CN115685679A - Curable resin composition, pattern, and image display device - Google Patents
Curable resin composition, pattern, and image display device Download PDFInfo
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- CN115685679A CN115685679A CN202110823867.7A CN202110823867A CN115685679A CN 115685679 A CN115685679 A CN 115685679A CN 202110823867 A CN202110823867 A CN 202110823867A CN 115685679 A CN115685679 A CN 115685679A
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Abstract
The present invention relates to a curable resin composition comprising an alkali-soluble resin, a thermosetting compound, a curing agent, a photopolymerizable compound and a photopolymerization initiator, a pattern including the curable resin composition, and an image display device including the pattern.
Description
Technical Field
The present invention relates to a curable resin composition, a pattern comprising the curable resin composition, and an image display device.
Background
In the field of displays, curable resin compositions are used to form various cured patterns such as photoresists, insulating films, protective films, black matrices, column spacers, and the like. Specifically, in the process of forming a desired pattern by selectively exposing and developing a curable resin composition by a photolithography process, a curable resin composition having high sensitivity is required in order to improve the yield in the process and improve the physical properties of an application target. The curable resin composition can be classified into thermosetting and photocurable (photosensitive) compositions according to the curing mechanism.
The pattern formation of the photocurable resin composition relies on photolithography, i.e., a change in polarity of a polymer and a crosslinking reaction caused by photoreaction. In particular, the change characteristics of solubility to a solvent such as an aqueous alkali solution after exposure are utilized.
The pattern formation based on the photocurable resin composition can be classified into a positive etching type and a negative etching type according to the solubility of the photosensitive portion for development. The positive-working photoresist is a type in which an exposed portion is dissolved in a developer, and the negative-working photoresist is a type in which an exposed portion is insoluble in a developer and a non-exposed portion is dissolved to form a pattern, and the positive-working photoresist and the negative-working photoresist are different from each other in terms of a binder resin, a crosslinking agent, and the like used.
Recently, the use of touch screens equipped with touch panels has increased explosively, and recently flexible touch screens have been receiving attention. Accordingly, materials for various substrates of touch screens and the like must have flexibility, and therefore, usable materials are also limited to flexible polymer materials, and manufacturing processes are also required to be performed under milder conditions. Therefore, the curing conditions of the thermosetting resin composition are also changed from the conventional high-temperature curing requirements to low-temperature curing, and low-temperature curing has a problem in that reactivity is lowered, and durability and chemical resistance of a formed pattern are lowered.
Accordingly, many studies on flexible displays have been recently conducted, and as for korean patent No. 10-1464312, a photosensitive resin composition capable of low-temperature curing is disclosed, but curing cannot be performed in a range of less than 100 ℃, and thus there is a problem that it cannot be used when forming a pattern on a flexible substrate of a high molecular compound, a polymer, etc., particularly, a substrate having an organic layer in a lower layer.
Therefore, in order to provide a pattern formed by low-temperature curing with excellent adhesion even after treatment with an etchant or a stripper without causing problems such as surface damage, expansion, or film shrinkage, it is necessary to develop a curable resin composition having improved reliability in solvent resistance, ITO resistance, etching resistance, and the like.
[ Prior art documents ]
[ patent document ]
(patent document 1) Korean patent laid-open No. 10-1464312
Disclosure of Invention
Technical problem
The present invention is directed to improving the problems of the prior art as described above, and an object thereof is to provide a curable resin composition having improved reliability in solvent resistance, ITO resistance, etching resistance, and the like, so that a pattern formed by low-temperature curing has excellent adhesion even after treatment with an etchant or a stripper, without problems such as surface damage, expansion, or film shrinkage.
However, the technical problems to be solved by the present invention are not limited to the technical problems described above, and other technical problems not mentioned above can be clearly understood by those skilled in the art through the following descriptions.
Technical scheme
In order to achieve the above object, the present invention provides a curable resin composition comprising an alkali-soluble resin, a thermosetting compound, a curing agent, a photopolymerizable compound, and a photopolymerization initiator, wherein the curing agent comprises at least one selected from a melamine-based curing agent and a urea-based curing agent, and when a thickness of a cured film formed from the curable resin composition is 2.5 ± 0.1 μm, the thickness of the cured film is T1, and the thickness of the cured film after immersion in N-methyl-2-pyrrolidone for 120 seconds at 70 ℃ is T2, the T2/T1 is 0.90 or more.
Also, the present invention provides a pattern formed from the curable resin composition.
Also, the present invention provides an image display device including the pattern.
Technical effects
The curable resin composition of the present invention can be used for producing a photo-curable and thermosetting pattern having improved reliability, which is improved in adhesion and curing density even in low-temperature curing, and which does not cause surface damage or swelling or film shrinkage to a release solution on a flexible substrate.
Also, the curable resin composition according to the present invention can be cured even at a temperature of less than 100 ℃, so that it can be applied to a flexible film or flexible equipment, and can exhibit excellent chemical resistance to a stripping liquid used in a manufacturing process.
Detailed Description
The present invention relates to a curable resin composition comprising an alkali-soluble resin, a thermosetting compound, a curing agent, a photopolymerizable compound, and a photopolymerization initiator, a pattern formed from the curable resin composition, and an image display device including the pattern.
The curable resin composition of the present invention can be used for producing a photo-curable and thermosetting pattern having improved reliability, which is improved in adhesion and curing density even in low-temperature curing, and which does not cause surface damage or swelling or film shrinkage to a release agent.
Also, the curable resin composition according to the present invention can be cured even at a temperature of less than 100 ℃, and can exhibit excellent chemical resistance to a stripping liquid used in a post-process.
< curable resin composition >
The curable resin composition according to the present invention includes an alkali-soluble resin, a thermosetting compound, a curing agent, a photopolymerizable compound, and a photopolymerization initiator, and may further include a thiol compound, an additive, and a solvent as needed.
The curable resin composition according to the present invention is characterized in that when the thickness of a cured film formed from the composition is 2.5 ± 0.1 μm, T2/T1 is 0.90 or more, where T1 is the thickness of the cured film, and T2 is the thickness of the cured film after immersion in N-methyl-2-pyrrolidone at 70 ℃ for 120 seconds.
Alkali soluble resin
The curable resin composition according to the present invention includes an alkali-soluble resin, and as the alkali-soluble resin, at least one selected from a photocurable alkali-soluble resin and a thermally curable alkali-soluble resin may be included.
The alkali-soluble resin has reactivity and alkali solubility by the action of light or heat, functions as a dispersion medium for a solid phase component contained in the photosensitive resin composition, and may be a resin known in the art to which the present invention belongs without particular limitation as long as it performs a function of a binder resin. Also, the photocurable alkali-soluble resin may have both photocurability and thermosetting property substantially, and the thermosetting alkali-soluble resin may be an alkali-soluble resin that does not contain a double bond and can only achieve thermosetting.
Specifically, the alkali-soluble resin is preferably a copolymer of an unsaturated carboxyl group-containing monomer and another monomer copolymerizable therewith, and developability may be affected by the carboxyl group.
Examples of the unsaturated carboxyl group-containing monomer include unsaturated carboxylic acids having one or more carboxyl groups in the molecule, such as unsaturated monocarboxylic acids, unsaturated dicarboxylic acids, and unsaturated polyvalent carboxylic acids.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, α -chloroacrylic acid, cinnamic acid, and the like.
Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid.
The unsaturated polyvalent carboxylic acid may also be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. The unsaturated polyvalent carboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, and examples thereof include: monosuccinate (2-acryloyloxyethyl), monosuccinate (2-methacryloyloxyethyl), monophthalate (2-acryloyloxyethyl), monophthalate (2-methacryloyloxyethyl). The unsaturated polyvalent carboxylic acid may also be a mono (meth) acrylate of its two terminal dicarboxyl polymers, and examples thereof include omega-carboxy polycaprolactone monoacrylate, omega-carboxy polycaprolactone monomethacrylate, and the like.
The unsaturated carboxyl group-containing monomers may be used alone or in combination of two or more.
Examples of the other monomer copolymerizable with the unsaturated carboxyl group-containing monomer include the following monomers: aromatic vinyl compounds such as styrene, α -methylstyrene, o-vinyltoluene, m-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinylbenzyl methyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, indene, etc.; <xnotran> , , , , n- , n- , i- , i- , n- , n- , i- , i- , sec- , sec- , t- , t- , 2- , 2- , 2- , 2- ,3- ,3- , 2- , 2- ,3- ,3- ,4- ,4- , , , , , , , , , 2- , 2- , 2- , 2- , , , , , , , , </xnotran> Unsaturated carboxylic acid esters such as methoxy dipropylene glycol methyl acrylate, isobornyl methyl acrylate, dicyclopentadienyl methyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerin monoacrylate, and glycerin monoacrylate; aminoalkyl esters of unsaturated carboxylic acids such as 2-aminoethyl acrylate, 2-dimethylaminoethyl acrylate, 2-aminopropyl acrylate, 2-aminomethylpropyl methacrylate, 2-dimethylaminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl methacrylate, 3-aminomethylpropyl methacrylate, 3-dimethylaminopropyl acrylate, 3-dimethylaminopropyl methacrylate, and 3-dimethylaminomethyl methacrylate; unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methyl acrylate; vinyl carboxylates such as vinyl acetate, vinyl propionate, vinyl butyrate, and vinyl benzoate; unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether, and allyl glycidyl ether; vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α -chloroacrylonitrile, vinylidene cyanide and the like; unsaturated amides such as acrylamide, methacrylamide, α -chloroacrylamide, N-2-hydroxyethylacrylamide, N-2-hydroxyethylmethacrylamide, and the like; unsaturated imides such as maleimide, N-benzylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like; aliphatic conjugated dienes such as 1, 3-butadiene, isoprene and chloroprene; and giant monomers having a monoacryl group or a monomethacryl group at the terminal of the polymer molecular chain of polystyrene, polymethacrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, polysiloxane, and the like. These monomers may be used alone or in combination of two or more.
The alkali-soluble resin may have a weight average molecular weight (Mw) of 4,000 to 10,000g/mol, preferably 6,000 to 8,000g/mol, an acid value of 20 to 90mg KOH/g, and preferably 30 to 70mg KOH/g, based on a solid content, and a molecular weight distribution (Mw/Mn) of 1.7 to 2.3, and preferably 1.9 to 2.2. Accordingly, the developability in alkali development is improved, the generation of residue is suppressed, and the adhesion of the pattern can be improved.
The alkali soluble resin may be included by 20 to 50 wt%, and preferably may be included by 30 to 40 wt%, with respect to the total weight of the composition. When the alkali soluble resin is included in the range, it has sufficient solubility to a developer, whereby developability becomes excellent and physical and mechanical properties of a pattern can be improved.
Thermosetting compound
The curable resin composition according to the present invention includes a thermosetting compound, which may be a multifunctional epoxy oligomer.
In the present invention, the polyfunctional epoxy oligomer promotes the polymerization reaction of the alkali-soluble resin and is not particularly limited as long as it is a polyfunctional oligomer containing an epoxy group as a component for inducing the formation of a crosslink.
In one embodiment, the multifunctional epoxy oligomer may include a triphenylmethane structure.
The epoxy group of the polyfunctional epoxy oligomer is subjected to ring opening and promotes the polymerization reaction of the alkali soluble resin, and thus the epoxy group is preferably included in the repeating unit of the oligomer, whereby maximization of the reaction promoting effect can be achieved.
In one embodiment, the multifunctional epoxy oligomer has a softening point measured by a ring and ball method of 100 ℃ or less, and preferably 50 ℃ or more and 100 ℃ or less, and more preferably 60 ℃ or more and 100 ℃ or less, and an Epoxy Equivalent Weight (EEW) may be 250g/eq. When the softening point is included in the range, there is an advantage that the reaction is easily achieved in the heat curing process, and when the epoxy equivalent is included in the range as described above, there may be an advantage that a high curing density is exhibited.
The thermosetting compound may be comprised between 1 and 15% by weight, preferably between 3 and 10% by weight, with respect to the total weight of the composition. When included in the above range, high curing density may be exhibited after a thermal process, and chemical resistance of a pattern may be improved.
Curing agent
The curable resin composition according to the present invention includes a curing agent, and as the curing agent, a thermal curing agent including at least one selected from a melamine-based curing agent and a urea-based curing agent is preferable. Examples of the curing agent used in the present invention include melamine derivatives and urea-aldehyde derivatives, and two or more other curing agents may be used together as necessary.
Specifically, the melamine-based curing agent may include a compound represented by the following chemical formula 1.
[ chemical formula 1]
In the chemical formula 1, R 1 To R 6 Each independently of the others, is hydrogen, an alcohol group having 1 to 3 carbon atoms, an ether group having 1 to 3 carbon atoms, R 1 To R 6 Is preferably-CH 2 OCH 3 。
For example, the melamine-based curing agent may be a compound represented by the following chemical formula 1-1, chemical formula 1-2, or chemical formula 1-3, but is not limited thereto.
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
Specifically, the urea-based curing agent may include compounds represented by the following chemical formulas 2-1 to 2-3.
[ chemical formula 2-1]
In the chemical formula 2-1, R 7 And R 10 Each independently of the others, is an alkoxy group having 1 to 3 carbon atoms or an ether group having 1 to 3 carbon atoms, R 8 And R 9 Each independently of the others, is hydrogen or alkoxy having 1 to 3 carbon atoms, R 7 To R 10 Is preferably-CH 2 OCH 3 or-OCH 3 。
[ chemical formula 2-2]
In the chemical formula 2-2, R 11 And R 14 Each independently of the others, is an alkoxy group having 1 to 3 carbon atoms, R 12 And R 13 Each independently of the others, is hydrogen or alkoxy having 1 to 3 carbon atoms, R 11 To R 14 Is preferably-OCH 3 。
[ chemical formulas 2-3]
In the chemical formula 2-3, R 15 To R 18 Each independently of the others, is an alkoxy group having 1 to 3 carbon atoms, R 15 To R 18 Is preferably-OCH 3 。
For example, the urea-based curing agent may be a compound represented by the following chemical formula 2-1-1, chemical formula 2-1-2, chemical formula 2-2-1, or chemical formula 2-3-1, but is not limited thereto.
[ chemical formula 2-1-1]
[ chemical formula 2-1-2]
[ chemical formula 2-2-1]
[ chemical formula 2-3-1]
In order to form contact holes with the curable resin composition of the present invention and easily ensure a chemical resistance process margin, it is necessary to control the degree of curing based on the reactive unsaturated bonds of the composition and the amount of exposure. Ideally, the difference in the degree of curing at the interface between the exposed portion and the non-exposed portion clearly appears as a difference in developability to clearly show the taper angle of the contact hole, but in the structure of the display device, the taper angle is required to be 45 ° or less in some cases. Therefore, in order to secure a margin in the developing process, it is necessary to adjust the amount of reactive unsaturated bonds or to control the degree of curing according to the exposure amount, but other characteristics such as thermal stability and chemical resistance are changed due to the change in the amount of unsaturated bonds at this time. The introduction of the curing agent improves the thermal stability of the resin composition through a post-baking process, and also plays a role in improving chemical resistance.
The curing agent may comprise 0.1 to 20 wt%, preferably may comprise 0.5 to 10 wt%, relative to the total weight of the composition. If the content of the curing agent is included in the range by the standard, the step formation is facilitated upon development of the curable resin composition, and in the composition, the alkali-soluble resin and the thermosetting compound (compound including an epoxy group) increase the heat-based curing degree, thereby improving the film hardness and chemical resistance, and thus it is preferable.
Photopolymerizable compound
The curable resin composition according to the present invention includes a photopolymerizable compound including a photopolymerizable unsaturated monomer.
In the present invention, the photopolymerizable unsaturated monomer is not particularly limited as long as it is used in the technical field to which the present invention belongs, as a compound that can be polymerized by the action of a photopolymerization initiator described later, increases the crosslinking density, and is a component for enhancing the mechanical properties of a pattern.
In one embodiment, the photopolymerizable unsaturated monomer may include a monofunctional monomer, a 2-functional monomer, and the remaining multifunctional monomer.
Specific examples of the monofunctional monomer include the following: nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone and the like.
Specific examples of the 2-functional monomer include the following: 1, 6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.
Specific examples of the other polyfunctional monomers include the following: trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.
The photopolymerizable compound may be contained in an amount of 30 to 70 wt%, preferably 40 to 50 wt%, based on the total weight of all solid phase components of the composition. If contained in the range, the durability of the pattern and the developability of the composition can be improved.
Photopolymerization initiator
In the present invention, the photopolymerization initiator may be used without any particular limitation as long as it is capable of polymerizing the photopolymerizable unsaturated monomer.
In one embodiment, the photopolymerization initiator may include: at least one compound selected from the group consisting of acetophenone compounds, benzophenone compounds, triazine compounds, bisimidazole compounds, thioxanthone compounds, and oxime ester compounds.
The photopolymerization initiator may be contained in an amount of 0.5 to 10% by weight, preferably 1 to 8% by weight, based on the total weight of the composition. When included in the above range, the strength and straightness of the pattern can be improved.
The photopolymerization initiator may be used in combination with a photopolymerization initiation auxiliary agent. In the photopolymerization initiator, a photopolymerization initiation auxiliary is used in combination, whereby the sensitivity of the composition containing these materials is further increased, and therefore, when the photopolymerization initiator is used to form an organic insulating film, productivity is improved, and therefore, it is preferable.
The photopolymerization initiation auxiliary can be used for improving the polymerization efficiency, and at least one compound selected from the group consisting of amine compounds, alkoxyanthracene compounds, thioxanthone compounds, carboxylic acids and sulfonic acid compounds can be used, and preferably selected from the group consisting of carboxylic acids and sulfonic acid compounds.
The photopolymerization initiator aid is used in an amount of usually 10 moles or less, preferably 0.01 to 5 moles per 1 mole of the photopolymerization initiator. When the photopolymerization initiation auxiliary is used in the above range, it is expected that the polymerization efficiency will be improved and the productivity will be effectively improved.
Thiol compounds
The curable resin composition of the present invention may further contain a thiol compound having 3 or more functions, as required by those skilled in the art, in addition to the above-mentioned components, without impairing the object of the present invention.
The thiol compound having 3 or more functions is used together with the alkali-soluble resin and the multifunctional epoxy oligomer as a primary ring-opening agent for opening the epoxy groups of the multifunctional epoxy oligomer, thereby increasing the crosslinking density, so that the durability of the cured pattern and the adhesion to the substrate are improved, and the yellowing phenomenon at high temperature can be prevented.
The 3-or more-functional thiol compound has 3 or more thiol compounds as functional groups, and is not particularly limited as long as it is a compound that can be used in the curable resin composition, but is preferably a 4-or more-functional thiol compound, and examples of the 3-or more-functional thiol compound (F) include the following: 1,3, 5-tris (3-mercaptobutoxyethyl) -1,3, 5-triazine-2, 4,6 (1H, 3H, 5H) -trione, trimethylolpropane (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl ester), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), tetraethyleneglycol bis (3-mercaptopropionate). However, it is not limited thereto.
The thiol compound may be included by 0.5 to 20 wt%, preferably 1 to 15 wt%, with respect to the total weight of the composition. If included in the range, excellent curing properties can be exhibited at lower temperatures.
Additive agent
The curable resin composition of the present invention may contain additives, in addition to the above-mentioned components, as required by those skilled in the art, within a range not detrimental to the object of the present invention.
The additive may include, for example, at least one selected from the group consisting of an antioxidant, a surfactant, and the like.
The additives may be added to the composition as appropriate by those skilled in the art within the range not detrimental to the effects of the present invention. For example, the additive may be used in an amount of 0.05 to 10 parts by weight, preferably 0.1 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the total of the curable resin composition, but is not limited thereto.
In the present invention, any organic solvent that is generally used in the art may be used without any particular limitation. Examples of the solvent (E) include ethers, acetates, aromatic hydrocarbons, ketones, alcohols, esters, and the like, and 1 or more kinds thereof may be selected from them and used, but the solvent (E) is not limited thereto.
The solvent (E) may comprise the balance to bring the total weight of the composition to 100 wt.%. Specifically, in the present invention, the "margin" has the following meaning: so that the total weight of the composition comprising the essential ingredients of the present invention, and the remaining additional ingredients, amounts to 100% by weight. The meaning of the "balance" does not limit the inclusion of additional ingredients in the compositions of the present invention.
In one embodiment, the solvent may be contained in an amount of 60 to 90 wt%, preferably 70 to 85 wt%, with respect to the total weight of the composition. When the content of the solvent is included in the above range, the coating using a coating device such as a roll coater, a spin coater, a seam coater (also referred to as a "die coater"), or an ink jet printer tends to be excellent in coatability, and thus is preferable.
< Pattern >
The pattern according to the present invention can be produced by a method known in the art to which the present invention belongs, in addition to the point of formation using the curable resin composition as described above.
In one embodiment, the pattern may be a pattern selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, and a black column spacer.
The pattern according to the present invention is formed on a substrate, and a glass substrate or a polymer plate is used as the substrate, and a flexible substrate is preferably used. The flexible substrate means a substrate having flexibility. As the glass substrate, soda lime glass, barium-or strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, quartz, or the like can be used preferably. Examples of the polymer sheet include polycarbonate, acryl, polyethylene terephthalate, polyether sulfide, polysulfone, and the like. And, the substrateThe method comprises the following steps: siN is formed on one surface of the substrate x A film or a substrate of an organic layer.
At this time, in order to be able to obtain a desired thickness, coating may be performed by a wet coating method using a coating device such as a roll coater, a spin coater, a seam coater (also referred to as a "die coater"), an inkjet printer, or the like.
The prebaking is performed by heating by an oven, a hot plate, or the like. At this time, the heating temperature and the heating time in the prebaking are selected depending on the solvent used, and are performed, for example, at a temperature of 80 to less than 100 ℃ for 1 to 30 minutes.
The exposure performed after the prebaking is performed by an exposure device, and exposure is performed through a mask, so that only a portion corresponding to the pattern is exposed to light. The light irradiated at this time may be, for example, visible light, ultraviolet light, X-rays, electron beams, or the like.
The alkali development after the exposure is performed for the purpose of removing the curable resin composition at the unremoved portion of the non-exposed portion, thereby forming a desired pattern by development. Using 0.02 to 0.06 wt% KOH aqueous alkali, performed at a temperature of 10 to 50 c, and preferably at a temperature of 20 to 40 c, using a developer or ultrasonic cleaner, etc.
The post-baking is preferably performed by performing a heat treatment at a temperature of 80 to 100 ℃ less than full for 10 to 120 minutes for the purpose of improving the adhesion between the patterned film and the substrate. Specifically, when a flexible substrate having weak heat resistance is used or an organic layer is present on one surface of the substrate, the heat treatment is preferably performed at a low temperature of 80 to 100 ℃. Like the pre-bake, the post-bake is also performed using an oven, a hot plate, or the like.
< image display apparatus >
The image display device according to the present invention includes a structure well known in the art to which the present invention belongs, in addition to the point of including the pattern as described above, and as specific examples, a liquid crystal display device, an OLED, a flexible display, an electroluminescence display device, a plasma display device, an electroluminescence display device, and the like may be cited, but is not limited thereto.
The present invention will be described in more detail below with reference to examples and comparative examples. However, the embodiments described below are intended to disclose the present invention exemplarily, and the present invention is not limited by the embodiments described below, which can be variously modified and changed.
The present invention will be described in more detail below with reference to examples. However, the examples described below are intended to illustrate the present invention more specifically, and the scope of the present invention is not limited by the examples described below. In the following examples and comparative examples, "%" and "part(s)" used to indicate contents are all on a weight basis unless otherwise specifically noted.
Production example 1: photocuring alkali-soluble resin A-1
100 parts of propylene glycol monomethyl ether acetate, 100 parts of propylene glycol monomethyl ether, 5 parts of AIBN, 23.0 parts of vinyltoluene, 1.6 parts of 4-methylstyrene, 46.0 parts of methyl glycidylacrylate and 3 parts of n-dodecylmercapto group were charged into a flask equipped with a stirrer, a thermometer reflux condenser, a titration neck and a nitrogen introduction tube, and nitrogen substitution was carried out. Then, the temperature was raised to 80 ℃ for 4 hours while stirring. Then, the temperature of the reaction solution was lowered to room temperature, the atmosphere in the flask was replaced with nitrogen gas to air, and then 0.2 part of triethylamine, 0.1 part of 4-methoxyphenol and 23.3 parts of acrylic acid were added thereto to carry out a reaction at 100 ℃ for 6 hours. Then, the temperature of the reaction solution was lowered to normal temperature, 6.0 parts of succinic anhydride was charged, and the reaction was carried out at 80 ℃ for 6 hours.
The solid content acid value of the alkali-soluble resin A-1-1 thus synthesized was 32.8 mg KOH/g, and the weight average molecular weight Mw measured by GPC was about 6350. The molecular weight distribution (Mw/Mn) was 1.7.
Production example 2: photocuring alkali-soluble resin A-1-2
Into a flask equipped with a stirrer, a thermometer reflux condenser, a titration neck and a nitrogen introduction tube were charged 120 parts of propylene glycol monomethyl ether acetate, 80 parts of propylene glycol monomethyl ether, 2 parts of AIBN, 13.0 parts of the above acrylic acid, 10 parts of benzyl methacrylate, 57.0 parts of 4-methylstyrene, 20 parts of methyl methacrylate and 3 parts of n-dodecylmercapto group, and nitrogen substitution was performed. Then, the temperature of the reaction solution was raised to 80 ℃ while stirring and reacted for 8 hours.
The alkali-soluble resin A-1-2 thus synthesized had an acid value of a solid content of 98.2 mg KOH/g and a weight-average molecular weight Mw measured by GPC of about 14950. The molecular weight distribution (Mw/Mn) was 1.95.
Production example 3: thermosetting alkali-soluble resin A-2-1
In a 1L flask equipped with a reflux cooler, a titration funnel and a stirrer, nitrogen gas was flowed at a flow rate of 0.02L/min to create an atmosphere of nitrogen gas, and 150g of diethylene glycol methyl ethyl ether was charged and heated to 70 ℃ while stirring. Next, 132.2g (0.60 mol) of the following chemical formula 3 was taken, and 55.3g (0.30 mol) of methyl 3-ethyl-3-oxetanylacrylate and 8.6g (0.10 mol) of methacrylic acid were dissolved in diethylene glycol methyl ethyl ether to prepare a solution.
[ chemical formula 3]
The produced solution was dropped into a flask by using a titration funnel, 27.9g (0.11 mol) of 2,2' -azobis (2, 4-dimethylvaleronitrile) as a polymerization initiator was dissolved in 200g of diethylene glycol methyl ethyl ether, and the solution obtained by the dissolution was dropped into the flask over 4 hours by using a special titration funnel. After the titration of the polymerization initiator solution was completed, the solution was maintained at 70 ℃ for 4 hours, and then cooled to room temperature, and a solution of a copolymer (resin a-2-1) having a solid content of 41.8 mass% and an acid value of 62 mg KOH/g (solid content conversion) was obtained.
The alkali-soluble resin A-2-1 obtained had a weight-average molecular weight Mw of 7,700 and a molecular weight distribution (Mw/Mn) of 1.82.
Production example 4: heat-curable alkali-soluble resin A-2
The same procedures as in production example 3 were carried out except that the temperature was maintained at 70 ℃ for 8 hours, thereby obtaining a copolymer (resin A-2-2) solution having a solid content of 41.8 mass% and an acid value of 42 mg KOH/g (in terms of solid content).
The alkali-soluble resin A-2-2 obtained had a weight-average molecular weight Mw of 12,300 and a molecular weight distribution (Mw/Mn) of 1.41.
Examples and comparative examples: curable resin composition
The curable resin compositions according to examples and comparative examples were manufactured by referring to the compositions and contents described in tables 1 and 2 shown below.
[ Table 1]
[ Table 2]
A-1-1 preparation of the alkali-soluble resin of example 1
A-1-2 preparation of alkali-soluble resin of example 2
A-2-1 preparation of the alkali-soluble resin of example 3
A-2-2 preparation of alkali-soluble resin of example 4
B-1 SCT-150 (manufactured by Shinatnc corporation; EEW:150 to 200 g/eq)
B-2
B-3
B-4
G1:2,4, 6-tris [ bis (methoxymethyl) amino ] -1,3, 5-triazine (compound of the following chemical formula 1-1)
[ chemical formula 1-1]
G2 Tetramethoxymethylglycine (compound of the following chemical formula 2-3-1)
[ chemical formula 2-3-1]
G3 Pentamethoxymethyl Melamine (Compound of the following chemical formula 1-3)
[ chemical formulas 1-3]
G4:4, 5-dimethoxy-1, 3-bis (methoxymethyl) imidazolin-2-one (compound of the following chemical formula 2-2-1)
[ chemical formula 2-2-1]
G5:1, 3-dimethoxyurea (compound of the following chemical formula 2-1-2)
[ chemical formula 2-1-2]
G6:BI26X-F(
Chaori organic chemical industry manufacturing)
G7:BIOC-E(
Chaori organic chemical industry manufacturing)
G8:3PC(
Chaori organic chemical industry manufacturing)
G9:BIR-PC(
Chaori organic chemical industry manufacturing)
G10:BOP-ANT(
Chaori organic chemical industry manufacturing)
Dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Japan explosive Co., ltd.)
Irgacure OXE-01 (manufactured by Basf corporation)
Trimethyl propane tris (3-mercaptopropionate) (SC organic Chemie)
F, sumilizer GP (chemical manufacturing Sumitomo)
H is propylene glycol monomethyl ether acetate
Production example 5: pattern production using curable resin composition
Glass Substrate (SiO) with length and width of 5 cm 2 Eagle 2000; manufactured by corning corporation), or SiN x To be provided with
The substrate having a thickness formed on the upper portion is washed with a neutral detergent, water, and alcohol in this order, and then dried. On this glass substrate, the curable resin compositions produced in the examples and comparative examples were spin-coated, respectively, and then pre-baked at a temperature of 80 ℃ for 120 seconds using a hot plate. The pre-baked substrate was cooled to room temperature, and then the distance between the substrate and a quartz glass photomask was set to 50 μm, and the thickness of the substrate was adjusted to 30mJ/cm by using an exposure apparatus (MA 6; manufactured by Karl suss Co., ltd.) 2 The exposure amount (365 nm standard) of (1) was measured. At this time, the photomask mask uses a photomask mask in which the next pattern is formed on the same plane.
Square openings (hole patterns) having a 30 μm square hole pattern (square pattern) were spaced at a pitch of 100 μm, and were exposed to light irradiation, developed in a 2.38 wt% aqueous tetramethylammonium hydroxide solution for 60 seconds, washed with ultrapure water, and dried in nitrogen gas to form a pattern on the curable resin film. The postbaking was carried out in an oven at a temperature of 85 ℃ for 2 hours.
Experimental example 1: thickness ratio measurement
The same procedure as in production example 5 was carried out except that the curable resin compositions produced in the examples and comparative examples were coated on a glass substrate to a thickness of 2.5 ± 0.1 μm, thereby producing a cured film, and the thickness (T1) thereof was measured.
The thickness (T2) of the cured film obtained by immersing the cured film produced as described above in N-methyl-2-pyrrolidone (NMP) at 70 ℃ for 120 seconds was measured, and the thickness (T1) of the cured film before immersion, the thickness (T2) of the cured film after immersion, and the thickness ratio (T2/T1) before and after immersion were shown in table 3 below.
[ Table 3]
Referring to table 3, it can be confirmed that the cured film formed from the curable resin composition according to the present invention has excellent chemical resistance against N-methyl-2-pyrrolidone since the thickness ratio before and after immersion in N-methyl-2-pyrrolidone is 0.9 or more.
Experimental example 2: evaluation of physical Properties of Pattern 1-adhesiveness
The patterns produced in production example 5 were immersed in NMP aqueous solutions for 6 minutes, respectively, and then taken out. Then, the adhesiveness was evaluated by attaching an adhesive tape on the surface scribed with a cutter and peeling the tape according to the ASTM D-3359-08 standard test conditions, and the results thereof are shown in table 4 shown below according to the evaluation criteria described below.
After the liquid sample treatment, the degree of occurrence of peeling of the coating film in the Cutting/Tape test was classified into 0B to 5B by the standard test method, and 5B was judged to have the most excellent performance.
< evaluation criteria >
5B stripping 0%
4B stripping 0% over 5% of the deficiency
3B, stripping more than 5% and less than 15%
2B stripping more than 15% and 35% of the deficiency
1B stripping more than 35% and 65% of the deficiency
0B stripping of more than 65%
Experimental example 3: evaluation of residual film ratio
The photosensitive resin composition was formed into a film by the same method as in production example 5, and then exposed to light through the entire surface without a mask of 50mJ/cm 2 And then the film thickness of the pattern was measured by a film thickness measuring device (DEKTAK 6 m.
The substrate whose thickness was measured was immersed in the KOH aqueous solution developing solution at pH 10.5 for 80 seconds again to be developed, and then the thickness was measured and calculated by the following equation, and the results are shown in table 4 below.
Residual film ratio (%) = [ thickness after development (μm)/thickness before development (μm) ] × 100
Experimental example 4: evaluation of physical Properties of Pattern 2-reliability
(1) ITO manufacturability evaluation (ITO resistance)
On the pattern manufactured in the manufacturing example 5, ITO was sputter coated
The thickness was measured to measure the change in the state of wrinkles of the film, and the results are shown in table 4 below according to the evaluation criteria described below.
< evaluation criteria >
O: state of absence of film wrinkles
X: the state of the membrane wrinkle
(2) Evaluation of etching resistance
The upper surface of the pattern manufactured in the manufacturing example 5 was immersed in an etching solution (MA-SO 2, dongyu fine chemistry) at a temperature of 60 ℃ for 10 minutes, and then the film thickness change before and after the immersion was measured to be shown in percentage, and the results thereof were shown in table 4 according to the evaluation criteria described below.
< evaluation criteria >
O: over 98 percent
95% over 98% deficient
X is 95% or less
[ Table 4]
The following facts can be confirmed with reference to said table 4: the patterns manufactured through examples 1 to 10, which are the curable resin compositions manufactured according to the present invention, exhibit excellent technical effects in terms of all of the sticking force, the residual film ratio, and the reliability.
Production example 6: production of cured films depending on curing conditions
(1) Thermal curing (30 min heat treatment at 230 ℃ C.)
The same as in the manufacturing example 5 was performed except that the curable resin compositions manufactured in the examples and comparative examples were coated on a glass substrate to a thickness of 2.5 ± 0.1 μm, and then the prebaked substrate was postbaked in an oven at a temperature of 230 ℃ for 2 hours in a non-light manner, thereby manufacturing a heat cured film.
(2) Photocuring (30 mJ/cm) 2 Light irradiation)
The curable resin compositions produced in the examples and comparative examples were applied to glassCoating the glass substrate to a thickness of 2.5 + -0.1 μm, and pre-baking the substrate at 30mJ/cm 2 The procedure of production example 5 was repeated except that light irradiation was performed at the exposure amount (365 nm standard) of (a) c, and then no separate heat treatment was performed, thereby producing a photocured film.
(3) Photocuring and thermocuring (30 mJ/cm) 2 Light irradiation and heat treatment at 85 ℃ for 2 hours
The same procedure as in the manufacturing example 5 was performed except that the curable resin compositions manufactured in the examples and comparative examples were coated on a glass substrate to a thickness of 2.5 ± 0.1 μm, thereby manufacturing a light-cured and heat-cured film.
Experimental example 5: evaluation of 1-NMP resistance based on physical Properties of cured film according to curing conditions
The thickness (T1) of the cured film manufactured in the manufacturing example 6 was measured separately in the same manner as in the experimental example 1, and the thickness (T2) of the cured film was measured after immersion in N-methyl-2-pyrrolidone (NMP) at 70 ℃ for 120 seconds.
The thickness change rate [ (T2/T1) × 100 (%) ] before and after the immersion of NMP was calculated from the thickness measured as described above, and the results thereof are shown in table 5 shown below according to the evaluation criteria shown below.
< evaluation criteria for NMP resistance >
Very high 98% or more
95% or more and 98% of deficiency
And (delta): more than 90% and 95% of the deficiency
X:90% of the deficiency
Experimental example 6: evaluation of physical Properties of cured film according to curing conditions 2-adhesion force
As in experimental example 2, the cured films produced in production example 6 were immersed in NMP aqueous solutions for 6 minutes, respectively, and then taken out. Then, the adhesion force was evaluated by a method of attaching a tape on the surface scribed with a cutter and peeling the tape according to the ASTM D-3359-08 standard test conditions, and the results thereof were represented in table 5 shown below according to the evaluation criteria.
After the liquid sample treatment, the degree of occurrence of peeling of the coating film in the Cutting/Tape test was classified into 0B to 5B by the standard test method, and 5B was judged to have the most excellent performance.
< evaluation criteria for adhesion force >
O5B (0% peeling)
Delta: 4B (0% over 5% peeled)
X:4B deficiency (peeling more than 5%)
[ Table 5]
The following facts can be confirmed with reference to said table 5: in the case of using the curable resin composition according to the present invention, a cured film having excellent chemical resistance and adhesion can be produced by photocuring and low-temperature thermal curing.
Claims (11)
1. A curable resin composition comprising an alkali-soluble resin, a thermosetting compound, a curing agent, a photopolymerizable compound and a photopolymerization initiator,
the curing agent comprises at least one selected from melamine curing agents and urea curing agents,
when the thickness of a cured film formed from the curable resin composition is 2.5. + -. 0.1. Mu.m, T2/T1 is 0.90 or more, where T1 is the thickness of the cured film, and T2 is the thickness of the cured film after immersion in N-methyl-2-pyrrolidone at 70 ℃ for 120 seconds.
2. The curable resin composition according to claim 1, wherein the melamine-based curing agent comprises a compound represented by the following chemical formula 1, the urea-based curing agent comprises at least one of compounds represented by the following chemical formulae 2-1 to 2-3,
[ chemical formula 1]
In the chemical formula 1, the reaction mixture is,
R 1 to R 6 Each independently of the others, is hydrogen, an alcohol group having 1 to 3 carbon atoms, or an ether group having 1 to 3 carbon atoms,
[ chemical formula 2-1]
In the chemical formula 2-1,
R 7 and R 10 Independently of one another, an alkoxy group having 1 to 3 carbon atoms or an ether group having 1 to 3 carbon atoms,
R 8 and R 9 Each independently of the others, is hydrogen or an alkoxy group having 1 to 3 carbon atoms,
[ chemical formula 2-2]
In the chemical formula 2-2,
R 11 and R 14 Each independently of the others, an alkoxy group having 1 to 3 carbon atoms,
R 12 and R 13 Each independently of the others, is hydrogen or an alkoxy group having 1 to 3 carbon atoms,
[ chemical formulas 2-3]
In the chemical formula 2-3,
R 15 to R 18 Each independently is an alkoxy group having 1 to 3 carbon atoms.
3. The curable resin composition according to claim 2, wherein the melamine-based curing agent comprises a compound represented by the following chemical formula 1-1, chemical formula 1-2, or chemical formula 1-3:
[ chemical formula 1-1]
[ chemical formulas 1-2]
[ chemical formulas 1-3]
4. The curable resin composition according to claim 2, wherein the urea-based curing agent comprises a compound represented by the following chemical formula 2-1-1, chemical formula 2-1-2, chemical formula 2-2-1, or chemical formula 2-3-1:
[ chemical formula 2-1-1]
[ chemical formula 2-1-2]
[ chemical formula 2-2-1]
[ chemical formula 2-3-1]
5. The curable resin composition according to claim 1, wherein the alkali-soluble resin comprises at least one selected from a photocurable alkali-soluble resin and a thermally curable alkali-soluble resin.
6. The curable resin composition according to claim 1, wherein the thermosetting compound comprises a polyfunctional epoxy oligomer.
7. The curable resin composition according to claim 1, wherein the photopolymerizable compound comprises a photopolymerizable unsaturated monomer.
8. The curable resin composition according to claim 1, further comprising at least one selected from a thiol compound, an additive and a solvent.
9. A pattern formed from the curable resin composition according to any one of claims 1 to 8.
10. The pattern of claim 9, wherein the pattern is selected from the group consisting of an array planarization film pattern, a protective film pattern, an insulating film pattern, a photoresist pattern, a black matrix pattern, a column spacer pattern, and a black column spacer.
11. An image display device comprising the pattern of claim 9.
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| CN202110823867.7A CN115685679A (en) | 2021-07-21 | 2021-07-21 | Curable resin composition, pattern, and image display device |
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| Country | Link |
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