers having high solubility with respect to an aqueous solution of TMAH may be used as a raw material for the preparation of siloxane resin with high sensitivity.
  • a cured film is formed by post-curing a photosensitive resin composition including a siloxane polymer at the temperature of about 230°C
  • it is required to have chemical resistance with respect to an etching solution of indium zinc oxide (IZO) or a rework solution, which is used after forming an organic film.
  • the etching solution or the rework solution may penetrate into the cured film to induce the swelling of the cured film.
  • the thickness of the cured film may be recovered returned to the original one before swelling when additional post-curing is performed, defects of generating cracks may arise in an inorganic film such as IZO which is deposited on the organic film.
  • an etching solution or rework solution may be easily penetrated into a cured film which is formed using a siloxane polymer having high solubility with respect to an aqueous solution of TMAH, and it is hard satisfy both high sensitivity and good chemical resistance.
  • siloxane polymers are used where at least one siloxane polymer having a significantly rapid dissolution rate relative to an aqueous solution of 1.5 wt% TMAH is mixed with at least one siloxane polymer having a common dissolution rate relative to an aqueous solution of 2.38 wt% TMAH.
  • the mixture of siloxane polymers (A) includes (A-1) a first siloxane polymer having a dissolution rate of 400 to 2,000 ⁇ /sec after pre-curing with respect to an aqueous solution of 2.38 wt% TMAH; and (A-2) a second siloxane polymer having a dissolution rate of 1,900 to 8,000 ⁇ /sec after pre-curing with respect to an aqueous solution of 1.5 wt% TMAH.
  • the dissolution rate of the single siloxane polymer and the mixture of the siloxane polymers with respect to an aqueous solution of TMAH may be measured as follows: a siloxane polymer specimen is added to propylene glycol monomethyl ether acetate (PGMEA, solvent) so that the solid content is 17 wt%, and stirred and dissolved using a stirrer at room temperature for 1 hour to prepare a siloxane polymer solution.
  • PGMEA propylene glycol monomethyl ether acetate
  • 3 cc of the siloxane polymer solution thus prepared was dropped on the central part of a 6-inch silicon wafer with a thickness of 525 ⁇ m using a pipette in a clean room under the conditions of a temperature of 23.0 ⁇ 0.5°C and a humidity of 50 ⁇ 5.0%, and the wafer was spin coated to give a coated film having a thickness of 2 ⁇ 0.1 ⁇ m.
  • the silicon wafer is heated on a hot plate at 105°C for 90 seconds to remove solvents, and the film thickness of a cured film is measured using a spectroscopic ellipsometer (Woollam Co.).
  • a dissolution rate is measured from the silicon wafer having the cured film by measuring a thickness with respect to dissolution time using an aqueous solution of 2.38 wt% TMAH or an aqueous solution of 1.5 wt% TMAH by a thin film analyzer (TFA-11CT, Shinyoung Co.).
  • the siloxane polymers include a silane compound and/or the condensate of the hydrolysate thereof.
  • the silane compound or the hydrolysate thereof may be a mono- to tetra-functional silane compounds.
  • the siloxane polymer may include siloxane structural units selected from the following Q, T, D and M types.
  • siloxane structural unit including a silicon atom and four adjacent oxygen atoms, which may be derived from e.g. , a tetrafunctional silane compound or the hydrolysate of a silane compound having four hydrolysable groups.
  • - T type siloxane structural unit a siloxane structural unit including a silicon atom and three adjacent oxygen atoms, which may be derived from e.g. , a trifunctional silane compound or the hydrolysate of a silane compound having three hydrolysable groups.
  • - D type siloxane structural unit a siloxane structural unit including a silicon atom and two adjacent oxygen atoms, which may be derived from e.g. , a difunctional silane compound or the hydrolysate of a silane compound having two hydrolysable groups.
  • siloxane structural unit including a silicon atom and one adjacent oxygen atom, which may be derived from e.g. , a monofunctional silane compound or the hydrolysate of a silane compound having one hydrolysable group.
  • the siloxane polymer may include at least one structural unit derived from a silane compound represented by the following formula 2.
  • each of the first siloxane polymer and the second siloxane polymer may be a silane compound represented by the following formula 2 and/or the condensate of the hydrolysate thereof.
  • R 3 may be alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 10 carbon atoms, or aryl having 6 to 15 carbon atoms, in the case where a plurality of R 3 is present in the same molecule, each R 3 may be the same or different, in the case where R 3 is alkyl, alkenyl, or aryl, hydrogen atoms may be partially or wholly substituted and R 3 may include a structural unit having a heteroatom;
  • R 4 is hydrogen, alkyl having 1 to 6 carbon atoms, acyl having 2 to 6 carbon atoms, or aryl having 6 to 15 carbon atoms, in the case where a plurality of R 4 is present in the same molecule, each R 4 may be the same or different, in the case where R 4 is alkyl, acyl, or aryl, hydrogen atoms may be partially or wholly substituted; and
  • n is an integer of 0 to 3.
  • R 3 including the structural unit having a heteroatom may include ether, ester and sulfide.
  • the silane compound may be a tetrafunctional silane compound where n is 0, a trifunctional silane compound where n is 1, a difunctional silane compound where n is 2, and a monofunctional silane compound where n is 3.
  • the silane compound may include, e.g. , as the tetrafunctional silane compounds, tetraacetoxysilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetraphenoxysilane, tetrabenzyloxysilane, and tetrapropoxysilane; as the trifunctional silane compounds, methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, pentafluorophenyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane,
  • tetrafunctional silane compounds are tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane; preferred among the trifunctional silane compounds are methyltrimethoxysilane, methyltriethoxysilane, methyltriisopropoxysilane, methyltributoxysilane, phenyltrimethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, ethyltriisopropoxysilane, ethyltributoxysilane, butyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethyltriethoxysi
  • Such silane compounds may be used alone or in combination of two or more thereof.
  • the conditions for preparing the hydrolysate of the silane compound represented by formula 2 or the condensate thereof are not specifically limited.
  • the desired hydrolysate or the condensate may be prepared by diluting the silane compound of formula 2 in a solvent such as ethanol, 2-propanol, acetone, and butyl acetate; adding thereto water necessary for the reaction and, as a catalyst, an acid (e.g. , hydrochloric acid, acetic acid, nitric acid, oxalic acid, and the like) or a base (e.g. , ammonia, triethylamine, cyclohexylamine, TMAH, and the like); and then stirring the mixture thus obtained to complete the hydrolytic polymerization reaction.
  • a solvent such as ethanol, 2-propanol, acetone, and butyl acetate
  • an acid e.g. , hydrochloric acid, acetic acid, nitric acid, oxalic
  • the weight average molecular weight of the condensate (siloxane polymer) obtained by the hydrolytic polymerization of the silane compound of formula 2 is preferably in a range of 500 to 50,000, and within this range, the photosensitive resin composition may have desirable film forming properties, solubility, and dissolution rates in a developer.
  • the kinds or amounts of the solvent, and the acid or base catalyst used for the preparation of the hydrolysate or the condensate thereof may be optionally selected without limitation.
  • the hydrolytic polymerization may be carried out at a low temperature of 20°C or less, but the reaction may also be promoted by heating or refluxing.
  • the time required for the reaction may vary according to the kind or concentration of a silane monomer, the reaction temperature, and the like. Generally, the reaction time required for obtaining a condensate having a weight average molecular weight of about 500 to 50,000 is in a range of 15 minutes to 30 days; however, the reaction time in the present invention is not limited thereto.
  • the siloxane polymer may include a linear siloxane structural unit (i.e. , D type siloxane structural unit).
  • the linear siloxane structural unit may be derived from a difunctional silane compound, for example, a silane compound of formula 2 where n is 2.
  • the siloxane polymer may include the structural unit derived from the silane compound of formula 2 where n is 2 in the amount of 0.5 to 50 mol%, and preferably, 1 to 30 mol% on the basis of the mole of Si atoms. Within this range, a cured film may maintain a constant hardness and exhibit flexibility, thereby further improving crack resistance to external stress.
  • the siloxane polymer may include a structural unit derived from a silane compound of formula 2 where n is 1 (i.e. , T type structural unit).
  • the siloxane polymer may include the structural unit derived from the silane compound of formula 2 where n is 1, in a ratio of 40 to 85 mol%, and preferably, 50 to 80 mol% on the basis of the mole of Si atoms.
  • the photosensitive resin composition may be more advantageous to form a more precise pattern.
  • the siloxane polymer may preferably include a structural unit derived from a silane compound having an aryl group in consideration of the hardness, sensitivity and retention rate of a cured film.
  • the siloxane polymer may include a structural unit derived from a silane compound having an aryl group in a molar ratio of 30 to 70 mol%, and preferably 35 to 50 mol% on the basis of the mole of Si atoms.
  • the compatibility of a siloxane polymer and an 1,2-quinonediazide compound (B) is good, and thus the excessive decrease in sensitivity may be prevented while attaining more favorable transparency of a cured film.
  • the structural unit derived from the silane compound having an aryl group as R 3 may be a structural unit derived from a silane compound of formula 2 where R 3 is aryl, preferably, a silane compound of formula 2 where n is 1 and R 3 is aryl, and particularly, a silane compound of formula 2 where n is 1 and R 3 is phenyl ( i.e. , T-phenyl type structural unit).
  • the siloxane polymer may include a structural unit derived from a silane compound of formula 2 where n is 0 (i.e. , Q type structural unit).
  • the siloxane polymer may include the structural unit derived from the silane compound of formula 2 where n is 0 in a molar ratio of 10 to 40 mol%, or 15 to 35 mol% on the basis of the mole of Si atoms.
  • the photosensitive resin composition may maintain its solubility in an aqueous alkaline solution at a proper degree during forming a pattern, thereby preventing any defects caused by a reduction in the solubility or a drastic increase in the solubility of the composition.
  • mol% on the basis of the mole of Si atoms refers to the percentage of the number of moles of Si atoms contained in a specific structural unit with respect to the total number of moles of Si atoms contained in all of the structural units constituting the siloxane polymer.
  • the mole amount of the siloxane unit in the siloxane polymer may be measured from the combination of Si-NMR, 1 H-NMR, 13 C-NMR, IR, TOF-MS, elementary analysis, determination of ash, and the like.
  • Si-NMR Si-NMR
  • 1 H-NMR 1 H-NMR
  • 13 C-NMR 13 C-NMR
  • IR TOF-MS
  • elementary analysis determination of ash, and the like.
  • an Si-NMR analysis is performed on a total siloxane polymer, a phenyl bound Si peak area and a phenyl unbound Si peak area are then analyzed, and the mole amount can thus be computed from the peak area ratio therebetween.
  • the photosensitive resin composition of the present invention may include the siloxane polymer in an amount ratio of 50 to 95 wt%, and preferably 65 to 90 wt% on the basis of the total solid content excluding solvents. Within the range, the resin composition can maintain its developability at a suitable level, thereby producing a cured film with improved film retention rate and pattern resolution.
  • he mixture of siloxane polymers may include the second siloxane polymer (A-2) in an amount ratio of 1 to 40 wt%, and preferably, 1 to 20 wt% of on the basis of the total amount of the mixture of siloxane polymers.
  • the resin composition can maintain its developability at a suitable level, thereby producing a cured film with improved film retention rate and pattern resolution.
  • the mixture of siloxane polymers may include the first siloxane polymer (A-1) in an amount ratio of 60 to 99 wt%, and preferably, 80 to 99 wt% on the basis of the total amount of the mixture of siloxane polymers.
  • the resin composition can maintain its developability at a suitable level, thereby producing a cured film with improved film retention rate and pattern resolution.
  • the photosensitive resin composition according to the present invention includes 1,2-quinonediazide compound (B).
  • the 1,2-quinonediazide compound may be any compound used as a photosensitive agent in the photoresist field.
  • Examples of the 1,2-quinonediazide compound may include an ester of a phenolic compound with 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid; an ester of a phenolic compound with 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulfonic acid; a sulfonamide of a compound in which a hydroxyl group of a phenolic compound is substituted with an amino group with 1,2-benzoquinonediazide-4-sulfonic acid or 1,2-benzoquinonediazide-5-sulfonic acid; a sulfonamide of a compound in which a hydroxyl group of a phenolic compound is substituted with an amino group with 1,2-naphthoquinonediazide-4-sulfonic acid or 1,2-naphthoquinonediazide-5-sulf
  • phenolic compound may include 2,3,4-trihydoxylbenzophenone, 2,4,6-trihydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2,3,3',4-tetrahydroxybenzophenone, 2,3,4,4'-tetrahydroxybenzophenone, bis(2,4-dihydroxyphenyl)methane, bis( p -hydroxyphenyl)methane, tri( p- hydroxyphenyl)methane, 1,1,1-tri( p -hydroxyphenyl)ethane, bis(2,3,4-trihydroxyphenyl)methane, 2,2-bis(2,3,4-trihydroxyphenyl)propane, 1,1,3-tris(2,5-dimethyl-4-hydroxyphenyl)-3-phenylpropane, 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol, bis(2,
  • 1,2-quinonediazide compound may include an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-4-sulfonic acid, an ester of 2,3,4-trihydroxybenzophenone and 1,2-naphthoquinonediazide-5-sulfonic acid, an ester of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-4-sulfonic acid, an ester of 4,4'-[1-[4-[1-[4-hydroxyphenyl]-1-methylethyl]phenyl]ethylidene]bisphenol and 1,2-naphthoquinonediazide-5-sulfonic acid, (2-diazo-1-naphthone-5-sulfonyl chloride) ester with 4,4'-[
  • the 1,2-quinonediazide compound may be included in the photosensitive resin composition in an amount ranging from 1 to 40 parts by weight, and preferably, 3 to 20 parts by weight on the basis of 100 parts by weight of the mixture of siloxane polymers (A). Within the amount range, the resin composition may form a pattern more readily, without defects such as a rough surface of a coated film and scum at the bottom portion of the pattern upon development.
  • the photosensitive resin composition of the present invention uses an epoxy compound together with a siloxane polymer so as to increase the internal density of a siloxane binder, to thereby improving the chemical resistance of a cured film prepared therefrom.
  • the epoxy compound (C) may include the repeating unit of the following formula 1.
  • R 1 is hydrogen or C 1-4 alkyl
  • R 2 is C 1-10 alkylene, C 6-10 arylene, C 3-10 cycloalkylene, C 3-10 heterocycloalkylene, C 2-10 heteroalkylene, R 5 -O-R 6 , or ;
  • R 5 to R 10 are each independently C 1-10 alkylene.
  • R 1 may include hydrogen, methyl, ethyl, propyl, n-butyl, isobutyl and tert-butyl, and preferably include hydrogen or methyl.
  • R 2 may include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, phenylene, -C 2 H 4 -O-C 2 H 4 -, -C 4 H 8 -O-C 4 H 8 -, -C 4 H 8 -O-CH 2 -, -C 4 H 8 -O-C 2 H 4 -, -C 2 H 4 -O-CH 2 -, -C 2 H 4 -COO-C 2 H 4 -, -C 4 H 8 -COO-C 4 H 8 -, -C 4 H 8 -COO-CH 2 -, -C 4 H 8 -COO-CH 2 -, -C 4 H 8 -COO-C 2 H 4 -, -C 2 H 4 -COO-C 2 H 4 -, -C 2 H 4 -COO-CH
  • the term "homooligomer” used herein means an oligomer having the same repeating unit for polymerization unless otherwise noted, includes a case where two or more kinds of repeating units of formula 1, and includes a case where 90 wt% or more of the repeating unit of formula 1.
  • the epoxy compound (C) of the present invention may be a homooligomer between monomers forming the repeating unit of formula 1.
  • the compound including the repeating unit of formula 1 used in the present invention may be synthesized by well-known methods.
  • the epoxy compound may additionally include a structural unit derived from a monomer other than the structural unit (repeating unit) of formula 1.
  • Particular examples of the structural unit derived from monomers other than the structural unit of formula 1 may include structural units derived from styrene; styrenes having an alkyl substituent such as methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, triethylstyrene, propylstyrene, butylstyrene, hexylstyrene, heptylstyrene, and octylstyrene; styrenes having a halogen such as fluorostyrene, chlorostyrene, bromostyrene and iodostyrene; styrenes having an alkoxy substituent such as methoxystyrene, ethoxystyrene, and propoxystyrene; p- hydroxy- ⁇ -methylsty
  • the structural unit derived from the above exemplary compounds may be included alone or in a combination of two or more in the epoxy compound.
  • the styrene-based compounds are preferable in consideration of polymerizability.
  • the epoxy compound does not contain a carboxyl group, by not using a structural unit derived from a monomer containing a carboxyl group among these compounds.
  • the structural unit derived from the monomer other than the structural unit of formula 1 may be included in a molar ratio of 1 to 70 mol%, and more preferably, 10 to 60 mol%, on the basis of the total structural unit constituting the epoxy compound. Within the preferable range, a cured film may have desirable hardness.
  • the epoxy compound may preferably have a weight average molecular weight of 100 to 30,000, and more preferably, 1,000 to 15,000. In the case where the weight average molecular weight of the epoxy compound is 100 or more, the hardness of a thin film may be improved, and in the case where the weight average molecular weight is 30,000 or less, a cured film may have a uniform thickness, which is suitable for planarizing any steps thereon.
  • the weight average molecular weight means a weight average molecular weight using polystyrene standards and measured by gel permeation chromatography (GPC, using tetrahydrofuran as eluent).
  • the epoxy compound (C) may be included in the photosensitive resin composition in an amount of 1 to 40 parts by weight, and preferably, 5 to 27 parts by weight on the basis of 100 parts by weight of the mixture of siloxane polymers (A). Within the amount range, the sensitivity and chemical resistance of the photosensitive resin composition may be improved.
  • the photosensitive resin composition of the present invention may be prepared as a liquid phase composition by mixing the above components with a solvent.
  • the solvent may be, for example, an organic solvent.
  • the amount of the solvent in the photosensitive resin composition of the present invention is not specifically limited, but may be adjusted to have the solid content of 10 to 70 wt%, and preferably 15 to 60 wt% on the basis of the total weight of the photosensitive resin composition.
  • the solid content means the constituent components excluding solvents from the resin composition of the present invention. With the amount of the solvent in the amount range, coating may be smoothly performed, and an appropriate degree of flowability may be maintained.
  • the solvent of the present invention may be any one which can dissolve each component and which is chemically stable, without limitation, and may include, e.g. , alcohols, ethers, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbons, ketones, esters, and the like.
  • the solvent may include methanol, ethanol, tetrahydrofuran, dioxane, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetoacetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate
  • ethylene glycol alkyl ether acetates diethylene glycols, propylene glycol monoalkyl ethers, propylene glycol alkyl ether acetates, ketones, and the like are preferably, and diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, methyl 2-methoxypropionate, ⁇ -butyrolactone, 4-hydroxy-4-methyl-2-pentanone, and the like are particularly preferable.
  • the above exemplary solvents may be used alone or in combination of two or more thereof.
  • the photosensitive resin composition of the present invention may further include a surfactant as occasion demands to enhance its coatability.
  • the kind of the surfactant is not limited, but preferred are fluorine-based surfactants, silicon-based surfactants, non-ionic surfactant and the like.
  • the surfactants may include fluorine-based surfactants and silicon-based surfactants such as FZ-2122 manufactured by Dow Corning Toray Co., Ltd, BM-1000, and BM-1100 manufactured by BM CHEMIE Co., Ltd., Megapack F-142 D, F-172, F-173, and F-183 manufactured by Dai Nippon Ink Kagaku Kogyo Co., Ltd., Florad FC-135, FC-170 C, FC-430, and FC-431 manufactured by Sumitomo 3M Ltd., Sufron S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, and SC-106 manufactured by Asahi Glass Co., Ltd., Eftop EF301, EF303, and EF352 manufactured by Shinakida Kasei Co., Ltd., SH-28 PA, SH-190, SH-193, SZ-6032, SF-8428, DC-
  • the surfactant (E) may be contained in an amount of 0.001 to 5 parts by weight, and preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the mixture of siloxane polymers (A) in the photosensitive resin composition. Within the amount range, the properties of coating and leveling of the composition may be improved.
  • additive components may be additionally included as long as the physical properties of the photosensitive resin composition are not adversely affected.
  • the photosensitive resin composition of the present invention may be used as a positive-type photosensitive resin composition.
  • the conventional properties may be maintained and excellent chemical resistance may be satisfied when compared to a single siloxane polymer having the same degree of dissolution rate.
  • the photosensitive resin composition of the present invention may induce excellent retention rate and high resolution due to the use of two or more siloxane polymers having different dissolution rates, and thus, a cured film having chemical resistance and high sensitivity may be formed.
  • the present invention also provides a cured film formed from the photosensitive resin composition.
  • the cured film may be formed by a well-known method in the art, for example, through processes of coating a photosensitive resin composition on a substrate and curing.
  • the coating may be performed by a method including a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, and the like, to a desired thickness, e.g. , a thickness of 2 to 25 ⁇ m.
  • the composition coated on a substrate may be subjected to pre-bake at a temperature of, for example, 60 to 130°C to remove solvents; then exposed to light using a photomask having a desired pattern; and subjected to development using a developer, for example, a TMAH solution, to form a pattern on the coated film.
  • the light exposure may be carried out at an exposure rate of 10 to 200 mJ/cm 2 based on a wavelength of 365 nm in a wavelength band of 200 to 500 nm.
  • a low pressure mercury lamp, a high pressure mercury lamp, an extra high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. may be used; and X-ray, electron beam, etc., may also be used, if desired.
  • the coated film with a pattern is subjected to post-bake, if necessary, for instance, at a temperature of 150 to 300°C for 10 minutes to 5 hours to manufacture a desired cured film.
  • the cured film thus patterned has excellent physical properties in consideration of chemical resistance, adhesiveness, heat resistance, transparency, dielectricity, solvent resistance, acid resistance and alkali resistance.
  • the cured film has excellent light transmittance without surface roughness when the composition is subjected to heat treatment or is immersed in, or comes into contact with a solvent, an acid, a base, and the like.
  • the cured film can be used effectively as a planarization film for a TFT substrate of a liquid crystal display or an organic EL display; a partition of an organic EL display; an interlayer dielectric of a semiconductor device; a core or cladding material of an optical waveguide, and the like.
  • the present invention provides electronic parts including the cured film as a protective film.
  • the weight average molecular weight is determined by gel permeation chromatography (GPC) using a polystyrene standard.
  • a dissolution rate of the siloxane polymer thus synthesized with respect to an aqueous solution of TMAH was measured by the above-mentioned method in the disclosure, and the dissolution rate thereof after pre-curing with respect to an aqueous solution of 2.38 wt% TMAH was 1,959.5 ⁇ /sec.
  • a dissolution rate of the siloxane polymer thus synthesized with respect to an aqueous solution of TMAH was measured by the above-mentioned method in the disclosure, and the dissolution rate thereof after pre-curing with respect to an aqueous solution of 2.38 wt% TMAH was 1,483.8 ⁇ /sec.
  • a dissolution rate of the siloxane polymer thus synthesized with respect to an aqueous solution of TMAH was measured by the above-mentioned method in the disclosure, and the dissolution rate thereof after pre-curing with respect to an aqueous solution of 1.5 wt% TMAH was 1,921.7 ⁇ /sec.
  • a dissolution rate of the siloxane polymer thus synthesized with respect to an aqueous solution of TMAH was measured by the above-mentioned method in the disclosure, and the dissolution rate thereof after pre-curing with respect to an aqueous solution of 1.5 wt% TMAH was 7,648.3 ⁇ /sec.
  • a dissolution rate of the siloxane polymer thus synthesized with respect to an aqueous solution of TMAH was measured by the above-mentioned method in the disclosure, and the dissolution rate thereof after pre-curing with respect to an aqueous solution of 2.38 wt% TMAH was 480 ⁇ /sec.
  • a dissolution rate of the siloxane polymer thus synthesized with respect to an aqueous solution of TMAH was measured by the above-mentioned method in the disclosure, and the dissolution rate thereof after pre-curing with respect to an aqueous solution of 2.38 wt% TMAH was 100 ⁇ /sec or less.
  • a dissolution rate of the siloxane polymer thus synthesized with respect to an aqueous solution of TMAH was measured by the above-mentioned method in the disclosure, and the dissolution rate thereof after pre-curing with respect to an aqueous solution of 1.5 wt% TMAH was 4,358.4 ⁇ /sec.
  • a three-necked flask was equipped with a cooling condenser and disposed on a stirrer provided with an automatic temperature regulator. Then, 100 parts by weight of a monomer consisting of glycidyl methacrylate (100 mol%), 10 parts by weight of 2,2'-azobis(2-methylbutyronitrile), and 100 parts by weight of PGMEA were put in the flask, and nitrogen was injected thereto. Then, the solution was slowly stirred and the temperature of the solution was increased to 80°C and maintained for 5 hours to synthesize an epoxy compound having a weight average molecular weight of about 6,000 to 10,000 Da. Then, PGMEA was added thereto to adjust the solid content thereof to be 20 wt%.
  • D-2 gamma-butyrolactone (GBL), BASF Co., Ltd.
  • E silicon-based leveling surfactant, FZ-2122, Dow Corning Toray Co., Ltd.
  • compositions obtained in the examples and comparative examples were coated on a glass substrate by spin coating, and the coated substrate was pre-baked on a hot plate kept at 110°C for 90 seconds to remove solvents and to form a dried film.
  • the dried film was exposed to light, through a mask having a pattern consisting of square holes in sizes ranging from 2 ⁇ m to 25 ⁇ m, at an exposure rate to 200 mJ/cm 2 based on a wavelength of 365 nm for a certain time period using an aligner (model name: MA6), which emits light having a wavelength of 200 nm to 450 nm, and was developed by spraying an aqueous developer of 2.38 wt% TMAH through puddle nozzles at 23°C.
  • the exposed film was then heated in a convection oven at 230°C for 30 minutes to obtain a cured film having a thickness of 3.0 ⁇ m.
  • the sensitivity was evaluated as good if the hole size was near 10 ⁇ m or greater than 10 ⁇ m, and as not good if the hole size was less than 10 ⁇ m.
  • compositions obtained in the examples and comparative examples were coated on a glass substrate by spin coating and pre-baked on a hot plate kept at 110°C for 90 seconds to form a dried film having a thickness of 3.1 ⁇ m.
  • the dried film was developed with an aqueous solution of 2.38 wt% TMAH through puddle nozzles at 23°C for 60 seconds.
  • the developed film was exposed through a pattern mask to light at an exposure rate of 200 mJ/cm 2 based on a wavelength of 365 nm for a certain period using an aligner (model name: MA6), which emits light having a wavelength of 200 nm to 450 nm (bleaching process).
  • the exposed film was then heated in a convection oven at 230°C for 30 minutes to obtain a cured film.
  • the thickness (T1) of the cured film was measured using a non-contact type thickness measuring device (SNU Precision).
  • a rework chemical product name: LT-360 was introduced to a constant temperature bath and then the temperature was maintained at 50°C.
  • the cured film was immersed in the bath for 2 minutes, washed with deionized water, and the rework chemical was removed by air. Then, the thickness (T2) of the cured film was measured.
  • Swelling thickness ( ⁇ ) film thickness after immersing into rework chemical (T2) - film thickness before immersing into rework chemical (T1)
  • the chemical resistance was recognized as good if the swelling thickness was less than 1,000 ⁇ .
  • Each of the photosensitive resin compositions obtained in the examples or comparative examples was coated on a glass substrate via spin coating, and the coated substrate was pre-baked on a hot plate kept at 110°C for 90 seconds to remove solvents and to form a dried film.
  • the dried film was exposed to light, through a mask having a pattern consisting of rod holes in sizes ranging from 1 ⁇ m to 25 ⁇ m, at an exposure rate to 200 mJ/cm 2 based on a wavelength of 365 nm for a certain time period using an aligner (model name: MA6), which emits light having a wavelength of 200 nm to 450 nm, and was developed by spraying an aqueous developer of 2.38 wt% TMAH through puddle nozzles at 23°C.
  • the exposed film was then heated in a convection oven at 230°C for 30 minutes to obtain a cured film having a thickness of 3.0 ⁇ m.
  • the shape of the rod pattern which has a pattern to space ratio of 1:1 and has widths ranging from 1 ⁇ m to 10 ⁇ m, was observed using an optical microscope (STM6-LM manufactured by Olympus Co., Ltd.). That is, if the distance between patterns of the patterned rod pattern is kept clean and constant, the adhesion of the pattern is recognized to be secured. The smaller the observed pattern size is, the higher the adhesion is.
  • the adhesion is ⁇ in the case where the size of the smallest pattern securing adhesion is 4 ⁇ m or less, ⁇ for 6 ⁇ m or less, and X for 8 ⁇ m or less.
  • compositions of the examples included in the scope of the present invention exhibited equally good chemical resistance, sensitivity and adhesion. On the contrary, the compositions of the comparative examples not included in the scope of the present invention exhibited at least one inferior result.

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Abstract

L'invention concerne une composition de résine photosensible et un film durci préparé à partir de celle-ci. La composition de résine photosensible comprend un mélange d'au moins deux polymères de siloxane ayant des vitesses de dissolution différentes par rapport à une solution aqueuse d'hydroxyde de tétraméthylammonium. La composition conserve une haute transparence et une haute sensibilité, qui sont des avantages d'une composition contenant un polymère de siloxane, et présente une excellente résistance chimique, ce qui permet d'obtenir un film durci ayant une excellente stabilité dans un post-traitement.
PCT/KR2017/003421 2016-05-19 2017-03-29 Composition de résine photosensible et film durci préparé à partir de celle-ci WO2017200201A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
JP2018556382A JP6983812B2 (ja) 2016-05-19 2017-03-29 感光性樹脂組成物及びそれから調製される硬化膜
US16/097,883 US20190137877A1 (en) 2016-05-19 2017-03-29 Photosensitive resin composition and cured film prepared therefrom
CN201780025959.2A CN109073971B (zh) 2016-05-19 2017-03-29 光敏树脂组合物和由其制备的固化膜
US18/065,798 US20230109843A1 (en) 2016-05-19 2022-12-14 Photosensitive resin composition and cured film prepared therefrom

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KR20160061371 2016-05-19
KR10-2016-0061371 2016-05-19
KR10-2017-0039208 2017-03-28
KR1020170039208A KR102310794B1 (ko) 2016-05-19 2017-03-28 감광성 수지 조성물 및 이로부터 제조된 경화막

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US18/065,798 Continuation US20230109843A1 (en) 2016-05-19 2022-12-14 Photosensitive resin composition and cured film prepared therefrom

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130216952A1 (en) * 2010-08-24 2013-08-22 Az Electronic Materials Usa Corp. Positive photosensitive siloxane composition
US20140335452A1 (en) * 2011-05-20 2014-11-13 Az Electronic Materials Usa Corp. Positive photosensitive siloxane composition
JP2015146332A (ja) * 2014-01-31 2015-08-13 国立大学法人 奈良先端科学技術大学院大学 保護膜を具備する薄膜トランジスタ基板およびその製造方法
US20150291749A1 (en) * 2012-11-22 2015-10-15 Az Electronic Materials (Luxembourg) S.A.R.L. Positive-type photosensitive siloxane composition
EP1171801B1 (fr) * 1998-10-01 2015-11-11 FUJIFILM Electronic Materials U.S.A, Inc. Compositions photosensibles avec precurseur a base de polybenzoxadole

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1171801B1 (fr) * 1998-10-01 2015-11-11 FUJIFILM Electronic Materials U.S.A, Inc. Compositions photosensibles avec precurseur a base de polybenzoxadole
US20130216952A1 (en) * 2010-08-24 2013-08-22 Az Electronic Materials Usa Corp. Positive photosensitive siloxane composition
US20140335452A1 (en) * 2011-05-20 2014-11-13 Az Electronic Materials Usa Corp. Positive photosensitive siloxane composition
US20150291749A1 (en) * 2012-11-22 2015-10-15 Az Electronic Materials (Luxembourg) S.A.R.L. Positive-type photosensitive siloxane composition
JP2015146332A (ja) * 2014-01-31 2015-08-13 国立大学法人 奈良先端科学技術大学院大学 保護膜を具備する薄膜トランジスタ基板およびその製造方法

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