WO2011062446A2 - Photosensitive resin composition - Google Patents

Photosensitive resin composition Download PDF

Info

Publication number
WO2011062446A2
WO2011062446A2 PCT/KR2010/008212 KR2010008212W WO2011062446A2 WO 2011062446 A2 WO2011062446 A2 WO 2011062446A2 KR 2010008212 W KR2010008212 W KR 2010008212W WO 2011062446 A2 WO2011062446 A2 WO 2011062446A2
Authority
WO
WIPO (PCT)
Prior art keywords
resin composition
photosensitive resin
weight
group
unsaturated carboxylic
Prior art date
Application number
PCT/KR2010/008212
Other languages
French (fr)
Korean (ko)
Other versions
WO2011062446A3 (en
Inventor
양필례
윤경근
이윤재
Original Assignee
코오롱인더스트리 주식회사
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 KR1020100107219A external-priority patent/KR101759929B1/en
Application filed by 코오롱인더스트리 주식회사 filed Critical 코오롱인더스트리 주식회사
Priority to CN201080061583.9A priority Critical patent/CN102713754B/en
Priority to US13/574,354 priority patent/US8968984B2/en
Publication of WO2011062446A2 publication Critical patent/WO2011062446A2/en
Publication of WO2011062446A3 publication Critical patent/WO2011062446A3/en

Links

Images

Classifications

    • 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
    • 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
    • G03F7/0755—Non-macromolecular compounds containing Si-O, Si-C or Si-N bonds

Definitions

  • the present invention relates to a photosensitive resin composition for an organic insulating film.
  • TFT-LCD Thin Film Transistor Liquid Crystal Dispaly
  • TFT-LCD Thin Film Transistor Liquid Crystal Dispaly
  • Such LCDs can be classified into reflective, transmissive and transflective types depending on the source of halo used.
  • the reflection type reflects an external light source and uses it as a back light, and a predetermined reflection plate is required.
  • the transmission type uses an internal light source as a back light and uses its own light of the backlight unit.
  • Transflective type is a mixture of reflection type and transmission type, and uses both external and internal light sources. That is, the transflective liquid crystal display device includes both a reflecting plate and a backlight unit, partly using external light reflected by the reflecting plate, and another part using internal light emitted from the backlight unit.
  • Another method is to increase the luminance of the transmissive liquid crystal display itself. In this case, there is a problem in that power consumption is increased because a high brightness backlight is used for high brightness.
  • This method has the advantage of increasing the brightness, but has the disadvantage that the resolution is degraded by the use of the white pixel and additional image processing process is required.
  • the present invention provides a photosensitive resin composition for an organic insulating film which can not only improve flatness, sensitivity, heat resistance and transparency, but also significantly improve patternability at a high taper angle.
  • One embodiment of the present invention is an [A] alkali-soluble resin, [B] an acrylic monomer having an ethylenically unsaturated bond, [C] photoinitiator, [D] a compound represented by the following formula (1) or a compound represented by the formula (2) and [E] A photosensitive resin composition containing a solvent.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 2 is a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms
  • m is an integer of 1 to 10
  • R is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an epoxy group and a hydroxy group, ie, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group , May be randomly selected from the group consisting of an epoxy group and a hydroxyl group.
  • Another embodiment of the present invention is a compound represented by the above [D] formula (1) or a compound represented by the formula (2) is a photosensitive resin composition having an epoxy equivalent of 500 to 2000g / eq.
  • the photosensitive resin composition is the [A] alkali-soluble resin 5 to 60% by weight; 5 to 70% by weight of an acrylic monomer having the [B] ethylenically unsaturated bond; 0.5 to 20% by weight of the [C] photopolymerization initiator; 5 to 70% by weight of the compound represented by Chemical Formula 1 or the compound represented by Chemical Formula 2; And it is a photosensitive resin composition containing 14 to 80 weight% of said [E] solvent.
  • the [A] alkali-soluble resin is one or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; And a copolymer of an [a2] epoxy group-containing unsaturated compound, or a mixture of one or two or more selected from [a1] unsaturated carboxylic acids and unsaturated carboxylic anhydrides; And [a2] epoxy group-containing unsaturated compounds and [a3] olefinically unsaturated carboxylic ester compounds other than the above [a1] and [a2]; And [a4] A photosensitive resin composition which is a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3].
  • the [A] alkali-soluble resin has a weight ratio of one or two or more mixtures selected from the above [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride and an [a2] epoxy group-containing unsaturated compound It is a photosensitive resin composition which is 1: 1.3 to 2.5.
  • the [A] alkali-soluble resin is one or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; And [a2] epoxy group-containing unsaturated compounds and [a3] olefinically unsaturated carboxylic ester compounds other than the above [a1] and [a2]; And [a4] In the case of a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3], the [A] alkali-soluble resin is [a3] above [a1] and [ olefinic unsaturated carboxylic ester compound other than a2]; And [a4] 20 to 65% by weight of one or more compounds selected from olefinically unsaturated compounds other than the above [a1], [a2] and [a3].
  • the photosensitive resin composition is a photosensitive resin composition having a viscosity of 2 to 35cps.
  • Another embodiment of the present invention is an organic insulating film obtained from the photosensitive resin composition.
  • Another embodiment of the present invention is a display device including the organic insulating layer.
  • the photosensitive resin composition according to the present invention not only improves flatness, sensitivity, heat resistance and transparency, but also has an effect of remarkably improving patternability at a high taper angle, thereby allowing a semi-transmissive thin film liquid crystal display device (TFT-LCD). It is useful for pattern formation of substrates and interlayer insulating layers, and especially when applied to semi-transmissive displays, it has a wide viewing angle and high visibility, and can realize low power consumption, and it is also excellent in outdoor visibility while maintaining the brightness of the screen. There is an advantage that you can see the screen clearly without.
  • 3D profiler 3D-profiler
  • R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 2 is a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms
  • m is an integer of 1 to 10.
  • R is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an epoxy group and a hydroxy group, ie, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group , May be randomly selected from the group consisting of an epoxy group and a hydroxyl group.
  • the alkali-soluble resin may be selected from the group consisting of a single or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as mixture a1); And a copolymer of an [a2] epoxy group-containing unsaturated compound (hereinafter referred to as compound a2) or a mixture [a1] and a compound [a2] and [a3] an olefinically unsaturated carboxylic acid other than [a1] and [a2].
  • Ester compounds (hereinafter referred to as compound a3); And [a4] a copolymer obtained by radical polymerization of at least one compound selected from olefinically unsaturated compounds (hereinafter referred to as compound a4) other than [a1], [a2], and [a3].
  • This copolymer is called Copolymer A.
  • the compound [a1] include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids.
  • acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and availability.
  • These compounds [a1] can be used individually or in combination.
  • Copolymer A which can be used in the present invention contains 5 to 40% by weight, preferably 10 to 30% by weight of structural units derived from compound [a1] in terms of heat resistance, chemical resistance, surface hardness and storage stability. desirable.
  • the compound [a2] include glycidyl acrylate, glycidyl methacrylate, glycidyl a-ethyl acrylate, glycidyl an-propyl acrylate, glycidyl an-butyl acrylate, glycidyl acrylate, acrylic acid-3, 4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, a-ethyl acrylic acid-6,7-epoxy heptyl, o- Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferably used in view of copolymerization reactivity and heat resistance and hardness of the resulting protective film
  • Copolymer A which can be used in the present invention contains 10 to 70% by weight, preferably 15 to 60% by weight of structural units derived from compound [a2], in terms of heat resistance, surface hardness and storage stability of the cured film. Do.
  • the compound [a3] include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Meta, such as cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, isoboroyl methacrylate Krylic acid cycloalkyl esters; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate and isobononyl acrylate;
  • Copolymer A which can be used in the present invention preferably contains 10 to 70% by weight, preferably 5 to 50% by weight of structural units derived from compound [a3] in view of storage stability, heat resistance and surface hardness.
  • the compound [a4] include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl chloride Leaden, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like.
  • Dual styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene and the like are preferred in view of copolymerization reactivity and heat resistance.
  • These compounds [a4] can be used alone or in combination.
  • Copolymer A which can be used in the present invention contains 5 to 70% by weight, preferably 5 to 60% by weight of structural units derived from compound [a4] in terms of heat resistance, chemical resistance, surface hardness and storage stability. desirable.
  • the copolymer A has a weight ratio of the mixture [a1] and the compound [a2] of 1: 1.3 to 2.5 in terms of pattern developability, stability, heat resistance and surface hardness.
  • the copolymer A is a copolymer obtained by polymerizing at least one compound selected from the mixture [a1] and the compound [a2], the compound [a3] and the compound [a4], the copolymer A is the compound [a3] and the compound. It is preferable to contain 20 to 65% by weight of one or more compounds selected from [a4].
  • the copolymer obtained by radical polymerization of at least one selected from the compound [a3] and the compound [a4] is included in the above range, there is an advantage of increasing pattern developability, heat resistance, and surface hardness.
  • Such alkali-soluble resin may have a solid content of 10 to 70% by weight in the alkali-soluble resin, preferably 20 to 60% by weight.
  • the content is less than 10% by weight, there is a problem in that the polymerization is not controlled well when preparing a polymer including all of the storage stability of the copolymer A and the components of [a1] to [a4], resulting in a solidification of 70% by weight.
  • the polymerization is not controlled well when preparing a polymer including all of the storage stability of the copolymer A and the components of [a1] to [a4], resulting in a solidification of 70% by weight.
  • the alkali-soluble resin is included in the range of 5 to 60% by weight, preferably 10 to 60% by weight in the photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, it is possible to obtain an appropriate developing effect.
  • Copolymer A obtained from the compounds [a1], [a2], [a3] and [a4] as described above has a carboxyl group or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating without using a special curing agent. have.
  • Alcohol such as methanol and ethanol
  • Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether
  • Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate, etc. are preferable.
  • a normal radical polymerization initiator can be used as a polymerization initiator which can be used for the said copolymer A synthesis
  • a normal radical polymerization initiator can be used.
  • a peroxide is used as a radical polymerization initiator, you may use it as a redox initiator by using a peroxide together with a reducing agent.
  • acrylic monomer having an ethylenically unsaturated bond a polyfunctional acrylic monomer having one or more ethylenically unsaturated bonds can be used.
  • Monofunctional, bifunctional or trifunctional or higher (meth) acrylates are preferred as the polyfunctional acrylic monomers of the present invention from the viewpoint of polymerizability and the heat resistance and surface hardness of the resulting protective film.
  • (meth) acrylate more than trifunctional for example, tris hydroxyethyl isocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, can be used.
  • the acrylic monomer having the ethylenically unsaturated bond is included in the range of 5 to 70% by weight in the photosensitive resin composition, when the content of the acrylic monomer having the ethylenically unsaturated bond is in the above range can be obtained a high hardness effect.
  • the photopolymerization initiator in the present invention means a compound which causes decomposition or bonding upon exposure and generates an active species capable of initiating polymerization of an acrylic monomer having the above-mentioned [B] ethylenically unsaturated bond such as radicals, anions, and cations. .
  • photopolymerization initiator examples include Irgacure 907, Irgacure 369, Irgacure ox01, Irgacure 242, thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, and 4,4'-bis (di Ethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, a, a'-dimethoxyacetoxy benzophenone, 2,2'-dimethoxy-2-petylacetophenone, p-methoxyacetophenone, 2 -Methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1
  • the content of the photopolymerization initiator may have a range of 0.5 to 20% by weight in the photosensitive resin composition. If the content of the photopolymerization initiator is less than 0.5% by weight, the sensitivity of the protective film is insufficient, so that the protective film is easily lost in the developing step, and even if the protective film is maintained in the developing step, it is difficult to obtain a protective film having a sufficiently high crosslink density. In addition, when the content of the photopolymerization initiator is more than 20% by weight, heat resistance, planarization property, etc. of the protective film tend to be lowered.
  • the photosensitive resin composition according to the present invention includes a compound represented by Formula 1 or a compound represented by Formula 2.
  • R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
  • R 2 is a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms
  • m is an integer of 1 to 10.
  • R is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an epoxy group and a hydroxy group, ie, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group , May be randomly selected from the group consisting of an epoxy group and a hydroxyl group.
  • alkyl group examples include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl and hexyl groups.
  • alkoxy group examples include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, isobutoxy, pentoxy, hexoxy and the like.
  • the compound represented by the formula (1) has an epoxy group, as shown in the formula (1), and has an epoxy equivalent.
  • Epoxy equivalent is the equivalent (g / eq) per epoxy group, and average molecular weight divided by the number of epoxy groups per molecule.
  • Compound represented by the formula (1) is an epoxy equivalent of 500 to 2000g / eq.
  • the epoxy equivalent is in the above range, the effect of increasing stability, heat resistance, flatness, adhesion, and hardness can be obtained.
  • the compound represented by Formula 1 or the compound represented by Formula 2 is included in the range of 5 to 70% by weight in the photosensitive resin composition, when the content of the photosensitive resin composition is less than 5% by weight, heat resistance, transparency, hardness is inferior In the case of exceeding 70% by weight, there is a problem that development is not possible in the developing step.
  • the top / bottom ratio in forming a pattern using the photosensitive resin composition for an organic insulating film.
  • the compound represented by Formula 1 or Formula 2 described above in the photosensitive resin composition for an organic insulating film is required.
  • the compound represented by the above content is included, the effect of improving the top / bottom ratio can be obtained.
  • the top / bottom ratio can be obtained by measuring a pattern using a scanning electron microscope or a 3D profiler.
  • the shape of the pattern generally has a shape similar to a trapezoid, and the length of the lower portion (b) is the length of the upper portion (a).
  • the top (a) length of the pattern shape should be equal to the bottom (b) length, and the pattern is made of a photosensitive composition comprising the compound represented by Formula 1 or the compound represented by Formula 2
  • the length of the top (a) and the length of the bottom (b) is almost the same to obtain the effect of increasing the top / bottom ratio, the higher the top / bottom ratio can be obtained the effect of increasing the taper angle. It is.
  • the solvent the following materials may be used as the solvent for preparing the copolymer or maintaining the solid content and the viscosity of the composition.
  • Alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether;
  • propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate.
  • the solvent may also be used with high boiling solvents.
  • High boiling point solvents that can be used include, for example, N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl Ethers.
  • the solvent is included in the range of 14 to 80% by weight in the photosensitive resin composition, when the content of the solvent is in the range can be obtained a desired coating effect.
  • the photosensitive resin composition containing the above-mentioned components has a viscosity of 2 to 35 cps.
  • the viscosity is the above-mentioned composition, [A] alkali-soluble resin, [B] acrylic monomer having an ethylenically unsaturated bond, [C] photopolymerization initiator and [D] the compound represented by the formula (1) or the compound represented by the formula (2) It is controlled by the content of and the content of the solvent [E], when the viscosity of the photosensitive resin composition is in the above range can be obtained the effect of obtaining the desired film thickness when using a spin (spin) and spinless coater (spinless coater) .
  • the viscosity may vary depending on the characteristics of the added composition even if the content of the solvent is the same, the range of the viscosity is determined by the film thickness. The higher the film thickness to be formed, the higher the viscosity. In the case of spin and spinless coaters, both the viscosity and the content of the constituents are considered to form the film thickness. Therefore, when the viscosity is within the above range, a desired film thickness can be obtained when using a spin and a spinless coater.
  • the photosensitive resin composition of the present invention may include an additive in addition to the above-described composition.
  • paintability examples include fluorine and silicone-based surfactants, for example, 3M's FC-129, FC-170C, FC-430, DIC's F-172, F-173, F-183, F-470, F-475, KP322, KP323, KP340, KP341 by Shin-Etsu Silicone, etc. are mentioned.
  • Such surfactant may be included in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, based on 100 parts by weight of the [A] alkali-soluble resin. If the content of the surfactant exceeds 5 parts by weight, there is a problem that foaming occurs during the application, this problem affects the developability and surface tension is undesirable.
  • an adhesion aid may be included as an additive in order to improve the adhesion with the base.
  • a functional silane coupling agent is preferably used.
  • trimethoxysilyl benzoic acid, -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, -isocyanatepropyl Triethoxysilane, -glycidoxy propyl trimethoxysilane, etc. are mentioned.
  • the adhesive aid may be included in 20 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of the [A] alkali-soluble resin. If the content of the adhesion assistant exceeds 20 parts by weight, there is a problem that the heat resistance is lowered.
  • the organic insulating film can be provided by a conventional manufacturing method using the photosensitive resin composition which concerns on this invention.
  • the display device according to the present invention can be manufactured using the organic insulating film according to a known manufacturing method.
  • Alkaline soluble resins A and B as photosensitive materials, propylene glycol monomethyl ether acetate as solvent, OXE-01 (CIBA) as photopolymerization initiator and dipentaerythritol hexa (meth) acryl as acrylic monomer having ethylenically unsaturated bonds
  • the rate was blended and the compound represented by Formula 1 (R 1 is a methyl group, R 2 is a methoxy group, m is 3) was blended while varying the content as shown in Table 1 below to prepare a photosensitive resin.
  • the content unit is weight%.
  • Alkaline soluble resins A and B as photosensitive materials, propylene glycol monomethyl ether acetate as solvent, OXE-01 (CIBA) as photopolymerization initiator and dipentaerythritol hexa (meth) acryl as acrylic monomer having ethylenically unsaturated bonds
  • the rate was blended and the compound represented by Chemical Formula 2 (R has an epoxy group, a methoxy group, a hydroxy group, and a methyl group) was mixed with varying contents as shown in Table 2 below to prepare a photosensitive resin.
  • the content units in Table 2 below are by weight.
  • Viscosity was measured at 25 with a Brookfield viscometer.
  • Each photosensitive resin composition prepared on the glass substrate was spin-coated and pre-dried under a condition of 100 and 85 seconds on a hot plate to form a photoresist film having a film thickness of 2. After exposing the glass substrate on which such a film was formed, it was developed in 0.04% KOH aqueous solution for 60 seconds and subjected to strong heat treatment for 220 and 30 minutes again.
  • the film thickness at the time of predrying and the thickness of the formed film after solvent removal through post-cure were measured, and the residual film rate was measured by ratio measurement.
  • Each photosensitive resin composition prepared on the glass substrate patterned with color resist was spin coated and pre-dried under a condition of 100 and 85 seconds on a hot plate to form a photoresist film having a thickness of 2. After exposing the glass substrate on which such a film was formed, it was developed in 0.04% KOH aqueous solution for 60 seconds and subjected to strong heat treatment for 220 and 30 minutes again. The flatness was measured by measuring the thickness of 5 points of the dry coating film obtained here. The flatness was measured, and when the thickness deviation was less than 0.025,?, 0.026 to 0.05 were represented by ⁇ , and 0.06 to 0.1 were represented by?, And 0.1 was represented by ⁇ .
  • Each photosensitive resin composition prepared on a glass substrate was coated with a spin of 500 rpm, preliminarily dried on a hot plate at 100 and 85 seconds, and the exposure dose was 60 mJ /, 70 mJ /, 80 mJ /, 90 mJ /, 100 mJ /, 150 mJ /, and After each exposure to 200mJ / was developed for 60 seconds in 0.04% KOH aqueous solution and again subjected to a strong heat treatment for 220, 30 minutes. The thickness of the coating film obtained at this time was measured. The thickness was measured to obtain 90% or more of the thickness of the coating film obtained at 200 mJ /, and the sensitivity was selected for each composition.
  • the widths of the top, bottom, left and right sides of the pattern film formed by the sensitivity measurement were measured. At this time, when the change rate of each angle is 0 to 10% before baking (250, 30 minutes), ⁇ , 11 to 20% when ⁇ , 21 to 40% when ⁇ , 40% when the case is ⁇ Indicated.
  • Each photosensitive resin composition prepared on a glass substrate was spin coated and pre-dried on a hot plate at 100 and 85 seconds, and the exposure dose was 60 mJ /, 70 mJ /, 80 mJ /, 90 mJ /, 100 mJ /, 150 mJ /, and 200 mJ /.
  • After each exposure to 0.04% KOH aqueous solution was developed for 60 seconds and again subjected to a strong heat treatment for 220, 1 hour.
  • the obtained coating film was cut into 100 equal parts, and then attached and detached using 3M Scotch maic tape. At this time, the number of remaining coatings was counted. In the above measurement, ⁇ , 90-99% ⁇ , 80-89% ⁇ , ⁇ , and less than 80% of the remaining coating film were indicated by ⁇ .
  • Each photosensitive resin composition prepared on a glass substrate was spin-coated and pre-dried under a condition of 100 and 85 seconds on a hot plate, and the exposure dose was 40, 60, 70, 80, 90, 100, 150, After exposure to 200mJ / was developed for 60 seconds in a 0.04% KOH aqueous solution and then subjected to a strong heat treatment for 220, 30 minutes.
  • the formed patterns were measured for CD size of Top and Bottom using a 3D profiler.
  • permeability measured the transmittance
  • Example 6 Viscosity (cps) Flatness Sensitivity (mJ / cm2) Heat resistance Adhesiveness Residual rate (%) Transmittance (%) t / b ratio (%)
  • Example 6 5 ⁇ 50 ⁇ ⁇ 90.3 91.5 82.1
  • Example 7 5 ⁇ 50 ⁇ ⁇ 91.0 95.0 86.7
  • Example 8 5 ⁇ 50 ⁇ ⁇ 92.6 97.6 90.8
  • Example 9 5 ⁇ 50 ⁇ ⁇ 91.3 97.2 87.4
  • Example 10 5 ⁇ 50 ⁇ ⁇ 92.7 98.2 91.2 Comparative Example 1 5 ⁇ 60 ⁇ ⁇ 87.8 88.0 75.0 Comparative Example 2 5 ⁇ 70 ⁇ ⁇ 88.5 89.0 76.1
  • the photosensitive resin compositions prepared in Examples 1 to 5 and Examples 6 to 10 were excellent in heat resistance, adhesiveness, residual film rate, and transmittance, and particularly tapered angles as the top / bottom ratio was high. It was found that the taper angle and patternability can be effectively applied to the organic insulating film in various display processes.
  • the photosensitive resin composition which concerns on this invention can be used for an organic insulating film.

Abstract

The present invention relates to a photosensitive resin composition for an organic insulating layer. More specifically, the invention can be used for forming a substrate of a transflective thin film transistor liquid crystal display (TFT-LCD) or a pattern of an interlayer insulating layer by improving remarkably a pattern property with a high taper angle besides improvement of flatness, sensitivity, heat resistance, and transparency. Particularly, the photosensitive resin composition can provide low power dissipation besides a wide viewing angle and high visibility when being applied to a transflective type display. In addition, the photosensitive resin composition can provide a clear screen under natural light without a backlight by maintaining the brightness of a screen and prominent field visibility.

Description

감광성 수지 조성물Photosensitive resin composition
본 발명은 유기 절연막용 감광성 수지 조성물에 관한 것이다.The present invention relates to a photosensitive resin composition for an organic insulating film.
TFT-LCD(Thin Film Transistor Liquid Crystal Dispaly)는 TFT-array가 형성된 유기기판과 컬러 필터가 형성된 유리기판과 일정한 간격을 유지할 수 있도록 합착한 후 두 장의 유리 기판 사이에 액정을 주입하여 패널을 형성한 후 전기적인 신호를 인가하여 디스플레이하는 것을 말한다. TFT-LCD (Thin Film Transistor Liquid Crystal Dispaly) is a panel formed by injecting liquid crystal between two glass substrates after bonding them together to maintain a constant distance between the TFT-array-formed organic substrate and the color filter-formed glass substrate. It refers to the display after applying the electrical signal.
이러한 LCD는 사용되는 후광의 소스에 따라 반사형, 투과형 및 반투과형으로 분류할 수 있다. 반사형은 외부광원을 반사시켜 이를 후광으로 이용하는 것으로 소정의 반사판이 필요한 형태이고, 투과형은 후광으로써 내부광원을 이용하는 것으로 백라이트유니트의 자체 빛을 이용하는 형태이다. Such LCDs can be classified into reflective, transmissive and transflective types depending on the source of halo used. The reflection type reflects an external light source and uses it as a back light, and a predetermined reflection plate is required. The transmission type uses an internal light source as a back light and uses its own light of the backlight unit.
반투과형은 반사형과 투과형이 혼합된 형태로 외부광원과 내부광원을 모두 이용한다. 즉 반투과형 액정표시장치는 반사판과 백라이트 유니트가 모두 구비되어 일부는 반사판에 의해 반사되는 외부광을 이용하고 또 다른 일부는 백라이트유니트에서 방출되는 내부광을 이용하는 형태이다. Transflective type is a mixture of reflection type and transmission type, and uses both external and internal light sources. That is, the transflective liquid crystal display device includes both a reflecting plate and a backlight unit, partly using external light reflected by the reflecting plate, and another part using internal light emitted from the backlight unit.
한편 주변 조도에 비해 액정표시장치의 밝기가 상대적으로 밝지 못한 경우 명암비의 차이로 인해 표시성능이 떨어지는 문제점이 있다. 이를 해결할 수 있는 방법으로는 반투과형 액정표시장치를 이용하여 외부광을 일부 이용하는 방법과 투과형 액정표시장치의 자체 휘도를 증가시키는 방법이 있다. 반투과형 액정표시장치의 경우, 밝은 환경하에서 외부광을 이용하여 휘도를 향상시킬 수 있다는 장점이 있으나, 반사모드로 작동되는 반사형 셀이 전체 개구면적의 50%를 차지하고 있고 반사모드에서는 효율이 5% 미만으로 매우 낮기 때문에 어두운 환경하에서는 휘도가 떨어진다는 단점이 있다. On the other hand, when the brightness of the LCD is relatively bright compared to the ambient illuminance, there is a problem in that display performance is lowered due to a difference in contrast ratio. As a solution to this problem, there is a method of partially using external light using a transflective liquid crystal display and a method of increasing the luminance of the transmissive liquid crystal display. In the case of the transflective liquid crystal display, there is an advantage that the brightness can be improved by using external light in a bright environment, but the reflective cell operated in the reflective mode occupies 50% of the total opening area, and the efficiency is 5 in the reflective mode. Since it is very low to less than%, there is a disadvantage that the brightness is lowered in a dark environment.
또한, 외부광이 갖고 있는 빛의 성질과 내부광이 갖고 있는 빛의 성질이 서로 다르기 때문에 시간에 따라 이를 보정하여야할 필요가 있는 것이다. In addition, since the light properties of the external light and the light of the internal light are different from each other, it is necessary to correct this according to time.
다른 방법으로는 투과형 액정표시장치의 자체 휘도를 증가시키는 방법이 있다. 이 경우, 높은 휘도를 위해 고휘도 백라이트를 사용하기 때문에 소비전력이 증가되는 문제점이 있다. Another method is to increase the luminance of the transmissive liquid crystal display itself. In this case, there is a problem in that power consumption is increased because a high brightness backlight is used for high brightness.
최근에는 화이트 픽셀을 사용하여 내부광원의 투과율을 향상시키는 방법이 제안되었다. 이 방법은 휘도를 증가시킬 수 있다는 장점이 있으나, 화이트 픽셀 사용에 따라 해상도가 저하되고 추가적인 영상처리 과정이 필요하다는 단점이 있다. Recently, a method of improving transmittance of an internal light source using a white pixel has been proposed. This method has the advantage of increasing the brightness, but has the disadvantage that the resolution is degraded by the use of the white pixel and additional image processing process is required.
이에 따라 해상도 저하가 없으면서도 외부광을 충분히 활용할 수 있는 반투과형 액정표시장치의 개발이 필요하며, 이에 따른 패턴 형성이 용이한 감광성 수지 조성물을 개발하는 것이 절실한 실정이다.Accordingly, it is necessary to develop a semi-transmissive liquid crystal display device that can fully utilize external light without degrading the resolution, and thus, it is urgent to develop a photosensitive resin composition that can easily form a pattern.
본 발명은 평탄도, 감도, 내열성 및 투명성을 향상시킬 뿐만 아니라 높은 테이퍼 앵글(taper angle)로 패턴성을 현저히 향상시킬 수 있는 유기 절연막용 감광성 수지 조성물을 제공하는 것이다.The present invention provides a photosensitive resin composition for an organic insulating film which can not only improve flatness, sensitivity, heat resistance and transparency, but also significantly improve patternability at a high taper angle.
본 발명의 일 구현예는 [A]알칼리 가용성 수지, [B]에틸렌성 불포화 결합을 갖는 아크릴 모노머, [C]광중합 개시제, [D]하기 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물 및 [E]용매를 포함하는 감광성 수지 조성물이다.One embodiment of the present invention is an [A] alkali-soluble resin, [B] an acrylic monomer having an ethylenically unsaturated bond, [C] photoinitiator, [D] a compound represented by the following formula (1) or a compound represented by the formula (2) and [E] A photosensitive resin composition containing a solvent.
<화학식 1><Formula 1>
[규칙 제26조에 의한 보정 31.01.2011]　
Figure WO-DOC-MATHS-1
 [Revision 31.01.2011 under Rule 26]
Figure WO-DOC-MATHS-1
(상기 식에서, R1은 수소원자 또는 탄소수 1 내지 5의 알킬기이고, R2은 수소원자, 탄소수 1 내지 5의 알콕시기 또는 탄소수 1 내지 5의 알킬기이고, m은 1 내지 10의 정수이다.)(Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 is a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and m is an integer of 1 to 10).
<화학식 2><Formula 2>
[규칙 제26조에 의한 보정 31.01.2011]　
Figure WO-DOC-MATHS-2
 [Revision 31.01.2011 under Rule 26]
Figure WO-DOC-MATHS-2
(상기 식에서, R은 수소원자, 탄소수 1 내지 10의 알킬기, 알콕시기, 에폭시기 및 히드록시기로 이루어진 군으로부터 선택된 적어도 1종 이상이다. 즉, 상기 R은 수소원자, 탄소수 1 내지 10의 알킬기, 알콕시기, 에폭시기 및 히드록시기로 이루어진 군으로부터 무작위적으로 선택될 수 있다.)Wherein R is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an epoxy group and a hydroxy group, ie, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group , May be randomly selected from the group consisting of an epoxy group and a hydroxyl group.)
본 발명의 다른 일 구현예는 상기 [D]화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물은 에폭시 당량이 500 내지 2000g/eq인 감광성 수지 조성물이다. Another embodiment of the present invention is a compound represented by the above [D] formula (1) or a compound represented by the formula (2) is a photosensitive resin composition having an epoxy equivalent of 500 to 2000g / eq.
본 발명의 다른 일 구현예는 감광성 수지 조성물은 상기 [A]알칼리 가용성 수지 5 내지 60중량%; 상기 [B]에틸렌성 불포화 결합을 갖는 아크릴 모노머 5 내지 70중량%; 상기 [C]광중합 개시제 0.5 내지 20중량%; 상기 [D]화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물 5 내지 70중량%; 및 상기 [E]용매 14 내지 80중량%를 포함하는 감광성 수지 조성물이다. Another embodiment of the present invention, the photosensitive resin composition is the [A] alkali-soluble resin 5 to 60% by weight; 5 to 70% by weight of an acrylic monomer having the [B] ethylenically unsaturated bond; 0.5 to 20% by weight of the [C] photopolymerization initiator; 5 to 70% by weight of the compound represented by Chemical Formula 1 or the compound represented by Chemical Formula 2; And it is a photosensitive resin composition containing 14 to 80 weight% of said [E] solvent.
본 발명의 다른 일 구현예는 상기 [A]알칼리 가용성 수지는 [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중에서 선택된 1종 또는 2종 이상의 혼합물; 및 [a2]에폭시기 함유 불포화 화합물의 공중합체이거나, [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중에서 선택된 1종 또는 2종 이상의 혼합물; 및 [a2]에폭시기 함유 불포화 화합물과 [a3]상기 [a1] 및 [a2] 이외의 올레핀계 불포화 카르복실산 에스테르 화합물; 및 [a4]상기 [a1], [a2] 및 [a3] 이외의 올레핀계 불포화 화합물 중에서 선택된 1종 이상의 화합물의 공중합체인 감광성 수지 조성물이다. Another embodiment of the present invention, the [A] alkali-soluble resin is one or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; And a copolymer of an [a2] epoxy group-containing unsaturated compound, or a mixture of one or two or more selected from [a1] unsaturated carboxylic acids and unsaturated carboxylic anhydrides; And [a2] epoxy group-containing unsaturated compounds and [a3] olefinically unsaturated carboxylic ester compounds other than the above [a1] and [a2]; And [a4] A photosensitive resin composition which is a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3].
본 발명의 다른 일 구현예는 상기 [A]알칼리 가용성 수지는 상기 [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중에서 선택된 1종 또는 2종 이상의 혼합물 및 [a2]에폭시기 함유 불포화 화합물의 중량비가 1:1.3 내지 2.5인 감광성 수지 조성물이다. According to another embodiment of the present invention, the [A] alkali-soluble resin has a weight ratio of one or two or more mixtures selected from the above [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride and an [a2] epoxy group-containing unsaturated compound It is a photosensitive resin composition which is 1: 1.3 to 2.5.
본 발명의 다른 일 구현예는 상기 [A]알칼리 가용성 수지가 [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중에서 선택된 1종 또는 2종 이상의 혼합물; 및 [a2]에폭시기 함유 불포화 화합물과 [a3]상기 [a1] 및 [a2] 이외의 올레핀계 불포화 카르복실산 에스테르 화합물; 및 [a4]상기 [a1], [a2] 및 [a3] 이외의 올레핀계 불포화 화합물 중에서 선택된 1종 이상의 화합물의 공중합체인 경우, 상기 [A]알칼리 가용성 수지는 [a3]상기 [a1] 및 [a2] 이외의 올레핀계 불포화 카르복실산 에스테르 화합물; 및 [a4]상기 [a1], [a2] 및 [a3] 이외의 올레핀계 불포화 화합물 중에서 선택된 1종 이상의 화합물을 20 내지 65중량%로 포함하는 감광성 수지 조성물이다. Another embodiment of the present invention, the [A] alkali-soluble resin is one or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride; And [a2] epoxy group-containing unsaturated compounds and [a3] olefinically unsaturated carboxylic ester compounds other than the above [a1] and [a2]; And [a4] In the case of a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3], the [A] alkali-soluble resin is [a3] above [a1] and [ olefinic unsaturated carboxylic ester compound other than a2]; And [a4] 20 to 65% by weight of one or more compounds selected from olefinically unsaturated compounds other than the above [a1], [a2] and [a3].
본 발명의 다른 일 구현예는 상기 감광성 수지 조성물은 점도가 2 내지 35cps인 감광성 수지 조성물이다. Another embodiment of the present invention is the photosensitive resin composition is a photosensitive resin composition having a viscosity of 2 to 35cps.
본 발명의 다른 일 구현예는 상기 감광성 수지 조성물로부터 얻어지는 유기 절연막이다. Another embodiment of the present invention is an organic insulating film obtained from the photosensitive resin composition.
본 발명의 다른 일 구현예는 상기 유기 절연막을 포함하는 디스플레이 장치이다. Another embodiment of the present invention is a display device including the organic insulating layer.
본 발명에 따른 감광성 수지 조성물은 평탄도, 감도, 내열성 및 투명성을 향상시킬 뿐만 아니라 높은 테이퍼 앵글(taper angle)로 패턴성을 현저히 향상시키는 효과를 가짐에 따라 반투과형 박막액정 표시장치(TFT-LCD)의 기판이나 층간 절연층의 패턴 형성에 유용하고, 특히 반투과형 디스플레이에 적용시 광시야각과 높은 시인성을 가지는 동시에 저소비전력도 실현할 수 있고, 화면의 밝기를 유지하면서 야외 시인성 또한 우수해 자연광에서 백라이트 없이도 화면을 뚜렷하게 볼 수 있는 장점이 있다. The photosensitive resin composition according to the present invention not only improves flatness, sensitivity, heat resistance and transparency, but also has an effect of remarkably improving patternability at a high taper angle, thereby allowing a semi-transmissive thin film liquid crystal display device (TFT-LCD). It is useful for pattern formation of substrates and interlayer insulating layers, and especially when applied to semi-transmissive displays, it has a wide viewing angle and high visibility, and can realize low power consumption, and it is also excellent in outdoor visibility while maintaining the brightness of the screen. There is an advantage that you can see the screen clearly without.
도 1은 본 발명의 일 구현예에 따른 일례로 3차원 프로파일러(3D-profiler)를 이용하여 패턴을 측정한 것이다1 is a pattern measured using a 3D profiler (3D-profiler) as an example according to an embodiment of the present invention
본 발명의 일 구현예에 따르면, [A]알칼리 가용성 수지, [B]에틸렌성 불포화 결합을 갖는 아크릴 모노머, [C]광중합 개시제, [D]하기 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물 및 [E]용매를 포함하는 감광성 수지 조성물을 제공하는 것이다. According to one embodiment of the present invention, [A] alkali-soluble resin, [B] acrylic monomer having an ethylenically unsaturated bond, [C] photopolymerization initiator, [D] a compound represented by the following formula (1) It is providing the photosensitive resin composition containing a compound and [E] solvent.
<화학식 1><Formula 1>
[규칙 제26조에 의한 보정 31.01.2011]　
Figure WO-DOC-MATHS-3
 [Revision 31.01.2011 under Rule 26]
Figure WO-DOC-MATHS-3
상기 식에서, R1은 수소원자 또는 탄소수 1 내지 5의 알킬기이고, R2은 수소원자, 탄소수 1 내지 5의 알콕시기 또는 탄소수 1 내지 5의 알킬기이고, m은 1 내지 10의 정수이다. Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 is a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and m is an integer of 1 to 10.
<화학식 2><Formula 2>
[규칙 제26조에 의한 보정 31.01.2011]　
Figure WO-DOC-MATHS-4
 [Revision 31.01.2011 under Rule 26]
Figure WO-DOC-MATHS-4
(상기 식에서, R은 수소원자, 탄소수 1 내지 10의 알킬기, 알콕시기, 에폭시기 및 히드록시기로 이루어진 군으로부터 선택된 적어도 1종 이상이다. 즉, 상기 R은 수소원자, 탄소수 1 내지 10의 알킬기, 알콕시기, 에폭시기 및 히드록시기로 이루어진 군으로부터 무작위적으로 선택될 수 있다.)Wherein R is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an epoxy group and a hydroxy group, ie, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group , May be randomly selected from the group consisting of an epoxy group and a hydroxyl group.)
이하 본 발명의 일 구현예에 따른 감광성 수지 조성물에 포함되는 각 성분에 대하여 구체적으로 살펴본다. Hereinafter, each component included in the photosensitive resin composition according to the exemplary embodiment of the present invention will be described in detail.
[A]알칼리 가용성 수지 [A] alkali-soluble resin
상기 알칼리 가용성 수지는 [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중 선택된 단독 또는 2종 이상의 혼합물(이하, 혼합물 a1이라 함); 및 [a2]에폭시기 함유 불포화 화합물(이하, 화합물 a2라 함)의 공중합체이거나, 혼합물 [a1] 및 화합물 [a2]과 [a3]상기 [a1] 및 [a2] 이외의 올레핀계 불포화 카르복실산 에스테르 화합물(이하, 화합물 a3라 함); 및 [a4]상기 [a1], [a2] 및 [a3] 이외의 올레핀계 불포화 화합물(이하, 화합물 a4라 함) 중 선택된 1종 이상의 화합물을 라디칼 중합하여 얻어진 공중합체일 수 있다. The alkali-soluble resin may be selected from the group consisting of a single or a mixture of two or more selected from [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride (hereinafter referred to as mixture a1); And a copolymer of an [a2] epoxy group-containing unsaturated compound (hereinafter referred to as compound a2) or a mixture [a1] and a compound [a2] and [a3] an olefinically unsaturated carboxylic acid other than [a1] and [a2]. Ester compounds (hereinafter referred to as compound a3); And [a4] a copolymer obtained by radical polymerization of at least one compound selected from olefinically unsaturated compounds (hereinafter referred to as compound a4) other than [a1], [a2], and [a3].
상기 공중합체를 공중합체 A라 한다. This copolymer is called Copolymer A.
상기 화합물 [a1]의 구체적인 예로서는, 아크릴산, 메타크릴산, 크로톤산 등의 모노카르복시산; 말레산, 푸마르산, 시트라콘산, 메사콘산, 이타콘산 등의 디카르복시산; 및 이들 디카르복시산의 무수물 등을 들 수 있다. 이 중에서, 아크릴산, 메타크릴산, 무수 말레산 등이 공중합 반응성, 내열성 및 입수가 용이한 점에서 바람직하게 사용된다. 이러한 화합물 [a1]은 단독 또는 조합해서 사용할 수 있다. Specific examples of the compound [a1] include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; And anhydrides of these dicarboxylic acids. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and availability. These compounds [a1] can be used individually or in combination.
본 발명에서 사용할 수 있는 공중합체 A는 화합물 [a1]으로부터 유도된 구성단위를 5 내지 40중량%, 바람직하게는 10 내지 30중량%로 함유하는 것이 내열성, 내약품성, 표면경도 및 보존안정성 측면에서 바람직하다. Copolymer A which can be used in the present invention contains 5 to 40% by weight, preferably 10 to 30% by weight of structural units derived from compound [a1] in terms of heat resistance, chemical resistance, surface hardness and storage stability. desirable.
상기 화합물 [a2]의 구체적인 예로는, 아크릴산 글리시딜, 메타크릴산 글리시딜, a-에틸 아크릴산 글리시딜, a-n-프로필 아크릴산 글리시딜, a-n-부틸 아크릴산 글리시딜, 아크릴산-3,4-에폭시 부틸, 메타크릴산-3,4-에폭시 부틸, 아크릴산-6,7-에폭시 헵틸, 메타크릴산-6,7-에폭시 헵틸, a-에틸 아크릴산-6,7-에폭시 헵틸, o-비닐 벤질 글리시딜 에테르, m-비닐 벤질 글리시딜 에테르, p-비닐 벤질 글리시딜 에테르 등이 공중합 반응성 및 얻어지는 보호막의 내열성, 경도를 높인다는 점에서 바람직하게 사용된다. 이러한 화합물 [a2]는 단독으로 또는 조합해서 사용할 수 있다. Specific examples of the compound [a2] include glycidyl acrylate, glycidyl methacrylate, glycidyl a-ethyl acrylate, glycidyl an-propyl acrylate, glycidyl an-butyl acrylate, glycidyl acrylate, acrylic acid-3, 4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, a-ethyl acrylic acid-6,7-epoxy heptyl, o- Vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferably used in view of copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds [a2] can be used individually or in combination.
본 발명에서 사용할 수 있는 공중합체 A는 화합물 [a2]로부터 유도된 구성단위를 10 내지 70중량%, 바람직하게는 15 내지 60중량%로 함유하는 것이 경화막의 내열성, 표면경도 및 보존안정성 측면에서 유리하다. Copolymer A which can be used in the present invention contains 10 to 70% by weight, preferably 15 to 60% by weight of structural units derived from compound [a2], in terms of heat resistance, surface hardness and storage stability of the cured film. Do.
상기 화합물 [a3]의 구체적인 예로는, 메틸 메타크릴레이트, 에틸 메타크릴레이트, n-부틸 메타크릴레이트, sec-부틸 메타크릴레이트, t-부틸 메타크릴레이트 등의 메타크릴산 알킬 에스테르; 메틸 아크릴레이트, 이소프로필 아크릴레이트 등의 아크릴산 알킬 에스테르; 시클로헥실 메타크릴레이트, 2-메틸 시클로헥실 메타크릴레이트, 디사이클로펜테닐 아크릴레이트, 디시클로펜테닐 메타크릴레이트, 디시클로펜테닐옥시에틸 메타크릴레이트, 이소보로닐 메타크릴레이트 등의 메타크릴산 시클로알킬 에스테르; 시클로헥실 아크릴레이트, 2-메틸 시클로헥실 아크릴레이트, 디시클로펜테닐 아크릴레이트, 디시클로펜테닐옥시에틸 아크릴레이트, 이소보노닐 아크릴레이트 등의 아크릴산 시클로알킬 에스테르; 페닐 메타크릴레이트, 벤질 메타크릴레이트 등의 메타크릴산 아릴 에스테르; 페닐 아크릴레이트, 벤질 아크릴레이트 등의 아크릴산 아릴 에스테르; 말레산 디에틸, 프마르산 디에틸, 이타콘산 디에틸 등의 디카르복시산 디에스테르; 2-히드록시 에틸 메타크릴레이트, 2-히드록시 프로필 메타크릴레이트 등의 히드록시알킬 에스테르 등을 들 수 있다. 이러한 화합물 [a3]은 단독으로 또는 조합하여 사용할 수 있다. Specific examples of the compound [a3] include methacrylic acid alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate; Acrylic acid alkyl esters such as methyl acrylate and isopropyl acrylate; Meta, such as cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl acrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, isoboroyl methacrylate Krylic acid cycloalkyl esters; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate and isobononyl acrylate; Methacrylic acid aryl esters such as phenyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fmarate and diethyl itaconic acid; Hydroxyalkyl esters, such as 2-hydroxy ethyl methacrylate and 2-hydroxy propyl methacrylate, etc. are mentioned. These compounds [a3] can be used alone or in combination.
본 발명에서 사용할 수 있는 공중합체 A는 화합물 [a3]으로부터 유도된 구성단위를 10 내지 70중량%, 바람직하게는 5 내지 50중량% 함유하는 것이 보존안정성, 내열성 및 표면경도 측면에서 바람직하다. Copolymer A which can be used in the present invention preferably contains 10 to 70% by weight, preferably 5 to 50% by weight of structural units derived from compound [a3] in view of storage stability, heat resistance and surface hardness.
상기 화합물 [a4]의 구체적인 예로는, 스티렌, o-메틸 스티렌, m-메틸 스티렌, p-메틸 스티렌, 비닐 톨루엔, p-메톡시 스티렌, 아크릴로니트릴, 메타크릴로니트릴, 염화 비닐, 염화 비닐리덴, 아크릴 아미드, 메타크릴 아미드, 초산 비닐, 1,3-부타디엔, 이소프렌, 2,3-디메틸-1,3-부타디엔 등을 들 수 있다. 이중 스티렌, t-부틸 메타크릴레이트, 디시클로펜테닐 메타크릴레이트, p-메톡시 스티렌, 2-메틸 시클로헥실 아크릴레이트, 1,3-부타디엔 등이 공중합 반응성 및 내열성의 관점에서 바람직하다. 이러한 화합물 [a4]는 단독으로 또는 조합하여 사용할 수 있다. Specific examples of the compound [a4] include styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl chloride Leaden, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Dual styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene and the like are preferred in view of copolymerization reactivity and heat resistance. These compounds [a4] can be used alone or in combination.
본 발명에서 사용할 수 있는 공중합체 A는 화합물 [a4]으로부터 유도된 구성단위를 5 내지 70중량%, 바람직하게는 5 내지 60중량%로 함유하는 것이 내열성, 내약품성, 표면경도 및 보존안정성 측면에서 바람직하다. Copolymer A which can be used in the present invention contains 5 to 70% by weight, preferably 5 to 60% by weight of structural units derived from compound [a4] in terms of heat resistance, chemical resistance, surface hardness and storage stability. desirable.
상기 공중합체 A는 혼합물 [a1] 및 화합물 [a2]의 중량비가 1:1.3 내지 2.5인 것이 패턴 현상성, 안정성, 내열성, 표면경도 면에서 바람직하다. It is preferable that the copolymer A has a weight ratio of the mixture [a1] and the compound [a2] of 1: 1.3 to 2.5 in terms of pattern developability, stability, heat resistance and surface hardness.
상기 공중합체 A가 혼합물 [a1] 및 화합물 [a2]과 화합물 [a3] 및 화합물 [a4] 중에서 선택된 1종 이상의 화합물을 중합하여 얻어진 공중합체인 경우, 상기 공중합체 A는 상기 화합물 [a3] 및 화합물 [a4] 중에서 선택된 1종 이상의 화합물을 20 내지 65중량%로 포함하는 것이 바람직하다. 상기 화합물 [a3] 및 상기 화합물 [a4] 중에서 선택된 1종 이상을 라디칼 중합하여 얻어진 공중합체를 상기 범위 내로 포함하는 경우 패턴 현상성, 내열성, 표면경도를 높일 수 있는 장점이 있다. When the copolymer A is a copolymer obtained by polymerizing at least one compound selected from the mixture [a1] and the compound [a2], the compound [a3] and the compound [a4], the copolymer A is the compound [a3] and the compound. It is preferable to contain 20 to 65% by weight of one or more compounds selected from [a4]. When the copolymer obtained by radical polymerization of at least one selected from the compound [a3] and the compound [a4] is included in the above range, there is an advantage of increasing pattern developability, heat resistance, and surface hardness.
이러한 알칼리 가용성 수지는 고형분 함량이 알칼리 가용성 수지 중에 10 내지 70중량%일 수 있으며, 바람직하게는 20 내지 60중량%일 수 있다. 상기 함량이 10중량% 미만인 경우는 공중합체 A의 보존안정성 및 [a1] 내지 [a4]의 구성요소를 모두 포함하는 중합체를 제조시 중합 조절이 잘 되지 않아 고체화가 되는 문제가 있고, 70중량%를 초과하는 경우에는 공중합체 A의 현상성, 내열성 및 표면경도 등이 저하되는 문제가 있다.Such alkali-soluble resin may have a solid content of 10 to 70% by weight in the alkali-soluble resin, preferably 20 to 60% by weight. When the content is less than 10% by weight, there is a problem in that the polymerization is not controlled well when preparing a polymer including all of the storage stability of the copolymer A and the components of [a1] to [a4], resulting in a solidification of 70% by weight. When exceeding, there exists a problem that developability, heat resistance, surface hardness, etc. of copolymer A fall.
상기 알칼리 가용성 수지는 감광성 수지 조성물 중에 5 내지 60중량%, 바람직하게는 10 내지 60중량%의 범위로 포함한다. 상기 알칼리 가용성 수지의 함량이 상기 범위 내에 있는 경우 적절한 현상성 효과를 얻을 수 있다. The alkali-soluble resin is included in the range of 5 to 60% by weight, preferably 10 to 60% by weight in the photosensitive resin composition. When the content of the alkali-soluble resin is within the above range, it is possible to obtain an appropriate developing effect.
상기와 같은 화합물 [a1], [a2], [a3] 및 [a4]로부터 얻어진 공중합체 A는 카르복실기 또는 카르복시산 무수물기 및 에폭시기를 갖고 있으며, 특별한 경화제를 병용하지 않더라도 가열에 의하여 용이하게 경화시킬 수 있다. Copolymer A obtained from the compounds [a1], [a2], [a3] and [a4] as described above has a carboxyl group or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating without using a special curing agent. have.
상기 공중합체 A의 합성에 사용되는 용매로는 메탄올, 에탄올 등의 알코올류; 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류; 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로필렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류 등이 바람직하다.As a solvent used for the synthesis | combination of the said copolymer A, Alcohol, such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates, such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate, etc. are preferable.
상기 공중합체 A 합성에 사용할 수 있는 중합개시제로는 통상의 라디칼 중합개시제를 사용할 수 있다. 예컨대, 2,2'-아조비스 이소부티로니트릴, 2,2'-아조비스-(2,4-디메틸발레로니트릴), 2,2'-아조비스-(4-메톡시-2,4-디메틸발레로니트릴) 등의 아조 화합물; 벤조일 퍼옥시드, t-부틸 퍼옥시 피바레이트, 1,1'-비스-(t-부틸 퍼옥시)시클로 헥산 등의 유기 과산화물 및 과산화수소를 들 수 있다. 라디칼 중합 개시제로서 과산화물을 이용한 경우에는 과산화물을 환원제와 함께 이용하여 레독스(redox) 개시제로 사용해도 무방하다. As a polymerization initiator which can be used for the said copolymer A synthesis | combination, a normal radical polymerization initiator can be used. For example, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2,4 Azo compounds such as -dimethylvaleronitrile); Organic peroxides and hydrogen peroxide, such as benzoyl peroxide, t-butyl peroxy pibarate and 1,1'-bis- (t-butyl peroxy) cyclohexane. When a peroxide is used as a radical polymerization initiator, you may use it as a redox initiator by using a peroxide together with a reducing agent.
[B]에틸렌성 불포화 결합을 갖는 아크릴 모노머[B] Acrylic monomers having ethylenically unsaturated bonds
상기 에틸렌성 불포화 결합을 갖는 아크릴 모노머는 1개 이상의 에틸렌성 불포화결합을 갖는 다관능성 아크릴 모노머를 사용할 수 있다. 단관능, 2관능 또는 3관능 이상의 (메타)아크릴레이트가 중합성 및 얻어지는 보호막의 내열성, 표면 경도 측면에서 본 발명의 다관능성 아크릴 모노머로 바람직하다. As the acrylic monomer having an ethylenically unsaturated bond, a polyfunctional acrylic monomer having one or more ethylenically unsaturated bonds can be used. Monofunctional, bifunctional or trifunctional or higher (meth) acrylates are preferred as the polyfunctional acrylic monomers of the present invention from the viewpoint of polymerizability and the heat resistance and surface hardness of the resulting protective film.
단관능 (메타)아크릴레이트로는, 예컨대 2-히드록시 에틸 (메타)아크릴레이트, 카비톨 (메타)아크릴레이트, 이소보닐(메타)아크릴레이트, 3-메톡시 부틸 (메타)아크릴레이트, 2-(메타)아크릴로일 옥시 에틸 2-히드록시 프로필 프탈레이트가 사용될 수 있다. As monofunctional (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl (meth) acrylate, 2 -(Meth) acryloyl oxy ethyl 2-hydroxy propyl phthalate can be used.
2관능 (메타)아크릴레이트로는, 예컨대 에텔렌글리콜 (메타)아크릴레이트, 1,6-헥산디올 (메타)아크릴레이트, 1,9-노난디올 (메타)아크릴레이트, 프로필렌글리콜 (메타)아크릴레이트, 테트라에틸렌글리콜 (메타)아크릴레이트, 비스페녹시 에틸알콜 플루오렌 디아크릴레이트, 폴리에틸렌글리콜아크릴레이트(에틸렌글리콜 반복수=3~40), 폴리에틸렌글리콜메타크릴레이트 (에틸렌글리콜 반복수=3~40), 폴리부틸렌글리콜아크릴레이트(부틸렌글리콜 반복수=3~40), 폴리부틸렌글리콜메타크릴레이트(부틸렌글리콜 반복수는 3 내지 40이다) 등을 들 수 있다. As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) acrylate, and propylene glycol (meth) acryl Rate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, polyethylene glycol acrylate (ethylene glycol repeat number = 3-40), polyethylene glycol methacrylate (ethylene glycol repeat number = 3) 40), polybutylene glycol acrylate (butylene glycol repeating number = 3-40), polybutylene glycol methacrylate (butylene glycol repeating number is 3-40), etc. are mentioned.
3관능 이상의 (메타)아크릴레이트로는, 예컨대 트리스히드록시에틸이소시아누레이트 트리(메타)아크릴레이트, 트리메틸프로판 트리(메타)아크릴레이트, 펜타에리스리톨 트리(메타)아크릴레이트, 펜타에리스리톨테트라(메타)아크릴레이트, 디펜타에리스리톨 헥사(메타)아크릴레이트가 사용될 수 있다. As (meth) acrylate more than trifunctional, for example, tris hydroxyethyl isocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, can be used.
상기 에틸렌성 불포화 결합을 갖는 아크릴 모노머는 감광성 수지 조성물 중에 5 내지 70중량%의 범위로 포함하는데, 상기 에틸렌성 불포화 결합을 갖는 아크릴 모노머의 함량이 상기 범위 내에 있는 경우 고경도효과를 얻을 수 있다. The acrylic monomer having the ethylenically unsaturated bond is included in the range of 5 to 70% by weight in the photosensitive resin composition, when the content of the acrylic monomer having the ethylenically unsaturated bond is in the above range can be obtained a high hardness effect.
[C]광중합 개시제[C] photopolymerization initiator
본 발명에서의 광중합 개시제란 노광에 의해 분해 또는 결합을 일으키며 라디칼, 음이온, 양이온 등의 상기 [B]에틸렌성 불포화 결합을 갖는 아크릴 모노머의 중합을 개시할 수 있는 활성종을 발생시키는 화합물을 의미한다. The photopolymerization initiator in the present invention means a compound which causes decomposition or bonding upon exposure and generates an active species capable of initiating polymerization of an acrylic monomer having the above-mentioned [B] ethylenically unsaturated bond such as radicals, anions, and cations. .
상기 광중합 개시제로는 Irgacure 907, Irgacure 369, Irgacure ox01, Irgacure 242, 티옥산톤, 2,4-디에틸 티옥산톤, 티옥산톤-4-술폰산, 벤조페논, 4,4'-비스(디에틸아미노)벤조페논, 아세토페논, p-디메틸아미노아세토페논, a,a'-디메톡시아세톡시 벤조페논, 2,2'-디메톡시-2-페틸아세토페논, p-메톡시아세토페논, 2-메틸[4-(메틸티오)페닐]-2-모르폴리노-1-프로파논, 2-벤질-2-디에틸아미노-1-(4-모르폴리노페닐)-부탄-1-온, 2-히드록시-2-메틸-1-페닐프로판-1-온, 4-(2-히드록시에톡시)페닐-(2-히드록시-2-프로필)케톤, 1-히드록시시클로헥실 페닐케톤 등의 케톤류; 안트라퀴논, 1,4-나프토퀴논 등의 퀴논류; 1,3,5-트리스(트리클로로메틸)-s-트리아진, 1,3-비스(트리클로로메틸)-5-(2-클로로페닐)-s-트리아진, 1,3-비스(트리클로로페닐)-s-트리아진, 페나실클로라이드, 트리브로모메틸페닐술폰, 트리스(트리클로로메틸)-s-트리아진 등의 할로겐 화합물; 디-t-부틸 퍼옥사이드 등의 과산화물; 2,4,6-트리메틸 벤조일 디페닐 포스핀 옥사이드 등의 아실 포스핀 옥사이드류가 사용될 수 있다. 본 발명에서 상기 광중합 개시제는 단독 또는 조합하여 사용될 수 있다. Examples of the photopolymerization initiator include Irgacure 907, Irgacure 369, Irgacure ox01, Irgacure 242, thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, and 4,4'-bis (di Ethylamino) benzophenone, acetophenone, p-dimethylaminoacetophenone, a, a'-dimethoxyacetoxy benzophenone, 2,2'-dimethoxy-2-petylacetophenone, p-methoxyacetophenone, 2 -Methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone Ketones such as these; Quinones such as anthraquinone and 1,4-naphthoquinone; 1,3,5-tris (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2-chlorophenyl) -s-triazine, 1,3-bis (trichloro Halogen compounds such as rophenyl) -s-triazine, phenacyl chloride, tribromomethylphenyl sulfone and tris (trichloromethyl) -s-triazine; Peroxides such as di-t-butyl peroxide; Acyl phosphine oxides, such as 2,4,6-trimethyl benzoyl diphenyl phosphine oxide, can be used. In the present invention, the photopolymerization initiator may be used alone or in combination.
상기 광중합 개시제의 함량은 감광성 수지 조성물 중에 0.5 내지 20중량%의 범위를 가질 수 있다. 상기 광중합 개시제의 함량이 0.5중량% 미만이면 보호막의 감도가 충분하지 않아 현상 공정에서 보호막이 유실되기 쉽고, 현상 공정에서 보호막이 유지된다고 하더라도 충분히 높은 가교밀도를 갖는 보호막을 얻기 어렵다. 또한, 상기 광중합 개시제의 함량이 20중량% 초과하면 보호막의 내열성, 평탄화성 등이 저하되기 쉽다. The content of the photopolymerization initiator may have a range of 0.5 to 20% by weight in the photosensitive resin composition. If the content of the photopolymerization initiator is less than 0.5% by weight, the sensitivity of the protective film is insufficient, so that the protective film is easily lost in the developing step, and even if the protective film is maintained in the developing step, it is difficult to obtain a protective film having a sufficiently high crosslink density. In addition, when the content of the photopolymerization initiator is more than 20% by weight, heat resistance, planarization property, etc. of the protective film tend to be lowered.
[D]하기 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물[D] A compound represented by the following Chemical Formula 1 or a compound represented by the Chemical Formula 2
본 발명에 따른 감광성 수지 조성물은 하기 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물을 포함한다. The photosensitive resin composition according to the present invention includes a compound represented by Formula 1 or a compound represented by Formula 2.
<화학식 1><Formula 1>
[규칙 제26조에 의한 보정 31.01.2011]　
Figure WO-DOC-MATHS-5
 [Revision 31.01.2011 under Rule 26]
Figure WO-DOC-MATHS-5
상기 식에서, R1은 수소원자 또는 탄소수 1 내지 5의 알킬기이고, R2은 수소원자, 탄소수 1 내지 5의 알콕시기 또는 탄소수 1 내지 5의 알킬기이고, m은 1 내지 10의 정수이다. Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 is a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and m is an integer of 1 to 10.
<화학식 2><Formula 2>
[규칙 제26조에 의한 보정 31.01.2011]　
Figure WO-DOC-MATHS-6
 [Revision 31.01.2011 under Rule 26]
Figure WO-DOC-MATHS-6
(상기 식에서, R은 수소원자, 탄소수 1 내지 10의 알킬기, 알콕시기, 에폭시기 및 히드록시기로 이루어진 군으로부터 선택된 적어도 1종 이상이다. 즉, 상기 R은 수소원자, 탄소수 1 내지 10의 알킬기, 알콕시기, 에폭시기 및 히드록시기로 이루어진 군으로부터 무작위적으로 선택될 수 있다.)Wherein R is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an epoxy group and a hydroxy group, ie, R is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group , May be randomly selected from the group consisting of an epoxy group and a hydroxyl group.)
상기 알킬기의 구체적인 예로는 메틸기, 에틸기, 프로필기, 부틸기, sec-부틸기, tert-부틸기, 펜틸기, 헥실기. 헵틸기, 옥틸기, 노닐기, 데실기, 운데실기, 도데실기, 트리데실기, 테트라데실기, 펜타데실기, 헥사데실기, 헵타데실기, 옥타데실기, 노나데실기, 이코실기, 헨이코실기, 토코실기 등을 들 수 있다. Specific examples of the alkyl group include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl and hexyl groups. Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, isocyl group, hen Ecosil group, a tocosyl group, etc. are mentioned.
상기 알콕시기의 구체적인 예로는 메톡시, 에톡시, 프로폭시, 이소프로폭시, 부톡시, tert-부톡시, 이소부톡시, 펜톡시, 헥속시 등을 들 수 있다.Specific examples of the alkoxy group include methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, isobutoxy, pentoxy, hexoxy and the like.
상기 화학식 1로 표시되는 화합물은 상기 화학식 1에서 보는 바와 같이 에폭시기를 가지고 있어, 에폭시 당량을 가진다. 에폭시 당량이란 에폭시기 한 개에 대한 당량(g/eq)이며 평균 분자량을 1 분자당 에폭시 기의 수로 나눈 값이다. The compound represented by the formula (1) has an epoxy group, as shown in the formula (1), and has an epoxy equivalent. Epoxy equivalent is the equivalent (g / eq) per epoxy group, and average molecular weight divided by the number of epoxy groups per molecule.
상기 화학식 1로 표시되는 화합물은 에폭시 당량이 500 내지 2000g/eq인 것이다. 상기 에폭시 당량이 상기 범위 내에 있는 경우 안정성, 내열성, 평탄화도, 밀착성, 경도를 높이는 효과를 얻을 수 있다. Compound represented by the formula (1) is an epoxy equivalent of 500 to 2000g / eq. When the epoxy equivalent is in the above range, the effect of increasing stability, heat resistance, flatness, adhesion, and hardness can be obtained.
상기 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물은 감광성 수지 조성물 중에 5 내지 70중량%의 범위로 포함하는데, 상기 감광성 수지 조성물의 함량이 5중량% 미만인 경우는 내열성, 투명성, 경도가 떨어지고, 70중량%를 초과하는 경우에는 현상공정에서 현상이 안 되는 문제가 있다. The compound represented by Formula 1 or the compound represented by Formula 2 is included in the range of 5 to 70% by weight in the photosensitive resin composition, when the content of the photosensitive resin composition is less than 5% by weight, heat resistance, transparency, hardness is inferior In the case of exceeding 70% by weight, there is a problem that development is not possible in the developing step.
특히, 유기 절연막용 감광성 수지 조성물을 사용하여 패턴을 형성하는데 있어서 상하단 비율(top/bottom ratio)을 높이는 것이 요구되는데, 이러한 유기 절연막용 감광성 수지 조성물에 상술한 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물을 상기 함량으로 포함하는 경우 top/bottom ratio가 향상되는 효과를 얻을 수 있다. In particular, it is required to increase the top / bottom ratio in forming a pattern using the photosensitive resin composition for an organic insulating film. The compound represented by Formula 1 or Formula 2 described above in the photosensitive resin composition for an organic insulating film is required. When the compound represented by the above content is included, the effect of improving the top / bottom ratio can be obtained.
이를 구체적으로 설명하면, 주사전자현미경이나 3차원 프로파일러(3D-profiler)를 이용하여 패턴을 측정함으로써 top/bottom ratio를 구할 수 있다. Specifically, the top / bottom ratio can be obtained by measuring a pattern using a scanning electron microscope or a 3D profiler.
도 1은 3차원 프로파일러로 패턴을 측정한 것으로 도 1을 일례로 들어 이를 설명하면 패턴의 모양은 일반적으로 사다리꼴과 유사한 형태를 가지고 있는데, 하단(b)의 길이를 상단(a)의 길이로 나눈 후 100을 곱한 값(=a/b×100)을 top/bottom ratio로 정의하고 있으며, 패턴의 사다리꼴 모양에서 밑면과 옆면이 이루는 각(c)을 테이퍼 앵글(taper angle)이라고 한다. 1 is a measurement of a pattern with a three-dimensional profiler. Referring to FIG. 1 as an example, the shape of the pattern generally has a shape similar to a trapezoid, and the length of the lower portion (b) is the length of the upper portion (a). After dividing, the value multiplied by 100 (= a / b × 100) is defined as the top / bottom ratio, and the angle (c) formed by the bottom and side surfaces in the trapezoidal shape of the pattern is called a taper angle.
즉, top/bottom ratio을 높이기 위해서는 패턴 모양의 상단(a) 길이를 하단(b) 길이와 같아지도록 해야 하는데, 상기 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물을 포함하는 감광성 조성물로 패턴을 형성하는 경우 상단(a)의 길이와 하단(b)의 길이가 거의 같아지게 되어 top/bottom ratio가 높아지는 효과를 얻을 수 있고, top/bottom ratio가 높아짐에 따라 테이퍼 앵글도 높아지는 효과를 얻을 수 있는 것이다. That is, in order to increase the top / bottom ratio, the top (a) length of the pattern shape should be equal to the bottom (b) length, and the pattern is made of a photosensitive composition comprising the compound represented by Formula 1 or the compound represented by Formula 2 In the case of forming the length of the top (a) and the length of the bottom (b) is almost the same to obtain the effect of increasing the top / bottom ratio, the higher the top / bottom ratio can be obtained the effect of increasing the taper angle. It is.
[E]용매 [E] solvent
상기 용매로는 상기 공중합체의 제조 또는 조성물의 고형분 및 점도 유지를 위한 용매로는 다음과 같은 물질을 사용할 수 있다. 예컨대, 메탄올, 에탄올 등의 알코올류; 테트라하이드로퓨란, 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르 등의 에테르류; 프로필렌 글리콜 메틸 에테르 아세테이트, 프로필렌 글리콜 에틸 에테르 아세테이트, 프로펠렌 글리콜 프로필 에테르 아세테이트, 프로필렌 글리콜 부틸 에테르 아세테이트 등의 프로필렌 글리콜 알킬 에테르 아세테이트류 등을 들 수 있다. 이러한 용매 가운데에서 용해성, 각 성분과의 반응성 및 도막 형성의 편리성의 관점에서 디에틸렌글리콜디메틸에테르, 디에틸렌글리콜디에틸에테르, 프로펠렌 글리콜 메틸 에테르 아세테이트류 메틸에틸케톤, 시클로헥사논, 4-히드록시-4-메틸-2-펜타난 등의 케톤류 아세트산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 2-히드록시프로피온산의 에틸에스테르, 메틸에스테르; 2-히드록시-2-메틸프로피온산의 에틸에스테르; 히드록시아세트산의 메틸에스테르, 에틸에스테르, 부틸 에스테르; 젖산에틸, 젖산프로필, 젖산부틸; 메톡시아세트산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 프로폭시아세트산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 부톡시아세트산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 2-메톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 2-에톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 2-부톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 3-메톡시프로판의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 3-에톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르; 3-부톡시프로피온산의 메틸에스테르, 에틸에스테르, 프로필에스테르, 부틸에스테르 등의 에스테르류의 사용이 바람직하다. As the solvent, the following materials may be used as the solvent for preparing the copolymer or maintaining the solid content and the viscosity of the composition. Alcohols such as methanol and ethanol; Ethers such as tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether; And propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, and propylene glycol butyl ether acetate. Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate methyl ethyl ketone, cyclohexanone, 4-hydride from the viewpoint of solubility, reactivity with each component, and convenience of coating film formation among these solvents Methyl esters, ethyl esters, propyl esters, butyl esters of ketones and acetic acid such as oxy-4-methyl-2-pentanane; Ethyl ester and methyl ester of 2-hydroxypropionic acid; Ethyl ester of 2-hydroxy-2-methylpropionic acid; Methyl esters, ethyl esters, butyl esters of hydroxyacetic acid; Ethyl lactate, propyl lactate, butyl lactate; Methyl esters, ethyl esters, propyl esters, butyl esters of methoxyacetic acid; Methyl esters, ethyl esters, propyl esters, butyl esters of propoxyacetic acid; Methyl esters, ethyl esters, propyl esters, butyl esters of butoxyacetic acid; Methyl ester, ethyl ester, propyl ester, butyl ester of 2-methoxypropionic acid; Methyl ester, ethyl ester, propyl ester, butyl ester of 2-ethoxypropionic acid; Methyl ester, ethyl ester, propyl ester, butyl ester of 2-butoxypropionic acid; Methyl ester, ethyl ester, propyl ester, butyl ester of 3-methoxypropane; Methyl ester, ethyl ester, propyl ester, butyl ester of 3-ethoxypropionic acid; Use of esters, such as methyl ester of 3-butoxypropionic acid, ethyl ester, propyl ester, and butyl ester, is preferable.
또한 상기 용매는 고비등점 용매와 함께 사용될 수 있다. 사용 가능한 고비등점 용매로는, 예컨대 N-메틸 포름아미드, N,N-디메틸 포름아미드, N-메틸 아세트아미드, N,N-디메틸 아세트아미드, N-메틸 피롤리돈, 디메틸 설폭시드, 벤질 에틸 에테르를 들 수 있다. The solvent may also be used with high boiling solvents. High boiling point solvents that can be used include, for example, N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl Ethers.
상기 용매는 감광성 수지 조성물 중에 14 내지 80중량%의 범위로 포함하는데, 상기 용매의 함량이 상기 범위 내에 있는 경우 원할한 코팅성 효과를 얻을 수 있다. The solvent is included in the range of 14 to 80% by weight in the photosensitive resin composition, when the content of the solvent is in the range can be obtained a desired coating effect.
또한 상술한 성분들을 포함하는 감광성 수지 조성물은 점도가 2 내지 35cps인 것이 바람직하다. 상기 점도는 위에서 언급한 조성물, [A]알칼리 가용성 수지, [B]에틸렌성 불포화 결합을 갖는 아크릴 모노머, [C]광중합 개시제 및 [D]상기 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물의 함량과 [E]용매의 함량에 의해 조절되는 것으로서, 상기 감광성 수지 조성물의 점도가 상기 범위 내에 있는 경우 스핀(spin) 및 스핀레스 코터(spinless coater) 사용시 원하는 도막두께를 얻는 효과를 얻을 수 있다. 이를 구체적으로 설명하면, 점도는 용매의 함량이 동일하더라도 첨가되는 구성의 특성에 따라 달라질 수 있는데, 점도의 범위는 막두께에 의해 결정하게 된다. 형성하고자 하는 막두께가 높을수록 점도는 증가하게 되는데, 스핀 및 스핀레스 코터의 경우 점도와 구성성분의 함량 모두가 고려가 되어 막두께를 형성하게 된다. 따라서, 상기 점도가 상기 범위 내에 있는 경우 스핀(spin) 및 스핀레스 코터(spinless coater) 사용시에 원하는 막두께를 얻을 수 있는 것이다. In addition, it is preferable that the photosensitive resin composition containing the above-mentioned components has a viscosity of 2 to 35 cps. The viscosity is the above-mentioned composition, [A] alkali-soluble resin, [B] acrylic monomer having an ethylenically unsaturated bond, [C] photopolymerization initiator and [D] the compound represented by the formula (1) or the compound represented by the formula (2) It is controlled by the content of and the content of the solvent [E], when the viscosity of the photosensitive resin composition is in the above range can be obtained the effect of obtaining the desired film thickness when using a spin (spin) and spinless coater (spinless coater) . Specifically, the viscosity may vary depending on the characteristics of the added composition even if the content of the solvent is the same, the range of the viscosity is determined by the film thickness. The higher the film thickness to be formed, the higher the viscosity. In the case of spin and spinless coaters, both the viscosity and the content of the constituents are considered to form the film thickness. Therefore, when the viscosity is within the above range, a desired film thickness can be obtained when using a spin and a spinless coater.
한편, 본 발명의 감광성 수지 조성물은 전술한 조성 외에도 첨가제를 포함할 수 있다. On the other hand, the photosensitive resin composition of the present invention may include an additive in addition to the above-described composition.
상기 첨가제로는 도포성을 향상하기 위한 계면활성제를 들 수 있다. 상기 계면활성제로는 불소 및 실리콘계 계면활성제를 들 수 있는데, 예를 들면 3M사의 FC-129, FC-170C, FC-430, DIC사의 F-172, F-173, F-183, F-470, F-475, 신에츠실리콘사의 KP322, KP323, KP340, KP341 등을 들 수 있다. 이러한 계면활성제는 [A]알칼리 가용성 수지 100 중량부를 기준으로 하여 5 중량부 이하, 바람직하게는 2 중량부 이하로 포함될 수 있다. 계면활성제의 함량이 5 중량부를 초과하는 경우 도포시 거품이 발생하는 문제가 있고, 이러한 문제는 현상성 및 표면장력에 영향을 주어 바람직하지 않다. As said additive, surfactant for improving applicability | paintability is mentioned. Examples of the surfactant include fluorine and silicone-based surfactants, for example, 3M's FC-129, FC-170C, FC-430, DIC's F-172, F-173, F-183, F-470, F-475, KP322, KP323, KP340, KP341 by Shin-Etsu Silicone, etc. are mentioned. Such surfactant may be included in an amount of 5 parts by weight or less, preferably 2 parts by weight or less, based on 100 parts by weight of the [A] alkali-soluble resin. If the content of the surfactant exceeds 5 parts by weight, there is a problem that foaming occurs during the application, this problem affects the developability and surface tension is undesirable.
또한 기체와의 밀착성을 향상시키기 위해 접착 조제를 첨가제로서 포함할 수 있다. 상기 접착 조제로는 관능성 실란 커플링제가 바람직하게 사용되는데, 예를 들면 트리메톡시실릴 안식향산, -메타크릴록시프로필트리메톡시실란, 비닐트리아세톡시실란, 비닐트리메톡시실란, -이소시아네이트프로필트리에톡시실란, -글리시독시프로필트리메톡시실란 등을 들 수 있다. 상기 접착 조제는 [A]알칼리 가용성 수지 100 중량부를 기준으로 하여 20 중량부 이하, 바람직하게는 10 중량부 이하로 포함될 수 있다. 상기 접착 조제의 함량이 20 중량부를 초과하는 경우 내열성이 저하되는 문제가 있다. In addition, an adhesion aid may be included as an additive in order to improve the adhesion with the base. As the adhesion aid, a functional silane coupling agent is preferably used. For example, trimethoxysilyl benzoic acid, -methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, -isocyanatepropyl Triethoxysilane, -glycidoxy propyl trimethoxysilane, etc. are mentioned. The adhesive aid may be included in 20 parts by weight or less, preferably 10 parts by weight or less based on 100 parts by weight of the [A] alkali-soluble resin. If the content of the adhesion assistant exceeds 20 parts by weight, there is a problem that the heat resistance is lowered.
본 발명의 일 구현예에 따르면, 상술한 감광성 수지 조성물로부터 얻어지는 유기 절연막을 제공하는 것이다. According to one embodiment of the present invention, to provide an organic insulating film obtained from the photosensitive resin composition described above.
본 발명에 따른 감광성 수지 조성물을 이용하여 통상의 제조방법에 의하여 유기 절연막을 제공할 수 있다. The organic insulating film can be provided by a conventional manufacturing method using the photosensitive resin composition which concerns on this invention.
또한, 본 발명에 따른 디스플레이 장치는 공지의 제조방법에 따라 상기 유기 절연막을 사용하여 제조할 수 있다. In addition, the display device according to the present invention can be manufactured using the organic insulating film according to a known manufacturing method.
이하 본 발명의 바람직한 실시예 및 비교예를 설명한다. 그러나 하기한 실시예는 본 발명의 바람직한 일 실시예일뿐 본 발명이 하기한 실시예에 한정되는 것은 아니다. Hereinafter, preferred examples and comparative examples of the present invention will be described. However, the following examples are only preferred embodiments of the present invention and the present invention is not limited to the following examples.
제조예 1: 알칼리 가용성 수지 A의 제조Preparation Example 1 Preparation of Alkali Soluble Resin A
냉각관과 교반기가 구비된 반응 용기에 광중합 개시제로서 2,2'-아조비스 이소부티로니트릴 10중량부를 용매 프로필렌글리콜 모노메틸에테르 아세테이트 200중량부에 녹였다. 이어서 스티렌 65중량부, 메타크릴산 15중량부, 메타크릴산 글리시딜 20중량부를 투입하고 질소 치환한 후 부드럽게 교반을 시작하였다. 용액의 온도를 70로 상승시키고, 이 온도를 4시간 동안 유지하여 공중합체를 포함한 중합체 용액을 얻었다. 얻어진 중합체 용액의 고형분 농도는 35중량%이었다. In a reaction vessel equipped with a cooling tube and a stirrer, 10 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of a solvent propylene glycol monomethyl ether acetate as a photopolymerization initiator. Subsequently, 65 parts by weight of styrene, 15 parts by weight of methacrylic acid, and 20 parts by weight of glycidyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 70, and this temperature was maintained for 4 hours to obtain a polymer solution including a copolymer. Solid content concentration of the obtained polymer solution was 35 weight%.
제조예 2: 알칼리 가용성 수지 B의 제조Preparation Example 2 Preparation of Alkali Soluble Resin B
스티렌 65중량부 대신 스티렌 45중량부 및 디사이클로펜테닐 아크릴레이트 20중량부를 사용하는 것을 제외하고는 상기 제조예 1과 동일한 방법으로 실시하였다. 얻어진 중합체 용액의 고형분 농도는 33중량%이었다The same procedure as in Preparation Example 1 was repeated except that 45 parts by weight of styrene and 20 parts by weight of dicyclopentenyl acrylate were used instead of 65 parts by weight of styrene. Solid content concentration of the obtained polymer solution was 33 weight%
실시예 1 내지 5 및 비교예 1 내지 2Examples 1-5 and Comparative Examples 1-2
감광성 물질로서 알카리 가용성 수지 A, B와 용매로서 프로필렌글리콜 모노메틸에테르 아세테이트, 광중합 개시제로서 OXE-01(시바(CIBA社) 및 에틸렌성 불포화 결합을 갖는 아크릴 모노머로서 디펜타에리트리톨 헥사(메타)아크릴레이트를 배합하고 여기에 화학식 1로 표시되는 화합물(R1은 메틸기, R2는 메톡시기, m은 3)을 하기 표 1에 나타낸 바와 같이 함유량을 변화시켜 가면서 배합하여 감광성 수지를 제조하였다. 이때, 하기 표 1의 함량 단위는 중량%이다. Alkaline soluble resins A and B as photosensitive materials, propylene glycol monomethyl ether acetate as solvent, OXE-01 (CIBA) as photopolymerization initiator and dipentaerythritol hexa (meth) acryl as acrylic monomer having ethylenically unsaturated bonds The rate was blended and the compound represented by Formula 1 (R 1 is a methyl group, R 2 is a methoxy group, m is 3) was blended while varying the content as shown in Table 1 below to prepare a photosensitive resin. In Table 1, the content unit is weight%.
표 1
알칼리 가용성 수지A 알칼리 가용성 수지B 에틸렌성 불포화 결합을 갖는 아크릴 모노머 화학식 1로 표시되는 화합물 광중합개시제 용매
실시예 1 9 0 15 5 1 70
실시예 2 9 0 10 10 1 70
실시예 3 9 0 5 15 1 70
실시예 4 0 9 10 10 1 70
실시예 5 0 9 5 15 1 70
비교예 1 9 0 20 0 1 70
비교예 2 0 9 20 0 1 70
Table 1
Alkali Soluble Resin A Alkali Soluble Resin B Acrylic monomer with ethylenically unsaturated bond Compound represented by formula (1) Photopolymerization Initiator menstruum
Example 1 9 0 15 5 One 70
Example 2 9 0 10 10 One 70
Example 3 9 0 5 15 One 70
Example 4 0 9 10 10 One 70
Example 5 0 9 5 15 One 70
Comparative Example 1 9 0 20 0 One 70
Comparative Example 2 0 9 20 0 One 70
상기 실시예 1 내지 5 및 비교예 1 내지 2에서 제조된 조성물에 대하여 하기와 같이 물성 평가하였으며, 그 결과를 하기 표 3에 나타내었다. The physical properties of the compositions prepared in Examples 1 to 5 and Comparative Examples 1 and 2 were evaluated as follows, and the results are shown in Table 3 below.
실시예 6 내지 10 및 비교예 1 내지 2Examples 6-10 and Comparative Examples 1-2
감광성 물질로서 알카리 가용성 수지 A, B와 용매로서 프로필렌글리콜 모노메틸에테르 아세테이트, 광중합 개시제로서 OXE-01(시바(CIBA社) 및 에틸렌성 불포화 결합을 갖는 아크릴 모노머로서 디펜타에리트리톨 헥사(메타)아크릴레이트를 배합하고 여기에 화학식 2로 표시되는 화합물(R은 에폭시기, 메톡시기, 히드록시기, 메틸기를 가짐.)을 하기 표 2에 나타낸 바와 같이 함유량을 변화시켜 가면서 배합하여 감광성 수지를 제조하였다. 이때, 하기 표 2의 함량 단위는 중량%이다. Alkaline soluble resins A and B as photosensitive materials, propylene glycol monomethyl ether acetate as solvent, OXE-01 (CIBA) as photopolymerization initiator and dipentaerythritol hexa (meth) acryl as acrylic monomer having ethylenically unsaturated bonds The rate was blended and the compound represented by Chemical Formula 2 (R has an epoxy group, a methoxy group, a hydroxy group, and a methyl group) was mixed with varying contents as shown in Table 2 below to prepare a photosensitive resin. The content units in Table 2 below are by weight.
표 2
알칼리 가용성 수지A 알칼리 가용성 수지B 에틸렌성 불포화 결합을 갖는 아크릴 모노머 화학식 2로 표시되는 화합물 광중합개시제 용매
실시예 6 9 0 15 5 1 70
실시예 7 9 0 10 10 1 70
실시예 8 9 0 5 15 1 70
실시예 9 0 9 10 10 1 70
실시예 10 0 9 5 15 1 70
비교예 1 9 0 20 0 1 70
비교예 2 0 9 20 0 1 70
TABLE 2
Alkali Soluble Resin A Alkali Soluble Resin B Acrylic monomer with ethylenically unsaturated bond Compound represented by formula (2) Photopolymerization Initiator menstruum
Example 6 9 0 15 5 One 70
Example 7 9 0 10 10 One 70
Example 8 9 0 5 15 One 70
Example 9 0 9 10 10 One 70
Example 10 0 9 5 15 One 70
Comparative Example 1 9 0 20 0 One 70
Comparative Example 2 0 9 20 0 One 70
상기 실시예 6 내지 10 및 비교예 1 내지 2에서 제조된 조성물에 대하여 다음과 같이 물성 평가하였으며, 그 결과를 하기 표 4에 나타내었다. The physical properties of the compositions prepared in Examples 6 to 10 and Comparative Examples 1 to 2 were evaluated as follows, and the results are shown in Table 4 below.
(1) 점도(1) viscosity
점도는 25에서 브룩필드(BROOKFIELD) 점도계로 측정하였다. Viscosity was measured at 25 with a Brookfield viscometer.
(2) 잔막율(2) residual film rate
유리 기판에 제조된 각각의 감광성 수지 조성물을 스핀 코팅하고 핫플레이트에서 100, 85초의 조건으로 예비 건조를 행하여 막두께 2의 포토레지스트 막을 형성하였다. 이러한 막이 형성된 유리기판을 노광한 후 0.04% KOH 수용액에 60초간 현상하고 다시 220, 30분 동안 강한 열처리를 실시하였다. Each photosensitive resin composition prepared on the glass substrate was spin-coated and pre-dried under a condition of 100 and 85 seconds on a hot plate to form a photoresist film having a film thickness of 2. After exposing the glass substrate on which such a film was formed, it was developed in 0.04% KOH aqueous solution for 60 seconds and subjected to strong heat treatment for 220 and 30 minutes again.
예비 건조시의 막두께와 후경화를 통한 용매 제거후의 형성된 막의 두께를 측정하여 비율측정을 통하여 잔막율을 측정하였다. The film thickness at the time of predrying and the thickness of the formed film after solvent removal through post-cure were measured, and the residual film rate was measured by ratio measurement.
(3) 평탄성(3) flatness
컬러레지스트가 패턴닝된 유리기판에 제조된 각각의 감광성 수지 조성물을 스핀 코팅하고 핫플레이트에서 100, 85초의 조건으로 예비 건조를 행하여 막두께 2의 포토레지스트 막을 형성하였다. 이러한 막이 형성된 유리기판을 노광한 후 0.04% KOH 수용액에 60초간 현상하고 다시 220, 30분 동안 강한 열처리를 실시하였다. 여기서 얻어진 건조도막의 5point의 두께를 측정하여 평탄성을 측정하였다. 상기 평탄성을 측정하여 두께 편차가 0.025 미만인 경우 ◎, 0.026 내지 0.05인 경우를 ○, 0.06 내지 0.1인 경우를 △, 0.1 초과인 경우를 ×로 나타내었다. Each photosensitive resin composition prepared on the glass substrate patterned with color resist was spin coated and pre-dried under a condition of 100 and 85 seconds on a hot plate to form a photoresist film having a thickness of 2. After exposing the glass substrate on which such a film was formed, it was developed in 0.04% KOH aqueous solution for 60 seconds and subjected to strong heat treatment for 220 and 30 minutes again. The flatness was measured by measuring the thickness of 5 points of the dry coating film obtained here. The flatness was measured, and when the thickness deviation was less than 0.025,?, 0.026 to 0.05 were represented by ○, and 0.06 to 0.1 were represented by?, And 0.1 was represented by ×.
(4) 감도(4) sensitivity
유리기판에 제조된 각각의 감광성 수지 조성물을 스핀 500rpm으로 코팅하고 핫플레이트에서 100, 85초의 조건으로 예비 건조를 행하고 노광량을 60mJ/, 70mJ/, 80mJ/, 90mJ/, 100mJ/, 150mJ/, 및 200mJ/으로 각각 노광한 후 0.04%KOH 수용액에 60초간 현상하고 다시 220, 30분 동안 강한 열처리를 실시하였다. 이때 얻어진 도막의 두께를 측정하였다. 상기 두께를 측정하여 200mJ/에서 얻어진 도막의 두께 대비 90% 이상을 얻은 것을 각 조성에서 감도로 선택하였다. Each photosensitive resin composition prepared on a glass substrate was coated with a spin of 500 rpm, preliminarily dried on a hot plate at 100 and 85 seconds, and the exposure dose was 60 mJ /, 70 mJ /, 80 mJ /, 90 mJ /, 100 mJ /, 150 mJ /, and After each exposure to 200mJ / was developed for 60 seconds in 0.04% KOH aqueous solution and again subjected to a strong heat treatment for 220, 30 minutes. The thickness of the coating film obtained at this time was measured. The thickness was measured to obtain 90% or more of the thickness of the coating film obtained at 200 mJ /, and the sensitivity was selected for each composition.
(5) 내열성(5) heat resistance
상기 감도 측정에서 형성된 패턴 막의 상,하, 좌, 우의 폭을 측정하였다. 이때 각의 변화율이 베이크(250, 30분)전 기준, 0 내지 10%인 경우를 ◎, 11 내지 20% 인 경우를 ○, 21 내지 40%인 경우를 △, 40% 초과인 경우를 ×로 나타내었다. The widths of the top, bottom, left and right sides of the pattern film formed by the sensitivity measurement were measured. At this time, when the change rate of each angle is 0 to 10% before baking (250, 30 minutes), ◎, 11 to 20% when △, 21 to 40% when △, 40% when the case is × Indicated.
(6) 밀착성(6) adhesion
유리기판에 제조된 각각의 감광성 수지 조성물을 스핀 코팅하고 핫플레이트에서 100, 85초의 조건으로 예비 건조를 행하고 노광량을 60mJ/, 70mJ/, 80mJ/, 90mJ/, 100mJ/, 150mJ/, 및 200mJ/으로 각각 노광한 후 0.04% KOH 수용액에 60초간 현상하고 다시 220, 1시간 동안 강한 열처리를 실시하였다. 얻어진 도막을 100등분으로 컷팅을 한 후 3M 스카치 매직테이프(3M scotch maic tape)를 이용하여 부착 후 탈착을 하였다. 이때 남아있는 도막의 개수를 세었다. 상기 측정에서 남아있는 도막이 100% 경우를 ◎, 90 내지 99% 인 경우를 ○, 80 내지 89%인 경우를 △, 80% 미만인 경우를 ×로 나타내었다. Each photosensitive resin composition prepared on a glass substrate was spin coated and pre-dried on a hot plate at 100 and 85 seconds, and the exposure dose was 60 mJ /, 70 mJ /, 80 mJ /, 90 mJ /, 100 mJ /, 150 mJ /, and 200 mJ /. After each exposure to 0.04% KOH aqueous solution was developed for 60 seconds and again subjected to a strong heat treatment for 220, 1 hour. The obtained coating film was cut into 100 equal parts, and then attached and detached using 3M Scotch maic tape. At this time, the number of remaining coatings was counted. In the above measurement, ◎, 90-99% △, 80-89% △, △, and less than 80% of the remaining coating film were indicated by ×.
(7) Top/Bottom Ratio(7) Top / Bottom Ratio
유리기판에 제조된 각각의 감광성 수지 조성물을 스핀 코팅하고 핫플레이트에서 100, 85초의 조건으로 예비 건조를 행하고 40㎛ 패턴마스크를 이용하여 노광량을 40, 60, 70, 80, 90, 100, 150, 200mJ/으로 노광한 후 0.04%KOH 수용액에 60초간 현상하고 다시 220, 30분 동안 강한 열처리를 실시하였다. 형성된 패턴을 3D-프로파일러를 사용하여 Top과 Bottom의 CD 사이즈를 측정하였다. Each photosensitive resin composition prepared on a glass substrate was spin-coated and pre-dried under a condition of 100 and 85 seconds on a hot plate, and the exposure dose was 40, 60, 70, 80, 90, 100, 150, After exposure to 200mJ / was developed for 60 seconds in a 0.04% KOH aqueous solution and then subjected to a strong heat treatment for 220, 30 minutes. The formed patterns were measured for CD size of Top and Bottom using a 3D profiler.
(8) 투과율(8) transmittance
투과도는 분광광도계를 이용하여 400nm에서의 투과율을 측정하였다.The transmittance | permeability measured the transmittance | permeability in 400 nm using the spectrophotometer.
표 3
점도(cps) 평탄성 감도(mJ/㎠) 내열성 밀착성 잔막율(%) 투과율(%) t/b ratio(%)
실시예 1 5 ○ 60 ○ ○ 90 93 84.4
실시예 2 5 ○ 60 ○ ◎ 91.7 94.3 86.7
실시예 3 5 ○ 60 ○ ◎ 92.4 95.5 88.6
실시예 4 5 ○ 60 ◎ ○ 92.2 97.2 88.2
실시예 5 5 ○ 60 ◎ ○ 93.0 98.1 90.4
비교예 1 5 ○ 60 × △ 87.8 88.0 75.0
비교예 2 5 ○ 70 △ △ 88.5 89.0 76.1
TABLE 3
Viscosity (cps) Flatness Sensitivity (mJ / ㎠) Heat resistance Adhesiveness Residual rate (%) Transmittance (%) t / b ratio (%)
Example 1 5 ○ 60 ○ ○ 90 93 84.4
Example 2 5 ○ 60 ○ ◎ 91.7 94.3 86.7
Example 3 5 ○ 60 ○ ◎ 92.4 95.5 88.6
Example 4 5 ○ 60 ◎ ○ 92.2 97.2 88.2
Example 5 5 ○ 60 ◎ ○ 93.0 98.1 90.4
Comparative Example 1 5 ○ 60 × △ 87.8 88.0 75.0
Comparative Example 2 5 ○ 70 △ △ 88.5 89.0 76.1
표 4
점도(cps) 평탄성 감도(mJ/㎠) 내열성 밀착성 잔막율(%) 투과율(%) t/b ratio(%)
실시예 6 5 ○ 50 ○ ○ 90.3 91.5 82.1
실시예 7 5 ○ 50 ○ ◎ 91.0 95.0 86.7
실시예 8 5 ○ 50 ○ ◎ 92.6 97.6 90.8
실시예 9 5 ○ 50 ◎ ○ 91.3 97.2 87.4
실시예 10 5 ○ 50 ◎ ◎ 92.7 98.2 91.2
비교예 1 5 ○ 60 × △ 87.8 88.0 75.0
비교예 2 5 ○ 70 △ △ 88.5 89.0 76.1
Table 4
Viscosity (cps) Flatness Sensitivity (mJ / ㎠) Heat resistance Adhesiveness Residual rate (%) Transmittance (%) t / b ratio (%)
Example 6 5 ○ 50 ○ ○ 90.3 91.5 82.1
Example 7 5 ○ 50 ○ ◎ 91.0 95.0 86.7
Example 8 5 ○ 50 ○ ◎ 92.6 97.6 90.8
Example 9 5 ○ 50 ◎ ○ 91.3 97.2 87.4
Example 10 5 ○ 50 ◎ ◎ 92.7 98.2 91.2
Comparative Example 1 5 ○ 60 × △ 87.8 88.0 75.0
Comparative Example 2 5 ○ 70 △ △ 88.5 89.0 76.1
상기 표 3과 표 4에서 보는 바와 같이 실시예 1 내지 5, 실시예 6내지 10에서 제조한 감광성 수지 조성물은 내열성, 밀착성, 잔막율 및 투과율이 우수하였으며 특히 top/bottom ratio가 높음에 따라 테이퍼 앵글(taper angle)과 패턴성이 좋아 다양한 디스플레이 공정에서 유기 절연막에 유효적절하게 적용할 수 있음을 알 수 있었다. As shown in Tables 3 and 4, the photosensitive resin compositions prepared in Examples 1 to 5 and Examples 6 to 10 were excellent in heat resistance, adhesiveness, residual film rate, and transmittance, and particularly tapered angles as the top / bottom ratio was high. It was found that the taper angle and patternability can be effectively applied to the organic insulating film in various display processes.
본 발명의 단순한 변형 또는 변경은 모두 이 분야의 통상의 지식을 가진 자에 의하여 용이하게 실시될 수 있으며 이러한 변형이나 변경은 모두 본 발명의 영역에 포함되는 것으로 볼 수 있다. All simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.
본 발명에 따른 감광성 수지 조성물은 유기 절연막에 이용가능하다.The photosensitive resin composition which concerns on this invention can be used for an organic insulating film.

Claims (9)

  1. [규칙 제26조에 의한 보정 31.01.2011]　

    　
    [A]알칼리 가용성 수지, [B]에틸렌성 불포화 결합을 갖는 아크릴 모노머, [C]광중합 개시제, [D]하기 화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물 및 [E]용매를 포함하는 감광성 수지 조성물. <화학식 1>
    Figure WO-DOC-MATHS-7
     (상기 식에서, R1은 수소원자 또는 탄소수 1 내지 5의 알킬기이고, R2은 수소원자, 탄소수 1 내지 5의 알콕시기 또는 탄소수 1 내지 5의 알킬기이고, m은 1 내지 10의 정수이다.) <화학식 2>
    Figure WO-DOC-MATHS-8
     (상기 식에서, R은 수소원자, 탄소수 1 내지 10의 알킬기, 알콕시기, 에폭시기 및 히드록시기로 이루어진 군으로부터 선택된 적어도 1종 이상이다.)     [Revision 31.01.2011 under Rule 26]


    [A] alkali-soluble resin, [B] acrylic monomer having an ethylenically unsaturated bond, [C] photopolymerization initiator, [D] a compound represented by the following formula (1) or a compound represented by the formula (2) and a solvent (E) Photosensitive resin composition. <Formula 1>
    Figure WO-DOC-MATHS-7
     (Wherein R 1 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R 2 is a hydrogen atom, an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and m is an integer of 1 to 10). <Formula 2>
    Figure WO-DOC-MATHS-8
     (Wherein, R is at least one selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an epoxy group and a hydroxy group.)
  2. 제1항에 있어서, 상기 [D]화학식 1로 표시되는 화합물은 에폭시 당량이 500 내지 2000g/eq인 감광성 수지 조성물.The photosensitive resin composition of claim 1, wherein the compound represented by [D] Formula 1 has an epoxy equivalent of 500 to 2000 g / eq.
  3. 제1항에 있어서, 감광성 수지 조성물은 상기 [A]알칼리 가용성 수지 5 내지 60중량%; 상기 [B]에틸렌성 불포화 결합을 갖는 아크릴 모노머 5 내지 70중량%; 상기 [C]광중합 개시제 0.5 내지 20중량%; 상기 [D]화학식 1로 표시되는 화합물 또는 화학식 2로 표시되는 화합물 5 내지 70중량%; 및 상기 [E]용매 14 내지 80중량%를 포함하는 감광성 수지 조성물.The photosensitive resin composition of claim 1, wherein the photosensitive resin composition comprises 5 to 60% by weight of the [A] alkali-soluble resin; 5 to 70% by weight of an acrylic monomer having the [B] ethylenically unsaturated bond; 0.5 to 20% by weight of the [C] photopolymerization initiator; 5 to 70% by weight of the compound represented by Chemical Formula 1 or the compound represented by Chemical Formula 2; And 14 to 80% by weight of the solvent [E].
  4. 제1항에 있어서, 상기 [A]알칼리 가용성 수지는 [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중에서 선택된 1종 또는 2종 이상의 혼합물; 및 [a2]에폭시기 함유 불포화 화합물의 공중합체이거나,The method of claim 1, wherein the alkali soluble resin [A] is one or a mixture of two or more selected from [a1] unsaturated carboxylic acids and unsaturated carboxylic anhydrides; And a copolymer of the [a2] epoxy group-containing unsaturated compound,
    [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중에서 선택된 1종 또는 2종 이상의 혼합물; 및 [a2]에폭시기 함유 불포화 화합물과 [a3]상기 [a1] 및 [a2] 이외의 올레핀계 불포화 카르복실산 에스테르 화합물; 및 [a4]상기 [a1], [a2] 및 [a3] 이외의 올레핀계 불포화 화합물 중에서 선택된 1종 이상의 화합물의 공중합체인 감광성 수지 조성물. one or two or more kinds selected from [a1] unsaturated carboxylic acids and unsaturated carboxylic anhydrides; And [a2] epoxy group-containing unsaturated compounds and [a3] olefinically unsaturated carboxylic ester compounds other than the above [a1] and [a2]; And [a4] A photosensitive resin composition which is a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3].
  5. 제4항에 있어서, 상기 [A]알칼리 가용성 수지는 상기 [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중에서 선택된 1종 또는 2종 이상의 혼합물 및 [a2]에폭시기 함유 불포화 화합물의 중량비가 1:1.3 내지 2.5인 감광성 수지 조성물. The weight ratio of the one or two or more mixtures selected from the above-mentioned [a1] unsaturated carboxylic acid and unsaturated carboxylic anhydride and the [a2] epoxy group-containing unsaturated compound is 1: Photosensitive resin composition which is 1.3-2.5.
  6. 제4항에 있어서, 상기 [A]알칼리 가용성 수지가 [a1]불포화 카르복실산 및 불포화 카르복실산 무수물 중에서 선택된 1종 또는 2종 이상의 혼합물; 및 [a2]에폭시기 함유 불포화 화합물과 [a3]상기 [a1] 및 [a2] 이외의 올레핀계 불포화 카르복실산 에스테르 화합물; 및 [a4]상기 [a1], [a2] 및 [a3] 이외의 올레핀계 불포화 화합물 중에서 선택된 1종 이상의 화합물의 공중합체인 경우, 상기 [A]알칼리 가용성 수지는 [a3]상기 [a1] 및 [a2] 이외의 올레핀계 불포화 카르복실산 에스테르 화합물; 및 [a4]상기 [a1], [a2] 및 [a3] 이외의 올레핀계 불포화 화합물 중에서 선택된 1종 이상의 화합물을 20 내지 65중량%로 포함하는 감광성 수지 조성물. The method according to claim 4, wherein the alkali soluble resin [A] is one or a mixture of two or more selected from [a1] unsaturated carboxylic acids and unsaturated carboxylic anhydrides; And [a2] epoxy group-containing unsaturated compounds and [a3] olefinically unsaturated carboxylic ester compounds other than the above [a1] and [a2]; And [a4] In the case of a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3], the [A] alkali-soluble resin is [a3] above [a1] and [ olefinic unsaturated carboxylic ester compound other than a2]; And [a4] 20 to 65% by weight of one or more compounds selected from olefinically unsaturated compounds other than the above [a1], [a2] and [a3].
  7. 제1항에 있어서, 상기 감광성 수지 조성물은 점도가 2 내지 35cps인 감광성 수지 조성물. The photosensitive resin composition of claim 1, wherein the photosensitive resin composition has a viscosity of 2 to 35 cps.
  8. 제1항 내지 제7항 중 어느 한 항에 따른 감광성 수지 조성물로부터 얻어지는 유기 절연막. The organic insulating film obtained from the photosensitive resin composition of any one of Claims 1-7.
  9. 제8항에 따른 유기 절연막을 포함하는 디스플레이 장치.Display device comprising the organic insulating film according to claim 8.
PCT/KR2010/008212 2009-11-20 2010-11-19 Photosensitive resin composition WO2011062446A2 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201080061583.9A CN102713754B (en) 2009-11-20 2010-11-19 Photosensitive resin composition, organic insulating layer and display device
US13/574,354 US8968984B2 (en) 2009-11-20 2010-11-19 Photosensitive resin composition

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20090112861 2009-11-20
KR10-2009-0112861 2009-11-20
KR10-2010-0107219 2010-10-29
KR1020100107219A KR101759929B1 (en) 2009-11-20 2010-10-29 Photosensitive resin composition

Publications (2)

Publication Number Publication Date
WO2011062446A2 true WO2011062446A2 (en) 2011-05-26
WO2011062446A3 WO2011062446A3 (en) 2011-10-20

Family

ID=44060210

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2010/008212 WO2011062446A2 (en) 2009-11-20 2010-11-19 Photosensitive resin composition

Country Status (1)

Country Link
WO (1) WO2011062446A2 (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007256481A (en) * 2006-03-22 2007-10-04 Asahi Kasei Electronics Co Ltd Photosensitive resin laminate
JP2008225162A (en) * 2007-03-14 2008-09-25 Jsr Corp Radiation-sensitive resin composition, interlayer insulation film and microlens, and method for producing the same
JP2009086414A (en) * 2007-10-01 2009-04-23 Taiyo Ink Mfg Ltd Photosensitive resin composition and cured product thereof
JP2009205137A (en) * 2007-12-27 2009-09-10 Sumitomo Chemical Co Ltd Photosensitive resin composition

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007256481A (en) * 2006-03-22 2007-10-04 Asahi Kasei Electronics Co Ltd Photosensitive resin laminate
JP2008225162A (en) * 2007-03-14 2008-09-25 Jsr Corp Radiation-sensitive resin composition, interlayer insulation film and microlens, and method for producing the same
JP2009086414A (en) * 2007-10-01 2009-04-23 Taiyo Ink Mfg Ltd Photosensitive resin composition and cured product thereof
JP2009205137A (en) * 2007-12-27 2009-09-10 Sumitomo Chemical Co Ltd Photosensitive resin composition

Also Published As

Publication number Publication date
WO2011062446A3 (en) 2011-10-20

Similar Documents

Publication Publication Date Title
KR100655045B1 (en) Photosensitive resin composition and black matrix thereof
KR101759929B1 (en) Photosensitive resin composition
KR101830204B1 (en) Curable resin composition, anti-reflective coating using same, solid-state imaging element, and camera module
WO2013027936A2 (en) Black photosensitive resin composition and image display device having same
KR20170113390A (en) Photosensitive resin composition for light-shielding film, display substrate having the light-shielding film obtained by curing the same, and manufacturing method of display substrate
WO2012044070A2 (en) Photosensitive resin composition for organic insulator
WO2012091401A2 (en) Photosensitive resin composition for resin black matrix
KR100671107B1 (en) Photosensitive resin composition and black matrix thereof
WO2010090406A2 (en) Colored photosensitive resin composition, color filter, and liquid crystal display device comprising same
WO2011062446A2 (en) Photosensitive resin composition
WO2018182134A1 (en) Blue photo-sensitive resin composition, color filter manufactured using same, and image display device
KR20170037196A (en) Photosensitive resin composition for organic insulating film
WO2015194892A1 (en) Photo-crosslinking resin composition, insulating film formed therefrom and organic light-emitting diode
CN104777714A (en) Photosensitive resin composition and color filter using the same
WO2019146814A1 (en) Black photosensitive resin composition, black matrix for image display device manufactured therefrom, column spacer, and black matrix integrated column spacer
KR101316397B1 (en) Photosensitive resin composition for organic insulator
CN115368583B (en) Multi-branched polymer, alkali-soluble resin, and photocurable composition
KR102008491B1 (en) Photosensitive resin composition for organic insulator
KR20180107716A (en) Photosensitive compositions
KR20110030171A (en) Photosensitive resin composition
US20230244140A1 (en) Photosensitive resin composition, and photosensitive resin film and color filter manufactured by using same
WO2021187853A1 (en) Photosensitive resin composition, photosensitive resin film prepared using same, and display device
WO2011139111A1 (en) Resin composition, insulating film using the same, and electronic component
KR101247621B1 (en) Colored photosensitive resin composition and color filter prepared by using same
WO2017057853A1 (en) Photosensitive resin composition and organic insulating film prepared therefrom

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 201080061583.9

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 10831813

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase in:

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 13574354

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 10831813

Country of ref document: EP

Kind code of ref document: A2