CN110412830B - Photosensitive resin composition, photocured pattern and image display device - Google Patents
Photosensitive resin composition, photocured pattern and image display device Download PDFInfo
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- CN110412830B CN110412830B CN201810394820.1A CN201810394820A CN110412830B CN 110412830 B CN110412830 B CN 110412830B CN 201810394820 A CN201810394820 A CN 201810394820A CN 110412830 B CN110412830 B CN 110412830B
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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
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
Abstract
The present invention relates to a photosensitive resin composition, a photocured pattern and an image display device, and more particularly, to the following photosensitive resin composition: by containing an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, and further containing a compound having a specific structure, a photocurable pattern can be formed which is excellent in reactivity and excellent in degree of curing even at low temperatures, and which is excellent in adhesion to a substrate and durability at the time of curing, and which can ensure excellent stability over time.
Description
Technical Field
The present invention relates to a photosensitive resin composition, a photocured pattern produced from the composition, and an image display device provided with the photocured pattern.
Background
In the field of displays, photosensitive resin compositions are used for forming various photocurable patterns such as photoresists, insulating films, protective films, black matrices, column spacers (column spacers), and the like. Specifically, a photosensitive resin composition having high sensitivity is required in order to form a desired photocurable pattern by selectively exposing and developing the photosensitive resin composition through a photolithography step, and in this process, to improve the yield in the step and to improve the physical properties of the application target.
Patterning of the photosensitive resin composition is based on a polarity change and a crosslinking reaction of a polymer due to photolithography, that is, a photoreaction. In particular, the change in solubility to a solvent such as an aqueous alkaline solution after exposure is utilized.
Patterning of the photosensitive resin composition is classified into positive type and negative type according to the solubility of the photosensitive portion to development. Positive photoresist is a pattern formed by dissolving an exposed portion in a developer, negative photoresist is a pattern formed by dissolving an unexposed portion without dissolving the exposed portion in the developer, and binder resins, crosslinking agents, and the like used for the positive and negative resists are different from each other.
In recent years, the use of touch screens provided with touch panels has increased dramatically, and flexible touch screens have recently received much attention. Therefore, materials used for various substrates used for touch panels are required to have flexible properties, and therefore, usable materials are limited to flexible polymer materials, and the manufacturing process is required to be performed under more mild conditions.
Accordingly, the curing conditions for the photosensitive resin composition also need to be changed from conventional high-temperature curing to low-temperature curing, but low-temperature curing has a problem that the reactivity is lowered and the durability of the formed pattern is lowered.
Korean registered patent No. 10-1302508 discloses a negative type photosensitive resin composition comprising a copolymer polymerized using a cyclohexene acrylate-based monomer, but has a limitation in satisfying required durability under low temperature curing conditions.
Documents of the prior art
Patent documents: korean registered patent No. 10-1302508
Disclosure of Invention
Problems to be solved
The purpose of the present invention is to provide a photosensitive resin composition which has excellent reactivity and excellent curing degree even at low temperatures, has excellent adhesion to a substrate and durability during curing, and can ensure excellent stability over time.
Another object of the present invention is to provide a photocurable pattern produced from the photosensitive resin composition and an image display device including the photocurable pattern.
Means for solving the problems
1. A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a solvent, further comprising a compound represented by the following chemical formula 1,
[ chemical formula 1]
(in the formula, R 1 And R 2 Each independently an alkylene group having 1 to 8 carbon atoms, R 3 And R 4 Each independently is an alkyl group having 1 to 8 carbon atoms, R 5 And R 6 Each independently hydrogen or methyl, and n is an integer from 1 to 3).
2. The photosensitive resin composition as described in 1 above, further comprising a compound represented by the following chemical formula 2,
[ chemical formula 2]
(in the formula, R 7 Is an alkylene group of 1 to 5 carbon atoms, R 8 、R 9 And R 10 Each independently an alkyl group having 1 to 8 carbon atoms).
3. The photosensitive resin composition of 2 includes 30 to 100 parts by weight of the compound of formula 2, based on 100 parts by weight of the compound of formula 1.
4. The photosensitive resin composition of 1, based on the photosensitive resin composition of 100 weight portions of solid content as the standard, contains the chemical formula 1 compounds 0.1 ~ 1.5 weight portions.
5. The photosensitive resin composition according to 1, wherein the alkali-soluble resin comprises at least one of a repeating unit represented by the following chemical formula 3 and a repeating unit represented by the following chemical formula 4,
[ chemical formula 3]
(in the formula, R 11 Is an alkylene group of 1 to 5 carbon atoms, R 12 Is hydrogen or alkyl of 1 to 8 carbon atoms, R 13 Is hydrogen or methyl)
[ chemical formula 4]
(in the formula, R 14 And R 15 Each independently hydrogen or methyl).
6. The photosensitive resin composition according to the above 5, wherein the alkali-soluble resin comprises 20 to 90 mol% of at least one of the repeating unit represented by the above chemical formula 3 and the repeating unit represented by the above chemical formula 4 based on 100 mol% of the alkali-soluble resin.
7. The photosensitive resin composition according to claim 5, wherein the alkali-soluble resin contains the repeating unit represented by chemical formula 3 and the repeating unit represented by chemical formula 4 at a molar ratio of 20.
8. The photosensitive resin composition according to claim 1, comprising 10 to 70 parts by weight of the alkali-soluble resin based on 100 parts by weight of the solid content of the photosensitive resin composition.
9. The photosensitive resin composition according to 1, which is curable at a low temperature of 70 to 100 ℃.
10. A photocurable pattern produced from the photosensitive resin composition according to any one of the above 1 to 9.
11. The photo-curing pattern according to claim 10, wherein the photo-curing 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, and a spacer pattern.
12. An image display device comprising the photocurable pattern of item 10 above.
Effects of the invention
The photosensitive resin composition of the present invention has excellent reactivity and excellent degree of curing even at low temperatures, has excellent adhesion to a substrate and durability during curing, and can form a photocured pattern capable of ensuring excellent stability over time.
Therefore, the photosensitive resin composition of the present invention can be effectively applied to the formation of a photocured pattern and the production of an image display device.
Detailed Description
The present invention relates to a photosensitive resin composition, and more particularly, to a photosensitive resin composition comprising: by including the alkali-soluble resin, the polymerizable compound, the photopolymerization initiator, and the solvent, and further including the compound represented by chemical formula 1, it is possible to form a photocured pattern that is excellent in reactivity and curing degree even at low temperature, and is excellent in adhesion to a substrate and durability at the time of curing, and can secure excellent stability over time.
The present invention will be described in detail below.
<Photosensitive resin composition>
The photosensitive resin composition of the present invention includes an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, a solvent, and further includes a compound represented by the following chemical formula 1.
Siloxane compound
The photosensitive resin composition of the present invention comprises a compound represented by the following chemical formula 1. The photosensitive resin composition of the present invention comprises the compound represented by the above chemical formula 1, and the functional group contained in the compound reacts with the substrate or the alkali-soluble resin, so that the photosensitive resin composition has excellent curing degree even at low temperature, excellent adhesion force with the substrate during curing, and improved reactivity with the alkali-soluble resin described later.
[ chemical formula 1]
In the above chemical formula 1, R 1 And R 2 Each independently an alkylene group having 1 to 8 carbon atoms, R 3 And R 4 Each independently an alkyl group having 1 to 8 carbon atoms, R 5 And R 6 Each independently hydrogen or methyl, and n is an integer from 1 to 3. Preferably, the above R is one which maintains the hydrophobicity of the alkyl group or the alkylene group as appropriate to improve the adhesion to the substrate or the reactivity of the alkali-soluble resin during curing 1 And R 2 Each independently may be an alkylene group having 1 to 5 carbon atoms, R 3 And R 4 Each independently may be an alkyl group having 1 to 5 carbon atoms, R 5 And R 6 May be hydrogen.
The term "alkyl" as used in the present specification includes straight-chain or branched-chain alkyl, and "alkylene" includes straight-chain or branched-chain alkylene.
The photosensitive resin composition of the present invention may further include a compound represented by the following chemical formula 2. The compound represented by the following chemical formula 2 can further improve the reactivity of the photosensitive resin composition of the present invention together with the compound represented by the above chemical formula 1, and further increase the adhesion to a substrate and chemical resistance at the time of curing.
[ chemical formula 2]
In the above chemical formula 2, R 7 Is alkylene of 1 to 5 carbon atoms, R 8 、R 9 And R 10 Each independently an alkyl group having 1 to 8 carbon atoms. Preferably, the first and second electrodes are formed of a metal, R is a group which improves the reactivity of the photosensitive resin composition by appropriately maintaining the hydrophobicity of the alkyl group or the alkylene group and improves the adhesion to the substrate at the time of curing 7 May be an alkylene group having 1 to 3 carbon atoms, R 8 、R 9 And R 10 Each independently may be an alkyl group having 1 to 5 carbon atoms.
In one embodiment, the photosensitive resin composition of the present invention may include 30 to 100 parts by weight of the compound represented by chemical formula 2, based on 100 parts by weight of the compound represented by chemical formula 1. When within the above range, the reactivity with the alkali-soluble resin and the substrate can be further increased.
The content of the compound represented by chemical formula 1 of the present invention is not particularly limited, and for example, the compound represented by chemical formula 1 may be contained in an amount of 0.1 to 1.5 parts by weight based on 100 parts by weight of the solid content of the photosensitive resin composition. When the content is less than 0.1 part by weight, reactivity with the alkali-soluble resin and adhesion to the substrate during curing of the photosensitive resin composition may be slightly improved, and when the content exceeds 1.5 parts by weight, the compound represented by the above chemical formula 1 that does not react with the substrate or the alkali-soluble resin remains, which is not preferable.
Alkali soluble resin
The alkali-soluble resin contained in the photosensitive resin composition of the present invention is a component that imparts solubility to an alkali developer used in a development treatment step and can form a coating film by imparting adhesion to a substrate. For example, the alkali-soluble resin can function as a binder resin of the photosensitive resin composition. The alkali-soluble resin has reactivity by the action of light or heat and has alkali solubility.
The alkali-soluble resin of the present invention can be used without limitation as long as it is an alkali-soluble resin used in a photosensitive resin composition in the art. For example, the alkali-soluble resin may include at least one of a repeating unit represented by the following chemical formula 3 and a repeating unit represented by the following chemical formula 4.
[ chemical formula 3]
(in the formula, R 11 Is alkylene of 1 to 5 carbon atoms, R 12 Is hydrogen or alkyl of 1 to 8 carbon atoms, R 13 Is hydrogen or methyl)
[ chemical formula 4]
(wherein R is 14 And R 15 Each independently hydrogen or methyl).
By including at least one of the repeating unit represented by the above chemical formula 3 and the repeating unit represented by the above chemical formula 4, the reactivity can be further improved when the thermal process, the exposure process, and the development process are performed after the photosensitive resin composition is applied, and the degree of curing can be further improved also in the low-temperature process.
In one embodiment, the content of at least one of the repeating unit represented by chemical formula 3 and the repeating unit represented by chemical formula 4 in the present invention is not particularly limited, and may be preferably 20 to 90 mol%, and more preferably 40 to 80 mol%, based on 100 mol% of the alkali-soluble resin. When the content is within the above range, a photosensitive resin composition having improved adhesion to a substrate during curing and capable of realizing a photocured pattern having excellent mechanical properties can be obtained.
In one embodiment, the alkali-soluble resin of the present invention may include both the repeating unit represented by the above chemical formula 3 and the repeating unit represented by the above chemical formula 4 in order to further improve the curing degree at low temperature and the reactivity of the photosensitive resin composition. Preferably, the alkali-soluble resin of the present invention may include the repeating unit represented by the above chemical formula 3 and the repeating unit represented by the above chemical formula 4 at a molar ratio of 20 to 80.
In one embodiment, the alkali-soluble resin of the present invention may further include a repeating unit formed of other monomers known in the art, in addition to the above repeating unit.
For example, in order to ensure alkali solubility, the alkali-soluble resin of the present invention may further comprise a repeating unit containing a carboxylic acid group. The repeating unit containing a carboxylic acid group may be formed using a monomer known in the art without limitation, for example, the repeating unit containing a carboxylic acid group may be a structure derived from a monomer selected from the group consisting of an unsaturated monocarboxylic acid, or a polycarboxylic acid having 2 or more carboxylic groups in the molecule, such as an unsaturated dicarboxylic acid or an unsaturated tricarboxylic acid.
Examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, and the like. Examples of the unsaturated polycarboxylic acid include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid. The polycarboxylic acid may be an acid anhydride, and examples of the unsaturated polycarboxylic acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride. The unsaturated polycarboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, and examples thereof include mono (2-acryloyloxyethyl) succinate, mono (2-methacryloyloxyethyl) succinate, mono (2-acryloyloxyethyl) phthalate, and mono (2-methacryloyloxyethyl) phthalate. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of a dicarboxylic polymer at both ends thereof, and examples thereof include ω -carboxy polycaprolactone monoacrylate, ω -carboxy polycaprolactone monomethacrylate and the like. The unsaturated polycarboxylic acid may be an unsaturated acrylate containing a hydroxyl group and a carboxyl group in the same molecule, and examples thereof include α - (hydroxymethyl) acrylate. Among them, acrylic acid, methacrylic acid, maleic anhydride, and the like are preferably used in view of high copolymerization reactivity.
In addition, in order to impart a photo/thermal curing property to the alkali-soluble resin, the alkali-soluble resin of the present invention may further include a repeating unit including an acrylate group. The repeating unit containing an acrylate group may be formed using a monomer known in the art without particular limitation, and for example, may be a structure derived from a monomer selected from unsubstituted or substituted alkyl ester compounds of unsaturated carboxylic acids such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy-o-phenylphenol propyl acrylate, aminoethyl (meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, cycloheptyl (meth) acrylate, cyclooctyl (meth) acrylate, menthyl (meth) acrylate, cyclopentenyl (meth) acrylate, cyclohexenyl (meth) acrylate, cycloheptenyl (meth) acrylate, cyclooctenyl (meth) acrylate, menthylene (meth) acrylate, isobornyl (meth) acrylate, pinanyl (meth) acrylate, adamantyl (meth) acrylate, norbornyl (meth) acrylate, pinenyl (meth) acrylate, tricyclo [ 5.0.1.0.0.0.1.0.0.0.0.1 2,6 ]Decyl ester, 3, 4-epoxy tricyclo (meth) acrylate [5.2.1.0 ] 2,6 ]Decyl esters and the like containing alicyclic substituentsUnsaturated carboxylic acid ester compounds containing a substituent having an aromatic ring such as benzyl (meth) acrylate, phenoxy (meth) acrylate, styrene, aromatic vinyl compounds such as α -methylstyrene and vinyltoluene, vinyl carboxylates such as vinyl acetate and vinyl propionate, vinyl cyanide compounds such as (meth) acrylonitrile and α -chloroacrylonitrile, maleimide compounds such as N-cyclohexylmaleimide and N-phenylmaleimide, and unsaturated alicyclic compounds such as norbornene.
In the present specification, "(meth) acrylic-" means "methacrylic-", "acrylic-" or both of them.
For example, the alkali-soluble resin of the present invention may include at least one of the resins represented by the following chemical formulas 5 to 7.
[ chemical formula 5]
(wherein a, b, c and d represent molar ratios, a represents 5 to 30 mol%, b represents 20 to 70 mol%, c represents 5 to 30 mol%, and d represents 20 to 60 mol%)
[ chemical formula 6]
(wherein a, b and c represent a molar ratio, a is 20 to 70 mol%, b is 20 to 60 mol%, and c is 5 to 30 mol%)
[ chemical formula 7]
(wherein a, b, c and d represent molar ratios, a represents 20 to 70 mol%, b represents 3 to 30 mol%, c represents 5 to 30 mol%, and d represents 5 to 60 mol%)
When at least one of the resins represented by chemical formulas 5 to 7 is contained, a photosensitive resin composition having excellent alkali solubility and developability during curing can be obtained in addition to the above advantages.
In the resins represented by chemical formulas 5 to 7, each repeating unit shown in parentheses may be freely located at any position in the chain within a predetermined mol% range. That is, each bracket of the above chemical formulas 5 to 7 is represented by one segment (block) for expressing mol%, but each repeating unit may be arranged in a segment or separately without limitation as long as it is in the corresponding resin.
The content of the alkali-soluble resin is not particularly limited, and may be appropriately adjusted in consideration of the resolution and pattern uniformity of the photocured pattern formed therefrom. In one embodiment, the alkali-soluble resin may be contained in an amount ranging from 10 to 70 parts by weight based on 100 parts by weight of the solid content of the photosensitive resin composition. When the content is within the above range, the solubility in the developer is sufficient, the developability is excellent, and a photocurable pattern having excellent mechanical properties can be formed.
The weight average molecular weight of the alkali-soluble resin of the present invention is not particularly limited, but may be 6,000 to 20,000, preferably 7,500 to 18,000, and more preferably 13,000 to 17,000, in terms of improving reactivity under low temperature conditions and improving chemical resistance of the photosensitive resin composition. When the above range is satisfied, a pattern having excellent resolution can be formed with a CD Bias (CD-Bias) of the pattern in an appropriate range, and chemical resistance and pencil hardness can also be improved. On the other hand, in the case where the weight average molecular weight of the alkali-soluble resin exceeds 20,000, the molecular weight becomes excessively large, compatibility with other components of the photosensitive resin composition is decreased, whitening of a coating film may occur in a developing step, and a line width of a pattern is also increased, and CD bias characteristics may be decreased.
Polymerizable compound
The polymerizable compound contained in the photosensitive resin composition of the present invention can increase the crosslinking density in the production process and enhance the mechanical properties of the photocured pattern.
The polymerizable compound may be any one used in the art, for example, a monofunctional monomer, a difunctional monomer, and a polyfunctional monomer, and the kind thereof is not particularly limited, and examples thereof include the following compounds.
Specific examples of the monofunctional monomer include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrrolidone. Specific examples of the bifunctional monomer include 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 monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaerythritol hexa (meth) acrylate, and the like. Among them, a polyfunctional monomer having two or more functions is preferably used.
The content of the polymerizable compound is not particularly limited, and is, for example, 10 to 90 parts by weight, preferably 30 to 80 parts by weight, based on 100 parts by weight of the alkali-soluble resin in the photosensitive resin composition as a solid content. When the polymerizable compound is contained in the above content range, the composition can have excellent durability and the developability of the composition can be improved.
Photopolymerization initiator
The photopolymerization initiator of the present invention is not particularly limited in kind as long as it can polymerize the polymerizable compound, and for example, at least one compound selected from the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, thioxanthone-based compounds, and oxime ester-based compounds, preferably oxime ester-based compounds, can be used.
In order to improve the sensitivity of the photosensitive resin composition of the present invention, the photopolymerization initiator may further contain a photopolymerization initiation aid. The photosensitive resin composition of the present invention contains a photopolymerization initiation aid, and thus can improve sensitivity and productivity.
Examples of the photopolymerization initiation aid include at least one compound selected from the group consisting of amine compounds, carboxylic acid compounds, and organic sulfur compounds having a mercapto group.
The content of the photopolymerization initiator is not particularly limited, and may be, for example, 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, based on the solid content, based on 100 parts by weight of the entire photosensitive resin composition. When the above range is satisfied, the photosensitive resin composition is preferably used in order to increase the sensitivity and shorten the exposure time, thereby improving productivity, maintaining high resolution, and improving the intensity of the formed pixel portion and the smoothness of the surface of the pixel portion.
Solvent(s)
Any solvent can be used without limitation as long as it is a solvent generally used in the art.
Specific examples of the solvent include ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, ethylene glycol alkyl ether acetates, alkylene glycol alkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol alkyl ether propionates, butylene glycol monoalkyl ethers, butylene glycol monoalkyl ether acetates, butylene glycol monoalkyl ether propionates, dipropylene glycol dialkyl ethers, aromatic hydrocarbons, ketones, alcohols, esters, cyclic esters, and the like. The solvents exemplified herein may be used each alone or in combination of two or more.
In view of coatability and drying properties, the above solvents are preferably alkylene glycol alkyl ether acetates, ketones, butylene glycol alkyl ether acetates, butylene glycol monoalkyl ethers, and esters, and more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like.
The content of the solvent may be 40 to 95 parts by weight, preferably 45 to 85 parts by weight, based on 100 parts by weight of the entire photosensitive resin composition. When the above range is satisfied, the coating properties are preferably improved when the coating is performed by a coating apparatus such as a spin coater, a slit coater (also referred to as a die coater or a curtain coater), or a spray coater.
Additive agent
The photosensitive resin composition of the present invention may further contain additives such as a filler, other high molecular compound, a leveling agent, an adhesion promoter, an antioxidant, an ultraviolet absorber, an anticoagulant, and a chain transfer agent, as needed.
<Photo-curing pattern and image display device>
The present invention aims to provide a photocured pattern produced from the photosensitive resin composition and an image display device comprising the photocured pattern.
The photocurable pattern produced from the photosensitive resin composition of the present invention is excellent in low-temperature curability, and for example, the temperature for heat curing (prebaking and/or postbaking) of the photosensitive resin composition of the present invention may be 70 to 100 ℃. In addition, the photo-cured pattern produced from the photosensitive resin composition of the present invention is excellent in adhesion, chemical resistance, heat resistance and the like even after curing at low temperature, and is excellent in stability over time.
Thus, the present invention can be used as various patterns in an image display device, for example, an adhesive layer, an array planarization film, a protective film, an insulating film pattern, and the like, and can also be used as a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, and the like.
As an image display device including such a photo-curing pattern or using the pattern in a manufacturing process, there are an image display device including a touch panel, a liquid crystal display device, an OLED, a flexible display, and the like, but the invention is not limited thereto, and any image display device known in the art can be exemplified.
The photocurable pattern can be produced by applying the photosensitive resin composition of the present invention to a substrate and forming a photocurable pattern (after a development step if necessary).
Hereinafter, preferred embodiments are disclosed to aid understanding of the present invention, but these embodiments are merely illustrative of the present invention and do not limit the scope of the appended claims, and various changes and modifications of the embodiments within the scope and technical spirit of the present invention will be apparent to those skilled in the art, and such changes and modifications also fall within the scope of the appended claims.
<Production example>
Production example 1: production of alkali-soluble resin (A-1)
In a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer, 250g of propylene glycol monomethyl ether acetate was introduced by introducing nitrogen gas at 0.02L/min to form a nitrogen atmosphere, and after raising the temperature to 100 ℃ after 2 hours, a solution prepared by adding 3.6g of 2,2' -azobis (2, 4-dimethylvaleronitrile) to a mixture comprising 32.4g (0.45 mol) of acrylic acid, 82.9g (0.45 mol) of (3-ethyl-3-oxetanyl) methyl methacrylate, 11.8g (0.10 mol) of vinyltoluene and 150g of propylene glycol monomethyl ether acetate was dropped from the dropping funnel into the flask and further stirred at 100 ℃ for 5 hours.
Subsequently, 49.8g of glycidyl methacrylate (0.35 mol (% by mol) was introduced into the flask under a nitrogen atmosphere in the flask, based on the acrylic acid used in the reaction), and the reaction was continued at 110 ℃ for 6 hours to obtain an unsaturated group-containing resin A-1 having a solid content of an acid value of 44 mg KOH/g (see chemical formula 5). The weight-average molecular weight in terms of polystyrene measured by GPC was 17,500, and the molecular weight distribution (Mw/Mn) was 2.20.
In this case, the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the dispersion resin were measured using an HLC-8120GPC (manufactured by Tosoh Co., ltd.), a column in which TSK-GELG4000HXL and TSK-GELG2000HXL were connected in series was used as the column, the column temperature was 40 ℃, the flow rate of a mobile phase solvent, tetrahydrofuran, was 1.0 ml/min, the injection amount was 50. Mu.l, RI was used as the detector, the measurement sample concentration was 0.6 mass% (solvent = tetrahydrofuran), and TSK standard polystyrenes F-40, F-4, F-1, A-2500, and A-500 (manufactured by Tosoh Co., ltd.) were used as calibration standard substances.
The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as the molecular weight distribution (Mw/Mn).
Production example 2: alkali soluble resin (A-2)
In a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at 0.02L/min to form a nitrogen atmosphere, 150g of diethylene glycol methyl ethyl ether was added, and the mixture was heated to 70 ℃ with stirring. Subsequently, 132.2g (0.60 mol), 55.3g (0.30 mol) of (3-ethyl-3-oxetanyl) methyl methacrylate, and 8.6g (0.10 mol) of methacrylic acid, which are a mixture of the following chemical formulae 8 and 9 (molar ratio is 50), were dissolved in 150g of diethylene glycol methyl ethyl ether to prepare a solvent.
After the prepared solution was dropped into the flask using a dropping funnel, a solution prepared by dissolving a polymerization initiator, 2' -azobis (2, 4-dimethylvaleronitrile), 27.9g (0.11 mol), in 200g of diethylene glycol monoethyl ether was dropped into the flask over a period of 4 hours using another dropping funnel. After the completion of the dropwise addition of the polymerization initiator solution, the reaction mixture was maintained at 70 ℃ for 4 hours, and then cooled to room temperature, whereby a solution of a copolymer A-2 (see the above chemical formula 6) having a solid content of 41.8% by mass and an acid value of 62mg-KOH/g (in terms of solid content) was obtained, and the weight-average molecular weight Mw was 8,000 and the molecular weight distribution was 1.82.
Production example 3: production of alkali-soluble resin (A-3)
In a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen gas was introduced at 0.02L/min to form a nitrogen atmosphere, 200g of propylene glycol monomethyl ether acetate was introduced, the temperature was raised to 100 ℃ and then, over 2 hours, a solution prepared by adding 3.6g of 2,2' -azobis (2, 4-dimethylvaleronitrile) to a mixture comprising 24.5g (0.34 mol) of acrylic acid, 4.7g (0.05 mol) of norbornene, 72.1g (0.61 mol) of vinyltoluene and 150g of propylene glycol monomethyl ether acetate was dropped from the dropping funnel into the flask, and the mixture was further stirred at 100 ℃ for 5 hours.
Subsequently, 28.4g of glycidyl methacrylate (0.20 mol%), [ 59 mol% relative to acrylic acid used in the present reaction ], was introduced into the flask under the atmosphere of nitrogen gas in the flask, and the reaction was continued at 110 ℃ for 6 hours to obtain a solid mg KOH/g unsaturated group-containing resin a-3 (see chemical formula 7). The weight average molecular weight in terms of polystyrene measured by GPC was 14,500, and the molecular weight distribution (Mw/Mn) was 2.1.
<Examples and comparative examples>
Photosensitive resin compositions of examples and comparative examples were prepared according to the compositions (parts by weight) described in table 1 below.
[ Table 1]
<Examples of the experiments>
A glass substrate (Eagle 2000, manufactured by Corning corporation) having a length and a width of 2 inches was washed with a neutral detergent, water and ethanol in this order and then dried. The photosensitive resin compositions produced in the examples and comparative examples were spin-coated on the glass substrate, and then baked at 80 ℃ for 120 seconds using a Hot plate (Hot plate). After the substrate after the pre-baking was cooled to room temperature, the substrate was spaced from a quartz glass photomask150 μm using an exposure machine (UX-1100 SM, manufactured by Nippon tailstocks) at 60mJ/cm 2 The exposure amount (365 nm standard) of (1) is irradiated with light.
After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 2.38% of TMAH at 25 ℃ for 60 seconds to develop, washed with water, and then postbaked in an oven at 90 ℃ for 1 hour. The physical property evaluation was performed on the pattern thus obtained as follows, and the results thereof are shown in table 2 below.
1. Evaluation of chemical resistance
The coating films of examples and comparative examples, which were heated at 90 ℃ for 1 hour to pass through the curing step, were immersed in an etchant solution for acid resistance evaluation at 50 ℃ (MA-S02, eastern fine chemical industry) or a stripping agent for stripping resistance evaluation at 50 ℃ (SAM-19, eastern fine chemical industry) for 10 minutes, respectively. The change in thickness when the solution was left to stand was observed, and chemical resistance was evaluated according to the following equation 1, and the evaluation criteria were as follows.
[ mathematical formula 1]
Thickness change rate = { (coating film thickness before solution treatment-coating film thickness after solution treatment)/(coating film thickness before solution treatment) } X100
O: the thickness change rate is less than 5%
And (delta): the thickness change rate is more than 5% and less than 10%
X: the thickness change rate is more than 10 percent
2. Evaluation of adhesion
The coating films of examples and comparative examples, which were heated at 90 ℃ for 1 hour to pass through the curing step, were immersed in an etchant solution for acid resistance evaluation at 50 ℃ (MA-S02, eastern fine chemical industry) or a stripping agent for stripping resistance evaluation at 50 ℃ (SAM-19, eastern fine chemical industry) for 2 minutes, respectively. Then, the adhesion was confirmed by a method of peeling off a surface adhesive Tape (Tape) cut (cut) with a cutter under the ASTM D-3359-08 standard test conditions. The evaluation criteria are as follows.
5B: 0% of peeling
4B: peeling is less than 5%
3B: peeling is more than 5 percent and less than 15 percent
2B: stripping rate is more than 15% and less than 35%
1B: the peeling rate is more than 35 percent and less than 65 percent
0B: stripping rate is above 65%
3. Evaluation of stability with time
The change rate between the development residual film rate after storing the coating films of each example and comparative example at 23 ℃ for 4 weeks and the development residual film rate before storage was calculated to evaluate the stability with time. The developing residual film ratio was calculated by the following equation 2, and the change rate of the developing residual film ratio was calculated by the following equation 3, and the evaluation criteria were as follows.
[ mathematical formula 2]
Development residual film rate (%) = (film thickness after postbake)/(film thickness after exposure) X100
[ mathematical formula 3]
Rate of change in developed residual film rate (%) = (developed residual film rate before storage-developed residual film rate after storage for 4 weeks)/developed residual film rate before storage X100
O: the rate of change of the developing film retention rate is 1% or less
And (delta): the rate of change of the development film retention rate is more than 1% and 10% or less
X: the change rate of the developing film retention rate exceeds 10 percent
[ Table 2]
Referring to table 2 above, it can be confirmed that the patterns of the examples of the present invention have excellent properties in chemical resistance, adhesion, and stability over time even at low temperature curing. However, the patterns according to the comparative examples were inferior in chemical resistance, adhesion, and the like, and the film retention rate after post-baking and before-baking were greatly changed, resulting in poor stability with time.
Claims (11)
1. A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a solvent, further comprising a compound represented by the following chemical formula 1,
the photosensitive resin composition comprises 0.1 to 1.5 parts by weight of a compound represented by the following chemical formula 1 based on 100 parts by weight of solid content of the photosensitive resin composition,
chemical formula 1
In the formula, R 1 And R 2 Each independently an alkylene group having 1 to 8 carbon atoms, R 3 And R 4 Each independently is an alkyl group having 1 to 8 carbon atoms, R 5 And R 6 Each independently hydrogen or methyl, and n is an integer from 1 to 3.
2. The photosensitive resin composition according to claim 1, further comprising a compound represented by the following chemical formula 2,
chemical formula 2
In the formula, R 7 Is alkylene of 1 to 5 carbon atoms, R 8 、R 9 And R 10 Each independently is an alkyl group having 1 to 8 carbon atoms.
3. The photosensitive resin composition according to claim 2, comprising 30 to 100 parts by weight of the compound represented by chemical formula 2, based on 100 parts by weight of the compound represented by chemical formula 1.
4. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin comprises at least one of a repeating unit represented by the following chemical formula 3 and a repeating unit represented by the following chemical formula 4,
chemical formula 3
In the formula, R 11 Is alkylene of 1 to 5 carbon atoms, R 12 Is hydrogen or alkyl of 1 to 8 carbon atoms, R 13 Is hydrogen or a methyl group,
chemical formula 4
In the formula, R 14 And R 15 Each independently hydrogen or methyl.
5. The photosensitive resin composition according to claim 4, wherein the alkali-soluble resin comprises 20 to 90 mol% of at least one of the repeating unit represented by chemical formula 3 and the repeating unit represented by chemical formula 4, based on 100 mol% of the alkali-soluble resin.
6. The photosensitive resin composition according to claim 4, wherein the alkali-soluble resin comprises the repeating unit represented by chemical formula 3 and the repeating unit represented by chemical formula 4 at a molar ratio of 20 to 80.
7. The photosensitive resin composition according to claim 1, comprising 10 to 70 parts by weight of the alkali-soluble resin based on 100 parts by weight of a solid content of the photosensitive resin composition.
8. The photosensitive resin composition according to claim 1, which is curable at a low temperature of 70 to 100 ℃.
9. A photocurable pattern produced from the photosensitive resin composition according to any one of claims 1 to 8.
10. The photo-curing pattern of claim 9, which is selected from the group consisting of an array planarization film pattern, a protection film pattern, an insulation film pattern, a photoresist pattern, a black matrix pattern, and a spacer pattern.
11. An image display device provided with the photocured pattern of claim 9.
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Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6253995A (en) * | 1985-09-02 | 1987-03-09 | Toray Ind Inc | Dialkoxysilane containing unsaturated ester group in molecule |
| JPS62153295A (en) * | 1985-12-26 | 1987-07-08 | Toray Ind Inc | Propenyldialkoxysilane having unsaturated carboxylic acid ester group in molecule |
| JPH0517555A (en) * | 1991-07-16 | 1993-01-26 | Dainippon Ink & Chem Inc | Curable resin composition |
| US5520952A (en) * | 1993-07-16 | 1996-05-28 | Tokyo Ohka Kogyo Co., Ltd. | Method for forming a protective coating film on electronic parts and devices |
| JP2005213516A (en) * | 2005-03-23 | 2005-08-11 | Sekisui Chem Co Ltd | Surface treatment method of substrate |
| CN101630124A (en) * | 2008-07-17 | 2010-01-20 | Jsr株式会社 | Radiation-sensitive linear composition for forming coloured layer, colour filter and colour liquid crystal display device |
| JP2011203577A (en) * | 2010-03-26 | 2011-10-13 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| JP2012014930A (en) * | 2010-06-30 | 2012-01-19 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| JP2013042618A (en) * | 2011-08-18 | 2013-02-28 | Citizen Holdings Co Ltd | Insulating film formation kit of coil winding core and insulating film formation method using the same and clock |
| JP2013160825A (en) * | 2012-02-02 | 2013-08-19 | Sumitomo Chemical Co Ltd | Photosensitive resin composition |
| KR20160006095A (en) * | 2014-07-08 | 2016-01-18 | 솔브레인 주식회사 | Low-temperature curable resin composition for screen printing |
| CN105319850A (en) * | 2014-07-01 | 2016-02-10 | 东友精细化工有限公司 | Photonasty resin composition |
| CN105867069A (en) * | 2015-02-10 | 2016-08-17 | 东友精细化工有限公司 | Negative-type photosensitive resin composition, photocuring pattern formed by using the same and image display device |
| CN105938298A (en) * | 2015-03-05 | 2016-09-14 | 东友精细化工有限公司 | Negative-type photosensitive resin composition, photocuring pattern using the composition and image display device |
| CN105974733A (en) * | 2015-03-11 | 2016-09-28 | 东友精细化工有限公司 | Negative-type photosensitive resin composition, pattern formed by using the same and image display device |
| JP2016183252A (en) * | 2015-03-26 | 2016-10-20 | 三菱レイヨン株式会社 | Active energy ray curable resin composition and article |
| CN106662817A (en) * | 2014-06-20 | 2017-05-10 | 大阪有机化学工业株式会社 | Photosensitive composition and cured film of same |
| CN106970504A (en) * | 2016-01-14 | 2017-07-21 | 东友精细化工有限公司 | Photosensitive polymer combination, photocuring pattern and image display device |
| CN107272342A (en) * | 2016-03-30 | 2017-10-20 | 东友精细化工有限公司 | Negative-type photosensitive resin composition |
| CN107849198A (en) * | 2015-07-30 | 2018-03-27 | 三键有限公司 | Photocurable resin composition, fuel cell and encapsulating method |
-
2018
- 2018-04-27 CN CN201810394820.1A patent/CN110412830B/en active Active
Patent Citations (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6253995A (en) * | 1985-09-02 | 1987-03-09 | Toray Ind Inc | Dialkoxysilane containing unsaturated ester group in molecule |
| JPS62153295A (en) * | 1985-12-26 | 1987-07-08 | Toray Ind Inc | Propenyldialkoxysilane having unsaturated carboxylic acid ester group in molecule |
| JPH0517555A (en) * | 1991-07-16 | 1993-01-26 | Dainippon Ink & Chem Inc | Curable resin composition |
| US5520952A (en) * | 1993-07-16 | 1996-05-28 | Tokyo Ohka Kogyo Co., Ltd. | Method for forming a protective coating film on electronic parts and devices |
| JP2005213516A (en) * | 2005-03-23 | 2005-08-11 | Sekisui Chem Co Ltd | Surface treatment method of substrate |
| CN101630124A (en) * | 2008-07-17 | 2010-01-20 | Jsr株式会社 | Radiation-sensitive linear composition for forming coloured layer, colour filter and colour liquid crystal display device |
| JP2011203577A (en) * | 2010-03-26 | 2011-10-13 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| JP2012014930A (en) * | 2010-06-30 | 2012-01-19 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| JP2013042618A (en) * | 2011-08-18 | 2013-02-28 | Citizen Holdings Co Ltd | Insulating film formation kit of coil winding core and insulating film formation method using the same and clock |
| JP2013160825A (en) * | 2012-02-02 | 2013-08-19 | Sumitomo Chemical Co Ltd | Photosensitive resin composition |
| CN106662817A (en) * | 2014-06-20 | 2017-05-10 | 大阪有机化学工业株式会社 | Photosensitive composition and cured film of same |
| CN105319850A (en) * | 2014-07-01 | 2016-02-10 | 东友精细化工有限公司 | Photonasty resin composition |
| KR20160006095A (en) * | 2014-07-08 | 2016-01-18 | 솔브레인 주식회사 | Low-temperature curable resin composition for screen printing |
| CN105867069A (en) * | 2015-02-10 | 2016-08-17 | 东友精细化工有限公司 | Negative-type photosensitive resin composition, photocuring pattern formed by using the same and image display device |
| CN105938298A (en) * | 2015-03-05 | 2016-09-14 | 东友精细化工有限公司 | Negative-type photosensitive resin composition, photocuring pattern using the composition and image display device |
| CN105974733A (en) * | 2015-03-11 | 2016-09-28 | 东友精细化工有限公司 | Negative-type photosensitive resin composition, pattern formed by using the same and image display device |
| JP2016183252A (en) * | 2015-03-26 | 2016-10-20 | 三菱レイヨン株式会社 | Active energy ray curable resin composition and article |
| CN107849198A (en) * | 2015-07-30 | 2018-03-27 | 三键有限公司 | Photocurable resin composition, fuel cell and encapsulating method |
| CN106970504A (en) * | 2016-01-14 | 2017-07-21 | 东友精细化工有限公司 | Photosensitive polymer combination, photocuring pattern and image display device |
| CN107272342A (en) * | 2016-03-30 | 2017-10-20 | 东友精细化工有限公司 | Negative-type photosensitive resin composition |
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