KR101427445B1 - Photosensitive resin composition for organic insulator - Google Patents
Photosensitive resin composition for organic insulator Download PDFInfo
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- KR101427445B1 KR101427445B1 KR20100095636A KR20100095636A KR101427445B1 KR 101427445 B1 KR101427445 B1 KR 101427445B1 KR 20100095636 A KR20100095636 A KR 20100095636A KR 20100095636 A KR20100095636 A KR 20100095636A KR 101427445 B1 KR101427445 B1 KR 101427445B1
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- resin composition
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- photosensitive resin
- organic insulating
- carboxylic acid
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
- G03F7/0758—Macromolecular compounds containing Si-O, Si-C or Si-N bonds with silicon- containing groups in the side chains
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/075—Silicon-containing compounds
- G03F7/0751—Silicon-containing compounds used as adhesion-promoting additives or as means to improve adhesion
Abstract
The present invention relates to a photosensitive composition which not only achieves high flatness, sensitivity, heat resistance, transparency and low residual film ratio but also significantly improves the adhesion between substrates, and more particularly to a silsesquioxane compound having a conventional epoxy functional group The introduction of silsesquioxane compounds having photosensitive functional groups in order to minimize excessive coating film loss during the development process of the organic insulating film introduced can increase the crosslinking density during the exposure process and minimize the loss of the coating film in the developing process As the photosensitive resin composition, a photosensitive resin composition suitable for an organic insulating film in various Display processes can be provided.
Description
The present invention relates to a photosensitive resin composition suitable for an organic insulating film in various display processes.
TFT-LCD (Thin Film Transistor Liquid Crystal Dispaly) is manufactured by forming a panel by injecting liquid crystal between an organic substrate on which a TFT-array is formed and a glass substrate on which a color filter is formed so as to maintain a predetermined gap therebetween, And then applying an electrical signal to display. However, since the LCD panel can not actively emit light, a light source that can emit a separate light is required, which is called a backlight source. It is important to obtain low power consumption and high brightness among TFT-LCD characteristics. The panel-related technology can improve the transmission efficiency of the polarizing plate, improve the transmittance of the color filter, and increase the aperture ratio of the TFT-array, that is, the area through which the light passes . The aperture ratio refers to the ratio of the open or transparent portion to the total surface area. Recently, the results for TFT-LCD have been focused on improvement of wide viewing angle and pixel aperture ratio. At this time, high aperture ratio realizes high brightness and reduces power consumption of backlight source.
Conventional organic insulating films have been used in some cases, such as PVA (Korean Patent Laid-Open No. 2002-008427), polyimide (Korean Patent Laid-Open No. 2003-0016981), and photoacryl (US Patent No. 6,232,157) Of the inorganic insulating film.
The present invention relates to an organic insulating film having excellent flatness, sensitivity, heat resistance, transparency, and adhesion, as well as an organic insulating film having low dielectric constant properties, which can increase the hardening density during the exposure process and minimize loss of patterns and loss of coating film during the development process. Composition.
One embodiment of the present invention relates to a photosensitive resin composition comprising an alkali-soluble resin (A), an unsaturated ethylenic monomer (B), a silsesquioxane compound of the following formula (1), a photopolymerization initiator (D) And a photosensitive resin composition for an organic insulating film.
≪ Formula 1 >
R 1 is an alkyl group or a hydrogen atom having 1 to 5 carbon atoms, R 2 is an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, m and n are each an integer of 1 to 5, 1 to 10).
Another embodiment of the present invention is a photosensitive resin composition for an organic insulating film, wherein the [C] silsesquioxane-based compound has a molecular weight of 1000 to 4000.
Another embodiment of the present invention is the photosensitive resin composition for an organic insulating film, wherein the [C] silsesquioxane-based compound is bifunctional or trifunctional.
Another embodiment of the present invention is the photosensitive resin composition for an organic insulating film, wherein the [C] silsesquioxane-based compound is contained in an amount of 5% by weight to 60% by weight with respect to the entire composition.
Another embodiment of the present invention relates to the above-mentioned [A] alkali-soluble resin, which is selected from the group consisting of [a1] an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; And [a2] an epoxy group-containing unsaturated compound.
Another embodiment of the present invention relates to the above-mentioned [A] alkali-soluble resin, which is selected from the group consisting of [a1] an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride; [a2] an epoxy group-containing unsaturated compound; And [a3] a copolymer of an olefinically unsaturated carboxylic acid ester compound other than the above [a1] and [a2]; Or [a1] an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, or a mixture of two or more thereof; [a2] an epoxy group-containing unsaturated compound; And [a4] a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3] Or [a1] an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, or a mixture of two or more thereof; [a2] an epoxy group-containing unsaturated compound; [a3] olefinically unsaturated carboxylic acid ester compounds other than the above [a1] and [a2]; And [a4] a copolymer of at least one compound selected from olefinically unsaturated compounds other than the above-mentioned [a1], [a2] and [a3].
Another embodiment of the present invention is a photosensitive resin composition for an organic insulating film, wherein the [a1]: [a2] component is contained in a weight ratio of 1: 1.3 to 2.5.
In another embodiment of the present invention, the [a1]: [a2] component is contained in a weight ratio of 1: 1.3 to 2.5, and the at least one compound selected from [a3] and [a4] Is 35 to 65% by weight based on the entire resin content.
Another embodiment of the present invention is the photosensitive resin composition for an organic insulating film, wherein the [A] alkali-soluble resin is contained in an amount of 5 to 50% by weight based on the total amount of the composition.
Another embodiment of the present invention is the photosensitive resin composition for an organic insulating film, wherein the [A] alkali-soluble resin has a solid content of 10 to 70% by weight.
In another embodiment of the present invention, the [B] unsaturated ethylenic monomer is an acrylic monomer having at least two unsaturated ethylene bonds, and is contained in an amount of 5 to 60% by weight based on the total amount of the composition. Photosensitive resin composition.
Another embodiment of the present invention is a photosensitive resin composition for an organic insulating film, which has a dielectric constant of 3.3 or less after forming a thin film.
Another embodiment of the present invention is a photosensitive resin composition for an organic insulating film, which has a viscosity of 3 to 30 cps.
Another embodiment of the present invention is an organic insulating film manufactured using the above composition.
Another embodiment of the present invention is a display device including the organic insulating film.
The photosensitive resin composition according to the present invention is excellent in low dielectric constant, flatness, sensitivity, heat resistance, transparency, and adhesion without loss of pattern and excessive coating film loss during the development process, Lt; / RTI >
[C] a silsesquioxane-based compound represented by the following general formula (1); [D] a photopolymerization initiator; [E] an alkali-soluble resin; ] Solvent for a photosensitive resin composition for an organic insulating film.
≪ Formula 1 >
R 1 is an alkyl group or a hydrogen atom having 1 to 5 carbon atoms, R 2 is an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, m and n are each an integer of 1 to 5, 1 to 10).
Hereinafter, the present invention will be described in more detail.
The photosensitive resin composition for an organic insulating film of the present invention comprises
[A] Alkali-soluble resin
([a1] a single or a mixture of two or more selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides;
[a2] an epoxy group-containing unsaturated compound;
[a3] olefinically unsaturated carboxylic acid ester compounds other than the above [a1] and [a2]; And
[a4] an olefinically unsaturated compound other than the above-mentioned [a1], [a2] and [a3]
A copolymer of [a1] and [a2] or a copolymer of at least one selected from [a3] and [a4] with [a1] and [a2], preferably an alkali-
[B] unsaturated ethylenic monomers,
[C] a silsesquioxane-based compound represented by the following general formula (1)
[D] Photopolymerization initiator and
[E] solvent.
≪ Formula 1 >
R 1 represents an alkyl group or a hydrogen atom of 1 to 5 carbon atoms; R 2 represents an alkoxy group of 1 to 5 carbon atoms; an alkyl group or a hydrogen atom of 1 to 5 carbon atoms; m and n each represents an integer of 1 to 5; To 10.
(2)
Wherein R 1 is an alkyl or hydrogen atom having 1 to 5 carbon atoms, R 2 is an alkyl or glycidyl group having 1 to 5 carbon atoms, Y is an alkyl or cycloalkyl group having 1 to 5 carbon atoms, Z is an alkyl group having 1 to 5 carbon atoms And x, y, z, and r are integers greater than or equal to 0, and x, y, z, and r are all 0s.
The photosensitive resin composition of the present invention preferably has a content of
[A] 5 to 50% by weight of an alkali-soluble resin,
5 to 60% by weight of [B] an unsaturated ethylenic monomer,
[C] 5 to 60% by weight of a silsesquioxane-based compound represented by the following general formula (1)
[D] 0.5 to 20% by weight of a photopolymerization initiator,
[E] 20 to 80% by weight of a solvent and
Other additives may be included.
The photosensitive resin composition for an organic insulating film of the present invention may have a dielectric constant of 3.3 or less after forming a thin film so as to provide a suitable low dielectric constant in a display process.
In addition, the photosensitive resin composition for an organic insulating film of the present invention may have a viscosity of 3 to 30 cps to form a uniform coating film upon coating.
Each component of the photosensitive resin composition according to the present invention will be described in detail.
[A] Alkali-soluble resin
The [A] alkali-soluble resin to be used in the present invention is preferably a resin comprising a single or a mixture of two or more of [a1] unsaturated carboxylic acid and unsaturated carboxylic acid anhydride; And [a2] an epoxy group-containing unsaturated compound, or [a1] an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, or a mixture of two or more thereof; [a2] an epoxy group-containing unsaturated compound; And [a3] a copolymer of an olefinically unsaturated carboxylic acid ester compound other than the above [a1] and [a2]; Or [a1] an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, or a mixture of two or more thereof; [a2] an epoxy group-containing unsaturated compound; And [a4] a copolymer of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3] Or [a1] an unsaturated carboxylic acid and an unsaturated carboxylic acid anhydride, or a mixture of two or more thereof; [a2] an epoxy group-containing unsaturated compound; [a3] olefinically unsaturated carboxylic acid ester compounds other than the above [a1] and [a2]; And [a4] a copolymer obtained by radical polymerization of at least one compound selected from olefinically unsaturated compounds other than [a1], [a2] and [a3].
As the unsaturated carboxylic acid and / or unsaturated carboxylic acid anhydride in the form of [a1], acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and anhydrides of these dicarboxylic acids may be used alone or in combination . Of these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used because they are excellent in copolymerization reactivity, heat resistance and availability.
Examples of the epoxy group-containing unsaturated compound [a2] include glycidyl acrylate ester, glycidyl methacrylate ester, glycidyl ester of? -Ethylacrylic acid, glycidyl? -Propyl acrylate,? -N-butyl acrylate Glycidyl ester, acrylic acid-3,4-epoxybutyl ester, methacrylic acid-3,4-epoxybutyl ester, acrylic acid-6,7-epoxyheptyl ester, methacrylic acid-6,7-epoxyheptyl ester, -Ethyl acrylate-6,7-epoxyheptyl ester, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like, and the heat resistance and hardness It is advantageously used in terms of increasing the amount of water. These compounds [a2] are used alone or in combination.
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; Alkyl acrylate esters such as methyl acrylate and isopropyl acrylate; Methacrylic acid cycloalkyl esters such as cyclohexyl methacrylate, 2-methylcyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate and isobornyl methacrylate; Acrylic acid cycloalkyl esters such as cyclohexyl acrylate, 2-methylcyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, and isobornyl acrylate; Methacrylic acid aryl esters such as pentyl methacrylate and benzyl methacrylate; Acrylic acid aryl esters such as phenyl acrylate and benzyl acrylate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate and diethyl itaconate; And hydroxyalkyl esters such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate.
Examples of the compound [a4] include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinyl chloride Acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene and the like.
The copolymer [A] used in the present invention may contain 5 to 50% by weight, based on the entire composition, wherein [a1]: [a2] is contained in a weight ratio of 1: 1.3 to 3.5, ] And [a4], the selected components [a3] and [a4] may be contained in an amount of 35 to 65% by weight based on the entire content of the [A] alkali-soluble resin.
The [A] alkali-soluble resin may have a solid content of 10 to 70% by weight, more preferably 20 to 50% by weight, based on the component [A]. When the solid content is less than 10% by weight, the polymer containing both of the storage stability of the copolymer [A] and the constituents of [a1] to [a4] tends to be solidified due to poor polymerization control during production, %, The developability, heat resistance and surface hardness of the copolymer [A] tends to be lowered.
Examples of the solvent used for the synthesis of the copolymer [A] include 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.
As the polymerization initiator used in the synthesis of the copolymer [A], those known as radical polymerization initiators can be used. Azo compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy- (4-dimethylvaleronitrile), organic peroxides such as benzoyl peroxide, t-butyl peroxypivalate, and 1,1'-bis- (t-butylperoxy) cyclohexane, and hydrogen peroxide. When a peroxide is used as a radical polymerization initiator, the peroxide may be used as a redox initiator together with a reducing agent.
[B] The unsaturated ethylenic monomer
The unsaturated ethylenic monomer used in the present invention is a monofunctional or multifunctional acrylic monomer having at least one unsaturated ethylenic bond, and the monofunctional, bifunctional, or trifunctional or more (meth) acrylate is preferably polymerizable , Heat resistance and surface hardness of the obtained protective film are improved.
Examples of the monofunctional (meth) acrylate include 2-hydroxyethyl (meth) acrylate, carbitol (meth) acrylate, isobonyl (meth) acrylate, 3-methoxybutyl (Meth) acryloyloxyethyl 2-hydroxypropyl phthalate, and the like.
Examples of the bifunctional (meth) acrylate include ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) (Meth) acrylate, tetraethylene glycol (meth) acrylate, and bisphenoxy ethyl alcohol fluorene diacrylate.
Examples of the (meth) acrylate having three or more functional groups include (meth) acrylic acid esters such as trishydroxyethylisocyanurate tri (meth) acrylate, trimethylpropanetri (meth) acrylate, pentaerythritol tri (Meth) acrylate, erythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like.
These monofunctional, bifunctional or trifunctional (meth) acrylates are used alone or in combination.
[C] silsesquioxane-based compound
The silsesquioxane-based compound having an epoxy group which is conventionally used does not participate in curing in the exposure process, and thus patterns are lost or a lot of loss occurs in a subsequent development process. The silsesquioxane-based compound used in the present invention has an acryl group or an oxetal degassing unit, which increases the curing density during the exposure process, minimizes pattern loss and loss of coating film during the development process, From the viewpoints of hardness and dielectric constant. The silsesquioxane used may also contain from 5 to 60% by weight based on the total composition. When the content of the constituent unit is less than 5% by weight, heat resistance, transparency, hardness and dielectric constant are inferior. When it exceeds 60% by weight, development in the development process tends to be difficult.
Specific examples of the silsesquioxane-based compound may be represented by the following general formula (1).
≪ Formula 1 >
R 1 is an alkyl group or a hydrogen atom having 1 to 5 carbon atoms; R 2 is an alkoxy group having 1 to 5 carbon atoms; an alkyl group or a hydrogen atom having 1 to 5 carbon atoms; m and n are each an integer of 1 to 5; To 10.
[D] Photopolymerization initiator
The photopolymerization initiator in the present invention means a compound which generates an active species capable of initiating polymerization of the [B] unsaturated ethylenic monomer such as a radical, an anion and a cation, which causes decomposition or bonding by exposure.
The photocurable resin composition of the present invention comprises a photopolymerization initiator in an amount of 0.5 to 20% by weight based on the total composition. If the content is less than 0.5% by weight, the sensitivity of the protective film is insufficient and the protective film tends to be lost in the developing process. Even if the protective film is maintained in the developing process, it is difficult to obtain a protective film having a sufficiently high crosslinking density. When the content of the photopolymerization initiator exceeds 20% by weight, the heat resistance and planarization property of the protective film are likely to be deteriorated.
Examples of such photopolymerization initiators include thioxanthone, 2,4-diethylthioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (diethylamino) benzophenone, acetophenone, p -Dimethoxyacetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl (2-hydroxy-2-methyl-1-phenylpropyl)] - 2-morpholino- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone and other ketones such as anthraquinone, 1,4- Tri (trichloromethyl) -s-triazine, 1,3-bis (trichloromethyl) -5- (2- chlorophenyl) -s- triazine, 1,3-bis (trichlorophenyl) -s-triazine, phenacyl chloride, tribromomethylphenylsulfone, tris (trichloromethyl) -s-triazine Of the like it can be mentioned halides di -t- butyl peroxide, 2,4,6-trimethylbenzoyl peroxide, such as diphenylphosphine acylphosphine oxides, such as oxides.
These photopolymerization initiators may be used alone or in combination.
[D] Solvent
As the solvent used in the present invention, the following materials can be used as a solvent which can maintain the solid content and viscosity of the copolymer [A] or the composition. Specifically, 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. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate, methyl ethyl ketone, cyclohexanone, 4-hydroxycyclohexanone and the like are preferable from the viewpoints of solubility, reactivity with each component, Methyl-2-pentanone; methyl esters, ethyl esters, propyl esters and butyl esters of acetic acid; Ethyl ester, 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 methoxy acetic acid; Methyl esters, ethyl esters, propyl esters, butyl esters of propoxyacetic acid; Methyl esters, ethyl esters, propyl esters and butyl esters of butoxyacetic acid; Methyl esters, ethyl esters, propyl esters, butyl esters of 2-methoxypropionic acid; Methyl esters, ethyl esters, propyl esters and butyl esters of 2-ethoxypropionic acid; Methyl esters, ethyl esters, propyl esters, and butyl esters of 2-butoxypropionic acid; Methyl esters, ethyl esters, propyl esters, and butyl esters of 3-methoxypropane; Methyl esters, ethyl esters, propyl esters, butyl esters of 3-ethoxypropionic acid; And esters such as methyl esters, ethyl esters, propyl esters and butyl esters of 3-butoxypropionic acid.
It is also possible to use a high boiling point solvent together with the above-mentioned solvent. Examples of the high boiling point solvent which can be used in combination include N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide , Benzyl ethyl ether and the like.
Other additives that may be added include surfactants for improving the coatability. F-172, F-173, F-183, F-470, and F-480 of 3M Company, for example, FC-129, FC-170C and FC- -475, KP322, KP323, KP340 and KP341 of Shin-Etsu Silicones. Such a surfactant is preferably used in an amount of 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. If the amount of the surfactant is more than 5 parts by weight, bubbling tends to occur at the time of application.
It is also possible to use an adhesive preparation to improve the adhesion with the substrate. As such an adhesion aid, a functional silane coupling agent is preferably used. For example, a functional silane coupling agent such as trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatepropyltriethoxysilane, -glycidoxypropyltrimethoxysilane, and the like. Such an adhesion aid is preferably used in an amount of 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion promoting agent exceeds 20 parts by weight, the heat resistance tends to decrease.
Hereinafter, preferred embodiments and comparative examples of the present invention will be described. However, the following embodiments are merely preferred embodiments of the present invention, and the present invention is not limited to the following embodiments.
≪ Preparation Example 1 > Preparation of alkali-soluble resin A
10 parts by weight of 2,2'-azobisisobutyronitrile as a photopolymerization initiator was dissolved in 200 parts by weight of a solvent propylene glycol monomethyl ether acetate in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 65 parts by weight of styrene, 15 parts by weight of methacrylic acid, and 20 parts by weight of glycidyl methacrylate were charged, purged with nitrogen, and gently stirred. The temperature of the solution was raised to 70 캜 and maintained at this temperature for 4 hours to obtain a polymer solution containing the copolymer. The solid concentration of the obtained polymer solution was 35% by weight. This was referred to as alkali-soluble resin A.
Preparation Example 2 Preparation of alkali-soluble resin B
A polymer solution was prepared in the same manner as in Preparation Example 1 except that 45 parts by weight of styrene and 20 parts by weight of dicyclopentyl acrylate were used instead of 65 parts by weight of styrene. The solid concentration of the obtained polymer solution was 33%. This was referred to as an alkali-soluble resin B.
≪ Examples 1 to 5 and Comparative Examples 1 to 3 >
Soluble reactive resins A and B as a photosensitive material, propylene glycol monomethyl ether acetate as a solvent, and a monomer having an unsaturated ethylene bond (dipentaerythritol hexa (meth) acrylate) were blended, and a silsesquioxane-based compound As shown in Table 1 below, the photosensitive resin was blended while varying the content.
Initiator
Note) 1) The content unit is% by weight.
2) The [C] silsesquioxane compound is a compound represented by the formula (1) according to the present invention, wherein R is an acrylic group, R1 / R2 is a methoxy group, m is 3,
3) The silsesquioxane-based compound having an [F] epoxy functional group is HQ504 as a commonly used compound.
The properties of the compositions prepared in the above Examples and Comparative Examples were evaluated as follows, and the results are shown in Table 2 below.
(1) Viscosity
The viscosity was measured with a BROOKFIELD viscometer at 25 ° C.
(2)
Each of the photosensitive resin compositions prepared on Glass was spin-coated and preliminarily dried on a hot plate at 100 DEG C for 120 seconds to form a photoresist film having a thickness of 3 mu m. After exposing the formed glass film, a 2.38% aqueous solution of TMAH For 60 seconds, and again subjected to a strong heat treatment at 220 占 폚 for 1 hour. The film thickness at the time of preliminary drying and the thickness of the film formed after removing the solvent through postcuring were measured, and the residual film ratio was measured by the ratio measurement.
(3) Flatness
Each of the photosensitive resin compositions prepared on the patterned glass of the color resist was spin-coated and preliminarily dried on a hot plate under the conditions of 100 DEG C and 120 seconds to form a photoresist film having a film thickness of 3 mu m. And then developed in a 2.38% TMAH aqueous solution for 60 seconds and again subjected to a strong heat treatment at 220 ° C for 1 hour. The flatness was measured by measuring the thickness of 5 points of the dry film thus obtained.
The flatness was measured. The results were as follows:?,?, 0.06 to 0.1 占 퐉,?,
(4) Sensitivity
Each of the photosensitive resin compositions prepared on Glass was coated at a spin of 800 rpm and preliminarily dried at 100 DEG C for 120 seconds on a hot plate and exposed at 60, 70, 80, 90, 100, 150, and 200 mJ / After exposure, the resist film was developed in a 2.38% TMAH aqueous solution for 60 seconds, and then subjected to a strong heat treatment at 220 占 폚 for 1 hour. The thickness of the obtained coating film was measured.
The thickness was measured to obtain a sensitivity of 90% or more based on the thickness of the coating film obtained at 200 mJ / cm 2.
(5) Heat resistance
The upper, lower, left, and right widths of the pattern film formed in the above sensitivity measurement were measured. A case where the rate of change of the angle is 0 to 10%, a case where the rate of change of the angle is before the midbake (100 DEG C, 2 minutes), a case where the rate of change is 11 to 20%, a case where the rate of change is 21 to 40% X, respectively.
(6) Adhesiveness
Each of the photosensitive resin compositions prepared on Glass was spin-coated and preliminarily dried on a hot plate under the conditions of 100 占 폚 for 120 seconds and exposed to light at 60, 70, 80, 90, 100, 150 and 200 mJ / And then developed in a 2.38% aqueous solution of TMAH for 60 seconds and then subjected to a strong heat treatment at 220 ° C for 1 hour. The obtained coating film was cut into 100 equal parts and then attached and detached using a 3M scotch maic tape. At this time, the number of remaining coatings was counted.
In the above measurement, the case where the remaining coating film is 100% is represented by?, The case where 90 to 99% is represented by?, The case of 80 to 89% is indicated by?, And the case of less than 80% is represented by X.
(7) Permittivity
The dielectric constant was obtained by measuring the electrostatic capacity of the kepperser and using the following equation. The dielectric thin film was coated to a predetermined thickness, and the capacitance was measured through an impedance analyzer. The dielectric constants of each dielectric constant were calculated by the following formula 1.
[Equation 1]
C (capacitance) = ε 0 (vacuum permittivity) * ε r (dielectric thin film relative dielectric constant) * A (effective area) / d (dielectric thin film thickness)
When the dielectric constant was calculated,? Was expressed as 2.8 to 3.0,? To 3.1 to 3.3 as?, 3.4 to 3.6 as?, And 3.7 or more as X. [
(8) Transmittance
The transmittance was measured using a spectrophotometer at 400 nm.
(9) Resolution
Each of the photosensitive resin compositions prepared on Glass was coated at a spin of 800 rpm and preliminarily dried at 100 DEG C for 120 seconds on a hot plate. Exposure was performed at an exposure amount of 100 mJ / cm2 using a mask of each pattern size (4 mu m - 100 mu m) And then developed in a 2.38% TMAH aqueous solution for 60 seconds and again subjected to a strong heat treatment at 220 ° C for 1 hour. At this time, the pattern size of the obtained coating film was measured.
Viscosity
(cps)
(mJ / cm 2)
(%)
(%)
(탆)
Table 2 shows that the photosensitive resin compositions prepared in Examples 1 to 5 according to the present invention have excellent heat resistance, adhesion, residual film and transmittance and low dielectric constant, thereby lowering power consumption and achieving a fine pattern without loss of patterns And thus it can be suitably applied to an organic insulating film in various display processes.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (15)
≪ Formula 1 >
R 1 is an alkyl group or a hydrogen atom having 1 to 5 carbon atoms, R 2 is an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms or a hydrogen atom, m and n are each an integer of 1 to 5, 1 to 10).
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20100095636A KR101427445B1 (en) | 2010-09-30 | 2010-09-30 | Photosensitive resin composition for organic insulator |
| JP2013531489A JP5699219B2 (en) | 2010-09-30 | 2011-09-28 | Photosensitive resin composition for organic insulating film |
| TW100135062A TWI557502B (en) | 2010-09-30 | 2011-09-28 | Photosensitive resin composition for organic insulator |
| PCT/KR2011/007156 WO2012044070A2 (en) | 2010-09-30 | 2011-09-28 | Photosensitive resin composition for organic insulator |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
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| KR20100095636A KR101427445B1 (en) | 2010-09-30 | 2010-09-30 | Photosensitive resin composition for organic insulator |
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| Publication Number | Publication Date |
|---|---|
| KR20120033895A KR20120033895A (en) | 2012-04-09 |
| KR101427445B1 true KR101427445B1 (en) | 2014-08-11 |
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| JP (1) | JP5699219B2 (en) |
| KR (1) | KR101427445B1 (en) |
| TW (1) | TWI557502B (en) |
| WO (1) | WO2012044070A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10533127B2 (en) | 2017-08-17 | 2020-01-14 | Samsung Electronics Co., Ltd. | Compositions, quantum dot polymer composite and layered structure produced therefrom, and electronic device including the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130132322A (en) * | 2012-05-25 | 2013-12-04 | 주식회사 엘지화학 | Photosensitive resin composition, pattern formed by using the same and display panel comprising the same |
| KR102002984B1 (en) * | 2012-12-28 | 2019-07-23 | 코오롱인더스트리 주식회사 | Photosensitive Resin Composition for Hard Coating |
| KR102250453B1 (en) * | 2014-11-11 | 2021-05-11 | 에스케이이노베이션 주식회사 | Composition for making hard coating layer |
| CN108885400A (en) * | 2016-03-31 | 2018-11-23 | 太阳油墨制造株式会社 | Hardening resin composition, dry film, solidfied material and printed circuit board |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060101811A (en) * | 2005-03-21 | 2006-09-26 | 동우 화인켐 주식회사 | Negative type liquid photoresist composition for display electrode |
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| JP3993691B2 (en) * | 1997-09-24 | 2007-10-17 | 関西ペイント株式会社 | Resist pattern forming method |
| JP2001181546A (en) * | 1999-12-22 | 2001-07-03 | Nippon Shokubai Co Ltd | Photosensitive colored resin composition |
| JP3797288B2 (en) * | 2002-07-23 | 2006-07-12 | Ｊｓｒ株式会社 | Resin composition and protective film |
| JP4711208B2 (en) * | 2006-03-17 | 2011-06-29 | 山栄化学株式会社 | Photosensitive thermosetting resin composition, resist film-coated smoothed printed wiring board, and method for producing the same. |
| JP5607346B2 (en) * | 2009-01-06 | 2014-10-15 | 住友化学株式会社 | Photosensitive resin composition, coating film, pattern and display device |
| KR101759929B1 (en) * | 2009-11-20 | 2017-07-20 | 코오롱인더스트리 주식회사 | Photosensitive resin composition |
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2010
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- 2011-09-28 TW TW100135062A patent/TWI557502B/en not_active IP Right Cessation
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060101811A (en) * | 2005-03-21 | 2006-09-26 | 동우 화인켐 주식회사 | Negative type liquid photoresist composition for display electrode |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10533127B2 (en) | 2017-08-17 | 2020-01-14 | Samsung Electronics Co., Ltd. | Compositions, quantum dot polymer composite and layered structure produced therefrom, and electronic device including the same |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2012044070A2 (en) | 2012-04-05 |
| WO2012044070A3 (en) | 2012-05-31 |
| JP5699219B2 (en) | 2015-04-08 |
| KR20120033895A (en) | 2012-04-09 |
| JP2013541733A (en) | 2013-11-14 |
| TWI557502B (en) | 2016-11-11 |
| TW201214043A (en) | 2012-04-01 |
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