CN107817652B - Photosensitive resin composition and photocured pattern produced therefrom - Google Patents
Photosensitive resin composition and photocured pattern produced therefrom Download PDFInfo
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- CN107817652B CN107817652B CN201710817026.9A CN201710817026A CN107817652B CN 107817652 B CN107817652 B CN 107817652B CN 201710817026 A CN201710817026 A CN 201710817026A CN 107817652 B CN107817652 B CN 107817652B
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
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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
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/133345—Insulating layers
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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
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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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
- G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
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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
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/86—Arrangements for improving contrast, e.g. preventing reflection of ambient light
- H10K50/865—Arrangements for improving contrast, e.g. preventing reflection of ambient light comprising light absorbing layers, e.g. light-blocking layers
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
- H10K59/10—OLED displays
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- Crystallography & Structural Chemistry (AREA)
- Materials For Photolithography (AREA)
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Abstract
The invention provides a photosensitive resin composition with improved chemical resistance and developability to a solvent and a photocured pattern manufactured by the photosensitive resin composition. The present invention relates to a photosensitive resin composition and a photocured pattern produced therefrom. More particularly, the present invention relates to a photosensitive resin composition and a photocured pattern manufactured therefrom, by which chemical resistance to a solvent and developability are simultaneously improved by including an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, wherein the polymerizable compound includes a compound represented by chemical formula 1 and a compound represented by chemical formula 2.
Description
Technical Field
The present invention relates to a photosensitive resin composition and a photocured pattern produced therefrom. More particularly, to a negative photosensitive resin composition having improved chemical properties and a photocurable pattern produced therefrom.
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, and columnar spacers. Specifically, in the process of forming a desired photocurable pattern by selectively exposing and developing a photosensitive resin composition through a photolithography process, a photosensitive resin composition having high sensitivity is required in order to improve the yield in the process and to improve the physical properties of the application object.
The patterning of the photosensitive resin composition is performed, for example, by a photolithography step including a polarity change of a high molecule due to photoreaction and a crosslinking reaction. After exposure, the change in solubility in a developer such as an aqueous alkali solution can be utilized.
The pattern component of the photosensitive resin composition is positive or negative depending on the solubility of the photosensitive part for development. A positive photoresist is a pattern formation method in which an exposed portion is dissolved in a developer, and a negative photoresist is a pattern formation method in which an exposed portion is not dissolved in a developer and an unexposed portion is dissolved. The positive type and the negative type are different from each other by a binder resin, a crosslinking agent, and the like used.
In recent years, the use of touch screens having touch panels has been increasing sharply, and recently flexible touch screens have received a great deal of attention. Thus, the material for various substrates used in touch panels has been required to have flexibility. Therefore, usable raw materials are limited to flexible polymer raw materials, and the production process is also required to be performed under relatively mild conditions.
Thus, the curing conditions for the photosensitive resin composition also need to be low-temperature curing rather than conventional high-temperature curing. However, low temperature curing has problems of reduced reactivity and reduced durability of the formed pattern.
Korean patent No. 1302508 discloses a photosensitive resin composition which contains a copolymer polymerized using a cyclohexene acrylate-based monomer, and thus has excellent heat resistance and light resistance and can improve the sensitivity. However, this composition does not satisfy the required durability under the conditions of low-temperature curing.
Documents of the prior art
Patent document
Patent document 1: korean patent No. 1302508
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a photosensitive resin composition which can be cured at low temperature, has excellent reactivity, and has excellent durability such as chemical resistance of a formed pattern.
Another object of the present invention is to provide a photosensitive resin composition having excellent patterning ability in a photolithography process.
Further, the present invention is directed to a photocurable pattern formed using the photosensitive resin composition.
Means for solving the problems
1. A photosensitive resin composition is characterized by comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a solvent, wherein the polymerizable compound comprises a compound represented by the following chemical formula 1 and a compound represented by the chemical formula 2.
(in chemical formula 1, R1And R2Each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, and m is an integer of 4 to 12. )
(in chemical formula 2, R3Is a C1-6 saturated hydrocarbon group or a saturated hydrocarbon group containing hetero atoms,
R4independently of each other, hydrogen, acryloxy, succinate or C1-5 linear or branched alkyl, R4Contains at least 2 acryloxy groups, and n is an integer of 3 to 8. )
2. The photosensitive resin composition of item 1, wherein R in the compound of chemical formula 11And R2Each independently hydrogen.
3. The photosensitive resin composition of item 1 above, wherein the compound of chemical formula 2 is represented by chemical formula 3 or 4 below.
4. The photosensitive resin composition of item 1, wherein the compound of chemical formula 1 is contained in an amount of 3 to 12 parts by weight based on 100 parts by weight of the total composition, and the compound of chemical formula 2 is contained in an amount of 3 to 15 parts by weight based on 100 parts by weight of the total composition.
5. The photosensitive resin composition of item 4 above, wherein the mixing ratio of the compound of chemical formula 1 to the compound of chemical formula 2 is 1: 4-3: 1.
6. the photosensitive resin composition of item 5 above, wherein the mixing ratio of the compound of chemical formula 1 to the compound of chemical formula 2 is 1: 2-1: 1.
7. the photosensitive resin composition of item 1 above, wherein the alkali-soluble resin comprises a binder resin represented by the following chemical formula 7.
(in chemical formula 7, a, b, c and d each represent a molar ratio, a is 5 to 50 mol%, b is 5 to 70 mol%, c is 10 to 70 mol%, and d is 5 to 70 mol%)
8. The photosensitive resin composition of item 1, wherein the alkali-soluble resin has a weight average molecular weight of 5000 to 35000.
9. A photocurable pattern produced from the photosensitive resin composition according to any one of the items 1 to 7.
10. The photocurable pattern of item 9 above, wherein the photocurable 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 columnar spacer pattern.
11. An image display device comprising the photocurable pattern according to item 9 above.
ADVANTAGEOUS EFFECTS OF INVENTION
When the photosensitive resin composition of the present invention is used, a photocurable film or a photocurable pattern having excellent adhesion to a substrate, chemical resistance and durability can be formed. In addition, the photocurable pattern can be formed with improved reactivity and developability. The photo-cured pattern has excellent chemical resistance and durability, and thus can be suitably used as various patterns of an image display device.
Drawings
Fig. 1a is an image showing evaluation criteria of developability according to an experimental example.
Fig. 1b is an image showing evaluation criteria of developability according to the experimental example.
Fig. 1c is an image showing evaluation criteria of developability according to the experimental example.
Fig. 2a is an image showing evaluation criteria of chemical resistance according to an experimental example.
Fig. 2b is an image showing evaluation criteria of chemical resistance according to an experimental example.
Fig. 2c is an image showing evaluation criteria of chemical resistance according to the experimental example.
Fig. 2d is an image showing evaluation criteria of chemical resistance according to an experimental example.
Fig. 2e is an image showing evaluation criteria of chemical resistance according to the experimental example.
Fig. 2f is an image showing evaluation criteria of chemical resistance according to the experimental example. .
Detailed Description
The present invention relates to a photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound having improved physical and chemical stability and improved reactivity such as developability by including compounds of chemical formula 1 and chemical formula 2 described later, a photopolymerization initiator, and a solvent.
The embodiments of the present invention are described in detail below. In the present specification, when a repeating unit, a compound, or a resin represented by each chemical formula has an isomer, the chemical formula representing the repeating unit, the compound, or the resin means a representative chemical formula including the isomer.
In the present invention, "(meth) acrylic" means "acrylic" or "methacrylic", or both.
In the present invention, each repeating unit should not be construed as being limited to the case shown, and can be freely present at any position of the chain within the range of defining mol% of the sub-repeating units in the bracket. That is, the parenthesis of each repeating unit is represented by one block in order to represent mol%, but each sub-repeating unit may be present as a block or may be present separately from each other without limitation as long as it is within the resin.
< photosensitive resin composition >
Polymerizable compound
The polymerizable compound used in the photosensitive resin composition according to the embodiment of the present invention is a compound that can be polymerized or crosslinked by the action of a photopolymerization initiator described later, and can increase the crosslinking density in the production process and enhance the mechanical properties of the photocured pattern.
The polymerizable compound includes a compound represented by the following chemical formula 1 and a compound represented by the chemical formula 2.
(in chemical formula 1, R is as defined above)1And R2Each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms,
the parentheses represent the repeating units in the main chain, and m is an integer of 4 to 12. )
(in chemical formula 2, R3Is a C1-6 saturated hydrocarbon group or a saturated hydrocarbon group containing hetero atoms,
R4independently of each other, hydrogen, an acryloyloxy group, a succinate group or a straight-chain or branched alkyl group having 1 to 5 carbon atoms, which contains at least 2 acryloyloxy groups, and n is an integer of 3 to 8. )
The polymerizable compound may include a mixture or blend (blend) of the compound of chemical formula 1 and the compound of chemical formula 2. By increasing chemical resistance such as solvent resistance after photocrosslinking, a photocurable pattern having improved adhesion to a substrate can be formed by the compound of chemical formula 1 having a large molecular weight or molecular size. In addition, by the carboxyl group-containing compound of chemical formula 2, reactivity such as developability is improved, and, for example, a hole pattern having a target size can be formed with high resolution.
In chemical formula 1, for example, R1And R2Each independently hydrogen. If m in chemical formula 1 is less than 4, the residual film ratio and chemical resistance may be lowered, and if it exceeds 12, the developability may be lowered. From this viewpoint, m may preferably be an integer of 4 to 10, and more preferably an integer of 4 to 8.
In the embodiment of the present invention, the compound of chemical formula 1 may be contained in an amount of 0.1 to 25 parts by weight based on 100 parts by weight of the total photosensitive resin composition. If the content of the compound of chemical formula 1 is less than 0.1 part by weight, the chemical resistance of a coating film formed from the composition is lowered, and a resist coating film having desired physical properties may not be formed. If the content of the compound of chemical formula 1 exceeds 25 parts by weight, the developability is significantly reduced, and a residual film may remain in the non-exposed region. The content of the compound of the above chemical formula 1 may preferably be 3 to 12 parts by weight if the above chemical resistance and developing property are considered together.
In chemical formula 2, R4Is through methylene (-CH)2-) and R3The n functional groups can be independently selected from hydrogen, acryloxy, succinate group or C1-5 straight-chain or branched alkyl.
R3For example, methylene, and the compound of the above chemical formula 2 may be represented by the following chemical formula 3.
R3For example, the compound of the above chemical formula 2 may be represented by the following chemical formula 4, represented by the following general formula 1 ("+" represents a bonding end).
In an embodiment of the present invention, the compound of chemical formula 2 may be contained in an amount of 3 to 50 parts by weight based on 100 parts by weight of the total photosensitive resin composition. If the content of the compound of chemical formula 2 is less than 3 parts by weight, the amount of the photopolymerizable monomer is insufficient, and development may not be efficiently performed, and a residual film may be generated in a non-exposed region, while if it exceeds 50 parts by weight, development of a coating film may be excessive, and chemical resistance may be excessively lowered. The content of the compound of the above chemical formula 2 may be preferably 3 to 40 parts by weight, and more preferably 3 to 15 parts by weight, if the above chemical resistance and developing property are considered together.
In one embodiment, the mixing ratio of the compound of chemical formula 1 to the compound of chemical formula 2 can be adjusted to about 1: 4 to about 3: 1, in the above range.
Within the above range of the mixing ratio, preferable chemical resistance and developability of a coating film or a photocured pattern formed from the photosensitive resin composition can be simultaneously achieved. From the viewpoint of simultaneously achieving chemical resistance and developability, it is preferable that the above mixing ratio can be adjusted to about 1: 2 to about 1: 1, in the above range.
The polymerizable compound may further contain a monofunctional monomer, a difunctional monomer, and another polyfunctional monomer.
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 dipentaerythritol hexa (meth) acrylate. Among them, a polyfunctional monomer having two or more functions is preferably used.
Alkali soluble resin
The alkali-soluble resin of the photosensitive resin composition according to the embodiment of the present invention is a component that can impart solubility to an alkali developing solution used in a developing 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 type of the alkali-soluble resin is not particularly limited as long as it is a type generally used in the technical field, for example, in the field of negative photosensitive resin compositions, and may be a polymer of monomers generally used in the field or a copolymer of 2 or more monomers, and the polymerization step and arrangement of the monomers are not particularly limited, as long as they do not depart from the object of the present invention.
For example, the alkali-soluble resin contains a repeating unit represented by the following chemical formula 5.
(in chemical formula 5, R5Is hydrogen or methyl, R6Is a direct bond or C1-5 alkylene, R7Is a C1-4 linear or branched alkyl or alkenyl group. )
The alkali-soluble resin is cured by a ring opening (ring opening) reaction and polymerization (polymerization) caused by the ring opening reaction, which are thermally induced, through a resin including a repeating unit having the chemical formula 5 in a stage of heat treatment, and thus, the etch resistance based on, for example, an etchant may improve the adhesion and chemical resistance.
The alkali-soluble resin may further have a repeating unit derived from another monomer known in the art, in addition to the repeating unit represented by chemical formula 5.
The other monomer is not particularly limited, and examples thereof include monomers selected from carboxylic acids, dicarboxylic acids, and anhydrides thereof; an aromatic vinyl compound; a vinyl cyanide compound; mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends; alkyl (meth) acrylates; alicyclic (meth) acrylates; aryl (meth) acrylates; (meth) acrylates ring-substituted with C4-16 cycloalkane or bicycloalkane; an unsaturated oxetane compound; unsaturated ethylene oxide compounds, etc. in 1 or 2 or more. More preferably, a (meth) acrylic monomer can be used.
The repeating unit derived from the (meth) acrylic monomer can be represented by, for example, the following chemical formula 6.
(in chemical formula 6, R8Is hydrogen or methyl, R9Is alkyl group having 1 to 6 carbon atoms or cycloalkyl group having 3 to 6 carbon atoms. )
For example, the alkali-soluble resin may include a binder resin represented by the following chemical formula 7.
(in chemical formula 7, a, b, c and d each represent a molar ratio, a is 5 to 50 mol%, b is 5 to 70 mol%, c is 10 to 70 mol%, and d is 5 to 70 mol%)
In chemical formula 7, each repeating unit in brackets can exist freely at any position of the chain within a limited range of mol%. That is, each bracket of chemical formula 7 is represented by one block in order to represent mol%, but each repeating unit may be present as a block or separately from each other without limitation as long as it is within the resin.
The weight average molecular weight of the alkali-soluble resin is not particularly limited, and may be in a range of about 5000 to 35000 from the viewpoint of improving the adhesion and the developability.
The content of the alkali-soluble resin may be appropriately adjusted in consideration of the resolution of a photocured pattern formed therefrom and the uniformity of the pattern. Specifically, the content of the alkali-soluble resin may be in the range of 10 to 50 parts by weight based on 100 parts by weight of the total photosensitive resin composition.
Photopolymerization initiator
The photopolymerization initiator according to the present invention can be used without any particular limitation as long as it can polymerize the polymerizable compound, and for example, at least 1 compound selected from acetophenone compounds, benzophenone compounds, triazine compounds, biimidazole compounds, thioxanthone compounds, and oxime ester compounds can be used, and preferably, biimidazole compounds and/or oxime ester compounds can be used.
In addition, in order to improve the sensitivity of the photosensitive resin composition of the present invention, the photopolymerization initiator may further comprise a photopolymerization initiation aid. The photosensitive resin composition according to the present invention contains a photopolymerization initiation aid, and therefore, the sensitivity is further improved and the productivity can be improved.
The photopolymerization initiator includes 1 or more compounds selected from amine compounds, carboxylic acid compounds, and organic sulfur compounds having a thiol 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 7 parts by weight, based on 100 parts by weight of the total of the photosensitive resin composition.
Within the above content range, the sensitivity and resolution of the exposure process can be improved without hindering the durability of the photocurable pattern.
Additive agent
The photosensitive resin composition of the present invention may further contain additives such as a filler, other macromolecular compound, a curing agent, an adhesion promoter, an antioxidant, a surfactant, an ultraviolet absorber, an anti-agglomerating agent, and a chain transfer agent, as required.
The above additives may be used alone in 1 kind, or in combination of 2 or more kinds.
The content of the additive is not particularly limited, and may be, for example, 0.001 to 2 parts by weight relative to 100 parts by weight of the photosensitive resin composition in total.
Solvent(s)
The solvent is not particularly limited, and any solvent can be used as long as it can dissolve the above-mentioned components, has an appropriate drying rate, and can form a uniform and smooth coating film after evaporation of the solvent.
As the solvent, esters such as alkylene glycol alkyl ether acetates, ketones, butylene glycol alkyl ether acetates, butylene glycol monoalkyl ethers, ethyl 3-ethoxypropionate, and methyl 3-methoxypropionate can be preferably used in consideration of coatability and drying property. More preferably, diethylene glycol methyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, methoxybutyl acetate, methoxybutanol, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.
The content of the solvent may be 30 to 70 parts by weight based on 100 parts by weight of the total photosensitive resin composition. If the above range is satisfied, the coating properties when coating is performed using a coating apparatus such as a spin coater, a slit and spin coater, a slit coater (also sometimes referred to as a "die coater", "curtain flow coater"), or an ink jet coater are preferable because the coating properties are good.
Photo-curing pattern and image display device
The invention aims to provide a photocuring pattern manufactured by the photosensitive resin composition and an image display device with the photocuring pattern.
The photo-cured pattern produced from the photosensitive resin composition has excellent low-temperature curability, chemical resistance, heat resistance and the like. This makes it possible to use the resist composition for various patterns in an image display device, such as an adhesive layer, an array planarization film, a protective film, and an insulating film pattern, and also for a photoresist, a black matrix, a column spacer pattern, a black column spacer pattern, and the like.
Examples of the image display device having such a photo-curing pattern or using the pattern in the manufacturing process include a liquid crystal display device, an OLED, a flexible display, and the like, but the present invention is not limited thereto, and all image display devices known in the applicable field can be used.
The photocurable pattern can be produced by applying the photosensitive resin composition of the present invention described above to a substrate, and if necessary, forming a photocurable pattern after a development step.
Preferred embodiments are given below to aid understanding of the present invention, but these embodiments are merely illustrative of the present invention and do not limit the appended patent claims. It is obvious to a person skilled in the art that within the scope of the scope and the technical idea of the invention, various variations and modifications can be applied to the embodiments, which naturally also belong to the appended patent claims.
Preparation example: synthesis of alkali soluble resin (A) (chemical formula 7)
In a 1L flask equipped with a reflux condenser, a dropping funnel and a stirrer, nitrogen was introduced at a rate of 0.02L/min to form a nitrogen atmosphere, and 250g of propylene glycol monomethyl ether acetate was charged. Then, a solution prepared by adding 3.6g of 2,2' -azobis (2, 4-dimethylvaleronitrile) to a mixture comprising 32.4g (0.45mol) of acrylic acid, 82.9g (0.45mol) of methyl (3-ethyl-3-oxetanyl) methacrylate, 11.8g (0.10mol) of vinyltoluene and 150g of propylene glycol monomethyl ether acetate was added to the flask with heating at 100 ℃ for 2 hours via a dropping funnel, and further stirring was continued at 100 ℃ for 5 hours.
The atmosphere in the flask was changed from nitrogen to air, and 49.8g of glycidyl methacrylate [0.35 mol% (78 mol% relative to acrylic acid used in the present reaction) ] was charged into the flask, and the reaction was continued at 110 ℃ for 6 hours. Thus, an unsaturated group-containing alkali-soluble resin having a solid acid value of 44mgKOH/g was obtained. The weight-average molecular weight in terms of polystyrene measured by GPC was 17500, and the molecular weight distribution (Mw/Mn) was 2.20.
Examples and comparative examples
Photosensitive resin compositions of examples and comparative examples were prepared in the compositions and contents (unit: parts by weight) shown in tables 1 and 2 below.
[ TABLE 1]
[ TABLE 2]
The components used in tables 1 and 2 are as follows.
A: the alkali-soluble resin (chemical formula 7) produced in production example
B-1: dipentaerythritol hexaacrylate (KAYARAD DPHA: manufactured by Nippon Kabushiki Kaisha)
B-2：
B-3：
C-1: biimidazole initiator
C-2: oxime ester initiator
D: antioxidant agent
E-1: diethylene glycol methyl ethyl ether
E-2: propylene glycol monomethyl ether acetate
Examples of the experiments
A2-inch square glass substrate (EAGLE 2000, manufactured by KANGNING corporation) was washed with a neutral detergent, water and alcohol in this order and then dried. On the glass substrate, the photosensitive resin compositions prepared in the above examples and comparative examples were respectively spin-coated and then prebaked at 90 ℃ for 125 seconds using a hot plate.
The substrate pre-baked as described above was cooled to room temperature, and then exposed to an exposure apparatus (UX-1100SM, Ushio Co., Ltd.) at a concentration of 50mJ/cm2The entire surface of the coating film was irradiated with light at an exposure (365nm basis). After the light irradiation, the coating film was immersed in an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 25 ℃ for 60 seconds, developed, and washed with water. Then, in an oven, post-baking was performed at 130 ℃ for 60 minutes. The thickness of the obtained coating film was 3.0. mu.m. The cured films thus obtained were subjected to the following physical property evaluations, and the results are shown in tables 3 and 4 below.
(1) Evaluation of developability
The photosensitive resin compositions of the examples and comparative examples were spin-coated on a glass substrate, and then prebaked. After the substrate subjected to the above prebaking was cooled to room temperature, it was immersed in a 0.04% KOH aqueous solution, and then the dissolution process of the coating film was observed for 60 seconds. The observation results were evaluated according to the following criteria, and a material having a dissolution type was judged to be the most suitable material.
< evaluation criteria >
Dissolving type: as shown in FIG. 1a, dissolution was completed within 30 seconds from the moment the coating film was immersed in the developer
Weak peeling type: as shown in FIG. 1b, the coating film was almost dissolved, but undissolved fine particles remained
Peeling type: as shown in FIG. 1c, the coating film was peeled off as a whole as shown in the photograph, and it took 60 seconds until it was dissolved gradually with the lapse of time
Non-development: the coating film itself is not completely peeled or dissolved even after 60 seconds or more in the state of being immersed in the developing solution
(2) Evaluation of chemical resistance
The photosensitive resin compositions prepared in examples and comparative examples were each spin-coated on a 2-inch square glass substrate (EAGLE 2000, manufactured by corning corporation), and prebaked at 80 ℃ for 125 seconds using a hot plate. The substrate pre-baked as described above was cooled to room temperature, and then exposed to an exposure apparatus (UX-1100SM, Ushio Co., Ltd.) at a concentration of 50mJ/cm2The exposure amount (365nm reference) of (A) was used to irradiate light on the entire surface without a mask. For the exposed coating film, the coating film was immersed in a 2.38% tetramethylammonium hydroxide aqueous solution at 25 ℃ for 60 seconds, developed, washed with water and dried, and then post-baked at 100 ℃ for 60 minutes using a clean oven.
The coating film having a film thickness of 1.5 μm formed as described above was immersed in an NMP solution and treated at 50 ℃ for 3 minutes. Then, the coating film was cut with a cutter under the conditions of the ASTM D-3359-08 standard test, and then a tape was attached to the surface of the film and peeled off, and chemical resistance was confirmed by this method. In the test of the dicing tape after the chemical treatment, the degree of peeling of the coating film was defined as 0B to 5B based on the standard of the standard test method, and the coating film having the most excellent performance was defined as 5B.
5B: 0% peeling (see FIG. 2a)
4B: peeling of less than 5% (see FIG. 2b)
3B: peeling of 5% or more and less than 15% (see FIG. 2c)
2B: peeling at 15% or more and less than 35% (see FIG. 2d)
1B: peeling of 35% or more and less than 65% (see FIG. 2e)
0B: peeling off 65% or more (see FIG. 2f)
(3) Determination of hole pattern size
The pore pattern size of the coating film obtained above at a film thickness of 1.5 μm was measured by SEM, and the pore size of the coating film when the mask pattern size was 10 μm is shown in the table below. In addition, when the hole and the glass substrate did not meet each other and a residual film was formed, it was shown that the size could not be measured.
[ TABLE 3]
[ TABLE 4]
As shown in tables 3 and 4, in the case of examples including both of the polymerizable compounds of chemical formulas 1 and 2, the development type was evaluated as dissolution as compared to the comparative examples as a whole, and it was confirmed that the pore size was large and the chemical resistance was improved. In addition, the mixing ratio between the polymerizable compounds of chemical formula 1 and chemical formula 2 is 1: 2-2: in examples 1 to 7 in the range of 1, the results of excellent chemical resistance and developability were obtained. In the case of example 10 in which the photopolymerizable monomer (B-1) was omitted, the pore size was slightly smaller than in examples 1 to 7.
In the case of comparative example 6, the chemical resistance was relatively excellent, but the coating film was not developed, and a residual film was formed so that the size of the pores could not be measured. In the case of comparative example 7, it was confirmed that the development type was "dissolved", and at the same time, the pore size was large and the chemical resistance was the worst.
Claims (10)
1. A photosensitive resin composition comprising an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator and a solvent, wherein the polymerizable compound comprises a compound represented by the following chemical formula 1 and a compound represented by the following chemical formula 2, the content of the compound represented by the chemical formula 1 is 3 to 12 parts by weight relative to 100 parts by weight of the composition in total, the content of the compound represented by the chemical formula 2 is 3 to 15 parts by weight relative to 100 parts by weight of the composition in total,
[ chemical formula 1]
In chemical formula 1, R1And R2Each independently hydrogen or a linear or branched alkyl group having 1 to 6 carbon atoms, m is an integer of 4 to 12,
[ chemical formula 2]
In chemical formula 2, R3Is a C1-6 saturated hydrocarbon group or a saturated hydrocarbon group containing hetero atoms,
R4independently of each other, hydrogen, acryloxy, succinate or C1-5 linear or branched alkyl, R4Contains at least 2 acryloxy groups, and n is an integer of 3 to 8.
2. The photosensitive resin composition according to claim 1Wherein R of the compound of formula 11And R2Each independently hydrogen.
3. The photosensitive resin composition according to claim 1, wherein the compound of chemical formula 2 is represented by the following chemical formula 3 or 4:
[ chemical formula 3]
[ chemical formula 4]
4. The photosensitive resin composition according to claim 1, wherein a mixing ratio of the compound of chemical formula 1 to the compound of chemical formula 2 is 1: 4-3: 1.
5. the photosensitive resin composition according to claim 4, wherein the mixing ratio of the compound of chemical formula 1 to the compound of chemical formula 2 is 1: 2-1: 1.
6. the photosensitive resin composition according to claim 1, wherein the alkali-soluble resin comprises a binder resin represented by the following chemical formula 7:
[ chemical formula 7]
In chemical formula 7, a, b, c and d each represent a molar ratio, and a is 5 to 50 mol%, b is 5 to 70 mol%, c is 10 to 70 mol%, and d is 5 to 70 mol%.
7. The photosensitive resin composition according to claim 1, wherein the alkali-soluble resin has a weight average molecular weight of 5000 to 35000.
8. A photocured pattern produced from the photosensitive resin composition according to any one of claims 1 to 6.
9. The photocurable pattern of claim 8, wherein the photocurable 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 columnar spacer pattern.
10. An image display device having the photocured pattern of claim 8.
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| CN111978239A (en) * | 2020-08-26 | 2020-11-24 | 阜阳欣奕华材料科技有限公司 | Compound and photosensitive resin composition |
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| JP2003295433A (en) * | 2002-03-28 | 2003-10-15 | Tamura Kaken Co Ltd | Photosensitive resin composition |
| CN103509151A (en) * | 2012-06-25 | 2014-01-15 | 东友Fine-Chem股份有限公司 | Alkali soluble resin and photosensitive resin composition containing the same |
| CN104345559A (en) * | 2013-08-09 | 2015-02-11 | 东友精细化工有限公司 | Colored photosensitive resin composition, color filter and liquid crystal display having the same |
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| JP5155920B2 (en) * | 2008-03-31 | 2013-03-06 | 富士フイルム株式会社 | Photosensitive transparent resin composition, method for producing color filter, and color filter |
| JP2011248274A (en) * | 2010-05-31 | 2011-12-08 | Sanyo Chem Ind Ltd | Photosensitive resin composition |
| EP2725423B1 (en) * | 2011-06-24 | 2021-09-01 | Tokyo Ohka Kogyo Co., Ltd. | Negative-type photosensitive resin composition, pattern forming method, cured film, insulating film, and color filter |
| WO2013012035A1 (en) * | 2011-07-20 | 2013-01-24 | 日本ゼオン株式会社 | Negative-type photosensitive resin composition, resin film, and electronic component |
| JP5827180B2 (en) * | 2012-06-18 | 2015-12-02 | 富士フイルム株式会社 | Imprint curable composition and substrate adhesion composition, and semiconductor device using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003295433A (en) * | 2002-03-28 | 2003-10-15 | Tamura Kaken Co Ltd | Photosensitive resin composition |
| CN103509151A (en) * | 2012-06-25 | 2014-01-15 | 东友Fine-Chem股份有限公司 | Alkali soluble resin and photosensitive resin composition containing the same |
| CN104345559A (en) * | 2013-08-09 | 2015-02-11 | 东友精细化工有限公司 | Colored photosensitive resin composition, color filter and liquid crystal display having the same |
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| TWI710855B (en) | 2020-11-21 |
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